JPS61284761A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve antitackiness and antistaticness by incorporating a specified fluoropolymer in a matting agent. CONSTITUTION:The matting agent is composed of articles each containing an F-containing polymer having monomer units derived from at least one monomer selected from alkyl vinyl ethers, acrylates, and acrylamides each being fluorinated. Said polymer contains, preferably, said monomer units in an amount of >=10 wt.%, much preferably, >=30 wt.%, and it can be easily synthesized by each known process of solution polymerization, bulk polymerization, and suspension polymerization, thus permitting not only antitackiness but also antistaticness to be improved.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material whose surface is matted with a matting agent, thereby improving adhesion resistance and antistatic properties.

[Conventional technology]

Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid, typically gelatin, as a paint. Therefore, when the surface of a photosensitive material is in a high-temperature, high-humidity atmosphere, its adhesion or tackiness increases, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between the photosensitive materials or between the photosensitive materials and other objects that come into contact with them during the production, storage, and photographing of the photosensitive materials, and has often resulted in serious failures. Particularly in color photosensitive materials, adhesiveness has been a major problem since the photographic layer contains many additives such as color couplers. To solve this problem, the outermost layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate and cellulose acetate propionate.
A method has been proposed in which the surface of a photosensitive material is roughened to make it so-called matte to reduce adhesiveness. In color photosensitive materials, it is necessary to use a large amount of matting agent for the reasons mentioned above. Such matting agents also have the effect of slightly improving the electrostatic properties of photosensitive materials, as described in US Pat. No. 2,322,037. Generally, photographic materials are constructed by coating an insulating photographic constituent layer, such as a photosensitive layer, on an insulating plastic film support. Therefore, when handling photographic materials, it is known that they are easily charged with electricity due to friction, peeling, etc., and that various developments such as dust attraction, electric shock, and ignition occur, thereby impairing commercial value. For example, a silver halide photographic material has a highly sensitive photographic layer coated on an insulating plastic film support as described above, and the manufacturing process,
In other words, during the winding and rewinding of the photosensitive material, the coating of various constituent layers including the photosensitive layer, and the transportation process during drying, the coating layer surface of the photosensitive material is subjected to friction and peeling from other substances. When the photosensitive material is charged and discharged, the photosensitive material is exposed to light, and after development, uneven exposure due to irregular static electricity called so-called static marks may occur. In addition, static electricity is generated in photographic materials not only during manufacture but also during processing to obtain images, which can cause them to become charged, have M dust attached to them, or cause static marks as described above. This may cause a malfunction. The antistatic effect of the above-mentioned matting agent can be achieved by minimizing the surface that contacts other surfaces of the adjacent photosensitive materials or the surface of the conveyor roll during the manufacturing process, and reduces the contact between the surface tiles. This is thought to be aimed at reducing the generation of static electricity caused by separation. However, most of the conventionally known matting agents are
Although it tends to slightly reduce charging on its own, it cannot be said to be very effective in terms of the amount of static electricity generated.Moreover, the recent advances in the sensitivity of photographic materials and the significant increase in coating speed during manufacturing Under conditions such as increased opportunities for harsh mechanical handling due to high-speed automatic processing, the contribution of these matting agents to antistatic properties is extremely small, and matting agents with a larger contribution to antistatic properties are needed. It is considered useful to develop.

[Purpose of the invention]

An object of the present invention is to provide a photographic material having a matting agent suitable for improving adhesion resistance and antistatic properties.

Structure of the Invention As a result of various studies regarding matting agents, including materials, structures, etc., we have arrived at the present invention. That is, the photographic light-sensitive material of the present invention is a photographic light-sensitive material in which at least one surface is roughened with a matting agent.
The matting agent includes alkyl vinyl ethers, alkyl isopropenyl ethers, each having a fluorine atom,
Particles containing a fluoropolymer having a monomer unit derived from at least one monomer selected from alkylcarbonyloxyethylenes, styrenes, alkylstyrenes, acrylic esters, and acrylamides. shall be. The present invention will be explained in detail below. Preferred monomer units derived from alkyl vinyl ethers having a fluorine atom and fulkylisopropenyl ethers having a fluorine atom include the following A:
Preferred monomer units derived from alkylcarbonyloxyethylenes having a fluorine atom include Group B below, and preferred monomer units derived from styrenes having a fluorine atom include the following: Examples of preferred monomer units derived from alkylstyrenes having a fluorine atom include Group C, and preferred examples of monomer units derived from acrylic esters having a fluorine atom include the following groups: Preferred RI R3 R2H is a monomer unit derived from acrylamide having a fluorine atom, including the following Group E. Here, R,,R2,R,,R,,R,,I'! , ,
, R, □, Rl 3 , R+ < , R+ 5, R11
qR1! and R2° each represent a hydrogen atom or a fluorine atom,
Rco and R16 each represent a hydrogen atom, a fluorine atom, or a methyl group (this methyl group may be substituted with a fluorine atom, etc.), and R4 and Rat each represent an alkyl group (this alkyl group has 7 atoms). May be replaced with, etc.
), Rs, Rs and RIG each represent a hydrogen atom, fluorine atom or chlorine atom, R21 and R22 each represent a hydrogen atom,
an alkyl group or a 7-aryl group, R1 and Rr each represent an alkyl group substituted with at least one fluorine atom, l
represents an integer from θ to 5, n represents an integer from 1 to 5, and n represents an integer from 2 to 5.
5, each Rt may be the same or different, and at least one of R2, R1 and cyR,
and at least one of R8, RIS, R16, and
One is a fluorine atom or a group containing a fluorine atom, and at least one of RI, RI, and Lo having an import of 0 is a fluorine atom. Next, the monomer units of group A will be explained in more detail. The alkyl group represented by R1 may be linear or branched, preferably having 1 to 15 carbon atoms, and this alkyl group may have a substituent other than 7 atoms (including substituent atoms, the same applies hereinafter). As the substituent, for example, an alkyloxy group (preferably one having 1 to 10 carbon atoms)
, an alkyloxycarbonyl group (preferably one having 2 to 11 carbon atoms), and the like. Preferable R1 is →CH2)p(CFz)c+X(: :: t',
pR1-10) Integer t&wo, q is an integer of 0 to 2, and X is a hydrogen atom, a fluorine atom, or a Mo7 unit of Group A. Specific examples are listed below. al: 2-12 8-1-c, , Fn: 1-10 Lid 0 (CFz) mcOOcnH2n++ ^-3-C)! 2-Cn- 0CH2 (CF2), H ^ro -CH2Cl- 0CH2CF. ^-6-CI+ 2-CI+ - 0CH2C3F? ^-7-CI+ 2-CH- ■ 0Cllz(CF2)2CF(CFz)zCF. "-CF2-C- CJ5 CF. ^-10-CF2-C- 0C4H1 Next, the monomer units of group B will be explained in more detail. The alkyl group substituted with a fluorine atom represented by R1 can be linear or branched. It preferably has 1 to 10 carbon atoms, and may have a substituent other than a fluorine atom (for example, a phenyl group). Specific examples of the monomer units of group B are listed below. -C1(2-CI(-0COCF. B-2-CH2CH- 0COC2F. B-3-C1, -CI-0COCaF+t Specific examples of the monomer units of group 0 are listed below. C-8-CFH-CF- Next The monomer units of group D will be explained below. The alkyl group substituted with a fluorine atom represented by R2 may be linear or branched, preferably has carbon atoms WL1 to 3, and has a substituent other than a fluorine atom ( For example, it may have a hydroxyl group). Specific examples of the monomer units of group D are listed below. The group represented by R+7 of group E is the same as described for R1 of group A above. Specific examples of monomer units of group E are listed below. -CF, -CF - C00C2H5 E-2 (F2-CF - 0OCH3 E' -CF2-CF- ■ C00C,H. Monomers of group F Specific examples of units include the following: F -3CF, -CF-, CONHC2Hs The fluorine-containing polymer in the present invention is a polymer having at least one monomer unit selected from the group A to F. It is preferable that it is a homopolymer, a copolymer having two or more types of monomer units selected from the group A to F, or a copolymer containing monomer units other than the monomer units of the present invention. Units other than the monomer unit of the present invention in the copolymer include, for example, a monomer unit formed from a monomer having at least one ethylenic double bond. For example, ethylene, propylene, 1-butene, isobutyne, 2-methylbutene, tetrafluoroethylene, vinyl heptafluoride, vinylidene heptafluoride,
Olefins such as triple oleoethylene, vinyl heptadide, vinylitine heptatide, trifluorochloroethylene, hexafluoropropene, vinyl chloride, vinylidene chloride, diolefins such as 1,1,4,4-tetramethylbutanoene esters of olefin carboxylic acids such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, ethyl acrylate, butyl acrylate, methyl vinyl ether , ethyl vinyl ether,
(such as olefin ethers, acrylonitrile, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, divinylbenzene, allyl acrylate, allyl methacrylate, 1,3-butylene diacrylate), 1.
3-butylene dimethacrylate, diethylene glycol noacrylate, diethylene glycol noacrylate, vinyl acrylate, vinyl methacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate, ethylene diacrylate, ethylene dimethacrylate), 1,6-hexane diacrylate , and those having two or more ethylenically unsaturated double bonds such as 1t6-hexane dimethacrylate. Among the above-mentioned copolymers, those containing fluorine atom-containing monomer units of the present invention are preferably 10% by weight or more, and 30% by weight or more.
More preferably, the amount is % by weight or more. Specific examples of polymers having units of group A include the following. (Hereinafter, the monomer ratio will be expressed as a molar ratio) PA-' ncF2cF2McF, -CFh. 0(CF,),C00C)I. PA' -(CF2 CFh.-(CF, -CFh. CJt OCH3(CF2)4H PA-7-(CF2-CFCllh.-(CH2-C)
lh. "0CH-(CF2)4H PA-8-ncF2-CFh. 0(CF, ), C00C) I. PA-9→CF2-CF+-r-b0 ε 0(CF2)zcOocl(.PA-13-fcF2CFh o QC4F. 2^-14-(CH2-CHho. 0C,F. PA-18 CF. PA-221 -fCF, -C juice.. 0C, H. Examples of polymers having units of group B include the following. 0COCzF70COCH3 -(CH2-CH± Specific examples of polymers having units of the 0 group include the following: PC-8-(CF2-CFh, PC-9-fCF2- CHh. Specific examples of polymers having units of group D include the following: CF. PD-3 Specific examples of polymers having units of group E include the following. PE-1-(CF, -CFh, -(CF, -CF-)
,. CF, C00CR. PE-4Yu CF2-CF too. . Specific examples of polymers having units of the C00CR3 F group include the following. PF-4-4CF2-CFho. Peek0CONHC2H5 All of the above polymers can be polymerized by conventionally known solution polymerization, bulk polymerization,
0, which can be easily synthesized by methods such as suspension polymerization
For example, in solution polymerization, a mixture of two or three monomers (usually 40% by weight or less, preferably 10% by weight or less, based on the solvent) at an appropriate concentration is generally used in a suitable solvent (e.g., ethanol, methanol, etc.). A mixture of two or three monomers at a concentration of ~25% by weight) in the presence of a polymerization initiator (e.g. benzoyl peroxide, azobisisobutyronitrile, etc.) at a suitable temperature (e.g. 40-120°C). , preferably 50 to 100°C), the copolymerization reaction is carried out. Thereafter, the unreacted mixture is separated off by pouring the reaction mixture into a medium such as water, allowing the product to settle, and then drying. Further, polymer P^-1 and the like are preferably reacted under pressure as described in Japanese Patent Publication No. 45-26303. In addition, polymers P^-2, PD-1, PD-2, etc. are described in British Patent No. 1023717, Journal of Polymers.
Science: Polymer Letters Editor (Jo
urnal of polymer 5cie
nce:Polymer Letters Edi
tion) Vol, 18. pp, 201-209 (19
80), etc., it can be produced by obtaining a polymer without fluorine atoms in advance and then fluorinating it. APC-7~pc-to is, for example, the Journal of Polymer Science (Journal of Polymer Science).
ser 5science) Part^-1, Vol, 6
．． pp, 171-191 (1968), Journal of Polymer Science
. Iyner 5science) Vol, 20tpp, 4
85-490 (1956) and Journal Op.
American Chemical Society (Journal o
r the^merican Chemical 5o
society) Vol, 75+p, 968-p, 973(
1953). PE-1~PE
-4 and PF-1 to PF-3 are, for example, U.S. Pat.
44,374, and the Journal of the American Chemical Society.
the American Chemical 5o
society) Vol. 100, p., 1948-p., 1950 (1948). Next, a synthesis example of the fluoropolymer of the present invention will be shown. Synthesis Example 1 Production of CF2 = CF-0-(CF2), C00CH, and copolymer of tetrafluoroethylene (P^-1) 346 m of a 4% aqueous solution of NazPHOl/7HxO was placed in a stainless steel autoclave with a capacity of ff14Q. ! l
, 1554 ml of distilled water degassed with nitrogen, (NH4
) 0-order CF mixed with 4 g of zszos and 15 g of commercially available ammonium perfluorooctanoate! =
CF-0-(CF2), C00CH, 70g and tetrafluoroethylene 30g were introduced, the pressure was increased, and distilled water 70g was introduced.
20+Q, 0.01% cupric sulfate aqueous solution 180-1 and sodium sulfide 18. 50ml of catalyst solution made from
I put it in 1. Heat to 40°C while stirring continuously,
The pressure was maintained at 8.4 kg 7 cm'' during the 2 hour reaction.
5 Ω of the above catalyst solution was added every 15 minutes during the reaction. Furthermore, over 1 hour, CFx=CF-0-(Fz)<CC
After the completion of 6 reactions in which 00CHs70 and 50g of tetrafluoroethylene were introduced, the outflow was reduced to 1 at a temperature of 25℃ and atmospheric pressure.
Got 6Q. This copolymer latex was frozen in dry ice/acetone, and the solid was separated, filtered, and dried to obtain 180 g of the desired copolymer P^-1. Synthesis Example 2 Production of copolymer (P^-18) of C12=Cl-0-CH2CF and vinyl acetate $l! 150 mQ of a 4% aqueous solution of N^2PHO,,7H,0 in a stainless steel autoclave at ill.
, 1500 ml of distilled water degassed with nitrogen gas t', (NH
<)Zs20s4g and (/0th order CH mixed with 10g of commercially available ammonium perfluorooctanoate, =
CH-0-C1, CFJOtr and 60 g of vinyl acetate were introduced to increase the pressure, and 720 mQ of distilled water, 180 mQ of 0.01% cupric sulfate aqueous solution and sulfurization were carried out) +7 Tsum 18
, 50 mQ of a catalyst solution prepared from . Heat to 40° C. with continuous stirring and reduce pressure to 3.0° C. during reaction for 2 hours.
5 mQ of the above catalyst f# liquid was added every 30 minutes during one reaction maintained at 5 kg/am''.
5 g was introduced. After the reaction was completed, the temperature was lowered to room temperature and the autoclave was opened to atmospheric pressure. This copolymer latex was heated at -20°C.
The solid was frozen and coagulated, and the solid was separated, filtered, and dried to obtain 310 g of the desired copolymer (P^-18). Synthesis Example 3 Production of copolymer (PB-2) of CH2=Cl1-OCOCJs and ethyl 7-taacrylate 500 taQ of degassed ethanol was placed in 7 Rasfs with 4 openings of 2Q and heated to 70°C. Dissolve 3 g of isobutyronitrile, CCl2=C)I-OCOC2
F553 and ethyl methacrylate 50. was introduced over 30 minutes. After 6 reactions, which were refluxed for 4 hours with stirring, the temperature was returned to room temperature, and the reaction solution was added to 3Q of distilled water with vigorous stirring to precipitate a white solid. When this solid was filtered and dried, the desired product was obtained. copolymer (PB-2)98. I got it. Synthesis Example 4 Production of copolymer (PC-5) of pentafluorostyrene, methyl methacrylate, and divinylbenzene Pour 500 mQ of degassed nooxane into 2Q lower 2 SCs at 70 mA.
Do not raise the temperature to °C.
65 g of pentafluorostyrene, 31 g of methyl methacrylate, and 10 g of divinylbenzene were introduced over 30 minutes. Keep it at 70℃ while stirring and after 4 hours
After the completion of the reaction in which 1 g of zobisin butyronitrile was added and the reaction was further continued for 2 hours, the reaction solution was added to 311 liters of distilled water with vigorous stirring to precipitate a white solid. When this solid was filtered and dried, the desired copolymer (PC-5
)95. I got it. Synthesis Example 5 Production of copolymer (PD-1) of styrene and vinylphenylhexafluorodimethylcarbinol Polystyrene (Styron-685D manufactured by Dow Chemical Co., Ltd. Mw = 3X
10') 15.6g carbon disulfide 240gj: dissolved Le
Dry ice/7 setsone reflux tower +t 50
It was placed in a 7 lasco with 0mQ. There ^QC'l* 6
g was added thereto, and the mixture was cooled and maintained at 5°C. 10 g of hexafluoroacetone was added dropwise over 30 minutes and stirring was continued for 2 hours.
After the reaction was completed, the reaction mixture was added to IQ distilled water with vigorous stirring, and then the mixture was heated to distill off the carbon dioxide. The same amount of the light-colored reaction product was dried at 60'C for 12 hours. This was dissolved in 100 d of methylene chloride and purified by precipitation with excess hexane to obtain a white solid, which was filtered and dried to obtain the desired polymer (PD-1). Particles containing a fluoropolymer according to the present invention include particles in which the entire particle is composed of the fluoropolymer according to the present invention, and particles in which a part of the particle is composed of the polymer, The latter particles include particles in which a core made of a substance other than the polymer is coated with the polymer. Substances constituting this core include, for example, inorganic compounds such as silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass, and talc, as well as polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, and cellulose acetate flour. Examples include substances constituting particles known as matting agents, such as bionate, ethyl cellulose, starch, benzoguanamine-formaldehyde condensates, etc. Substances other than those listed above may also be used as long as they do not adversely affect photographic properties. Can be used freely. Various methods can be used to produce particles using the fluoropolymer according to the present invention. For example, to produce particles in which the surface of the core is coated with the fluoropolymer of the present invention, the core particles are immersed in a solution of the fluoropolymer of the present invention that does not dissolve the particles, and then dried. Alternatively, the fluoropolymer can be made to exist on the surface of the core particle by grafting a t 7 y monomer onto the surface of the core particle by plasma polymerization. When a nucleus is not used, for example, a solution of a polymer in an organic solvent is injected into an aqueous surfactant solution (which may contain a hydrophilic colloid such as gelatin) under stirring, and the solvent is removed from the resulting emulsion under reduced pressure. After removal, the polymer particles may be fractionated by centrifugation. Furthermore, it may be made into fine particles by pulverization means. It is also possible to obtain particles immediately from the emulsion obtained by the polymerization reaction by centrifugation. The photographic light-sensitive material referred to in the present invention refers to a support used for photographic light-sensitive material subjected to subbing processing, and a photographic structure/I (including a backing layer) having one or more layers on the support.
Photographic constituent layers such as a silver halide emulsion layer, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, and a backing layer were coated on the intermediate photographic light-sensitive material and support coated with The invention includes all photographic materials as finished products, and the present invention refers to silver halide photographic materials (including general black-and-white, special black-and-white, color, printing, and X-ray materials) as finished products. The effect is particularly noticeable when applied to photographic materials (including intermediate products) that are In order to roughen at least one surface of the photographic light-sensitive material with a matting agent, for example, a matting agent is mixed into a coating composition for a layer to be coated on the support, that is, a photographic constituent layer (preferably the outermost layer). , it may be applied by ordinary coating means and dried. As another method, the matting agent of the present invention may be used alone or mixed with a binder such as gelatin, sprayed or supercoated, and then dried. It is not essential to form the particles without a nucleus into particles in advance; for example, the polymer of the present invention may be mixed with a low-boiling organic solvent such as ethyl acetate, butanol-containing ethyl acetate (less than 50% by weight of butanol), Particles are formed by dispersing a solution containing butanol in methanol (less than 50% by weight of butanol) in an equal width in a hydrophilic colloid liquid, such as an aqueous gelatin solution, under rapid stirring, and this dispersion is applied and dried. The surface can be roughened by Examples of the outermost layer include a surface protective layer, a back layer, and a non-photosensitive intermediate of an intermediate product in a multilayer photosensitive material coated with a snow layer, but in the present invention, a surface protective layer is particularly preferred. , The thickness of the outermost layer is 0.1 to 0.1 when gelatin is used as the bangu.
5μ is preferred, particularly 0.5 to 3μ. In the present invention, at least one surface of the photographic material is
[The surface is roughened by a matting agent. ] means that the surface of the outermost layer is roughened due to the presence of the matting agent. In other words, if the protrusions on the outermost surface are made of a matting agent and particles of the matting agent are exposed on the surface of the protrusion, the surface of the matting agent particles may be covered with the outermost layer material (the outermost layer composition other than the matting agent). ) Wrapped particulate matter protrudes from the outermost N surface, so that the surface of the protrusion is constituted by the outermost layer material. In the present invention, the average particle size of the matting agent is preferably 0.
．． The thickness is 1 to 10μ, more preferably 0.5 to 8μ, but if it is mixed with the outermost layer of banhgu, it should be larger than the dry film thickness (thickness of the part without protrusions caused by the matting agent). is preferable, and the particle size of the matting agent of the present invention is preferably 2 times or more than the dry film thickness at α of the antistatic effect, and more preferably 2 times or more.
．． It is particularly preferred that it is 5 times or more larger. Furthermore, the amount of the matting agent of the present invention to be applied is more effective for the purpose of improving the matting effect, and is 10 tag/m2.
or more is preferable, and more preferably 20I1g/lI2 or more, especially 5
0-g/s2 or more is preferable, and considering the influence on transparency and image sharpness, it is 500 mg/s2 or more.
112 or less, and preferably 200 g/s or less. The matting agent according to the present invention can be used in combination with other matting agents, but the It is preferable to use a smaller amount than the matting agent.The silver halide emulsion used when the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material includes silver bromide, silver iodobromide, silver iodochloride as silver halide. Any of the usual silver halide emulsions used in silver halide emulsions can be used, such as silver chloride, silver chlorobromide, and silver chloride. The particles may be obtained by either the ammonia method or the ammonia method.The particles may be grown all at once, or they may be grown after creating seed particles.The method for creating seed particles and the method for growing them are the same. 6 Silver halide emulsions may be made by mixing halide ions and silver ions at the same time, or by mixing one of them in a solution in which the other is present. Taking into account the critical growth rate of the crystal, it may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and pAFI in the mixing pot. This method allows the crystal to have a regular crystal shape. Silver halide grains with a nearly uniform grain size can be obtained.The halogen composition of the grains may be changed by using the convergitan method after growth.Silver halide grains are produced by the process of grain formation and/or growth. In the process, metal ions are removed using at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), lonotum salts (including complex salts), and iron salts (including complex salts). added to the inside of the particle and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. The silver halide emulsion may have unnecessary soluble salts removed after the growth of silver halide grains has finished, or may even contain them. When removing the salts, Research Disc
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter referred to as losure). The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. /NCl Silver denride grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. These particles may have a regular crystal shape such as a hedron or a tetradecahedron, or may have an irregular crystal shape such as a sphere or a plate.
Any ratio between the 101 plane and the (111) plane can be used. Also, it may have a composite form of these crystal forms,
Particles of various crystalline forms may be mixed. Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. Monodisperse emulsion as used herein refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less. In the case of silver, the diameter is shown; in the case of particles with a shape other than spherical, the diameter is shown when the projected image is converted into a circular image of the same area). A mixture of a dispersed emulsion and a monodispersed emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. Alternatively, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion. Silver halide emulsions are used during chemical ripening, at the end of chemical ripening, and/or for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of photographic light-sensitive materials, or to maintain stable photographic performance. After chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as anti-capri agents or stabilizers can be added. As a binder (or protective colloid) for silver halide emulsions, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, higher proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers may also be included. The photographic emulsion layer and other hydrophilic colloid layers used in the photographic light-sensitive material of the present invention contain one or two hardeners that crosslink binder (or protective colloid) molecules and increase film strength.
Hardening can be achieved by using more than one species. The hardening agent can be added to the photographic light-sensitive material in such an amount that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a photographic light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are A of the beans section of RD17643.
It is a compound described in . The photographic emulsion layer and other hydrophilic colloid layers of a photographic light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. In the emulsion layer of color photographic materials, aromatic primary amine developers (such as +rp-phenylenediamine derivatives and 7-minophenol derivatives) are used in color development processing.
A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized form of. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive milk 'MN, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, a silver halide color photographic light-sensitive material may be produced using a method different from the above combination. It is desirable that these dye-forming couplers have a group called a pallast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. The effect of color correction on color-forming power pullers, which can be either 4-equivalent, which requires the reduction of two silver ions, or bi-equivalent, which requires only two molecules of silver ions to be reduced. A development accelerator, a bleach accelerator, a developer, a silver halide solvent,
Compounds that release photographically useful 7-ragments such as toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known 7-syl-7-cetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used. As the cyan dye-forming coupler, commonly used phenol or 7-tole couplers can be used. Among dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds can be used using the solid dispersion method or latex dispersion method. Various methods can be used, such as , oil-in-water emulsion dispersion method, etc., and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
Usually, it is dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and stirred with a surfactant in a fresh aqueous paint such as gelatin aqueous solution. Homogenizer, homogenizer, colloid mill,
It may be emulsified and dispersed using a dispersing means such as a 70-knot mixer or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, 7-tar acid alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with a boiling point of 150°C or higher. Organic solvents are used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, trimethylsulfoxide, hexamethylphosphoramide,
Examples include diethylene glycol monophenyl ether and phenoxyethanol. When dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they are introduced into hydrophilic colloids as an alkaline aqueous solution. You can also. Anionic surfactants and nonionic surfactants are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. Agents, cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of a photographic light-sensitive material, causing color turbidity or deterioration of sharpness. ,
A color antifoggant can be used to prevent graininess from becoming noticeable. The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. Hydrophilic colloid layers such as protective layers and intermediate layers of photographic light-sensitive materials may contain an ultraviolet absorber. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of photographic materials, a formalin scavenger can be used in the photographic material. When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photographic light-sensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the photographic light-sensitive material. The compound that is preferred for use as a development accelerator is R01.
The compound is a compound described in Section XXI B to D of No. 7463, and the development retardant is a compound described in Section XXI E of No. R017643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may contain urea derivatives, imiguzole derivatives, etc. 1. A fluorescent brightener can be used in the photographic light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in RD 17843, item 7. The photosensitive material can be provided with auxiliary layers such as a filter layer, a halide prevention layer, a, a radiacian prevention layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. A lubricant can be added to photographic materials to reduce sliding friction. A surfactant can be used in the photographic emulsion layer and/or other hydrophilic colloid layer of the photographic light-sensitive material. The supports used in the photographic material of the present invention include papers laminated with a-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), visible reflective supports such as synthetic papers, cellulose acetate, Includes films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., visible supports with reflective layers on these films, glass, metals, ceramics, etc. It will be done. For photographic materials, corona discharge is applied to the surface of the support as necessary.
After ultraviolet irradiation, flame treatment, etc., the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, anti-Harley siding properties, friction properties, and/or other properties of the support surface can be improved directly or on the surface of the support. The hydrophilic colloid layer may be applied through one or more subbing layers for enhancement. When coating photographic light-sensitive materials, thickeners may be added to improve coating properties.For example, thickeners, such as hardeners, have quick reactivity and may be added to the coating solution in advance to form a gel before coating. For substances that cause chemical reaction, it is preferable to mix them using a static mixer or the like immediately before coating. As coating methods, Extrulamin coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Any known method can be used for developing the photographic material of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. If you are creating images using the reversal method, first perform a black and white negative development process,
The film is then exposed to white light or treated with a bath containing a capriagent for color development. (Also, silver dye bleaching may be used, in which a dye is contained in a photosensitive material, a black and white development process is performed after exposure to create a silver image, and this is used as a bleaching catalyst to bleach the dye.) As a black and white development process, , development process, fixing process,
A water washing process is performed. When a stopping process is performed after the development process or a stabilizing process is performed after the fixing process, the washing process may be omitted. Alternatively, the developing agent or its precursor may be incorporated into the photographic light-sensitive material, and the original image processing step may be carried out using only an alkaline solution. It's okay. Color development processing includes a color development processing process, a bleaching processing process,
A fixing process, a water washing process and, if necessary, a stabilizing process are performed, but instead of the process using a bleach solution and the process using a fixer, a one-bath bleach-fix solution is used.
A bleach-fixing process can be carried out, or a monobath process can be carried out using a one-bath development, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the photographic light-sensitive material and the development process is carried out using an activator solution. An activator treatment can be applied to the treatment. Among these processes, typical processes are shown below. (In these treatments, one of the following steps is performed as the final step: washing with water, washing with water, or stabilizing.)
Color development process - Bleach process Constant fixation process / Color development process - Bleach-fix process - Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleach process Constant fixation process - Water washing process - Post-hardening process/color development process - Water washing process - Supplementary color development process - Stop process - Bleaching process Constant fixation process/activator process - Bleach-fixing process/activator Treatment process - Bleaching treatment process Constant fixation treatment process / Monobath treatment process The treatment temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C. The black-and-white developer used in the black-and-white development process is a so-called black-and-white @1 developer used in the processing of color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic light-sensitive materials; Various additives added to the liquid can be included. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, and methylbenzthiazole, water softeners such as polyphosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds. etc. can be mentioned. The color developing solution is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and 7mino-7er7-el and p7z direthamine derivatives are used. These color developing agents can be used as salts of organic acids and Wi-free acids,
For example, salts such as 1fl acid, sulfate, p)luenesulfonate, sulfite, sitaurate, benzenesulfonate, etc. can be used. These compounds are generally preferably about 0.1 to 30% per color developer. , more preferably at a concentration of about 1 to 15 r for color developer IQ. For example, the aminophenol developer mentioned above is 0-7
Minophenol, p-ami/phenol, 5-7mi/-
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-7mi/-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Furkyl and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include I-N-N-dimethyl-p-7 22-diamine hydrochloride, N-/Til-p
7z Nylenediamine hydrochloride, N,N-dinotyl-p-phenylenecyamine hydrochloride, 2-ami/-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N
-β-Methanesulfone 7midoethyl-3-methyl-4-
7minoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-7mino3-methyl-N
. N-noethylaniline, 4-7minor N-(2-7toxyethyl)-N-ethyl-3-methyl7diphosphorus-p-)
Examples include luenesulfonate. Further, the color developing agents mentioned above may be used alone or in combination of two or more kinds.Furthermore, the color developing agents mentioned above may be incorporated into the color photographic material. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution. The color developing solution may contain an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. additives such as benzyl alcohol, alkali metal halide, such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained. The pH of the color developer is usually 7 or higher, preferably about 9.
~13. In addition, antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-7 di/ethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol are added to the color developer as necessary. 1,3-methyl ether or the like may be contained. In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents.For example, the chelating agents include amine polycarboxylic acids such as ethylenedi7minetetraacetic acid, quetintri7mino5'#acid, etc. Organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, ami/polyphosphonic acids such as 7-minotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phospho/ butane! , 2.4-) Phosphonocarboxylic acids such as recarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. As mentioned above, the bleaching process may be carried out simultaneously with the fixing process or separately. As the bleaching agent, metal complex salts of organic acids are used, such as polycarboxylic acids, 7-minoboric acid, etc. A carboxylic acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt, or copper is used. The most preferred among the above organic acids! Examples of acids include polycarboxylic acids or 7mi/polycarboxylic acids. Specific examples of these include ethylenecyaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenenoamine-N-(β-oxyethyl)-N,
N', N'-) diacetic acid, propylene diaminetetraacetic acid, nitrilotriacetic acid, cyclohexanoaminetitraacetic acid, iminodiacetic acid, dihydroxyethylglycinecitric acid (or tartaric acid), ethyl ether thyl diamine tetraacetic acid, glyfur ether diamine tetraacetic acid Examples include acetic acid, ethylenenoaminetetraprobionic acid, phenylenediaminetetraacetic acid, and the like. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches contain 5 to 450 g/Q, more preferably 2
Use at 0 to 250g/Q. In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, the bleaching solution may be a bleaching solution containing an ethylenecyaminetetraacetate iron (I[[) complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide.
:j In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used as gunnides. I can do it. Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 46-556, Belgian Patent No. 0,9
Various bleaching accelerators described in Japanese Patent Publication No. 10, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Application Publication No. 54-71634 and Japanese Patent Publication No. 49-42349, etc. can be added. The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0. A fixer having a commonly used composition can be used. As a fixing agent, compounds that react with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thiocyanate are used. Typical examples include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and 1,000-onythyl. These fixatives are 5
It is used in an amount of fIAll that can be dissolved at least g/Q, but generally it is used in an amount of 70 to 250 g/11. In addition,
A part of the fixing agent can be contained in the bleach bath, or conversely, a part of the bleach can be contained in the fixing bath. The bleaching solution and/or fixing solution may contain various pH 1 buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as human mixiamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as 7-polycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and water-soluble aluminum salts. Hardeners such as methanol,
Organic solvents such as dimethyl sulfonamide and dimethyl sulfoxide can be contained as appropriate. The pH of the fixer is 3.0 or higher, but it is generally 4.
, 5 to 10, preferably 5 to 9,5, and most preferably 6 to 9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process. The bleach-fixing solution contains a silver halide fixing agent other than the bleaching agent as mentioned above, and if necessary, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetic acid iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halide such as ammonium bromide may be used. A bleach-fix solution containing a large amount of iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate)
II [)* A special bleach-fix solution having a composition consisting of a combination of a salt bleach and a large amount of a halide such as ammonium bromide can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above-mentioned fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above. The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
It is 5. [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby. Example 1゜Titanium oxide matting agent (matting agent-1) 1 with an average particle size of 5μ
0g of exemplified polymer P^-18 dissolved in 10% acetone
After immersing in 500μ of water and dispersing for 30 minutes with an ultrasonic disperser, the resulting dispersion was sprayed in a suspended state into hot air at 70°C to 90°C with a spray gun to dissolve the fluorine-containing heavy A titanium oxide matting agent whose surface was coated by the coalescence was obtained. This matting agent is referred to as matting agent-2. Next, emulsion 1 is subjected to a second ripening process for a silver iodobromide gelatin high-sensitivity X#I emulsion containing 35 g of gelatin and ioog of silver iodobromide (containing 3 mol% silver iodide). Sometimes, after gold-sulfur sensitization, 4-hydroxy-
6-Methyl-1,3,3,7-titrazaindene, glyoxal as a hardening agent and saponin as a coating aid were added to give a dry film thickness of 7μ on a 175μ thick polyethylene terephthalate film support which had been subbed. Then, a protective layer having the following composition was coated and dried to give a dry film thickness of about 1.0 μm to obtain Sample 1. (Ho1llII! Composition) (
g/m2) Gelatin 1
．． 0g Nor 2-Ethylhexyl Sodium Sulfosuccinate 0.01g Glyoxal 0. Of. The sample obtained by adding the matting agent-1 to the above-mentioned retaining wIWX composition at a ratio of 30+ag/m'' was used as sample-1.
2, and further 30g of the above-mentioned matting agent-2 according to the present invention.
The sample obtained by adding the above-mentioned 1m composition to the ratio of /m2 is designated as sample-3. Next, each sample was conditioned for 4 hours in an atmosphere of 23° C. and 20% RH, and the amount of frictional charge using neoprene rubber was measured and a static mark generation test was conducted, with the results shown in Table 1 below. The above charge amount is the amount of frictional charge between neoprene rubber and the sample dark, and was measured in an atmosphere of 23°C and 20% RH.Static marks were measured in an atmosphere of 23°C and 20% RH for 4 hours. After adjusting the humidity of the sample, it was rubbed with a neoprene rubber rod, developed, and then the degree of blackening was observed and judged according to the following grade. Grade 1: No occurrence, 〃 2: Slight occurrence, 〃 3: Frequent occurrence, 〃 4: Slight occurrence, 〃 5: Occurred all over the surface. As shown in the table above, no matting agent was added to the protective layer. Sample-1 and Sample-2 to which a titanium oxide matting agent was added were both highly positively charged and had strong static marks. On the other hand, a sample to which matting agent-2 according to the present invention was added
In No. 3, the amount of charge was small, and there were almost no static marks. In addition, the samples of the present invention did not exhibit any decrease in sensitivity or occurrence of capri. Example 2 Sample-3 of Example 1 except that a matting agent consisting of particles with an average particle size of 3μ made of the polymer shown in Table 12 below was used as the matting agent, and the amount added was changed to the amount shown in Table 2. Samples 4 to 8 were prepared in the same manner as above. For each sample obtained, the amount of triboelectric charge was measured and the static mark generation test was conducted in the same manner as in Example 1. The results are shown in Table 2. As shown in Table 2, Sample 8, in which the anti-N layer contained a matting agent for comparison, was positively charged (charged) and had strong static marks.However, the mat according to the present invention In the samples to which the matting agent was added, the amount of charge was small, and almost no static marks were observed.In addition, P^-21, PC-7,
Good results similar to those of Samples 4 to 7 were obtained with samples prepared in the same manner as Samples 4 to 7 above except that PC-10, PE-1, PE-4, and PF-1 were used respectively. . Example 3 The following composition solution was coated on the back side of a cellulose triacetate film support at a rate of about 20all/2 by roll coating, dried at 90°C for 3 minutes, and then coated on the surface of the support using a conventional method. After the up-down treatment, the same high-sensitivity X#I emulsion and protective layer as in Sample-3 prepared in Example 1 were applied and dried to obtain Sample-9. (Composition liquid) Cellulose diacetate 20g methanol 700g acetone
300g On the other hand, add particles with an average particle size of 1μ of the polymer shown in Table 3 below to the above Group 1 & liquid at 60mH/
Samples 10 to 14 were prepared in the same manner as Sample 9 above, except that a2 was added. Each sample obtained and broken as described above was treated in the same manner as in Example 1, and the obtained results are shown in Table 3 below. As shown above, the sample in which the matting agent according to the present invention was added to the back coating layer of the support, ll was small, and almost no static marks were observed. Swelling and dissolution occurred, making it unusable. Example 4 Containing 300 g of gelatin per mole of silver halide,
And α-piparoyl-α-(
1-Benzylimidazolidin-2,4-dion-3-yl)-2-chloro-5[γ-L4-tert-7minophenoxy)butyramide]acetanilide 2,5X
A color limestone-sensitive silver iodobromide (silver iodide 7 mol %) emulsion containing 10-" moles of silver iodide was prepared. Together with this emulsion, matting agents and coating aids consisting of polymers shown in Table 4 below were used for the protective layer. agent (sodium dil-2-ethylhexylsuccinate) and hardener (per 1 g of gelatin!
A gelatin solution containing 10.02 g) was prepared, and an emulsion layer and an H-retention layer were coated on a cellulose triacetate film support having a subbing layer using a slide hopper method in order from the support to obtain samples 15 to 20. . None of the matting agents dissolved during application. Sample 21 without the addition of a matting agent was also prepared. Coating amount: matting agent 100+g/m", gelatin 0.5g
/m2. The antistatic property of each sample was examined using the following method. After conditioning the unexposed sample at 25°C and 25% RH for 2 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room with the same air conditioning conditions, and then developed, bleached, and fixed with the following processing solution. , washed with water and stabilized, and examined the degree of static mark occurrence. Processing process Temperature Processing time (1) Developer: 38℃ 3 minutes 15 seconds (2
) Bleaching...38℃ 4 minutes 30 seconds (3)
Fixation: 38°C, 4 minutes 20 seconds (4) Washing: 38°C, 3 minutes 15 seconds (5) Stabilization: 38°C, 1 minute, 5 seconds. The compositions of the solution, bleaching solution, fixing bath, and stabilizing bath are as follows. Developer (pH=10.05) Add water to make IQ. i-balloon white bath (pH=5.'70) Add water to make IQ. Fixing bath (pi = I3,50) Add water to make IQ. Stable bath (pH = 7.30) Add water to make IQ. The antistatic test results of these samples are shown in Table 5. In the table, the evaluation of the degree of static mark occurrence is 1: No static marks were observed and 2:
Slightly recognized 3: 〃
Quite acceptable 4: //
r! It was divided into 4p; 1Wl, which was observed on the entire surface. As is clear from Table 4, the matting agent of the present invention has an excellent antistatic effect with almost no static marks observed. Example 5 Samples 15 to 21 in Example 4 were cut into two pieces each having a size of 5 square meters, and each piece was stored in an atmosphere of 23°C and 80% RH for one day so as not to come into contact with each other, and then the same sample was cut out. The two protective layers of 800. The sample was stored in an atmosphere of 40° C. and 80% RH, and then the sample was peeled off and the area of the bonded portion was measured to measure the adhesion resistance. The evaluation criteria are as follows. Rank Area of adhesive part A 0-20% 8 21-40% C41-60% D 61% or more The results are shown in Table 5. From the results in Table 5, it can be seen that the adhesion resistance of the matting agent of the present invention is superior to that of the conventional matting agent. Example 6 A matting agent manufactured using polymer P^-14 and having a particle size shown in Table 6 was added to the protective layer of Sample 1 of Example 1 in the amount shown in Table 6, and the protective layer film was further added. Samples 22 to 27 were prepared by changing the thickness as shown in Table 6.Next, each sample was subjected to humidity control under the same conditions as in Example 1, and the amount of frictional charge was measured and a static mark generation test was conducted. , the results shown in Table 6 below were obtained. From Table 6 in the margin below, it can be seen that when the amount of the matting agent in the outermost layer is 50 mg/I12 or more, and as the ratio of the average particle diameter of the matting agent to the film thickness of the outermost layer containing the matting agent increases, the charging characteristics are improved. It can be seen that becomes larger. Further, when the same experiment as above was carried out using PB-1, PC-6 and PD-3 in place of the polymer P^-14, the same results as in the case of P^-14 were obtained. [Effects of the Invention] By using the matting agent of the present invention as a matting agent for photographic light-sensitive materials, not only the adhesion resistance but also the antistatic property can be improved. The matting agent of the present invention can impart good adhesion resistance to photographic materials, and can also impart good static electricity properties even in a low humidity atmosphere where static electricity is a particular problem. Furthermore, the matting agent of the present invention has the disadvantage that a large amount of the matting agent dissolves especially in the coating process during the production of photographic light-sensitive materials in which a coating solution containing a matting agent is coated and dried. When used, it is not essential to demineralize or demineralize the gelatin.

Claims (1)

[Claims] In a photographic light-sensitive material in which at least one surface is roughened with a matting agent, the matting agent includes alkyl vinyl ethers, alkyl isopropenyl ethers, alkyl carbonyloxyethylenes, styrenes, alkyl styrenes, each having a fluorine atom, At least one selected from acrylic esters and acrylamides
1. A photographic material comprising particles containing a fluorine-containing polymer having monomer units derived from two monomers.