Composition, functional material, and compound
A compound with a trialkylsilyl group and sulfobetaine or carbobetaine group, combined with an anionic surfactant, addresses electrostatic charge issues in silver halide photographic materials, improving coating uniformity and preventing dust adhesion, thus enhancing processing efficiency.
Patent Information
- Application Number
- PCT/JP2025/030824
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-08-30
- Filing Date
- 2025-09-01
- Publication Date
- 2026-03-05
AI Technical Summary
Silver halide photographic materials face issues with electrostatic charge buildup during manufacturing and use, leading to static fog and dust adhesion due to friction, which affects image quality and processing efficiency.
A composition containing a compound with a trialkylsilyl group and a sulfobetaine or carbobetaine group, combined with an anionic surfactant, effectively controls surface tension and reduces electrostatic charge, enhancing coating uniformity and preventing dust adhesion.
The composition achieves low surface tension, improving coating film uniformity and reducing dust adhesion, thereby enhancing the manufacturing and processing efficiency of silver halide photographic materials.
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Abstract
Description
Compositions, functional materials, and compounds
[0001] The present disclosure relates to compositions, functional materials, and compounds.
[0002] In recent years, significant improvements in sensitivity have been achieved in silver halide photographic materials to enhance user benefits. Furthermore, as the manufacturing, exposure, and processing processes of silver halide photographic materials become faster and more automated, they must be able to withstand contact with various rollers and other equipment, as well as friction between other materials. Photosensitive materials generally consist of an electrically insulating support and a photographic emulsion layer. Therefore, electrostatic charge is prone to buildup during the manufacturing process and use of the material due to contact with the surface of the same or different materials, friction caused by peeling, etc. If electrostatic charge builds up before development, the photosensitive layer is exposed to light due to the discharge of this charge, resulting in static fog after development. Furthermore, accumulated electrostatic charge can also lead to problems such as dust adhesion to the photosensitive material.
[0003] Anionic siloxane surfactants are known that are contained in silver halide color photographic materials for the purpose of improving image stability, etc. (Patent Document 1). Novel silicone-modified zwitterionic compounds that are highly soluble in various organic solvents and have low melting points are also known (Patent Document 2). Siloxane derivatives of amino acids that have surface-active properties are also known (Patent Document 3).
[0004] Patent Document 1: JP 2002-303956 A Patent Document 2: JP 2013-234157 A Patent Document 3: JP 2022-545010 A
[0005] An object of one embodiment of the present disclosure is to provide a composition for controlling surface tension.An object of another embodiment of the present disclosure is to provide a functional material or a novel compound that includes the composition.
[0006] Means for solving the above problems include the following aspects. <1> A composition containing compound A and surfactant S, wherein compound A has a trialkylsilyl group and a sulfobetaine group or a carbobetaine group and contains 2 to 6 silicon atoms, and surfactant S is an anionic surfactant that is a sulfonate or a sulfate. <2> The composition according to <1>, wherein compound A includes a structure represented by the following formula (1) or (2):
[0007]
[0008] In formula (1) and formula (2), Rx, Ry, and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by the following formula (3), and at least one of Rx, Ry, and Rz represents a group represented by the following formula (3), and R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, and n is an integer of 1 to 6.
[0009]
[0010] In formula (3), Sil 1 is a group represented by any one of the following formulas (Si-1), (Si-2), (Si-3), and (Si-4), and a plurality of Sil 1 may be the same or different, L 1 is a divalent linking group, and a plurality of L 1 may be the same or different, R is an (x+1)-valent organic residue containing a carbon atom, x is 1 or 2, and the wavy line represents N in formula (1) or formula (2). + represents the binding site with
[0011]
[0012] In formula (Si-1), R 1 is an alkyl group, and a plurality of R 1 may be the same or different. 2is an alkyl group, and a plurality of R 2 may be the same or different, and y is an integer of 1 to 5. In formula (Si-3), R 3 is an alkyl group, and a plurality of R 3 may be the same or different, and z is 2 or 3. In formula (Si-4), R 4 , R 4a , R 4b is an alkyl group, and a plurality of R 4 , R 4a , R 4b may be the same or different, q is 1 or 2, and when q is 1, p is an integer of 1 to 3, and when q is 2, p is 1. In formulas (Si-1), (Si-2), (Si-3), and (Si-4), * represents L in formula (3). 1 <3> The composition according to <2>, wherein the structure represented by formula (1) is a structure represented by the following formula (4):
[0013]
[0014] In formula (4), Sil 1 is a group represented by any one of formula (Si-1), formula (Si-2), formula (Si-3), and formula (Si-4), and R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 21 , R 22 , R 31 , and R 32may be the same or different, a and b each represent an integer of 2 to 6, Ry and Rz each independently represent an alkyl group or aryl group having 1 to 6 carbon atoms, or a group represented by formula (3), w is 0 or 1, i is 1 or 2, and n is an integer of 1 to 6. <4> The composition according to <2> or <3>, wherein the structure represented by formula (2) is a structure represented by the following formula (5):
[0015]
[0016] In formula (5), Sil 1 is a group represented by any one of formula (Si-1), formula (Si-2), formula (Si-3), and formula (Si-4), and R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 21 , R 22 , R 31 , and R 32may be the same or different, a and b each represent an integer of 2 to 6, Ry and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by formula (3), w is 0 or 1, i is 1 or 2, and n is an integer of 1 to 6. <5> The composition according to any one of <1> to <4>, in which the surfactant S is a sulfosuccinate-type anionic surfactant. <6> The composition according to any one of <1> to <5>, in which the surfactant S is sodium bis(2-ethylhexyl)sulfosuccinate. <7> The composition according to any one of <1> to <6>, in which the content ratio of the compound A to the surfactant S is 5:95 to 95:5 by mass. <8> A functional material having a support and, on the support, a layer which is a cured product of the composition according to any one of <1> to <7>. <9> The functional material according to <8>, which is a silver halide photographic light-sensitive material. <10> The functional material according to <8>, which is a diffusion transfer type silver halide photographic light-sensitive material. <11> A compound having a structure represented by the following formula (4) or formula (5):
[0017]
[0018] In formula (4) and formula (5), Sil 1 is a group represented by any one of the following formulas (Si-1) to (Si-4), 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 21 , R 22 , R 31 , and R 32may be the same or different, Ry and Rz each independently represent an alkyl group or an aryl group having 1 to 6 carbon atoms, w is 0 or 1, a and b each represent an integer of 2 to 6, i is 1 or 2, and n is an integer of 1 to 6.
[0019]
[0020] In formula (Si-1), R 1 is an alkyl group, and a plurality of R 1 may be the same or different. 2 is an alkyl group, and a plurality of R 2 may be the same or different, and y is an integer of 1 to 5. In formula (Si-3), R 3 is an alkyl group, and a plurality of R 3 may be the same or different, and z is 2 or 3. In formula (Si-4), R 4 , R 4a , R 4b is an alkyl group, and a plurality of R 4 , R 4a , R 4b may be the same or different, q is 1 or 2, and when q is 1, p is an integer of 1 to 3, and when q is 2, p is 1. In formulas (Si-1), (Si-2), (Si-3), and (Si-4), * represents a bonding site with C in formula (4) or (5).
[0021] According to one embodiment of the present disclosure, a composition for controlling surface tension can be provided. Furthermore, according to another embodiment of the present disclosure, a functional material or a novel compound including the composition can be provided.
[0022] The contents of the present disclosure are described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment. In this specification, the term "to" indicating a numerical range is used to mean that the numerical values before and after it are included as the upper and lower limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. Furthermore, in the description of groups (atomic groups) in this specification, a notation that does not specify whether they are substituted or unsubstituted encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "(meth)acrylic" is a term used as a concept encompassing both acrylic and methacrylic, and "(meth)acryloyl" is a term used as a concept encompassing both acryloyl and methacryloyl. Furthermore, the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, in this disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. Furthermore, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are values measured by gel permeation chromatography (GPC) unless otherwise specified. The GPC measurement was performed using an HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation) as a measuring device, three TSKgel (registered trademark) Super Multipore HZ-H columns (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and THF (tetrahydrofuran) as an eluent.The measurement conditions are a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection volume of 10 μL, and a measurement temperature of 40°C, and the measurement is performed using a refractive index (RI) detector. A calibration curve is prepared from eight samples of "Standard Sample TSK Standard, Polystyrene" from Tosoh Corporation: "F-40," "F-20," "F-4," "F-1," "A-5000," "A-2500," "A-1000," and "n-propylbenzene." In the present disclosure, "total solid content" refers to the total mass of the components excluding the solvent from the entire composition. Furthermore, as described above, "solid content" refers to the components excluding the solvent, and may be, for example, solid or liquid at 25°C. The present disclosure will be described in detail below.
[0023] (Composition) A composition according to one embodiment of the present disclosure contains Compound A and Surfactant S. Compound A has a trialkylsilyl group and a sulfobetaine group or a carbobetaine group, and contains 2 to 6 silicon atoms. Compound A is a compound having a zwitterionic structure. Surfactant S is an anionic surfactant that is a sulfonate or sulfate. The composition according to the present disclosure may contain water, and may also contain other components as necessary.
[0024] Since the composition according to an embodiment of the present disclosure contains both compound A and surfactant S, the surface tension of the composition (preferably an aqueous composition) can be controlled, and the surface tension can be kept low compared to when the composition according to an embodiment of the present disclosure is not used. A coating solution using the composition according to an embodiment of the present disclosure, a coating film formed by applying the coating solution, etc., has an excellently low surface tension, and is excellent in coating film uniformity, coating properties, etc. When the composition according to an embodiment of the present disclosure is used for film or layer formation, etc., the coating surface condition is excellent and the effects such as dust adhesion suppression effect are excellent.
[0025] Although the mechanism by which the composition according to one embodiment of the present disclosure exhibits a surface tension-reducing effect is unclear due to the above-described configuration, the inventors speculate as follows. That is, compound A is a compound having a zwitterionic structure, and although it has a surface tension-controlling effect, this effect is limited. It is speculated that the combined use of compound A and surfactant S causes the two to interact on the surface of the aqueous composition, restricting the molecular orientation of compound A and surfactant S, improving the orientation of hydrophobic groups on the surface of the aqueous composition, thereby exhibiting a surface tension-reducing effect.
[0026] <Surfactant S> The surfactant S is an anionic surfactant that is a sulfonate or sulfate. A conventionally known sulfonate or sulfate can be used as the anionic surfactant. One or more types of surfactant S may be used.
[0027] Examples of the surfactant S include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, α-sulfofatty acid ester salts, sulfosuccinates, etc. Examples of the alkyl ether sulfates include polyoxyethylene alkyl ether sulfates.
[0028] Examples of the counter ion of the anionic residue of the surfactant that is a salt include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; and alkanolamines having 1 to 3 alkanol groups each having 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).
[0029] As the surfactant S, from the viewpoints of water solubility and surface activity, sulfosuccinates are preferred, and sodium bis(2-ethylhexyl) sulfosuccinate is particularly preferred.
[0030] Preferred examples of surfactant S include the following surfactants S-1 to S-7.
[0031]
[0032] <Compound A> Compound A is a compound having a trialkylsilyl group as a hydrophobic group, a sulfobetaine group or a carbobetaine group as a hydrophilic group, and a zwitterionic structure. Compound A contains 2 to 6 silicon atoms. From the viewpoint of achieving both the solubility of Compound A in water and the reduction of the surface tension of the composition according to one embodiment of the present disclosure, the number of silicon atoms contained in Compound A is preferably 2 to 5, and more preferably 2 to 4. From the viewpoint of the reduction of the surface tension, the hydrophilic group contained in Compound A is preferably sulfobetaine. One or more types of Compound A may be used.
[0033] Compound A preferably contains a structure represented by the following formula (1) or (2):
[0034] In formula (1) and formula (2), Rx, Ry, and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by the following formula (3), and at least one of Rx, Ry, and Rz represents a group represented by the following formula (3), and R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, and n is an integer of 1 to 6.
[0035] R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms. 11 and R 12 may be the same or different. As the alkyl group, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. 11 and R 12 are each preferably a hydrogen atom from the viewpoints of water solubility and surfactant ability. n is an integer of 1 to 6, and from the viewpoints of water solubility and surfactant ability, n is preferably an integer of 2 to 4.
[0036] Rx, Ry, and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by the following formula (3). As the alkyl group, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. As the aryl group, a phenyl group can be mentioned.
[0037] Rx, Ry, and Rz may be a group represented by the following formula (3): At least one of Rx, Ry, and Rz is a group represented by the following formula (3).
[0038]
[0039] In formula (3), Sil 1 is a group represented by any one of the following formulas (Si-1), (Si-2), (Si-3), and (Si-4), and a plurality of Sil 1 may be the same or different, L 1 is a divalent linking group, and a plurality of L 1 may be the same or different, R is an (x+1)-valent organic residue containing a carbon atom, x is 1 or 2, and the wavy line represents N in formula (1) or formula (2). + represents the binding site with
[0040] In the formula (3), x is preferably 1 from the viewpoint of water solubility and surfactant ability.
[0041] Sil in formula (3) 1 The number of Si atoms in the above Sil is an integer of 2 to 6. From the viewpoint of water solubility and surface activity, the number is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 3. 1 Is, L 1 It is preferable that the above Sil is bonded to the silicon atom. 1The substituent on the Si atom in is not particularly limited, but from the viewpoint of water solubility and surface activity, it is preferably a hydrocarbon group or an alkoxy group other than a silyl group or a siloxy group, and more preferably a hydrocarbon group. From the viewpoint of water solubility and surface activity, the hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms (also referred to as "number of carbon atoms"), more preferably a methyl group, an ethyl group, or a branched alkyl group having 3 to 6 carbon atoms, even more preferably a t-butyl group or a methyl group, and particularly preferably a methyl group. In addition, when there are a plurality of Sil groups, 1 are preferably the same group.
[0042] The above Sil 1 is preferably a group represented by any one of the following formulas (Si-1) to (Si-4), and more preferably a group represented by the following formula (Si-3) or formula (Si-4), from the viewpoints of water solubility and surfactant ability.
[0043]
[0044] In formula (Si-1), R 1 is an alkyl group, and a plurality of R 1 may be the same or different. 2 is an alkyl group, and a plurality of R 2 may be the same or different, and y is an integer of 1 to 5. In formula (Si-3), R 3 is an alkyl group, and a plurality of R 3 may be the same or different, and z is 2 or 3. In formula (Si-4), R 4 , R 4a , R 4b is an alkyl group, and a plurality of R 4 , R 4a , R 4b may be the same or different, q is 1 or 2, and when q is 1, p is an integer of 1 to 3, and when q is 2, p is 1. In formulas (Si-1), (Si-2), (Si-3), and (Si-4), * represents a bonding site with C in formula (4) or (5).
[0045] R 1 ~R4 , R 4a and R 4b From the viewpoint of water solubility and surfactant properties, the hydrocarbon group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or a branched alkyl group having 3 to 6 carbon atoms, further preferably a t-butyl group or a methyl group, and particularly preferably a methyl group. 1 ~R 4 are preferably the same group. 4a or R 4b When present, they are preferably the same group. In formula Si-2, y is preferably an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1, from the viewpoints of water solubility and surfactant ability. In formula Si-3, z is preferably 2, from the viewpoints of water solubility and surfactant ability. In formula Si-4, p and q are preferably such that q is 2 and p is 1, from the viewpoints of water solubility and surfactant ability.
[0046] L in formula (3) 1 From the viewpoint of water solubility and surfactant ability, is preferably an alkylene group or a group in which an alkylene group is bonded to a polyalkyleneoxy group, more preferably an alkylene group or a group in which an alkylene group is bonded to a polyethyleneoxy group, and particularly preferably an alkylene group. The alkylene group is more preferably an alkylene group having 2 to 10 carbon atoms, even more preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms. In addition, when a plurality of L 1 are preferably the same group. Furthermore, R in formula (3) may be a group having an oxygen atom from the viewpoint of water solubility and surfactant ability. When R is a group having an oxygen atom, it is preferably a group having at least one bond selected from the group consisting of an ester bond and an ether bond, and more preferably a group having at least one ester bond.
[0047] The number of carbon atoms in R in formula (3) is preferably 2 to 20, more preferably 3 to 15, and even more preferably 4 to 10, from the viewpoints of water solubility and surfactant ability.
[0048] From the viewpoints of water solubility and surfactant activity, the structure represented by the above formula (1) is preferably a structure represented by the following formula (4), and the structure represented by the above formula (2) is preferably a structure represented by the following formula (5).
[0049]
[0050] In formula (4) and formula (5), R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 21 , R 22 , R 31 , and R 32 may be the same or different, a and b are each an integer of 2 to 6, w is 0 or 1, and i is 1 or 2. n is an integer of 1 to 6.
[0051] Sil in formula (4) and formula (5) 1 is Sil in formula (3). 1 The preferred embodiments are also the same as those of the formula (4) and the formula (5). 11 and R 12 is R in formula (1) or formula (2). 11 and R 12 The preferred embodiments are also the same.
[0052] The structure represented by formula (4) is included in the structure represented by formula (1) when at least Rx is a group represented by formula (3). The structure represented by formula (5) is included in the structure represented by formula (2) when at least Rx is a group represented by formula (3). Ry and Rz are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by formula (3). When i is 1, Ry and Rz in formulas (4) and (5) are each preferably independently an alkyl group or an aryl group having 1 to 6 carbon atoms. Preferred alkyl groups are methyl groups and ethyl groups, and more preferably methyl groups. Examples of aryl groups include phenyl groups. When i is 2, the structure represented by formula (1) when at least Rx and Rz are groups represented by formula (3), and the structure represented by formula (5) is included in the structure represented by formula (2) when at least Rx and Rz are groups represented by formula (3). When i is 1, Ry in formulas (4) and (5) is preferably an alkyl group or an aryl group having 1 to 6 carbon atoms. As the alkyl group, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. As the aryl group, a phenyl group can be mentioned.
[0053] R in formula (4) and formula (5) 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 21 , R 22 , R 31 , and R 32 may be the same or different. As the alkyl group, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. 21 , R 22 , R 31 , and R 32are preferably hydrogen atoms from the viewpoints of water solubility and surfactant ability. From the viewpoints of water solubility and surfactant ability, a and b preferably satisfy a+b=10 or less, more preferably a+b=8 or less, and even more preferably a+b=6 or less. w is 0 or 1. From the viewpoints of water solubility and surfactant ability, i is preferably 1. n is an integer of 1 to 6, and from the viewpoints of water solubility and surfactant ability, n is preferably an integer of 2 to 4.
[0054] Preferred specific examples of the structure represented by formula (1) or formula (2) include the following A-101 to A-113 and A-1 to A-14.
[0055]
[0056]
[0057]
[0058]
[0059]
[0060] From the viewpoints of water solubility and surfactant activity, the content ratio of compound A to surfactant S is preferably from 5:95 to 95:5, more preferably from 10:90 to 90:10, and even more preferably from 20:80 to 80:20, based on mass. For example, a mass ratio of compound A to surfactant S of 50:50 is also preferred.
[0061] The total content of compound A and surfactant S in the composition according to an embodiment of the present disclosure may be appropriately selected depending on the application, but is preferably 0.0001% by mass to 50% by mass, more preferably 0.001% by mass to 20% by mass, and particularly preferably 0.01% by mass to 10% by mass, relative to the total solid content of the composition according to an embodiment of the present disclosure.
[0062] <Binder> The composition according to an embodiment of the present disclosure may contain a binder. The binder is not particularly limited and may be appropriately selected depending on the application. Furthermore, known binders and known monomers (polymerizable compounds) may be used.
[0063] Examples of binders include epoxy resins, diallyl phthalate resins, silicone resins, phenolic resins, unsaturated polyester resins, polyimide resins, polyurethane resins, melamine resins, urea 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, fluororesins, polyoxymethylene resins, polyamide resins, polyaryl Examples of the resin include acrylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene-maleic acid copolymer resin, polystyrene-acrylic acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formal resin, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof.
[0064] Examples of the polymerizable compound (monomer) include (meth)acrylic monomers, epoxy monomers, oxetanyl monomers, vinyl monomers, etc. The (meth)acrylic monomer is not particularly limited, and examples thereof include known (meth)acrylate compounds, (meth)acrylamide compounds, (meth)acrylic acid, (meth)acrylonitrile, etc. Specific examples include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, and ethylhexyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and hydroxyhexyl (meth)acrylate; alkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; and benzyl (meth)acrylate. aromatic ring-containing (meth)acrylates such as styrene, α-methylstyrene, and chlorostyrene; alicyclic (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, cyclodecyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; N-hydroxyalkyl (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and N-hydroxybutyl (meth)acrylamide;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)acrylonitrile, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 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, and dipentaerythritol hexamethacrylate.
[0065] Examples of epoxy group-containing monomers that are epoxy-based monomers include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, diphenyl ether type epoxy resins, hydroquinone type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, fluorene type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, trifunctional type epoxy resins, tetraphenylolethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol A nucleus-containing polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic type epoxy resins, and heterocyclic type epoxy resins.
[0066] The composition according to an embodiment of the present disclosure may contain one type of binder alone, or may contain two or more types of binders. The content of the binder in the composition according to an embodiment of the present disclosure may be selected appropriately depending on the application, but is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 80% by mass, relative to the total solid content of the composition according to an embodiment of the present disclosure. Furthermore, when the composition according to an embodiment of the present disclosure contains other additives other than the binder, as described below, it is sufficient that the binder is contained in a proportion sufficient to form the desired functional film. In such cases, the content of the binder is preferably 0.5% by mass to 98% by mass, more preferably 2% by mass to 60% by mass, and may be 2% by mass to 50% by mass, relative to the total solid content of the composition according to an embodiment of the present disclosure.
[0067] <Polymerization initiator> The composition according to an embodiment of the present disclosure may contain a polymerization initiator. In particular, when the composition contains the polymerizable compound, it is preferable to contain a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator.
[0068] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. Examples of thermal polymerization initiators include diazo compounds, peroxides, onium salt compounds, etc.
[0069] The composition according to an embodiment of the present disclosure may contain one type of polymerization initiator alone or two or more types. The content of the polymerization initiator in the composition according to an embodiment of the present disclosure may be appropriately selected depending on the application, but is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and particularly preferably 1% by mass to 20% by mass, relative to the total solid content of the composition according to an embodiment of the present disclosure.
[0070] <Curing Agent> The composition according to one embodiment of the present disclosure may contain a curing agent. For example, curing agents for resins having hydroxyl groups include polyisocyanates, partial condensates and polymers of isocyanate compounds, adducts with polyhydric alcohols, low-molecular-weight polyester coatings, blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol, melamine resins, urea resins, polybasic acids or their anhydrides, etc. Furthermore, for example, curing agents for resins having epoxy groups include aliphatic polyamines, aromatic polyamines, polyamidoamines, modified polyamines, polymercaptans, acid anhydrides, phenol resols, phenol novolacs, etc.
[0071] <Solvent> The composition according to an embodiment of the present disclosure may contain a solvent from the viewpoint of coatability, etc. Examples of the solvent include water and a mixed solvent of water and an organic solvent. Water can be used as the solvent in the composition according to an embodiment of the present disclosure, and the composition may contain components other than water, such as an organic solvent.
[0072] As the water, distilled water, ion-exchanged water, etc. can be used. The organic solvent can be appropriately selected depending on the use or purpose of the liquid composition. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons, and alcohols.
[0073] Examples of the ester include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate solvents (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate solvents (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionate solvents (e.g., 2-oxypropionate, alkyl 3-oxypropionate, alkyl 4-oxypropionate, alkyl 5-oxypropionate, alkyl 6-oxypropionate, alkyl 7-oxypropionate, alkyl 8-oxypropionate, alkyl 9-oxypropionate, alkyl 10-oxypropionate, alkyl 11-oxypropionate, alkyl 12-oxypropionate, alkyl 13-oxypropionate, alkyl 14-oxypropionate, alkyl 15-oxypropionate, alkyl 16-oxypropionate, alkyl 17-oxypropionate, alkyl 18-oxypropionate, alkyl 19-oxypropionate, alkyl 20-oxypropionate, alkyl 21-oxypropionate, alkyl 22-oxypropionate, alkyl 23-oxypropionate, alkyl 24-oxypropionate, alkyl 25-oxypropionate, alkyl 26-oxypropionate, alkyl 27-oxypropionate, alkyl 28-oxypropionate, Examples of suitable solvents include methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (specifically, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), 2-oxy-2-methylpropionic acid alkyl ester solvents (methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate)), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, cyclohexyl acetate, and 1-methyl-2-methoxyethyl propionate.
[0074] 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 referred to as PEGMEA), diethylene glycol monoethyl ether acetate (also referred to as ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (also referred to as butyl carbitol acetate), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene.
[0075] Examples of alcohols include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol), and glycol 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, and ethylene glycol monophenyl ether).
[0076] From the viewpoint of further exerting leveling properties or surfactant effects, preferred examples of the solvent include water and at least one solvent selected from the group consisting of water-soluble solvents. Examples of the water-soluble solvent include the substances exemplified as alcohols above, as well as amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, and 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-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and acetone).
[0077] The composition according to an embodiment of the present disclosure may contain one solvent alone or two or more solvents. The content of the solvent in the composition according to an embodiment of the present disclosure may be appropriately selected depending on the application.
[0078] <Other Additives> In addition to the components described above, the composition according to one embodiment of the present disclosure may contain known additives depending on its intended use. Examples of other additives include colorants, surfactants other than Compound A and Surfactant S, leveling agents other than Compound A and Surfactant S, fillers, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, viscosity adjusters, dispersion stabilizers, rust inhibitors, and chelating agents.
[0079] (Functional Material) A functional material according to one embodiment of the present disclosure (hereinafter also referred to as functional material) has a support and a layer that is a cured product of a composition according to one embodiment of the present disclosure on the support.
[0080] The functional material is not particularly limited as long as it has a layer that is a cured product of the composition according to an embodiment of the present disclosure on a support, and suitable examples thereof include photosensitive materials, materials having a protective layer, materials having a conductive layer, materials having an undercoat layer, pressure-responsive materials, and heat-responsive materials. Among these, particularly suitable examples include silver halide photographic photosensitive materials and diffusion transfer type silver halide photographic photosensitive materials, which will be described later.
[0081] <Layer Formed by Curing the Composition According to an Embodiment of the Present Disclosure> Preferred aspects of the composition according to an embodiment of the present disclosure in the functional material are the same as the preferred aspects of the composition according to an embodiment of the present disclosure described above. The functional material may contain one or more types of the composition according to an embodiment of the present disclosure. The layer formed by curing the composition according to an embodiment of the present disclosure may be a single layer or multiple layers. When the functional material is composed of multiple layers, these layers may be formed sequentially or simultaneously by multi-layer coating or the like. The content of the composition according to an embodiment of the present disclosure in the layer of the functional material may be selected appropriately depending on the application. However, the total mass of the solid content of the composition according to an embodiment of the present disclosure relative to the total mass of the layer is preferably 0.0001% by mass to 50% by mass, more preferably 0.001% by mass to 20% by mass, and particularly preferably 0.01% by mass to 10% by mass.
[0082] The above layer may contain known components depending on its intended use. For example, it may contain the above-mentioned binder and polymerization initiator, a colorant, a surfactant other than Compound A and Surfactant S, a leveling agent other than Compound A and Surfactant S, a filler, an anti-fading agent, an emulsion stabilizer, a penetration enhancer, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, a viscosity adjuster, a dispersion stabilizer, a rust inhibitor, a chelating agent, etc. Furthermore, it may contain various components contained in the silver halide photographic light-sensitive material or the diffusion transfer type silver halide photographic light-sensitive material described below.
[0083] The average thickness of the layer is not particularly limited and may be selected depending on the application, but is preferably 0.01 μm to 1 mm, and more preferably 0.1 μm to 200 μm. In the present disclosure, the average thickness is measured as follows: a sample is cut along a plane parallel to the thickness direction, and the thickness is measured at five or more points on the cross section, and the average of these measurements is taken as the average thickness. A composition according to an embodiment of the present disclosure can particularly exhibit the effects of preventing cissing and improving surface condition when the outermost layer of the functional material contains a matting agent that is larger than the average film thickness of the layer. Specifically, the ratio (D / d) of the particle size D of the matting agent to the average film thickness 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 / m 2 ~800 mg / m 2 is preferred, and 20 mg / m 2 ~600 mg / m 2 More preferably, 30 mg / m 2 ~500 mg / m 2 In this case, the binder is preferably a water-soluble colloid, such as gelatin, carboxymethyl cellulose, or polyvinyl alcohol.
[0084] <Usable silicone surfactants> The silicone surfactants shown below can be used as the functional material. The silicone surfactant refers to a surfactant having a polysiloxane structure, and may have a functional group such as a hydrophilic group, a hydrophilic polymer chain, or the like, at a side chain, end, or the like, such as a polyether-modified group, a polyether-alkyl co-modified group, a polyglycerin-modified group, or a polyglycerin-alkyl co-modified group. More specifically, it is preferable to include a silicone surfactant represented by the following general formula (6):
[0085]
[0086] In formula (6), m is an integer of 1 or more and 200 or less, preferably an integer of 2 or more and 100 or less, more preferably an integer of 5 or more and 50 or less; n is an integer of 1 or more and 100 or less, preferably an integer of 2 or more and 80 or less, more preferably an integer of 4 or more and 50 or less. In formula (6), a is an integer of 0 or more and 40 or less, preferably an integer of 35 or less, more preferably an integer of 25 or less, and even more preferably an integer of 15 or less; b is an integer of 0 or more and 40 or less, preferably an integer of 2 or more and 35 or less, more preferably an integer of 4 or more and 25 or less, and even more preferably an integer of 6 or more and 20 or less. (a+b) is preferably an integer of 1 or more and 50 or less, more preferably an integer of 2 or more and 40 or less, and even more preferably an integer of 5 or more and 30 or less. The structural units m, n, a, and b may be block copolymers or random copolymers.
[0087] From the viewpoint of drying property 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. The ratio (m / n) can be determined by proton nuclear magnetic resonance ( 1 The ratio of modified Si element to unmodified Si element is calculated by H-NMR spectroscopy. 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.
[0088] R in general formula (6) 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 still more preferably a methyl group.
[0089] Examples of the polyether-modified silicone surfactant represented by general formula (6) include PEG-3 dimethicone, PEG-9 dimethicone, PEG-9PEG-9 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-11 methyl ether dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, dimethicone / (PEG-10 / 15) crosspolymer, and (PEG-15 / lauryl polydimethylsiloxyethyl dimethicone) crosspolymer.
[0090] 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, BYK-UV3530 (all trade names, manufactured by BYK Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-618, KF-642, KF-643, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-451 No. 5, KF-6011, KF-6012, KF-6013, KF-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 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SAG503A, SAG014 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), TEGO Examples of such silicone rubbers include WET240, TEGO WET270 (trade names, manufactured by Evonik), EMALEX-SS-5602, SS-1906EX (trade names, manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (trade names, manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (trade names, manufactured by BYK-Chemie Co., Ltd.), and TSF4440, TSF4452, TSF4453 (trade names, manufactured by Toshiba Silicon Co., Ltd.).
[0091] <Support> The functional material has a support. Examples of the support include a metal plate, a glass plate, a resin plate, a resin film, a paper support, and a metal foil. The support may also be a laminate having various functional layers. The support may also be surface-treated. The average thickness of the support is not particularly limited, but is preferably from 0.1 μm to 10 cm, and more preferably from 1 μm to 1 mm.
[0092] <Other Layers> The functional material may have other layers between the support and the above-mentioned layer or on the side of the support opposite to the side having the above-mentioned layer, depending on the intended use. The other layers are not particularly limited, and include known layers for known uses.
[0093] (Silver halide photographic light-sensitive material) The functional material is preferably a silver halide photographic light-sensitive material. The silver halide photographic light-sensitive material has a support and a layer containing a composition according to an embodiment of the present disclosure.
[0094] The silver halide photographic light-sensitive material is preferably a material that is sensitive to light, laser or X-ray irradiation, and is suitably selected from, for example, black-and-white reversal film, black-and-white negative film, color reversal film, color negative film, film in which a light-sensitive photographic element has been digitally scanned, black-and-white reversal paper, black-and-white paper, color paper, reversal color paper, paper in which a light-sensitive photographic element has been exposed by laser irradiation from a digital database, and heat-developed light-sensitive material.
[0095] A preferred embodiment of the composition according to an embodiment of the present disclosure in a silver halide photographic light-sensitive material is the same as the preferred embodiment of the composition according to an embodiment of the present disclosure described above. The silver halide photographic light-sensitive material may contain one or more types of compositions according to an embodiment of the present disclosure. The content of the composition according to an embodiment of the present disclosure in the layer of the silver halide photographic light-sensitive material may be appropriately selected depending on the application. The total mass of the solid content of the composition according to an embodiment of the present disclosure is preferably 0.0001% by mass to 50% by mass, more preferably 0.001% by mass to 20% by mass, and particularly preferably 0.01% by mass to 10% by mass, relative to the total mass of the layer.
[0096] The layer may be any layer constituting the silver halide photographic light-sensitive material described below. When a layer is formed by coating, it is preferably the outermost layer during coating. When multiple layers are sequentially laminated, it is preferably used as the outermost layer in each sequential coating. Furthermore, in the silver halide photographic light-sensitive material, the layer containing the composition according to an embodiment of the present disclosure may be one layer or two or more layers. The layer may contain various components contained in the silver halide photographic light-sensitive material described below.
[0097] In one embodiment of the present disclosure, when the composition according to an embodiment of the present disclosure is used in a layer of a photographic light-sensitive material, the aqueous coating composition containing the composition according to an embodiment of the present disclosure may consist only of the composition according to an embodiment of the present disclosure and water, or may contain other components as appropriate depending on the purpose.
[0098] In the above-described aqueous coating composition, a single type of composition according to an embodiment of the present disclosure may be used, or two or more types may be used in combination. Furthermore, a surfactant other than the composition according to an embodiment of the present disclosure may be used together with the composition according to an embodiment of the present disclosure. Usable surfactants include various anionic, cationic, and nonionic surfactants, and may be polymeric surfactants or silicone-based surfactants other than the composition according to an embodiment of the present disclosure. Among these, anionic or nonionic surfactants are more preferred. Specific examples include compounds that can be used in the functional material according to an embodiment of the present disclosure. Furthermore, when targeting photosensitive materials, nonionic surfactants having an alkylene oxide group, particularly among silicone-based surfactants, are preferred because they cause less sensitivity loss during storage of the photosensitive material and, particularly when used with diffusion transfer silver halide photographic photosensitive materials, cause less mordanting inhibition. Examples of surfactants that can be used in combination include those described in JP-A-62-215272 (pp. 649-706), Research Disclosure (RD) Item 17643, pp. 26-27 (December 1978), RD Item 18716, p. 650 (November 1979), and RD 307105, p. 875-876 (November 1989).
[0099] A typical example of a material that may be contained in the aqueous coating composition is a polymer compound. The polymer compound may be a polymer soluble in a water-soluble solvent (a soluble polymer) or an aqueous dispersion of a polymer (a so-called polymer latex). Soluble polymers are not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose. Examples of polymer latexes include homo- 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 nitriles, and other vinyl compounds (e.g., ethylene, vinylidene chloride)), and dispersions of condensation polymers (e.g., polyesters, polyurethanes, polycarbonates, and polyamides). Detailed examples of this type of polymer compound can be found, for example, in JP-A-62-215272 (pp. 707-763), Research Disclosure (RD) Item 17643, p. 651 (December 1978), RD Item 18716, p. 650 (November 1979), and RD Item 307105, p. 873-874 (November 1989).
[0100] The solvent in the aqueous coating composition may be water alone or a mixed solvent of water and an organic solvent other than water (e.g., methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, ethyl acetate, etc.). The proportion of water in the solvent in the aqueous coating composition is preferably 50% by mass or more.
[0101] The aqueous coating composition may contain various compounds depending on the layer of the photographic material to be used, and these may be dissolved or dispersed in the medium. Examples of these compounds include various couplers, ultraviolet absorbers, color mixing inhibitors, static inhibitors, scavengers, antifoggants, hardeners, dyes, and antifungal agents. In order to obtain effective antistatic properties and coating uniformity when used in a photographic material, it is preferable to use the composition in the uppermost hydrophilic colloid layer.
[0102] In this case, the coating composition for the layer may contain, in addition to the hydrophilic colloid (e.g., gelatin) and the composition according to one embodiment of the present disclosure, other surfactants, matting agents, slipping agents, colloidal silica, plasticizers, etc.
[0103] There is no particular limitation on the amount of the composition used according to an embodiment of the present disclosure, and the amount can be arbitrarily changed depending on the structures and applications of compound A and surfactant S in the composition according to an embodiment of the present disclosure, the types and amounts of compounds contained in the aqueous coating composition, the composition of the solvent, etc. For example, when the composition according to an embodiment of the present disclosure is used as a coating solution for the hydrophilic colloid (gelatin) layer that is the uppermost layer of a photographic light-sensitive material, which is a preferred embodiment of the present disclosure, the concentration in the coating solution is preferably 0.003% by mass to 0.5% by mass as the total mass of the solids of the composition according to an embodiment of the present disclosure, and is preferably 0.03% by mass to 10% by mass relative to the gelatin solids.
[0104] In one embodiment of the present disclosure, when a photographic material has a layer made of a hydrophobic binder component, the composition for producing the layer can be a composition according to one embodiment of the present disclosure and a hydrophobic binder component together with an organic solvent. In this case, preferred aspects are the same as those of the layer containing the composition according to one embodiment of the present disclosure described above.
[0105] A silver halide photographic material according to one embodiment of the present disclosure may have at least one photosensitive layer provided on a support. A typical example is a silver halide photographic material having at least one photosensitive layer formed on a support and composed of multiple silver halide emulsion layers having substantially the same color sensitivity but different photosensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue, green, or red light. In a multilayer silver halide color photographic material, the unit photosensitive layers are generally arranged in the following order from the support side: red-sensitive layer, green-sensitive layer, and blue-sensitive layer. However, depending on the purpose, the above arrangement order may be reversed, or a different photosensitive layer may be sandwiched between layers of the same color sensitivity. Non-photosensitive layers may be provided between the above silver halide photosensitive layers, as well as in the top and bottom layers. These may contain couplers, DIR compounds, color-mixing inhibitors, and the like, as described below. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are preferably arranged in two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, in order of decreasing sensitivity toward the support, as described in DE 1,121,470 or GB 923,045. Alternatively, a low-sensitivity emulsion layer may be arranged farther from the support and a high-sensitivity emulsion layer closer to the support, as described in JP-A Nos. 57-112751, 62-200350, 62-206541 and 62-206543.
[0106] Specific examples of the layers may be arranged in the order of low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH, etc., from the side farthest from the support.
[0107] Furthermore, as described in JP-B No. 55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Furthermore, as described in JP-A Nos. 56-25738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Furthermore, as described in JP-B No. 49-15495, an example of an arrangement is one in which the upper layer is a silver halide emulsion layer with the highest photosensitivity, the middle layer is a silver halide emulsion layer with a lower photosensitivity, and the lower layer is a silver halide emulsion layer with an even lower photosensitivity than the middle layer, with the photosensitivity decreasing sequentially toward the support. Even when the film is composed of three layers having different photosensitivities, the layers sensitive to the same color may be arranged in the order of a medium-sensitivity emulsion layer, a high-sensitivity emulsion layer, and a low-sensitivity emulsion layer from the side farthest from the support, as described in JP-A-59-202464.
[0108] Alternatively, the layers may be arranged in the order of high-sensitivity emulsion layer / low-sensitivity emulsion layer / mid-sensitivity emulsion layer, or low-sensitivity emulsion layer / mid-sensitivity emulsion layer / high-sensitivity emulsion layer. Furthermore, even when there are four or more layers, the arrangement may be changed as described above. To improve color reproducibility, it is preferred to arrange a donor layer (CL) with a bilayer effect that has a different spectral sensitivity distribution from the main photosensitive layers such as BL, GL, and RL adjacent to or close to the main photosensitive layers, as described in U.S. Pat. Nos. 4,663,271, 4,705,744, and 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
[0109] The preferred silver halide for use in one embodiment of the present disclosure is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol % or less of silver iodide, and particularly preferred is silver iodobromide or silver iodochlorobromide containing about 2 mol % to about 10 mol % of silver iodide.
[0110] The silver halide grains in the photographic emulsion may be of a regular crystal shape such as a cube, octahedron, or tetradecahedron, an irregular crystal shape such as a sphere or plate, or a crystal with crystal defects such as twin planes, or a combination of these. The grain size of the silver halide may be about 0.2 μm or less, or may be large grains with a projected area diameter of up to about 10 μm, and the emulsion may be either polydispersed or monodispersed.
[0111] Silver halide photographic emulsions that can be used in one embodiment of the present disclosure are described, for example, in Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types," and in Research Disclosure No. 18716 (November 1979), p. 648, "I. Emulsion preparation and types." 307105 (November 1989), pp. 863-865, P. Glafkides, "Physics and Chemistry of Photography", Paul Montel (1967), G.F. Duffin, "Photographic Emulsion Chemistry", Focal Press (1966), V.L. Zelikman, et al., "Making and Coating Photographic Emulsions", Focal Press (1967), The preparation can be carried out by the method described in, for example, "Emulsion, Focal Press, 1964."
[0112] Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628, 3,655,394, and GB 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in one embodiment of the present disclosure. In particular, to improve storage stability, it is preferable to use an emulsion in which 50% or more of the total projected area is occupied by silver halide tabular grains having an aspect ratio of 8 or more. There is no particular upper limit to the aspect ratio, but it is preferably 30 or less. Tabular grains can be readily prepared by the methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520, and GB 2,112,157.
[0113] The crystal structure may be uniform, or may have different halogen compositions in the interior and exterior, or may have a layered structure. Silver halides of different compositions may be epitaxially bonded together, for example, with compounds other than silver halide, such as silver rhodanide or lead oxide. Also, a mixture of grains with various crystal forms may be used.
[0114] The above emulsion may be a surface latent image type in which the latent image is formed mainly on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type in which the latent image is formed both on the surface and inside, but it must be a negative emulsion. Among internal latent image types, the core / shell internal latent image type emulsion described in JP-A No. 63-264740 may also be used, and its preparation method is described in JP-A No. 59-133542. The shell thickness of this emulsion varies depending on the development treatment, etc., but is preferably 3 nm to 40 nm, and particularly preferably 5 nm to 20 nm.
[0115] The silver halide emulsion is usually subjected to physical ripening, chemical ripening and spectral sensitization before use. Additives used in these processes are described in RD Nos. 17643, 18716 and 307105, and the relevant sections thereof are summarized in the table below.
[0116] In the silver halide photographic material according to one embodiment of the present disclosure, two or more types of emulsions differing in at least one of the properties of the photosensitive silver halide emulsion, such as grain size, grain size distribution, halogen composition, grain shape, and sensitivity, can be mixed and used in the same layer. Surface-fogged silver halide grains described in U.S. Pat. No. 4,082,553, internally fogged silver halide grains described in U.S. Pat. No. 4,626,498 and JP-A-59-214852, and colloidal silver are preferably applied to the photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. Internally or surface-fogged silver halide grains refer to silver halide grains that can be developed uniformly (non-imagewise) regardless of whether they are exposed or unexposed areas of the photosensitive material, and their preparation methods are described in U.S. Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grains whose grains are internally fogged may have a different halogen composition. The silver halide used for interior or surface fogging may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The average grain size of these fogged silver halide grains is preferably 0.01 μm to 0.75 μm, and more preferably 0.05 μm to 0.6 μm. The grain shape may be regular or may be a polydisperse emulsion, but monodisperse (at least 95% of the silver halide grains by mass or number have a grain diameter within ±40% of the average grain diameter) is preferred.
[0117] In one embodiment of the present disclosure, it is preferable to use non-photosensitive particulate silver halide. Non-photosensitive particulate silver halide refers to silver halide grains that are not exposed to light during imagewise exposure to obtain a dye image and are not substantially developed during the subsequent development process, and it is preferable that they are not pre-fogged. The particulate silver halide has a silver bromide content of 0 to 100 mol % and may contain silver chloride and / or silver iodide as necessary. Preferably, the particulate silver halide contains 0.5 to 10 mol % silver iodide. The average grain size (average value of the circle-equivalent 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.
[0118] The particulate silver halide can be prepared in the same manner as ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, nor does it need to be spectrally sensitized. However, prior to adding it to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound. Colloidal silver can be incorporated into this particulate silver halide grain-containing layer.
[0119] The coated silver amount of the silver halide photographic light-sensitive material according to one embodiment of the present disclosure is 6.0 g / m 2 Preferably, 4.5 g / m or less 2 The following is more preferred:
[0120] Photographic additives that can be used in one embodiment of the present disclosure are also described in the RD, and the relevant descriptions are shown in the table below.
[0121]
[0122] In the silver halide photographic light-sensitive material according to one embodiment of the present disclosure, various dye-forming couplers can be used, but the following couplers are particularly preferred. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (particularly Y-28 on page 18); couplers represented by formula (I) in claim 1 of EP 568,037A couplers represented by formula (I) in lines 45 to 55 of column 1 of U.S. Pat. No. 5,066,576; couplers represented by formula (I) in paragraph 0008 of JP-A No. 4-274425; couplers described in claim 1 on page 40 of EP 498,381 A1 (particularly D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969 A1 (particularly Y-1 (page 17) and Y-54 (page 41)); and couplers represented by formulas (II) to (IV) in lines 36 to 58 of column 7 of U.S. Pat. No. 4,476,219 (particularly II-17, II-19 (column 17) and II-24 (column 19)).
[0123] Magenta couplers: JP-A No. 3-39737 (L-57 (bottom right on page 11), L-68 (bottom right on page 12), L-77 (bottom right on page 13); A-4-63 (page 134), A-4-73,-75 (page 139) of EP 456,257; M-4,-6 (page 26), M-7 (page 27) of EP 486,965; M-45 (page 19) of EP 571,959A; (M-1) (page 6) of JP-A No. 5-204106; M-22 in paragraph 0237 of JP-A No. 4-362631.
[0124] Cyan couplers: CX-1, 3, 4, 5, 11, 12, 14, and 15 (pages 14 to 16) of JP-A-4-204843; C-7, 10 (page 35), 34, 35 (page 37), (I-1), and (I-17) (pages 42 to 43) of JP-A-4-43345; and couplers represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
[0125] Polymer couplers: P-1 and P-5 of JP-A No. 2-44345 (page 11). Preferred couplers producing color-forming dyes with appropriate diffusibility are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, and German Patent No. 3,234,533.
[0126] Preferred couplers for correcting unwanted absorption of color-forming dyes include yellow-colored cyan couplers represented by formulae (CI), (CII), (CIII), and (CIV) described on page 5 of European Patent Application Publication No. 456,257A1 (particularly YC-86 on page 84), yellow-colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) described in European Patent Application Publication No. 456,257A1, magenta-colored cyan couplers CC-9 (column 8) and CC-13 (column 10) described in U.S. Pat. No. 4,833,069, (2) (column 8) of U.S. Pat. No. 4,837,136, and colorless masking couplers represented by formula (A) in claim 1 of International Publication No. 92 / 11575 (particularly the exemplified compounds on pages 36 to 45).
[0127] Examples of couplers that release a photographically useful group include the following: Development inhibitor-releasing compounds: compounds represented by formula (I), (II), (III), and (IV) described on page 11 of European Patent Application Publication No. 378,236A1 (particularly 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 (particularly D-49 (page 51)), and compounds represented by formula (II) described on page 13 of European Patent Application Publication No. 436,938A2 (particularly D-49 (page 51)). Compounds represented by formula (1) in JP-A-568,037A (particularly (23) (page 11)), compounds represented by formulas (I), (II), (III) described on pages 5 to 6 in EP-A-440,195A2 (particularly I-(1) on page 29); bleach accelerator-releasing compounds: compounds represented by formulas (I) and (I') on page 5 in EP-A-310,125A2 (particularly (60) and (61) on page 61) and claim 1 in JP-A-6-59411 Ligand-releasing compounds: compounds represented by formula (I) (particularly (7) (page 7)); Ligand-releasing compounds: compounds represented by LIG-X (particularly compounds in columns 21 to 41 of column 12) described in claim 1 of U.S. Pat. No. 4,555,478; Leuco dye-releasing compounds: compounds 1 to 6 in columns 3 to 8 of U.S. Pat. No. 4,749,641; Fluorescent dye-releasing compounds: compounds represented by COUP-DYE (particularly compounds in columns 7 to 1 of U.S. Pat. No. 4,774,181) described in claim 1 of U.S. Pat. No. 4,656,123 (particularly, (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2; compounds which release a group that becomes a dye only upon detachment: compounds represented by formula (I) in claim 1 of U.S. Pat. No. 4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36).
[0128] The following are preferred additives other than couplers: dispersion media of oil-soluble organic compounds: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (pages 140 to 144) of JP-A-62-215272; impregnation latexes of oil-soluble organic compounds: latexes described in U.S. Pat. No. 4,199,363; oxidized developer scavengers: compounds represented by formula (I) in lines 54 to 62 of column 2 of U.S. Pat. No. 4,978,606 (particularly I-, (1), (2), (6), and (12) (columns 4 to 5), and compounds represented by formula (I) in lines 5 to 10 of column 2 of U.S. Pat. No. 4,923,787. (particularly Compound 1 (column 3); stain inhibitors: formulas (I) to (III) on page 4, lines 30 to 33 of European Patent Application Publication No. 298321A, particularly I-47, 72, III-1, and 27 (pages 24 to 48); discoloration inhibitors: A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, and 164 (pages 69 to 118) of European Patent Application Publication No. 298321A, II-1 to III-23 on columns 25 to 38 of U.S. Pat. No. 5,122,444, particularly III-10, European Patent Application I-1 to III-4, especially II-2, on pages 8 to 12 of Published Patent Application No. 471347A, and A-1 to A-48, especially A-39 and A-42, on columns 32 to 40 of U.S. Pat. No. 5,139,931; materials for reducing the amount of color-developing enhancer or color-mixing inhibitor used: I-1 to II-15, especially I-46, on pages 5 to 24 of Published European Patent Application No. 411324A; formalin scavenger: SCV-1 to SCV-28, especially SCV-8, on pages 24 to 29 of Published European Patent Application No. 477932A; hardener: H- on page 17 of JP-A-1-214845 1, 4, 6, 8, 14, compounds represented by formulas (VII) to (XII) (H-1 to H-54) in columns 13 to 23 of U.S. Pat. No. 4,618,573, compounds represented by formula (6) (H-1 to H-76) at the bottom right of page 8 of JP-A-2-214852, particularly H-14, and compounds described in claim 1 of U.S. Pat. No. 3,325,287; development inhibitor precursors: P-24, P-37, P-39 (pages 6 to 7) of JP-A-62-168139; compounds described in claim 1 of U.S. Pat. No. 5,019,492, particularly P-28 and P-29 in column 7;Antiseptics and antifungal agents: I-1 to III-43 in columns 3 to 15 of U.S. Pat. No. 4,923,790, particularly II-1, 9, 10, 18, and III-25; stabilizers and antifogging agents: I-1 to (14), in columns 6 to 16 of U.S. Pat. No. 4,923,793, particularly I-1, 60, (2), and (13); and compounds 1 to 65, in columns 25 to 32 of U.S. Pat. No. 4,952,483, particularly 36; chemical sensitizers: triphenylphosphine selenide, JP-A-5-4 Dyes: a-1 to b-20, particularly a-1, 12, 18, 27, 35, 36, b-5, and V-1 to 23, particularly V-1, on pages 15 to 29 of JP-A-3-156450; F-I-1 to F-II-43, particularly F-I-11 and F-II-8, on pages 33 to 55 of EP-A-445627A; III-1 to 36, particularly III-1 and III-3, on pages 17 to 28 of EP-A-457153A; Microcrystalline dispersions of Dye-1 to Dye-124 of 8 to 26 in International Publication No. 88 / 04794, compounds 1 to 22, particularly compound 1, of pages 6 to 11 in EP 319999A, compounds D-1 to D-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 U.S. Pat. No. 4,268,622 (columns 3 to 10), and compound (1) represented by formula (I) in U.S. Pat. No. 4,923,788. to (31) (columns 2 to 9); UV absorbers: compounds (18b) to (18r) and 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A-46-3335, compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (page 14) represented by formula (III) in EP-A-520938A, and compounds (1) to (31) (columns 2 to 9) represented by formula (1) in EP-A-521823A.
[0129] The silver halide photographic light-sensitive material according to an embodiment of the present disclosure can be applied to various color light-sensitive materials such as black-and-white photographic paper, black-and-white negative film, X-ray film, color negative film for general use or cinema, color reversal film for slides or television, color paper, color positive film, and color reversal paper. It is also suitable for use in the lens-fitted film units described in Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication No. 3-39784.
[0130] Suitable supports that can be used in one embodiment of the present disclosure are described, for example, in the above-mentioned RD. No. 17643, page 28, RD. No. 18716, page 647 (right column) to page 648 (left column), and RD. No. 307105, page 879.
[0131] In the silver halide photographic light-sensitive material according to an embodiment of the present disclosure, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. 1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. 1/2 is defined as the time it takes for the film thickness to reach half of the saturated film thickness, which is 90% of the maximum swollen film thickness reached when processed in a color developer at 30°C for 3 minutes and 15 seconds. The film thickness means the film thickness measured under conditioned conditions of 25°C and 55% relative humidity (for 2 days), and T 1/2 can be measured by using a swellometer of the type described by A. Green et al., Photogr. Sci. Eng., Vol. 19, pp. 2124-129. 1/2 The swelling ratio can be adjusted by adding a hardener to the gelatin binder or by changing the aging conditions after coating. The swelling ratio is preferably 150% to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the above conditions using the formula: (maximum swollen film thickness - film thickness) / film thickness.
[0132] In the silver halide photographic light-sensitive material according to one embodiment of the present disclosure, a hydrophilic colloid layer (referred to as a backing layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the emulsion layer. This backing layer preferably contains the above-mentioned light absorbers, filter dyes, ultraviolet absorbers, antistatic agents, film hardeners, binders, plasticizers, lubricants, coating aids, and surfactants. The swelling ratio of this backing layer is preferably 150% to 500%.
[0133] The silver halide photographic light-sensitive material according to one embodiment of the present disclosure can be developed by a conventional method described in the above-mentioned RD. No. 17643, pages 28 to 29, RD. No. 18716, left to right columns of section 651, and RD. No. 307105, pages 880 to 881.
[0134] In one embodiment of the present disclosure, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate, sulfonate, cationic polymers, ionic surfactant compounds, and π-electron conjugated conductive polymers. Preferable antistatic agents include ZnO, TiO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , SiO 2 , MgO, BaO, MoO 3 , V 2 O 5 At least one selected from the group having a volume resistivity of 10 7 Ω cm or less, more preferably 10 5 These particles are crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.) with a particle size of 0.001 μm to 1.0 μm and a viscosity of Ω·cm or less, or particles of sol-state metal oxides or composite oxides thereof. The content of these particles in a silver halide photographic light-sensitive material is 5 mg / m 2 ~500 mg / m 2 is preferred, and 10 mg / m 2 ~350 mg / m 2The ratio of the amount of the conductive crystalline oxide or composite oxide thereof to the binder is preferably 1 / 300 to 100 / 1, more preferably 1 / 100 to 100 / 5. Examples of π-electron conjugated conductive polymers include polythiophene compounds, polypyrrole compounds, and polyfuran compounds. Preferably, a latex-like aqueous dispersion containing a polythiophene compound and a polymeric polyanion compound can be used. For detailed structure of the compound, composition of the dispersion, and preferred embodiments of the dispersant used in combination, the methods described in JP-A-2003-330145, JP-A-4244541, JP-A-2016-120650, and JP-A-8-211615 can be used.
[0135] The silver halide photographic light-sensitive material according to an embodiment of the present disclosure preferably has slipperiness. A slip-agent-containing layer is preferably used on both the light-sensitive layer surface and the back surface. The preferred slipperiness is a dynamic friction coefficient of 0.01 to 0.25. The measurement is the value when conveyed at 60 cm / min against a 5 mm diameter stainless steel ball (25°C, 60% RH). Even if the light-sensitive layer surface is used as the counter material in this evaluation, the value is approximately the same.
[0136] Examples of usable slip agents in an embodiment of the present disclosure include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Examples of polyorganosiloxanes that can be used include polydimethylsiloxanes, polydiethylsiloxanes, polystyrylmethylsiloxanes, and polymethylphenylsiloxanes. The outermost layer or back layer of the emulsion layer is preferred as the additive layer. Polydimethylsiloxane or an ester having a long-chain alkyl group is particularly preferred.
[0137] The silver halide photographic light-sensitive material according to an embodiment of the present disclosure preferably contains a matting agent. The matting agent may be added to either the emulsion side or the backside, but it is particularly preferred to add it to the outermost layer on the emulsion side. The matting agent may be either soluble or insoluble in the processing solution, and it is preferable to use both. Examples of suitable matting agents include polymethyl methacrylate, poly(methyl methacrylate / methacrylic acid = 9 / 1 or 5 / 5 (molar ratio)), and polystyrene particles. The particle size is preferably 0.8 μm to 10 μm, and a narrow particle size distribution is also preferred, with 90% or more of the total particle number preferably falling within a range of 0.9 to 1.1 times the average particle size. To enhance matting properties, it is also preferable to simultaneously add particles of 0.8 μm or less. Examples include 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).
[0138] The silver halide photographic light-sensitive material according to an embodiment of the present disclosure may contain other known additives in each layer. Furthermore, even if the silver halide photographic light-sensitive material according to an embodiment of the present disclosure is not sensitive to X-ray radiation, the configuration and components of a silver halide photographic light-sensitive material that is sensitive to X-ray radiation, as described below, may be used, if necessary.
[0139] Further, silver halide photographic materials that are sensitive to X-ray irradiation will be explained below.
[0140] Preferred examples of the silver halide photographic light-sensitive material include silver halide photographic light-sensitive materials that are sensitive to X-ray irradiation.
[0141] [Silver Halide Emulsion] First, the silver halide emulsion used in the present disclosure will be described.
[0142] 1) Halogen Composition: Photosensitive silver halide grains can be silver chloride, silver chlorobromide, silver bromide, silver iodobromide, or silver iodochlorobromide. However, as mentioned above, from the viewpoint of rapid processing, the average iodine content of the photosensitive silver halide grains is preferably 0 mol % to 0.45 mol %. This iodine content is more preferably 0.05 mol % to 0.40 mol %, and even more preferably 0.10 mol % to 0.30 mol %. Here, the "average" iodine content of the photosensitive silver halide grains refers to the average iodine content determined from the halogen composition of each photosensitive silver halide grain. The halogen composition distribution within the photosensitive silver halide grains may be uniform, stepwise, or continuously varying. Furthermore, photosensitive silver halide grains having a core / shell structure may also be used.
[0143] 2) Grain Shape: Suitable examples of photosensitive silver halide grains include so-called halogen conversion type grains, as described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. Halogen conversion is usually achieved by adding an aqueous halide solution having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion. For example, conversion is achieved by adding an aqueous potassium bromide and / or potassium iodide solution to silver chloride or silver chlorobromide tabular grains, or by adding an aqueous potassium iodide solution to silver bromide or silver iodobromide tabular grains. The concentration of these aqueous solutions added is preferably low, preferably 30% or less, and more preferably 10% or less. Furthermore, it is preferred to add the conversion halide solution at a rate of 1 mol% per minute or less per mole of silver halide before halogen conversion. Furthermore, during halogen conversion, a sensitizing dye and / or a silver halide adsorbent may be present in part or in whole, and silver halide grains such as silver bromide, silver iodobromide, or silver iodide may be added instead of the converted halogen aqueous solution. The size of these fine grains is preferably 0.2 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. The halogen conversion method is not limited to the above-mentioned methods, and can be used in combination as appropriate depending on the purpose.
[0144] 3) Grain Size: Methods for forming photosensitive silver halide grains are well known in the art, and they can be prepared by using, for example, the methods described in JP-A No. 2-68539, U.S. Pat. No. 3,700,458, and Research Disclosure No. 17029, June 1978.
[0145] 4) Chemical sensitization methods that can be used include those described in JP-A No. 2-68539, page 10, upper right column, line 13 to lower left column, line 16, JP-A Nos. 5-313282 and 6-110144. Specific examples of methods for chemical sensitization of silver halide emulsions include known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization in the presence of a silver halide adsorbent, and these methods can be used alone or in combination.
[0146] Among the noble metal sensitization methods, gold sensitization is a typical example, using gold compounds, primarily gold complex salts. Complex salts of noble metals other than gold, such as platinum, palladium, and iridium, may also be used. Specific examples are described in U.S. Pat. No. 2,448,060 and British Patent No. 618,061. Sulfur sensitizers that can be used include sulfur compounds contained in gelatin, as well as various sulfur compounds, such as thiosulfates, thioureas, thiazoles, and rhodanines. Specific examples are described in U.S. Pat. Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, 5,501,313, and 3,656,955. Selenium sensitizers are described in JP-A-6-110144. The combined use of sulfur sensitization with thiosulfate, selenium sensitization, and gold sensitization is useful. As reduction sensitizers, stannous salts, amines, formamine disulfide acid, silane compounds, etc. can be used.
[0147] 5) Antifoggants and stabilizers Examples of antifoggants and stabilizers that can be used include those described in JP-A No. 2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7, and page 3, lower left column, line 2 to page 4, lower left column.
[0148] Specifically, compounds known as antifogging agents or stabilizers, such as azoles (for example, benzothiazolium salts, etroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, chromobenzimidazoles, nitroindazoles, benzotriazoles, and aminotriazoles); mercapto compounds (for example, mercaptothiazoles, mercaptobenzithiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidazoles, and mercaptotriazines); thioketo compounds such as oxadrinethione; azaindenes (for example, triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes); and benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide, may be added.
[0149] In particular, nitrones and derivatives thereof described in JP-A-60-76743 and JP-A-60-87322, mercapto compounds described in JP-A-60-80839, heterocyclic compounds described in JP-A-57-164735, and complex salts of heterocyclic compounds and acids (for example, 1-phenyl-5-mercaptotetrazoles) can be preferably used.
[0150] Furthermore, purines or nucleic acids, or polymeric compounds described in JP-B No. 61-36213 and JP-A No. 59-90844 can also be used. Among these, azaindenes, purines, and nucleic acids are particularly preferred. The amount of these compounds added is preferably 0.5 to 5.0 mmol, more preferably 0.5 to 3.0 mmol, per mol of silver halide.
[0151] 6) Color Tone Improver Examples of color tone improvers include those described in JP-A No. 62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20, and JP-A No. 3-94249, page 6, lower left column, line 15 to page 11, upper right column, line 19. Specifically, the covering power of the silver halide photographic emulsion layer is set to 60 or more, and the silver halide photographic emulsion layer and / or other layers can contain a dye having a maximum absorption wavelength between 520 nm and 560 nm and a dye having a maximum absorption wavelength between 570 nm and 700 nm, so that the increase in optical density due to the contained dyes in the transmission density of the unexposed area after development processing is 0.03 or less.
[0152] Typical examples of emulsions that provide a covering power of 60 or more for a silver halide photographic emulsion layer include tabular emulsions and grain emulsions. In particular, when the silver halide photographic emulsion is composed of tabular silver halide grains with a grain thickness of 0.4 μm or less, or when a mixed emulsion of a high iodine surface photosensitive emulsion and an emulsion composed of grains with internal fogging is used, the effect of improving color tone is significant. Dyes that can be used to improve color tone include a combination of a dye having a maximum absorption wavelength preferably between 520 nm and 560 nm, more preferably between 530 nm and 555 nm, and a dye having 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 when the dye is present in the photosensitive material.
[0153] Dyes having a predetermined maximum wavelength are selected from, for example, anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, etc. Taking into consideration stability to development processing, light fastness, and effects on photographic performance such as desensitization, fogging, and staining, preferred dyes are used from anthraquinone dyes, azo dyes, azomethine dyes, and indoaniline dyes. Preferred compounds are described in JP-A No. 62-276539, page 3, upper left column, line 5 to page 9, upper left column, line 9. Such dyes can be dispersed in emulsion layers and other hydrophilic colloid layers (e.g., intermediate layers, protective layers, antihalation layers, filter layers) by various known methods, and specific examples are described in JP-A No. 62-276539, page 9, upper left column, line 14 to page 10, lower left column, line 20.
[0154] 7) Spectral sensitizing dyes Examples of spectral sensitizing dyes include those described in JP-A No. 2-68539, page 4, line 4, lower right column to page 8, lower right column. Specific examples include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxonol dyes. Sensitizing dyes are described in, for example, U.S. Pat. Nos. 3,522,052, 3,617,197, 3,713,828, 3,615,643, 3,615,632, 3,617,293, 3,628,964, 3,703,377, 3,666,480, 3,667,960, 3,679,428, 3,672,897, 3,769,026, 3,556,800, 3,615,613, 3,613, These sensitizing dyes are described in, for example, Japanese Patent Application Laid-Open Nos. 638, 3,615,635, 3,705,809, 3,632,349, 3,677,765, 3,770,449, 3,770,440, 3,769,025, 3,745,014, 3,713,826, 3,567,458, 3,625,698, 2,526,632, 2,503,776, JP-A-48-76525, and Belgian Patent No. 691807. The amount of sensitizing dye added 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, per mole of silver halide. Specific examples of sensitizing dyes include II-1 to II-47 described on pages 5 to 8 of JP-A No. 2-68539.
[0155] 8) Antistatic Agent In one embodiment of the present disclosure, surfactants described in JP-A-2-68539, page 11, upper left column, line 14 to page 12, upper left column, line 9, can be used as a coating aid, antistatic agent, or charge control agent. Furthermore, a composition according to an embodiment of the present disclosure may be used as the coating aid, antistatic agent, or charge control agent. Specific examples of surfactants that can be used for such purposes include nonionic surfactants such as saponin (steroid-based), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, and silicone polyethylene oxide compounds), and sugar alkyl esters; anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyltaurines, 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 imidazolium salts.
[0156] Among these, anions such as saponin, dodecylbenzenesulfonate Na salt, di-2-ethylhexyl α-sulfosuccinate Na salt, p-octylphenoxyethoxyethanesulfonate Na salt, dodecyl sulfate Na salt, triisopropylnaphthalenesulfonate Na salt, and N-methyl-oleoyl taurine Na salt; cations such as dodecyltrimethylammonium chloride, N-oleoyl-N',N',N'-trimethylammoniodiaminopropane bromide and dodecylpyridinium chloride; betaines such as N-dodecyl-N,N-dimenalcarboxybetaine and N-oleyl-N,N-dimethylsulfobutylbetaine; and nonions such as poly(average polymerization degree n-10)oxyethylene cetyl ether, poly(n=25)oxyethylene p-nonylphenol ether, and bis(1-poly(n=15)oxyethylene-oxy-2,4-di-t-pentylphenyl)ethane can be particularly preferably used. As the antistatic agent, nonionic surfactants described in JP-A Nos. 60-80848, 61-112144, 62-172343, 62-173459, and the like, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides of these doped with antimony or the like can be preferably used.
[0157] 9) Matting Agents, Slipping Agents, and Plasticizers Examples of matting agents, slipping agents, and plasticizers include those described in JP-A No. 2-68539, page 12, upper left column, line 10 to the upper right column, line 10, and page 14, lower left column, line 10 to the lower right column, line 1. Specific examples of matting agents that can be used include fine particles of polymethyl methacrylate homopolymers or copolymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, as described in U.S. Pat. Nos. 2,992,101, 2,701,245, 4,142,894, and 4,396,706, and inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium. The particle size is preferably 1.0 μm to 10 μm, and particularly preferably 2 μm to 5 μm. In the surface layer of the silver halide photographic light-sensitive material according to an embodiment of the present disclosure, as a lubricant, in addition to silicone compounds described in U.S. Patent Nos. 3,489,576 and 4,047,958, and colloidal silica described in JP-B-56-23139, paraffin wax, higher fatty acid esters, starch derivatives, and the like can be used.
[0158] Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layers of the silver halide photographic light-sensitive material according to an embodiment of the present disclosure. Furthermore, plasticizers such as polymers and emulsions can be incorporated into the emulsion layers of the silver halide photographic light-sensitive material according to an embodiment of the present disclosure to improve pressure characteristics. For example, British Patent No. 738618 discloses heterocyclic compounds, British Patent No. 738637 discloses alkyl phthalates, British Patent No. 738639 discloses alkyl esters, U.S. Patent No. 2,960,404 discloses polyhydric alcohols, U.S. Patent No. 3,121,060 discloses carboxyl alkyl celluloses, Japanese Patent Laid-Open No. 49-5017 discloses paraffins and carboxylic acid salts, and Japanese Patent Publication No. 53-28086 discloses alkyl acrylates and organic acids. These methods can also be used in embodiments of the present disclosure.
[0159] 10) Hydrophilic colloid: 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 light-sensitive material according to one embodiment of the present disclosure, but other hydrophilic colloids can also be used. Examples of hydrophilic colloids include those described in JP-A No. 2-68539, page 12, upper right column, line 11 to lower left column, line 16.
[0160] For example, various synthetic hydrophilic polymeric substances can be used, such as gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; 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, polyvinylimidazole, and polyvinylpyrazole. In addition to lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin may also be used. Furthermore, gelatin hydrolysates and enzyme-decomposed products may also be used. Among these, it is preferable to use gelatin in combination with dextran or polyacrylamide having an average molecular weight of 100,000 or less. The methods described in JP-A-63-68887 and JP-A-63-149641 can also be used in an embodiment of the present disclosure.
[0161] 11) Hardeners The photographic emulsion and non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. Examples of hardeners include those described in JP-A No. 2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6. Specific examples of such compounds that can be used alone or in combination include chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, dimethicone aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl dantoin, 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)), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), isoxazoles, dialdehyde starch, and 2-chloro-6-hydroxytriazinylated gelatin. Of these, the active vinyl compounds described in JP-A Nos. 53-41221, 53-57257, 59-162546 and 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferred.
[0162] As the hardener, polymeric hardeners can also be effectively used. Examples of polymeric hardeners include polymers having an aldehyde group such as dialdehyde starch, polyacrolein, and acrolein copolymers described in U.S. Pat. No. 3,396,029, polymers having an epoxy group described in U.S. Pat. No. 3,623,878, polymers having a dichlorotriazine group described in U.S. Pat. No. 3,362,827 and Research Disclosure No. 17333 (1978), polymers having an active ester group described in JP-A-56-66841, and polymers having an active ester group described in JP-A-56-142524, U.S. Pat. No. 4,161,407, JP-A-54-65033, and Research Disclosure No. 17333 (1978). 16725 (1978), etc., and polymers having an active vinyl group or a group that will be its precursor are preferred, and among these, polymers in which an active vinyl group or a group that will be its precursor is bonded to the polymer main chain via a long spacer, as described in JP-A-56-142524, are particularly preferred. The hydrophilic colloid layer in the silver halide photographic light-sensitive material according to an embodiment of the present disclosure is preferably hardened with such a hardener so that the swelling ratio in water is 300% or less, particularly 230% or less.
[0163] 12) Support: Examples of the support include those described in JP-A No. 2-68539, page 13, upper right column, lines 7 to 20. Specifically, polyethylene terephthalate film or cellulose triacetate film is preferred. To improve adhesion to the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment. Alternatively, a subbing layer made of styrene butadiene latex, vinylidene chloride latex, or the like may be provided, and a gelatin layer may be further provided thereon. Alternatively, a subbing layer made of an organic solvent containing a polyethylene swelling agent and gelatin may be provided. Surface treatment of these subbing layers can further improve adhesion to the hydrophilic colloid layer.
[0164] 13) Crossover Cut Method It is well known in the art that crossover light significantly reduces sharpness. As a means for keeping the crossover light of a photographic material to 12% or less, U.S. Pat. No. 4,130,429 and JP-A-61-116354 disclose methods for absorbing light of a wavelength that coincides with the emission wavelength of an X-ray fluorescent screen using a sensitizing dye or dye.
[0165] Furthermore, U.S. Pat. No. 4,800,150 discloses a technique in which a dye is present in the form of a microcrystalline dispersion between the support and the emulsion layer, thereby reducing crossover light to 10% or less. Japanese Patent Application Laid-Open No. 63-305345 discloses a technique in which an anionic dye is fixed in a specific layer using a cationic polymer latex, and Japanese Patent Application Laid-Open No. 1-166031 discloses a technique in which the dye fixing layer is an undercoat layer of the support. While any of these methods can be used in the photosensitive material according to one embodiment of the present disclosure, it is preferred that the dye-colored layer be an undercoat layer, and that the dye be fixed by the method described in Japanese Patent Application Laid-Open No. 1-166031. It is particularly preferred that the dye be fixed in the undercoat layer in the form of a microcrystalline dispersion described in U.S. Pat. No. 4,803,150. In one embodiment of the present disclosure, these methods can be combined as appropriate. Preferred dyes include those described in Japanese Patent Application Laid-Open No. 2-264944, from the lower left column on page 4 to the upper right column on page 9. As the mordant layer, those described in the lower right column to the upper right column of page 14 of JP-A No. 2-264944 can be used.
[0166] 14) Polyhydroxybenzenes Examples of polyhydroxybenzenes include those described in JP-A No. 3-39948, page 11, upper left column to page 12, lower left column, and European Patent Application Publication No. 452772A. Specific examples include the compound of formula (III) described in JP-A No. 8-39948, page 11, upper left column, and specific compounds thereof, compounds (III)-1 to 25, described in JP-A No. 8-39948, page 11, lower left column to page 12, lower left column. The amount of these polyhydroxybenzene compounds to be added is 5×10 per mol of silver halide. -1It is sufficient if the amount is less than 5×10 mol per mol of silver halide. -3 moles ~ 1 x 10 -1 The amount added is in moles.
[0167] The silver halide photographic light-sensitive material according to an embodiment of the present disclosure is composed of a support and a silver halide emulsion layer (light-sensitive layer) containing photosensitive silver halide grains, and at least one non-photosensitive hydrophilic colloid layer such as an intermediate layer, a surface protective layer, a back layer, a back surface protective layer, an antihalation layer, or a filter layer. However, there are no particular limitations on the emulsion sensitization method and various additives used, and those described in, for example, JP-A-2-68539 can be suitably used.
[0168] 15) Surface Protective Layer and Back Protective Layer The silver halide photographic light-sensitive material according to one embodiment of the present disclosure preferably has a surface protective layer and a back protective layer, which contain various chemicals with a hydrophilic colloid such as gelatin as a binder. When the main component of the layer is gelatin, a preservative and the like are necessary. It is also preferable that the layer contains a matting agent, a lubricant, a plasticizer, an antistatic agent, a surfactant, a hardener, a thickener, a dye, a conductive substance, and the like as needed.
[0169] 16) Development Processing Method As a development processing method for a silver halide photographic light-sensitive material according to an embodiment of the present disclosure, the methods described in JP-A No. 2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15, JP-A No. 2-115837, page 3, lower right column, line 5 to page 6, upper column, line 10, and JP-A No. 2000-112078, page 34, left column, line 42 to page 35, left column, line 2 can be used. Furthermore, for thermally developable light-sensitive materials, the methods described in JP-A No. 2001-255617, page 37, left column, line 40 to page 35, left column, line 43 can be used.
[0170] One aspect of the silver halide photographic material according to an embodiment of the present disclosure is a photosensitive heat-developable photographic material. The technology for this is described in paragraphs 16 to 189 of Japanese Patent No. 5,623,921. In this aspect, the desired effect can be obtained when the surfactants described in paragraphs 181 to 183 of the publication are those described in the present application.
[0171] (Diffusion Transfer Type Silver Halide Photosensitive Material) A diffusion transfer type silver halide photosensitive material according to one embodiment of the present disclosure has a support and a layer containing a composition according to one embodiment of the present disclosure on the support.
[0172]
[0033] Preferred aspects of the ionic compound in the diffusion transfer silver halide photographic light-sensitive material according to an embodiment of the present disclosure are the same as the preferred aspects of the composition according to an embodiment of the present disclosure described above. The diffusion transfer silver halide photographic light-sensitive material according to an embodiment of the present disclosure may contain one type of composition according to an embodiment of the present disclosure alone, or two or more types of compositions. The content of the composition according to an embodiment of the present disclosure in the layer of the diffusion transfer silver halide photographic light-sensitive material according to an embodiment of the present disclosure may be appropriately selected depending on the application, but the total mass of the solids of the composition is preferably 0.0001% by mass to 50% by mass, more preferably 0.001% by mass to 20% by mass, and particularly preferably 0.01% by mass to 10% by mass, relative to the total mass of the layer.
[0173] The layer may be any layer constituting the diffusion transfer type silver halide photographic light-sensitive material described below. Preferably, it is a layer that forms an air-liquid interface during coating, and more preferably, it is the outermost layer of the finally laminated photosensitive material. Specific examples include an intermediate layer in a substrate for a photosensitive sheet, the outermost layer of a substrate, an intermediate layer in a photosensitive sheet, a protective layer, and a temperature compensation layer in a cover sheet. Among these, the outermost layer of a substrate in a substrate for a photosensitive sheet, a protective layer in a photosensitive sheet, and a temperature compensation layer in a cover sheet are particularly preferred. Furthermore, in the diffusion transfer type silver halide photographic light-sensitive material according to an embodiment of the present disclosure, the layer containing the composition according to an embodiment of the present disclosure may be one layer or two or more layers. The layer may contain various components contained in the diffusion transfer type silver halide photographic light-sensitive material described below.
[0174] A diffusion transfer type silver halide photographic light-sensitive material according to one embodiment of the present disclosure preferably comprises a light-sensitive sheet, a transparent cover sheet, and an alkaline processing composition-containing material spread between them.
[0175] [1] Alkali Processing Composition-Containing Body The alkali processing composition-containing body is uniformly spread on the photosensitive sheet after exposure to light, and has the functions of developing the photosensitive layer and, together with a light-shielding layer provided on the back side of the transparent support of the photosensitive sheet or in the photosensitive sheet, completely shielding the photosensitive layer from external light. Therefore, the alkali processing composition-containing body typically contains, in addition to alkali, a thickener, a light-shielding agent, and a developing agent, a development accelerator for controlling development, a development inhibitor for preventing deterioration of the developing agent, and an antioxidant for preventing deterioration of the developing agent.
[0176] (a) Alkali The alkali is not particularly limited as long as it can adjust the pH of the solution to 12 or higher. Examples of alkali include alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, and lithium hydroxide), alkali metal phosphates (e.g., potassium phosphate), guanidines, and quaternary amine hydroxides (e.g., tetramethylammonium hydroxide). Among these, potassium hydroxide and sodium hydroxide are preferred.
[0177] (b) Developing Agent Any developing agent may be used as long as it cross-oxidizes the dye image-forming compound and does not substantially produce stains even when oxidized. A single developing agent may be used, or two or more developing agents may be used, or they may be used in the form of a precursor. Examples of developing agents include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferred because they cause less staining. Specific examples of pyrazolidinones include 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1-(3'-methyl-phenyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone. The developing agent may be incorporated into the alkaline processing composition-containing material, or may be added to an appropriate layer of the photosensitive sheet.
[0178] (c) Light-blocking agent Any material having a light-blocking function can be used as a light-blocking agent without any particular limitation. Examples of light-blocking agents include carbon black and the decomposable dyes described in U.S. Pat. No. 4,615,966. Of these light-blocking agents, carbon black is preferred. Carbon black is not limited to carbon black obtained by a specific manufacturing method, and may be obtained by any manufacturing method. Examples of methods for manufacturing carbon black include the channel method described in Donnel Voet "Carbon Black" MarcelDekker, Inc. (1976), as well as the thermal method and furnace method.
[0179] When using carbon black as a light-blocking agent, it is preferable to prepare the carbon black in advance as an aqueous dispersion. Aqueous dispersions of carbon black are widely used in paints, inks, cosmetics, and photographic photosensitive materials, as black materials, or light-blocking materials. To prepare an aqueous dispersion of carbon black, carbon black is added to water containing a suitable dispersant, and the carbon black is coarsely dispersed using a coarse disperser (e.g., a high-speed stirring disperser such as the Dissolver described in Japanese Patent Application Publication No. 54-36045) to obtain an average particle size of approximately 10 μm to 100 μm. The particle size is then further reduced using a fine disperser (e.g., a sand grinder, homogenizer, colloid mill, etc.). This process allows for the production of an aqueous dispersion of carbon black having an average particle size of approximately 0.1 μm to 10 μm. Alternatively, as described in Japanese Patent Application Publication No. 58-52362, carbon black may be dispersed in an aqueous solution containing an organic solvent, followed by removal of the organic solvent to obtain an aqueous dispersion of carbon black.
[0180] Preferred dispersants include those described in "Dispersion Technology Comprehensive Data Collection" (Published by the Business Development Center), pages 255 to 257 and 501 to 539. An example of a commercially available dispersant is Demol N (trade name, manufactured by Kao Corporation).
[0181] The type and / or amount of the dispersant affects the sodium ion content, which will be described later. The type and / or amount of the dispersant must be determined so as to satisfy (a) the condition of imparting sufficient dispersibility to the light-shielding agent, as well as (b) the condition of the sodium ion content. To satisfy both the conditions of dispersibility and the sodium ion content, the blending amount of the dispersant is preferably 2% by mass to 100% by mass of the light-shielding agent.
[0182] (d) Optical Density The optical density of the alkali treatment composition-containing body is preferably 47 or more, more preferably 50 or more, and particularly preferably 55 or more. When the optical density is 47 or more, sufficient light-shielding properties are obtained and spot fogging is suppressed. It is preferable to determine the amount of light-shielding agent to be added so that the optical density is 47 or more. Although it depends on the type of light-shielding agent used, it is preferable to set the amount of light-shielding agent to about 10% by mass to 40% by mass in order to achieve an optical density of 47 or more.
[0183] (e) Sodium ion content The sodium ion content of the alkaline processing composition-containing material in the developed state is preferably 0.4 g / m 2 The sodium ion content is 0.35 g / m 2 More preferably, it is 0.25 g / m or less. 2 It is particularly preferred that:
[0184] The sodium ion content is primarily determined by the dispersant for the light-blocking agent and the thickener. Sodium carboxymethylcellulose is particularly preferred as a thickener. Sodium carboxymethylcellulose has sufficient spreadability and stability. The sodium ion content can be reduced by using polyvinyl alcohol, hydroxyethyl cellulose, or an alkali metal salt of carboxymethylcellulose other than sodium as a thickener. However, these do not have sufficient spreadability and stability, so their use alone is not appropriate. Therefore, it is preferable to use sodium carboxymethylcellulose primarily as a thickener, and to use polyvinyl alcohol, hydroxyethyl cellulose, or an alkali metal salt of carboxymethylcellulose other than sodium in combination.
[0185] Sodium ion content is 0.4 g / m 2It is preferable to adjust the degree of etherification of sodium carboxymethyl cellulose and the amount of addition so that the degree of etherification of sodium carboxymethyl cellulose is as follows: The degree of etherification of sodium carboxymethyl cellulose is preferably 0.5 to 2.7, and more preferably 1.0 to 2.4. The amount of sodium carboxymethyl cellulose added is preferably 1% by mass to 15% by mass, and more preferably 2% by mass to 10% by mass.
[0186] An alkali processing composition-containing material satisfying the above optical density and sodium ion content exhibits excellent light-blocking properties and dye transfer properties even when thinly spread on a photosensitive sheet. In this specification, "thinly spread" means that the alkali processing composition-containing material is spread on the photosensitive sheet to a thickness of 10 μm to 80 μm. The preferred spread thickness is 10 μm to 70 μm, and more preferably 20 μm to 60 μm.
[0187] [2] Photosensitive Sheet (a) First Transparent Support The support of the photosensitive sheet may be any of those commonly used for photographic materials. The support of the integrated color diffusion transfer film unit must be transparent. The support is preferably smooth. Examples of support materials include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. To prevent light piping, the support preferably contains a trace amount of dye or pigment such as titanium oxide. The thickness of the support of the photosensitive sheet is preferably 25 μm to 350 μm, more preferably 50 μm to 210 μm, and particularly preferably 70 μm to 150 μm. A primer layer (undercoat layer) is preferably provided on the front side of the support. Furthermore, a curl-balancing layer or an oxygen-blocking layer can be provided on the back side of the support as needed. The oxygen-blocking layer can be provided by referring to the description in JP-A-56-78833.
[0188] (b) Image-receiving layer: The image-receiving layer (dye image-receiving layer) of the photosensitive sheet preferably contains a mordant and a hydrophilic colloid. The image-receiving layer may be a single layer or may be a laminate of layers having different mordanting powers. Single-layer and multi-layer image-receiving layers can be provided by referring to the description in JP-A-61-252551.
[0189] The mordant is preferably a polymer mordant. The polymer mordant is a polymer containing a secondary and / or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation, or the like, and preferably has a molecular weight of 5,000 or more, particularly preferably 10,000 or more. The coating amount of the mordant is preferably 0.5 g / m 2 ~10g / m 2 and more preferably 1 g / m 2 ~5g / m 2 and particularly preferably 2 g / m 2 ~4g / m 2 is.
[0190] Examples of hydrophilic colloids include gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc. A preferred hydrophilic colloid is gelatin.
[0191] The image-receiving layer may contain a discoloration inhibitor. There are no particular restrictions on the discoloration inhibitor, but those described in, for example, JP-A Nos. 62-30620, 62-30621, and 62-215272 can be used. The thickness of the image-receiving layer may be the same as that of an image-receiving layer in a general color diffusion transfer film unit.
[0192] (c) White Reflective Layer The white reflective layer of the photosensitive sheet forms a white background for the color image and usually contains a white pigment and a hydrophilic binder.
[0193] 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 coating amount of the pigment. When the white pigment is titanium dioxide, the content of titanium dioxide is preferably 5 g / m 2 ~40g / m 2 and more preferably 10 g / m 2 ~25g / m 2 is.
[0194] The light reflectance of the white reflective layer is preferably 70% or more, and more preferably 78% to 85% for light with a wavelength of 540 nm.
[0195] 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. Non-film-forming polymer particles such as polystyrene can also be used as white pigments. Among these, titanium dioxide is preferred, with rutile titanium dioxide being particularly preferred. White pigments may be used alone or in combination of two or more. Using two or more white pigments makes it easier to achieve a preferred reflectance value for the white reflective layer.
[0196] The white pigment is preferably surface-treated with alumina, silica, zinc oxide, etc., and more preferably has a surface treatment amount of 5% or more. A white reflective layer containing a surface-treated white pigment exhibits high reflectance.
[0197] Examples of commercially available titanium dioxide include Ti-pure R931 (trade name) from DuPont and those described in Research Disclosure (RD) No. 15162.
[0198] Examples of the hydrophilic binder include alkali-permeable polymer matrices such as gelatin and polyvinyl alcohol, and cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose. When the binder is gelatin, the mass ratio of the white pigment to the gelatin is preferably 1 / 1 to 20 / 1, and more preferably 5 / 1 to 10 / 1.
[0199] The white reflective layer preferably contains an anti-fading agent. There are no particular restrictions on the anti-fading agent, but the anti-fading agents described in, for example, Japanese Patent Publication Nos. 62-30620 and 62-30621 can be used.
[0200] (d) Light-shielding layer The light-shielding layer is provided between the white reflective layer and the photosensitive layer. The light-shielding layer preferably contains a light-shielding agent and a hydrophilic binder.
[0201] The light-shielding agent may be any of those described in the above section [1] (c) Light-shielding agent of the alkali processing composition-containing composition. The content of the light-shielding agent varies depending on the sensitivity of the light-sensitive material to be shielded from light, but generally, an optical density of about 5 to 10 is preferred.
[0202] The binder for the light-shielding layer may be any material that can disperse a light-shielding agent such as carbon black, etc. A preferred binder is gelatin.
[0203] There are no particular limitations on the thickness of the light-shielding layer, as long as it exhibits sufficient light-shielding ability and does not make the photosensitive sheet too thick.
[0204] (e) Photosensitive Layer The photosensitive layer is adjacent to the light-shielding layer and preferably contains a dye image-forming compound and a silver halide emulsion. The photosensitive layer may be a multilayer consisting of a silver halide emulsion layer and a dye image-forming compound layer, or a single layer containing both a silver halide emulsion and a dye image-forming compound. The multilayer case will be explained below, but the same applies to a single layer case.
[0205] (f) Dye Image-Forming Compounds Dye image-forming compounds include yellow dye-forming compounds, magenta dye-forming compounds and cyan dye-forming compounds. Specific examples of yellow dye-forming compounds are described in U.S. Pat. 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, 4,336,322, JP-A-51-114930, JP-A-56-71072, Research Disclosure 17630 (1978), and Research Disclosure 16475 (1977).
[0206] Specific examples of magenta dye-forming compounds are disclosed in U.S. Pat. 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. No. 4,287,292, JP-A-52-106727, JP-A-53-23628, JP-A-55-36804, JP-A-56-73057, JP-A-56-71060, JP-A-55-134, JP-A-7-120901, JP-A-8-286343, JP-A-8-286344, and JP-A-8-292537.
[0207] Specific examples of cyan dye-forming compounds are those described in U.S. Pat. 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. No. 4,148,642, British Patent No. 1,551,138, JP-A-54-99431, JP-A-52-8827, JP-A-53-47823, JP-A-53-143323, JP-A-54-99431, JP-A-56-71061, European Patent (EP) No. 53,037, European Patent (EP) No. 53,040, Research Disclosure 17,630 (1978), and Research Disclosure 16,475 (1977), etc.
[0208] A dye image-forming compound that forms a dye by coupling can also be used as the dye image-forming compound. Examples of dye image-forming compounds that form a dye by coupling are described in JP-A Nos. 8-286340, 9-152705, 10-186564, and 10-293388.
[0209] Positive dye image-forming compounds can also be used. Examples of positive dye image-forming compounds are described in JP-A 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. Pat. No. 5,192,649. A positive dye image-forming compound is preferably combined with a negative silver halide emulsion, which will be described later.
[0210] The positive dye image-forming compound can be dispersed by the method described on pages 144 to 146 of JP-A No. 62-215272. The dispersion may also contain the compounds described on pages 137 to 144 of JP-A No. 62-215272. Specific examples of these dye image-forming compounds include the following compounds. In the following compounds, Dye represents a dye group, a dye group temporarily shortened in wavelength, or a dye precursor group.
[0211]
[0212]
[0213]
[0214] (g) Silver halide emulsions The silver halide emulsions may be negative-type silver halide emulsions in which latent images are formed mainly on the surfaces of silver halide grains, or may be internal latent image-type direct positive silver halide emulsions in which latent images are formed inside silver halide grains. Internal latent image-type direct positive silver halide emulsions include, for example, so-called "conversion type emulsions" which are made by utilizing the difference in solubility of silver halide, and "core / shell type emulsions" in which at least the photosensitive sites of inner core grains of silver halide that have been doped with metal ions or chemically sensitized, or both, are covered with an outer shell of silver halide, and these are described in U.S. Pat. These compounds are described in the specifications of, for example, British Patent Nos. 2,592,250, 3,206,313, British Patent No. 1,027,146, U.S. Patent Nos. 3,761,276, 3,935,014, 3,447,927, 2,297,875, 2,563,785, 3,551,662, 4,395,478, West German Patent No. 2,728,108, and U.S. Patent No. 4,431,730.
[0215] When an internal latent image type direct positive silver halide emulsion is used, it is necessary to provide surface fog nuclei after imagewise exposure using light or a nucleating agent. Examples of nucleating agents include hydrazines described in U.S. Pat. Nos. 2,563,785 and 2,588,982, hydrazines and hydrazones described in U.S. Pat. No. 3,227,552, heterocyclic quaternary salt compounds described in British Patent No. 1,283,835, JP-A-52-69613, U.S. Pat. Nos. 3,615,615, 3,719,494, 3,734,738, 4,094,683 and 4,115,122, and heterocyclic quaternary salt compounds having a nucleating substituent in the dye molecule described in U.S. Pat. No. 3,718,470. Sensitizing dyes, U.S. Patent Nos. 4,030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364, and British Patent No. 2,012,443, etc., described in thiourea-bonded acylhydrazine compounds, U.S. Patent Nos. 4,080,270, 4,278,748, and British Patent No. 2,011,391B, etc., described in heterocyclic groups (thioamide rings, triazole rings, tetrazole rings, etc.), and acylhydrazine compounds bonded as an adsorption group can be used. In order to reduce the sensitivity of re-reversal negative images and increase the reversal positive sensitivity, it is also preferable to use metal complexes described in JP-A-2002-40607 and JP-A-2003-107616. As a preferred method for producing a negative silver halide emulsion, the method described in JP-A No. 2006-113291 can be preferably used.
[0216] Spectral sensitizing dyes can be used in combination with silver halide emulsions, specific examples of which are described in JP-A-59-180550, JP-A-60-140335, RD17029, U.S. Pat. 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, 2,295,276, and U.S. Pat. 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.
[0217] (h) Configuration of the Photosensitive Sheet: The photosensitive sheet preferably has at least three silver halide emulsion layers with different color sensitivities and at least two color-mixing prevention layers containing a non-diffusible reducing agent located between the silver halide emulsion layers. To impart different color sensitivities to the at least three silver halide emulsion layers, it is effective and preferable to use the above-mentioned spectral sensitizing dyes with different absorption wavelength distributions. When imparting different color sensitivities to the silver halide emulsions, it is preferable that the spectral sensitivity distributions of the silver halide emulsions do not overlap as much as possible, but they do not need to be completely separated. When there is a relationship between the sensitivity of one emulsion layer at a specific wavelength that is at least twice that of at least two other silver halide emulsion layers, the color sensitivities can be considered to be different. It is desirable that the sensitivity relationship between the at least three silver halide emulsion layers be such that the sensitivity of one emulsion layer at a specific wavelength is preferably at least 5 times, more preferably at least 10 times, that of the other two silver halide emulsion layers. There are no particular limitations on the wavelengths that can establish these relationships, and any of the wavelengths in the visible, ultraviolet, or infrared ranges may be used. However, it is preferred that the silver halide emulsions in the at least three silver halide emulsion layers be selected from silver halide emulsions that are sensitive to any of blue, green, red, or infrared light.
[0218] The emulsion and the dye image-forming compound may be in separate layers, or may be contained in a single layer. When the dye image-forming compound has absorption in the spectral sensitivity region of the emulsion combined with it when coated, a separate layer is preferred.
[0219] The emulsion layer may be composed of emulsions having different sensitivities. Furthermore, any layer may be provided between the emulsion layer and the dye image-forming compound layer. For example, the density of the color image can be increased by providing a layer containing a nucleating development accelerator as described in JP-A-60-173541 or a partition wall layer as described in JP-B-60-15267, and the sensitivity of the photosensitive sheet can be increased by providing a reflective layer. The reflective layer is a layer containing a white pigment and a hydrophilic binder, with titanium oxide being preferred as the white pigment and gelatin being preferred as the hydrophilic binder. The coating amount of titanium oxide is 0.1 g / m 2~8g / m 2 It is preferable that the density is 0.2 g / m 2 ~4g / m 2 An example of the reflective layer is described in JP-A-60-91354.
[0220] In the case of a multilayer photosensitive layer, it is preferred that a blue-sensitive emulsion combination unit, a green-sensitive emulsion combination unit, and a red-sensitive emulsion combination unit are arranged in this order from the exposed side. Any layer can be provided between each emulsion layer unit as needed.
[0221] (i) Color-mixing prevention layer: In order to prevent the undesirable influence of the development effect of one emulsion layer on other emulsion layer units, it is preferable to have a color-mixing prevention layer containing a non-diffusible reducing agent located between emulsion layers. At least one color-mixing prevention layer is required between each emulsion layer, so it is preferable that the photosensitive sheet has at least two color-mixing prevention layers.
[0222] Any known compound can be preferably used as the non-diffusible reducing agent in the color-mixing preventing layer. For example, it is preferable to use the high-molecular-weight redox compounds described in JP-A-5-333501, the phenidone and hydrazine compounds described in WO 98 / 33760 and U.S. Pat. No. 4,923,787, and the redox compounds described in German Patent Application Publication No. 19618786-A1, European Patent Application Publication No. 839623-A1, European Patent Application Publication No. 842975-A1, German Patent Application Publication No. 19806846-A1, and French Patent Application Publication No. 2760460-A1. It is also preferable to use the lactones described in JP-A-2000-122243. Particularly preferred non-diffusible reducing agents for use in the color-mixing preventing layer are selected from non-diffusible hydroquinone derivatives, sulfonamidophenol derivatives, sulfonamido naphthol derivatives, and lactones. In particular, non-diffusible hydroquinone derivatives are preferred, and dialkylhydroquinone derivatives are particularly preferred. Here, the alkyl group includes a substituted or unsubstituted alkyl group, and the substituent is not particularly limited as long as it does not inhibit the "non-diffusibility" of the compound. Specific examples include an aryl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. The total number of carbon atoms in the "dialkyl group" is preferably 12 or more, and more preferably 16 or more.
[0223] The molecular weight of the non-diffusible reducing agent is preferably 350 or more, more preferably 390 or more, and particularly preferably 500 or more. When the color-mixing inhibitor is a polymer, the molecular weight is expressed as a number-average molecular weight. The upper limit of the molecular weight of the non-diffusible reducing agent is not particularly limited when the non-diffusible 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-diffusible reducing agent contained in at least two color-mixing prevention layers disposed between each silver halide emulsion layer varies depending on the coating amount, shape, grain size, and target maximum color density of the silver halide emulsion used. However, too much non-diffusible reducing agent results in a decrease in color density and a delay in image formation time, while too little results in cloudy color hues. Therefore, the amount of non-diffusible reducing agent should be determined taking these factors into consideration. The decrease in color density resulting from a reduction in the coated silver amount can be effectively suppressed by setting the coating amount of silver halide to the non-diffusible reducing agent at a specific ratio and using a specific amount of negative-working silver halide emulsion as the silver halide emulsion. The total coating mole number of silver halide is in the range of 5 to 10 times the total coating mole number of the non-diffusible reducing agent used in the color-mixing preventing layer. The total coating mole number of the non-diffusible reducing agent is preferably 0.5 mmol / m 2 ~1.5mmol / m 2 more preferably in the range of 0.8 mmol / m 2 ~1.2mmol / m 2 Specific examples of the non-diffusible reducing agent are given below, but the embodiment of the present disclosure is not limited thereto.
[0224]
[0225] The non-diffusible reducing agent is preferably dissolved in a high-boiling organic solvent and present in the color-mixing prevention layer as fine oil droplets obtained by emulsification and dispersion. The high-boiling organic solvent preferably has a dielectric constant in the range of 4.0 to 8.0. The high-boiling organic solvent may be a mixture of two or more types. Examples of preferred high-boiling organic solvents include esters such as phthalates and phosphates, organic acid amides, and ketones. 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 high-boiling organic solvent preferably has a boiling point of 140°C or higher and a melting point of 100°C or lower, and more preferably a boiling point of 160°C or higher and a melting point of 70°C or lower. The high-boiling organic solvent may be solid at room temperature; in this case, the dielectric constant is measured in the liquid (supercooled state). The amount (mass ratio) of the high-boiling organic solvent to the non-diffusible reducing agent in the color-mixing prevention layer is preferably 0.3 to 20, more preferably 0.5 to 10, and even more preferably 1 to 8.
[0226] There are no particular limitations on the thickness of the photosensitive layer, as long as it provides sufficient color reproducibility and does not make the photosensitive sheet too thick.
[0227] (j) Other The photosensitive sheet may have an anti-irradiation layer, a UV absorber layer, a protective layer, etc., as needed. The thickness of the photosensitive sheet is not particularly limited as long as it does not make the color diffusion transfer film unit too thick.
[0228] [3] Transparent Cover Sheet (a) Second Transparent Support The support for the transparent cover sheet may be any smooth transparent support commonly used for photographic materials. Preferred supports include cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc. The support preferably contains a trace amount of dye to prevent light piping. It is also preferred to provide an undercoat layer on the support.
[0229] (b) Layer having a neutralizing function The layer having a neutralizing function (neutralizing layer) is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried in from the alkaline processing composition-containing body. If necessary, it may have a multilayer structure comprising layers such as a neutralization rate adjusting layer (neutralization timing layer) and an adhesion enhancing layer.
[0230] Preferred acidic substances are substances containing an acidic group having a pKa of 9 or less (or a precursor group that generates an acidic group having a pKa of 9 or less upon hydrolysis), and more preferred acidic substances are higher fatty acids such as oleic acid described in U.S. Pat. No. 2,983,606, polymers of acrylic acid, methacrylic acid, or maleic acid, and their partial esters or acid anhydrides as disclosed in U.S. Pat. No. 3,362,819, copolymers of acrylic acid and acrylic acid esters as disclosed in French Patent No. 2,290,699, and latex-type acidic polymers as disclosed in U.S. Pat. No. 4,139,383 and RD No. 16102 (1977). Additionally, acidic substances disclosed in US Pat. No. 4,088,493, JP-A Nos. 52-153739, 53-1023, 53-4540, 53-4541, and 53-4542 are also preferred.
[0231] Other examples of acidic polymers include copolymers of vinyl monomers such as ethylene, vinyl acetate, and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate with acrylic acid, cellulose, and acetate hydrogen phthalate.
[0232] The acidic polymer can be used in combination with a hydrophilic polymer. Examples of the hydrophilic polymer include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and polymethyl vinyl ether. Among these, polyvinyl alcohol is preferred. The acidic polymer may be mixed with a polymer other than the hydrophilic polymer, such as cellulose acetate.
[0233] The amount of acidic polymer to be applied is determined by the amount of alkali in the alkaline processing composition-containing material. The equivalent ratio of acidic polymer to alkali per unit area is preferably 0.9 to 2.0. If the amount of acidic polymer is too small, the hue of the transferred dye will change and staining will occur on the white background. If the amount of acidic polymer is too large, problems such as changes in hue or reduced lightfastness will occur. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of hydrophilic polymer to be mixed is too large or too small, photographic quality will be reduced. The mass ratio k of hydrophilic polymer to acidic polymer is preferably 0.01 to 10, more preferably 0.1 to 3.0.
[0234] Additives can be incorporated into the neutralization layer for various purposes. For example, a general film-hardening agent may be added to the neutralization layer, or a polyhydroxyl compound such as polyethylene glycol, polypropylene glycol, or glycerin may be added to reduce film brittleness. Other additives, such as antioxidants, fluorescent brighteners, development inhibitors, and their precursors, may also be added as needed.
[0235] For the neutralization timing layer used in combination with the neutralization layer, useful are polymers that reduce alkali permeability, such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate; latex polymers that increase the activation energy of alkali permeation, in which a small amount of hydrophilic comonomer, such as an acrylic acid monomer, is copolymerized; and polymers having a lactone ring.
[0236] Among these, timing layers using cellulose acetate disclosed in JP-A-54-136328, U.S. Pat. Nos. 4,267,262, 4,009,030, and 4,029,849, etc.; acrylic resins disclosed in JP-A-54-128335, JP-A-56-69629, JP-A-57-6843, U.S. Pat. Nos. 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256,827, and 4,268,604, etc. Particularly useful are latex polymers copolymerized with a small amount of hydrophilic comonomers such as acids; polymers having monoacrylates or monomethacrylates of polyhydric alcohols as disclosed in JP-A-11-2890; polymers having lactone rings as disclosed in U.S. Pat. No. 4,229,516; and polymers disclosed in JP-A-56-25735, JP-A-56-97346, JP-A-57-6842, EP-A-31,957-A1, EP-A-37,724-A1, EP-A-48,412-A1, and the like.
[0237] Additionally, those described in the following documents can also be used: U.S. Pat. No. 3,421,893, U.S. Pat. No. 3,455,686, U.S. Pat. No. 3,575,701, U.S. Pat. No. 3,778,265, U.S. Pat. No. 3,785,815, U.S. Pat. No. 3,847,615, U.S. Pat. No. 4,088,493, U.S. Pat. No. 4,123,275, U.S. Pat. No. 4,148,653, U.S. Pat. No. 4,201,587, U.S. Pat. No. 4,288,523, U.S. Pat. No. 4,297,431, West German Patent Application Laid-Open (OLS) No. 1,622,936, West German Patent Application Laid-Open No. 2,162,277, RD 15162, No. 151 (1976), and the like.
[0238] The neutralization timing layer may contain a development inhibitor and / or a precursor thereof disclosed in U.S. Pat. No. 4,009,029, West German Patent Application (OLS) No. 2,913,164, West German Patent Application Publication No. 3,014,672, JP-A-54-155837, JP-A-55-138745, etc., a hydroquinone precursor disclosed in U.S. Pat. No. 4,201,578, other photographic additives or precursors thereof, etc. Furthermore, providing an auxiliary neutralization layer as described in JP-A-63-168648 and JP-A-63-168649 is effective in reducing changes in transfer density over time after processing.
[0239] The neutralization timing layer may contain a plurality of these materials. A plurality of materials may be contained in one layer, or may be contained in each of a plurality of layers.
[0240] (c) Other Layers The transparent cover sheet may have, in addition to the layer having a neutralizing function, layers having auxiliary functions such as a backing layer, a protective layer, and a filter dye layer.
[0241] The backing layer is provided to adjust curl and provide slippage. The backing layer may contain a filter dye. The protective layer is primarily used to prevent adhesion to the back surface of the cover sheet and to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are superimposed. If the transparent cover sheet contains a dye, the sensitivity of the photosensitive layer can be adjusted. A filter dye may be added to the support of the cover sheet, a layer with a neutralizing function, the backing layer, the protective layer, a capture mordant layer, etc. Alternatively, a layer containing only a filter dye may be provided.
[0242] The diffusion transfer type silver halide photographic light-sensitive material according to an embodiment of the present disclosure may contain other known additives in each layer.
[0243] (Compound) A compound according to one embodiment of the present disclosure is a novel compound having a structure represented by the following formula (4) or (5).
[0244]
[0245] In formula (4) and formula (5), Sil1 is a group represented by any one of the following formulas (Si-1), (Si-2), (Si-3), and (Si-4), 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 21 , R 22 , R 31 , and R 32 may be the same or different, Ry and Rz each independently represent an alkyl group or an aryl group having 1 to 6 carbon atoms, a and b each represent an integer of 2 to 6, w is 0 or 1, i is 1 or 2, and n is an integer of 1 to 6.
[0246]
[0247] In the compound according to one embodiment of the present disclosure, R in Formula (4), Formula (5), Formula (Si-1), Formula (Si-2), Formula (Si-3), and Formula (Si-4) 11 and R 12 A preferred embodiment of R 21 , R 22 , R 31 , and R 32 Preferred aspects of Ry and Rz, preferred aspects of a and b, preferred aspects of i, and preferred aspects of n are the same as those described in the description of the composition according to one embodiment of the present disclosure.
[0248] Preferred specific examples of formula (4) or formula (5) include A-1 to A-14 as explained above.
[0249] The compound according to an embodiment of the present disclosure is not particularly limited in its application, but can be suitably used as a leveling agent or surfactant. The compound according to an embodiment of the present disclosure can also be suitably used in known applications that use a leveling agent or surfactant. Furthermore, the compound according to an embodiment of the present disclosure can be suitably used for film formation. The compound according to an embodiment of the present disclosure can also be suitably used in photosensitive materials, surface modifiers, protective layer-forming compositions, conductive layer-forming compositions, undercoat layer-forming compositions, pressure-responsive materials, thermo-responsive materials, microcapsules, microgels, and the like. In particular, the compound according to an embodiment of the present disclosure can be particularly suitably used in silver halide photographic photosensitive materials and diffusion transfer type silver halide photographic photosensitive materials.
[0250] The present disclosure will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. In the examples, "%" and "parts" mean "% by mass" and "parts by mass," respectively, unless otherwise specified.
[0251] (Example A1) <Synthesis of Intermediate 1>
[0252]
[0253] 21.5 g (150 mmol) of 2-(dimethylamino)ethyl acrylate, 811 mg (7.50 mmol) of 1,5-cyclooctadiene (cod), and 60 mL of ethyl acetate (AcOEt) were weighed into a three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer. After purging with nitrogen, the mixture was stirred for 10 minutes at 45° C. 1008 mg (1.50 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer ([IrCl(cod)]2) was added and the mixture was stirred for an additional 10 minutes. 1,1,1,3,5,5,5-heptamethyltrisiloxane (33.4 g, 150 mmol) was then added dropwise over 30 minutes. After the dropwise addition was completed, the reaction was carried out at 45°C for 2 hours, and 1H-NMR spectrum measurement confirmed that 1,1,1,3,5,5,5-heptamethyltrisiloxane had completely disappeared and that Intermediate 1 had been produced. The ethyl acetate solvent was then removed by distillation under reduced pressure, and the resulting mixture was purified by silica gel column chromatography using ethyl acetate / hexane as a developing solvent, yielding 43.88 g of Intermediate 1.
[0254] <Synthesis of Compound A-1>
[0255]
[0256] Subsequently, the intermediate 1 obtained above, 80 mL of acetonitrile, and 27.6 g (203 mmol) of 1,4-butanesultone were weighed into a three-neck flask equipped with a stirrer, a condenser, and a thermometer, and the mixture was reacted for 6 hours in an oil bath at 100°C. After completion of the reaction, the mixture was cooled to 60°C, and then 150 mL of acetonitrile and 300 mL of methyl ethyl ketone were added, followed by gradual cooling to 5°C. The precipitated solid was collected by filtration and dried in a vacuum oven at 40°C, yielding 39.1 g of compound A-1. 1 H-NMR (MeOD): δ (ppm) = -0.10 to 0.10 ppm (21H), 0.65 to 0.75 ppm (2H), 1.68 to 1.76 ppm (2H), 1.82 to 1.96 ppm (2H), 2.24 to 2 .32ppm (2H), 2.70-2.82ppm (2H), 3.00-3.12ppm (6H), 3.30-3.40ppm (2H), 3.54-3.62ppm (2H), 4.38-4.46ppm (2H)
[0257] (Example A2) <Synthesis of Compound A-3>
[0258]
[0259]
[0260] Compound A-3 was synthesized in the same manner as compound A-1, except that 1,1,1,3,5,5,5-heptamethyltrisiloxane was used instead of 1,1,3,3,5,5,5-heptamethyltrisiloxane. 1 H-NMR (MeOD): δ (ppm) = 0.03 to 0.16 ppm (21H), 0.86 to 0.94 ppm (2H), 1.80 to 1.88 ppm (2H), 1.96 to 2.04 ppm (2H), 2.38 to 2 .46ppm (2H), 2.84-2.92ppm (2H), 3.10-3.22ppm (6H), 3.40-3.50ppm (2H), 3.68-3.74ppm (2H), 4.50-4.58ppm (2H)
[0261] (Example A3) <Synthesis of Compound A-6>
[0262]
[0263]
[0264] Compound A-6 was synthesized in the same manner as Compound A-1, except that 1,1,1,3,5,5,5-heptamethyltrisiloxane was replaced with 1,1,1,3,3-pentamethyldisiloxane. 1 H-NMR (MeOD): δ (ppm) = -0.05 ~ 0.05 ppm (15H), 0.76 ~ 0.84 ppm (2H), 1.70 ~ 1.78 ppm (2H), 1.84 ~ 1.96 ppm (2H), 2.28 ~ 2 .36ppm (2H), 2.76-2.82ppm (2H), 3.04-3.10ppm (6H), 3.32-3.38ppm (2H), 3.58-3.64ppm (2H), 4.42-4.48ppm (2H)
[0265] (Example A4) <Synthesis of Compound A-7>
[0266]
[0267] Intermediate 1 (1.00 g, 2.73 mmol), sodium chloroacetate (0.48 g, 4.1 mmol), sodium iodide (0.61 g, 4.1 mmol), and 10.0 mL of N,N-dimethylformamide (DMF) were weighed into a 50 mL recovery flask and reacted for 12 hours in an oil bath at 85°C. After cooling to room temperature, insoluble matter was removed by filtration and the mixture was concentrated under reduced pressure. This was purified by silica gel column chromatography (ethyl acetate / methanol) to obtain 0.72 g of compound A-7 as a colorless solid. 1 H-NMR (MeOD): δ (ppm) = 0.00 to 0.14 ppm (21H), 0.68 to 0.76 ppm (2H), 2.34 to 2.42 ppm (2H), 2.70 to 2 .82ppm (2H), 3.30-3.38ppm (6H), 3.44-3.50ppm (2H), 4.02-4.08ppm (2H), 4.50-4.56ppm (2H)
[0268] (Example A5) <Synthesis of Compound A-101>
[0269]
[0270]
[0271] 1,1,1,3,5,5,5-heptamethyltrisiloxane (3.00 g, 13.5 mmol), N,N-dimethylallylamine (2.30 g, 27.0 mmol), and platinum(IV) oxide (6.1 mg) were weighed into a three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, and the mixture was allowed to react for 12 hours in an oil bath at 70 °C. After cooling, the platinum(IV) oxide was removed by filtration, and excess N,N-dimethylallylamine was removed by distillation under reduced pressure to obtain oily Intermediate 4. 6.0 mL of acetonitrile and 1,4-butanesultone (2.48 g, 18.2 mmol) were added to this, and the mixture was allowed to react for 6 hours in an oil bath at 100 °C. After completion of the reaction, the mixture was cooled to 60 °C, and then 12 mL of acetonitrile and 24 mL of methyl ethyl ketone were added, followed by standing at room temperature overnight. The precipitated solid was collected by filtration and dried in a vacuum oven at 40° C. to obtain 1.90 g of compound A-101. 1H-NMR (MeOD): δ (ppm) = -0.10 ~ 0.10 ppm (21H), 0.34 ~ 0.42 ppm (2H), 1.60 ~ 1.74 ppm (4 H), 1.76-1.86ppm (2H), 2.70-2.76ppm (2H), 2.90-2.96ppm (6H), 3.10-3.26ppm (4H)
[0272] (Example A6) <Synthesis of Compound A-108>
[0273]
[0274]
[0275] 38.7 mL (368 mmol) of dimethylamine (9.5 M aqueous solution), 256 mL of MeOH, and 39.0 g (368 mmol) of sodium carbonate were weighed into a three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, and after purging with nitrogen, the mixture was stirred for 10 minutes at 60° C. 50.0 g (307 mmol) of 6-bromo-1-hexene was added dropwise over 30 minutes, and the reaction was carried out at 60° C. for 5 hours. 1 H-NMR spectroscopy confirmed that 6-bromo-1-hexene had completely disappeared and intermediate C6A had been produced. While ice-cooling the reaction solution, 383 mL of aqueous HCl (2N) was added, and the solvent was evaporated under reduced pressure. Subsequently, 192 mL of NaOH (1N) and 192 mL of toluene were added, and the precipitated solid was removed by filtration. The resulting filtrate was transferred to a separatory funnel, and the aqueous layer was removed, isolating intermediate C6A as a 22.4 g toluene solution. Subsequently, 33.6 g (151 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 245 μL (0.30 mmol) of Karstedt's catalyst, and 104 μL (0.91 mmol) of 2-ethylpyridine were weighed into a three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer. The mixture was then purged with nitrogen and stirred at 35°C for 10 minutes. A toluene solution of intermediate C6A (200 g, 9.6 w / w %, 151 mmol) was added dropwise over 30 minutes, and the mixture was allowed to react at 35° C. for 3 hours. 1H-NMR spectrum measurement confirmed that 1,1,1,3,5,5,5-heptamethyltrisiloxane had completely disappeared and intermediate C6B had been produced. 5.28 g of activated carbon was added, and after stirring for 30 minutes, the solids were removed by filtration. The filtrate was concentrated to obtain a crude product of intermediate C6B. Purification by distillation (60 Pa, 80°C) yielded 41.7 g of intermediate C6B. Subsequently, compound A-108 was obtained in the same manner as compound A-101, except that intermediate 4 was replaced with intermediate C6B. 1 H-NMR (MeOD): δ (ppm) = -0.10 to 0.10 ppm (21H), 0.36 to 0.44 ppm (2H), 1.24 to 1.38 ppm (6H), 1.60 to 1 .78ppm (4H), 1.80-1.90ppm (2H), 2.76-2.82ppm (2H), 2.92-3.00ppm (6H), 3.16-3.26ppm (4H)
[0276] (Example A7) <Synthesis of Compound A-113>
[0277]
[0278]
[0279] Compound A-113 was synthesized in the same manner as Compound A-108, except that 6-bromo-1-hexene was changed to 8-bromo-1-octene. 1 H-NMR (MeOD): δ (ppm) = -0.10 to 0.10 ppm (21H), 0.36 to 0.44 ppm (2H), 1.28 to 1.40 ppm (10H), 1.64 to 1.78ppm (4H), 1.80-1.90ppm (2H), 2.76-2.82ppm (2H), 2.92-3.00ppm (6H), 3.16-3.26ppm (4H)
[0280] (Comparative Example C2) <Synthesis of Intermediate Z-1 and Intermediate Z-2 for Comparative Compounds>
[0281]
[0282] A 1000 mL three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer was charged with 499.0 g of ethyl acetate (AcOEt), 24.30 g of ion-exchanged water, and palladium / carbon (Pd / C, 5% palladium, approximately 55% wet with water), and the atmosphere was replaced with nitrogen. The three-neck 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 dropwise addition, the mixture was returned to room temperature and allowed to react for 3 hours. After the reaction, the palladium / carbon was removed by filtration through Celite, and the mixture was concentrated under reduced pressure using a rotary evaporator to yield 100.5 g of a colorless, transparent liquid. This liquid was determined to be intermediate Z-1. 1 This was confirmed by H-NMR.
[0283] Next, 99.0 g of the obtained intermediate Z-1 and 285 g of toluene were added to a 500 mL three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, and the three-neck flask was immersed in an ice bath. After confirming that the temperature had reached 5°C or below, 32.5 g of pyridine was added dropwise, and stirring was continued until the temperature returned to 5°C or below. A solution was prepared by adding 18.4 g of toluene and 19.3 mL of dichloromethylsilane to a separate dropping funnel. The prepared solution was added dropwise to the three-neck flask over 30 minutes. After the addition was completed, the reaction solution was returned 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 subjected to a liquid separation operation. The liquid separation operation was performed twice using 350 mL of ion-exchanged water, and the organic layer was recovered. Magnesium sulfate was added to the organic layer, and the mixture was dehydrated for 30 minutes or more, and then concentrated under reduced pressure using a rotary evaporator. Crushed silica gel (Wakogel C-200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting liquid, and the mixture was stirred and then filtered under suction to obtain a colorless, transparent liquid. This liquid was identified as intermediate Z-2. 1 This was confirmed by H-NMR.
[0284] <Synthesis of Comparative Compound C-2>
[0285]
[0286]
[0287] Comparative Compound C-2 was synthesized in the same manner as Compound A-1, except that Intermediate Z-2 was used instead of 1,1,1,3,5,5,5-heptamethyltrisiloxane. 1H-NMR (MeOD): δ (ppm) = -0.12 to 0.06 ppm (21H), 0.64 to 0.72 ppm (2H), 1.68 to 1.76 ppm (2H), 1.82 to 1.96 ppm (2H), 2.28 to 2.36 ppm (2H), 2.70 to 2.82 ppm (2H), 3.00 to 3.12 ppm (6H), 3.30 to 3.40 ppm (2H), 3.54 to 3.62 ppm (2H), 4.38 to 4.46 ppm (2H).
[0288] (Examples 1-A to 1-O, and Comparative Examples 1-A to 1-M: Evaluation of Surface Tension in Aqueous Solution) Compound A or a comparative compound synthesized above, surfactant S, 33.0 parts by mass of gelatin, ion-exchanged water, and 10 parts by mass of methanol were mixed to prepare a sample for surface tension measurement. The prepared sample was kept at 40°C, and the surface tension was measured by the Wilhelmy method using an automatic surface tensiometer DY-300 manufactured by Kyowa Interface Science Co., Ltd., with a platinum plate as a probe. The measurement results are shown in Tables 2 and 3.
[0289]
[0290]
[0291] Surfactant S S-101 and comparative compound C-1 described in Tables 2 and 3 are shown below.
[0292]
[0293] (Examples 2-A to 2-G and Comparative Examples 2-A to 2-C: Preparation of composition for image-receiving film, production of film, and evaluation) As a coating liquid for the substrate-sixth layer, composition (P-A) was prepared containing the components shown in Table 4 per 1,000 g of the finished coating liquid. The remaining component in composition (P-A) was water.
[0294]
[0295] The composition (P-A) shown in Table 4 had a gelatin coating amount of 0.29 g / m2 It was applied so that
[0296] Separately, a substrate was prepared by laminating a backing layer on a polyethylene terephthalate support, followed by laminating a substrate-1 layer and a substrate-2 layer. Four layers, substrate-3 layer through substrate-6 layer, were simultaneously extruded onto this substrate from a Giesser onto a slide surface and coated at a coating speed of 60 m / min. After coating, the image-receiving film was stored at 25°C and 55% relative humidity for 7 days to harden. The sample thus obtained was designated image-receiving film substrate 101. The composition of each layer is shown in Table 5 below. Note that coarse particles with a diameter of 6 μm were intentionally added to the above composition (P-A) to forcibly evaluate its stability against cissing during coating. The inclusion of foreign matter in the coating environment or its peeling from the backing layer can cause cissing during coating. The addition of the coarse particles was for simulation purposes.
[0297]
[0298] Compositions (P-B) to (P-K) were prepared by changing only the type of compound in composition (P-A), which is the coating liquid for the substrate-6th layer. Details are shown in Table 6 below. Furthermore, image receiving film substrates 102 to 111 were each produced in the same manner as image receiving film substrate 101, except that only the type of substrate-6th layer coating liquid was changed. The obtained samples were evaluated as follows.
[0299] Evaluation 1) Coating surface condition - Evaluation of cissing resistance - The coated sample was 2 The frequency of cissing was evaluated by visual observation. The frequency of cissing for each sample was evaluated as a percentage of the number of cissings on the image receiving film substrate (silver halide photographic light-sensitive material) 101.
[0300] The evaluation results are also shown in Table 6.
[0301]
[0302] Details of each component other than those mentioned above, listed by the abbreviations used in Tables 4 to 6, are shown below. Note that surfactant (S-1) and surfactant (1) are the same.
[0303] Comparative compound C-3: the following compound
[0304] Surfactant (1) (Surfactant (S-1)): the following compound
[0305] Surfactant (1) (Surfactant (S-1)): the following compound
[0306]
[0307] Surfactant (3): the following compound
[0308]
[0309] Surfactant (6): the following compound
[0310]
[0311] Surfactant (7): the following compound
[0312]
[0313] Additive (1): the following compound
[0314]
[0315] Additive (5): the following compound
[0316]
[0317] Additive (8): Carboxymethyl cellulose (CMC Cellogen 6A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Additive (10): The following compound
[0318]
[0319] Additive (12): the following compound
[0320]
[0321] Additive (18): the following compound
[0322]
[0323] Matting agent (1): Polymethyl methacrylate spherical latex (average particle size 3 μm) Matting agent (2): Polymethyl methacrylate spherical latex (average particle size 6 μm) Hardener (1): The following compound Hardener (2): The following compound Hardener (4): The following compound
[0324]
[0325] Polymer mordant (1): the following compound
[0326]
[0327] Ultraviolet absorber (2): the following compound Ultraviolet absorber (3): the following compound
[0328]
[0329] When a functional material (functional film) was produced using a composition according to an embodiment of the present disclosure, a functional film with excellent coating surface condition was obtained.
[0330] In the preparation of the above film substrate sample, a composition was prepared by removing the matting agent and the leveling agent introduced by the matting agent from the composition formulation of the substrate-sixth layer, and the same evaluation was performed. As a result, it was confirmed that a substrate in which the occurrence of cissing was suppressed could be formed in the sample using the ionic compound according to the present disclosure.
[0331] (Examples 3-A to 3-C, and Comparative Examples 3-A and 3-B: Preparation of Composition, Production and Evaluation of Silver Halide Photosensitive Material) <Production of Substrate for Photosensitive Material> As shown in Table 4 of Examples 2-A to 2-G and Comparative Examples 2-A to 2-C above, a back layer was laminated on a polyethylene terephthalate support, and then substrate-1 to -6 layers were laminated to obtain a laminate substrate (Subs-1). In this case, the composition of the substrate-6 layer was the same as that of composition (A) of Comparative Example 2-A, but did not contain the matting agent (2) and the surfactant derived from the matting agent (surfactant (3)). After coating, this laminate substrate (Subs-1) was stored for 7 days under environmental conditions of 25°C and a relative humidity of 55% RH.
[0332] <Preparation of Photosensitive Material> A composition (QA) containing each of the components shown in Table 7 per 1,000 g of the finished coating solution was prepared as a coating solution for the 18th layer of a silver halide photosensitive material.
[0333]
[0334] The composition (Q-A) shown in Table 7 has a gelatin coating amount of 0.20 g / m 2 It was applied so that
[0335] Eighteen layers (layers 1 through 18) were simultaneously extruded onto a slide surface from a Giesser and coated at a coating speed of 60 m / min onto the substrate (Subs-1) prepared as described above. After coating, the photosensitive material was stored for 7 days at 25°C and 55% RH to allow the hardening reaction to proceed. The sample thus obtained was designated Comparative Silver Halide Photosensitive Material 201. The composition of each layer is shown in Tables 8 to 10. Note that coarse particles with a diameter of 6 μm were intentionally added to the above composition (Q-A) to forcibly evaluate the stability against cissing during coating. By intentionally adding coarse particles, which are rarely mixed in, it was possible to evaluate cissing over a small coating area.
[0336]
[0337]
[0338]
[0339] Furthermore, compositions (Q-B) to (Q-G) were prepared by changing the compounds in composition (Q-A) as shown in Table 13 below. Silver halide photographic light-sensitive materials 202 to 207 were prepared in the same manner as silver halide photographic light-sensitive material 201, except that only the type of coating solution for the 18th layer was changed.
[0340] The obtained photosensitive material samples were evaluated as follows.
[0341] Evaluation) Coated Surface Condition The coated surface condition was evaluated based on two criteria: cissing and uniformity.
[0342] - Evaluation of repelling - The coated sample was2 The frequency of cissing was evaluated by visual observation. The frequency of cissing for each sample was evaluated as a percentage of the number of cissings on the silver halide photographic light-sensitive material 201.
[0343] - Evaluation of uniformity - When the coating solution was extruded from the Giesser onto the slide surface and applied to the support, wind at a rate of about 2 m / sec was blown against the slide surface to forcibly coat the coating, making it easier to disturb the state of the coated surface. The coated photosensitive material was subjected to uniform exposure so that the post-processing density would be a gray of about 0.7, and then developed. The image was visually observed over an area 10 cm wide and 1 m long to evaluate the coating uniformity. Evaluation was primarily focused on streaky unevenness. The evaluation criteria are as follows: A: Unevenness due to wind is not discernible B: Unevenness due to wind is almost not discernible C: Unevenness due to wind is slightly discernible, but not problematic for practical use D: Streaky unevenness due to wind is discernible, and if the captured image is a uniform gray, it is a problem E: Streaky unevenness due to wind is discernible, and even if the captured image is not uniform and includes a pattern, it is a serious problem
[0344] - Evaluation of static marks - The prepared silver halide photographic light-sensitive material was exposed to gray light from the emulsion layer side, and then superposed with the transparent cover sheet. The processing solution was spread between the two materials to a thickness of 55 μm using a pressure roller. Processing was carried out at 15°C and 55% RH, and after 2 hours, the image was visually observed and evaluated for static marks. The evaluation criteria are as follows: A: No static marks were observed B: Slight static marks were observed C: Static marks were clearly observed
[0345] The silver halide photographic light-sensitive material prepared above is a diffusion transfer type silver halide photographic light-sensitive material, and its processing method involves spreading a thin layer of processing solution between an exposed silver halide photographic light-sensitive material (photosensitive sheet) and a transparent cover sheet for development. The transparent cover sheet contains cellulose acetate and an acid polymer. The alkali in the processing solution causes hydrolysis of the cellulose acetate, increasing the alkali's permeability. For approximately 10 minutes, the processing solution maintains a high pH, allowing development of the silver in the photosensitive material. Thereafter, neutralization by the acid polymer progresses, causing a rapid drop in pH within approximately 15 to 20 minutes, halting development. The processing solution was filled into a pressure-destructible container, and the container was crushed with a roller to achieve a spread thickness of the processing solution of 55 μm. The composition of the transparent cover sheet is shown in Table 11, and the composition of the processing solution is shown in Table 12. The evaluation results are shown in Table 13.
[0346]
[0347]
[0348]
[0349] Details of each component other than those mentioned above, which are described by the abbreviations used in Tables 7 to 13, are shown below. Ultraviolet absorber (1): the following compound
[0350]
[0351] Hardener (3): the following compound
[0352]
[0353] Hardener (5): the following compound
[0354]
[0355] Additive (2): the following compound
[0356]
[0357] Additive (3): The following compound Additive (4): The following compound Additives (6) to (8): The following compound Additive (9): Polyvinyl alcohol (PVA-220E manufactured by Kuraray Co., Ltd., degree of polymerization: approximately 2,000, degree of saponification: 88%) Additive (11): The following compound Additive (13): The following compound
[0358]
[0359] Additive (14): the following compound
[0360]
[0361] Additive (20): the following compound Additive (21): the following compound
[0362]
[0363] Additive (22): the following compound
[0364]
[0365] Additive (23): the following compound
[0366]
[0367] Nucleating agent (1): the following compound
[0368]
[0369] Surfactant (4): the following compound
[0370]
[0371] Surfactant (5): the following compound
[0372]
[0373] Compound (P-8): The following compound, Mw 33,700
[0374]
[0375] High-boiling point organic solvent (1): the following compound High-boiling point organic solvent (2): the following compound
[0376]
[0377] Yellow dye-releasing compound (1): the following compound Magenta dye-releasing compound (1): the following compound Cyan dye-releasing compound (1): the following compound
[0378]
[0379] Cyan dye-releasing compound (2): the following compound
[0380]
[0381] Temperature compensation polymer (1): the following compound Temperature compensation polymer (2): the following compound
[0382]
[0383] Acid polymer (1): the following compound
[0384]
[0385] Example 4 A composition (R) was prepared by changing the composition formulation of the substrate-sixth layer used in the silver halide photographic light-sensitive material of Example 3-A. A substrate (Subs-2) containing a compound according to the present disclosure was prepared in the same manner as in the substrate with functional layer (Subs-1), except that the composition of the sixth layer was changed to composition (R). The multilayer photosensitive material compositions used in the silver halide photographic light-sensitive materials 203 to 205 of Examples 3-A to 3-C were coated onto this substrate, and evaluations were performed in the same manner as in Example 3-A. As a result, it was found that samples containing a compound according to the present disclosure in both the substrate and the light-sensitive material laminated thereon exhibited excellent coated surface condition.
[0386]
[0387] Composition (R) is an aqueous composition, and the remaining component in composition (R) shown in Table 14 is water.
[0388] (Example 5: Photothermographic material) In Sample 7 in the example described in JP-A No. 2006-91780, 10.0 mg / m 2A sample was prepared in which the compound A-1 was substituted with compound A-1. The sample obtained was visually observed for reflected light under a brightness of 500 lux, and the surface condition was observed according to the following evaluation criteria. The evaluation result was A, which showed that the coated surface condition was excellent. A: No unevenness was discernible. B: No unevenness was almost discernible. C: A slight decrease in surface gloss was observed. D: A clear decrease in surface gloss was observed.
[0389] (Example 6: Photothermographic material) In Example 1 described in Japanese Patent No. 6,851,389, the fluorosurfactants F-1 and F-2 (total of 1 part by mass) in the non-photosensitive back protective layer were replaced with a compound A-1 (10 parts by mass). In addition, the fluorosurfactants F-1 and F-2 (total of 1 part by mass) in the second surface protective layer were replaced with a compound A-1 (10 parts by mass). When the surface condition of the prepared sample was evaluated using the same criteria as in Example 5, the evaluation result was A, indicating that the coated surface condition was excellent.
[0390] (Example 7: Industrial X-ray photosensitive material) A sample was prepared in which the coating aid-4 and coating aid-5 (total of 1 part by mass) in the surface protective layer of Example Sample No. 14 described in JP 2009-86332 A were replaced with a compound A-1 (10 parts by mass). The surface condition of the obtained sample was evaluated using the same criteria as in Example 5, and the evaluation result was A, indicating that the coated surface condition was excellent.
[0391] (Example 8: Thermal Recording Material) In Comparative Example 4 described in WO 2016 / 194915, the N-propyl-N-polyoxyethylene-perfluorooctanesulfonic acid amide sodium butylsulfonate and potassium perfluorooctanesulfonate (total of 1 part by mass) in the BPC layer (back protective layer) were replaced with a combined compound A-1 (10 parts by mass). Furthermore, Surflon S231W (manufactured by Seimi Chemical Co., Ltd.) and Plysurf A217 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (total of 1 part by mass) in the protective layer were replaced with a combined compound A-1 (10 parts by mass). The surface condition of the prepared sample was evaluated using the same criteria as in Example 5, and the evaluation result was A, indicating that the coated surface condition was excellent.
[0392] The disclosure of Japanese Patent Application No. 2024-150319, filed on August 30, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.
Claims
Contains compound A and surfactant S, the compound A has a trialkylsilyl group and a sulfobetaine group or a carbobetaine group, and contains 2 to 6 silicon atoms; The composition, wherein the surfactant S is an anionic surfactant that is a sulfonate or sulfate. The composition according to claim 1 , wherein the compound A comprises a structure represented by the following formula (1) or the following formula (2): In formula (1) and formula (2), Rx, Ry, and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by the following formula (3): At least one of Rx, Ry, and Rz is a group represented by the following formula (3): R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, Multiple R 11 and R 12 may be the same or different, n is an integer from 1 to 6. In formula (3), Sil 1 is a group represented by any one of the following formulas (Si-1), (Si-2), (Si-3), and (Si-4): Multiple Sil 1 may be the same or different, L 1 is a divalent linking group, Multiple L 1 may be the same or different, R is an (x+1)-valent organic residue containing a carbon atom; x is 1 or 2; The wavy line represents N in formula (1) or formula (2). + represents the binding site with In formula (Si-1), R 1 is an alkyl group, and a plurality of R 1 may be the same or different. In formula (Si-2), R 2 is an alkyl group, and a plurality of R 2 may be the same or different, and y is an integer of 1 to 5. In formula (Si-3), R 3 is an alkyl group, and a plurality of R 3 may be the same or different, and z is 2 or 3. In formula (Si-4), R 4 , R 4a , R 4b is an alkyl group, and a plurality of R 4 , R 4a , R 4b may be the same or different, q is 1 or 2, and when q is 1, p is an integer of 1 to 3, and when q is 2, p is 1. In formula (Si-1), formula (Si-2), formula (Si-3), and formula (Si-4), * represents L in formula (3). 1 represents the binding site with The composition according to claim 2, wherein the structure represented by formula (1) is a structure represented by the following formula (4): In formula (4), Sil 1 is a group represented by formula (Si-1), formula (Si-2), formula (Si-3), or formula (Si-4), R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, Multiple R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Multiple R 21 , R 22 , R 31 , and R 32 may be the same or different, a and b are each an integer from 2 to 6, Ry and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by formula (3), w is 0 or 1; i is 1 or 2; n is an integer from 1 to 6. The composition according to claim 2, wherein the structure represented by formula (2) is a structure represented by the following formula (5): In formula (5), Sil 1 is a group represented by formula (Si-1), formula (Si-2), formula (Si-3), or formula (Si-4), R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, Multiple R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Multiple R 21 , R 22 , R 31 , and R 32 may be the same or different, a and b are each an integer from 2 to 6, Ry and Rz each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, or a group represented by formula (3), w is 0 or 1; i is 1 or 2; n is an integer from 1 to 6.
2. The composition according to claim 1, wherein the surfactant S is an anionic surfactant of the sulfosuccinate type.
2. The composition according to claim 1, wherein the surfactant S is sodium bis(2-ethylhexyl) sulfosuccinate.
2. The composition according to claim 1, wherein the content ratio of the compound A to the surfactant S is, based on mass, compound A:surfactant S of 5:95 to 95:
5. A support; A layer that is a cured product of the composition according to any one of claims 1 to 7 is provided on the support. Functional materials.
9. The functional material according to claim 8, which is a silver halide photographic light-sensitive material.
9. The functional material according to claim 8, which is a diffusion transfer type silver halide photographic light-sensitive material. A compound having a structure represented by the following formula (4) or formula (5): In formula (4) and formula (5), Sil 1 is a group represented by any one of the following formulas (Si-1) to (Si-4): R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, Multiple R 11 and R 12 may be the same or different, R 21 , R 22 , R 31 , and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Multiple R 21 , R 22 , R 31 , and R 32 may be the same or different, Ry and Rz each independently represent an alkyl group or an aryl group having 1 to 6 carbon atoms; w is 0 or 1; a and b are each an integer from 2 to 6, i is 1 or 2; n is an integer from 1 to 6. In formula (Si-1), R 1 is an alkyl group, and a plurality of R 1 may be the same or different. In formula (Si-2), R 2 is an alkyl group, and a plurality of R 2 may be the same or different, and y is an integer of 1 to 5. In formula (Si-3), R 3 is an alkyl group, and a plurality of R 3 may be the same or different, and z is 2 or 3. In formula (Si-4), R 4 , R 4a , R 4b is an alkyl group, and a plurality of R 4 , R 4a , R 4b may be the same or different, q is 1 or 2, and when q is 1, p is an integer of 1 to 3, and when q is 2, p is 1. In formula (Si-1), formula (Si-2), formula (Si-3), and formula (Si-4), * represents a bonding site with C in formula (4) or formula (5).
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