JPH0642054B2 - Photographic material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which is excellent in coating properties and adhesion resistance and is excellent in antistatic storability.

[Prior art]

Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid represented by gelatin as a binder. Therefore, the adhesiveness or tackiness of the surface of the light-sensitive material increases under an atmosphere of high temperature and high humidity, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between the light-sensitive materials, or between the light-sensitive material and another object adhered to the light-sensitive material during manufacturing, storage, photographing, etc. of the light-sensitive material, and often causes a serious failure. In particular, in a color light-sensitive material, since a photographic layer contains a large number of additives such as color couplers, the adhesiveness has been a serious problem. In order to solve this problem, the outermost layer contains fine particles of an inorganic substance such as silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, etc., or fine particles of an organic substance such as polymethylmethacrylate, cellulose acetate propionate, etc. A method has been proposed in which the surface is roughened, so-called matte, and the adhesiveness is reduced. In the color light-sensitive material, it is necessary to use a large amount of matting agent for the above reason. In general, a photographic light-sensitive material is formed by coating an insulating plastic film support with an insulating photographic constituent layer, for example, a photosensitive layer. Therefore, when handling photographic light-sensitive materials, it is known that they are easily charged due to, for example, friction and peeling, and cause various phenomena such as suction of dust, electric shock, and ignition, thereby impairing the commercial value. As an example, the silver halide photographic light-sensitive material is coated with a high-sensitivity photographic light-sensitive layer on the insulating plastic film support as described above, and its manufacturing process,
That is, the film layer surface of the photosensitive material may not be rubbed or separated from other substances during winding, rewinding of the photosensitive material, or application of various constituent layers including the photosensitive layer, and a conveying step during drying. In some cases, the photosensitive material is exposed to charge and discharged, and the photosensitive material is exposed to light during discharge, and after development, irregular photosensitivity called so-called static marks may occur due to irregular static electricity. The photographic light-sensitive material generates static electricity not only at the time of its production but also at the time of processing for obtaining an image, which may cause electrification, dust adhesion, or static mark as described above. May cause a failure. The antistatic effect of the above matting agent is to minimize the contact surface with the other surface of the photographic light-sensitive material in contact with each other or the contact surface with the surface of the transport roll during the manufacturing process,
It is considered to reduce the generation of static electricity caused by contact separation between the surfaces. However, most of the conventionally known matting agents, by themselves, tend to slightly reduce the electrostatic charge, but from the viewpoint of the amount of static electricity generated, they cannot be said to be so effective. In situations where the sensitivity of materials is increased or the coating speed during manufacturing is greatly increased and the opportunities for severe mechanical handling due to high-speed automatic processing are increasing, the contribution of these matting agents to antistatic is extremely small and antistatic There was a problem that could not meet the demand for. As improving the above-mentioned adhesion resistance and antistatic property,
Japanese Examined Patent Publication No. 56-44411 discloses a photographic light-sensitive material in which the outermost layer contains a fluorosurfactant and the surface is roughened with a Teflon matting agent. However, the photosensitive material according to this technique has insufficient adhesion resistance and stability of antistatic property of the photosensitive material before development processing due to lapse of time from the production of the photosensitive material. We have found that it has a problem of unevenness.

[Object of the Invention]

An object of the present invention is to provide a photographic light-sensitive material which is excellent in antistatic storage stability and adhesion resistance and has good coating properties.

[Structure of the Invention] We are concerned with fluorine-containing matting agents and fluorine-based surfactants.
However, as a result of various studies, the present invention has been achieved. That is, at least one surface of the photographic light-sensitive material of the present invention contains a foil.
The surface is roughened with a fluorine matting agent, and the surface is
If the outermost layer of the layer contains a fluorosurfactant,
In a true light-sensitive material, the total amount of the matting agent and the surfactant is
The ratio of the matting agent to the amount is 85% by weight or more and 95% by weight or less.
It is characterized by being below. Hereinafter, the present invention will be described in more detail. In the present invention, the fluorine-containing matting agent is a fluorine-containing compound
A matting agent containing, preferably at least the surface
Are particles containing a fluorine-containing compound. Examples of the structure of the particles include those of the following groups.
To be Group I: Particles whose surface is coated with a fluorine-containing compound Group II: Particles made of a fluorine-containing polymer
Examples of the core to be further covered are silica, titanium oxide,
Barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate
Inorganic substances such as sium, glass, talc and polymethy
Polymethacrylate, polystyrene, polyvinyl acetate
Polyvinyl alcohol, cellulose acetate pro
Pionate, ethyl cellulose, starch, benzogua
Organic compounds such as namin-formaldehyde condensate
Listed as particles that are known as matting agents
And particles other than the above can adversely affect photographic properties.
It can be used freely within the range of
It The fluorine-containing compound in the particles of Group I has a low content.
Examples include child compounds and polymers. Replacement of the low molecular weight compound
The following are specific examples. (Exemplified compound) (1) CF_ThreeCOOH (2) C₉F₁₉COOH (3)(4)(5) CF_ThreeCH_TwoOH (6) (CF_Three)_TwoCHOH (7) C₉F₁₉C_TwoH_FourOH (8) CHF_TwoCF_TwoCF_TwoCH_TwoOH (9)(Ten) (11)(12)(13) C₈F₁₇C_TwoH_FourSi (OCH_Three)_Three The fluorine-containing compound as exemplified above is as shown below.
Can be obtained as a commercial product. For example, trifluoroacetic acid of Exemplified Compound (1) and its derivative
Conductor, exemplified compound (5) and exemplified compound (6)
Asahi Glass Co., Ltd. exemplifies Safuroisopropanol
Compound (9) of orthotrifluoromethylbenzyl al
Cole, an ortho-sortifluoromethyi of exemplified compound (10)
Rubenzaldehyde, an ortho sort of Exemplified compound (11)
Fluoromethyl benzoyl chloride, a compound of Exemplified Compound (3)
Russotrifluoromethylbenzoic acid is a central glass stock
Is the formula company, exemplified compound (13), Shin-Etsu Silicone Co., Ltd.
Each of these are commercially available. Among the above-mentioned fluorine-containing low molecular weight compounds,
Group, hydroxy group, aldehyde group, carbonyl chloride
Compounds having an id group or an epoxy group are especially
It has excellent covering power and is preferably used in the present invention.
You can The fluorine-containing low molecular weight compound of the present invention has the above-mentioned examples.
It is not limited to the compounds shown. Examples of the method of coating the low molecular compound include the above
In a solution of fluorine-containing low-molecular compound that does not dissolve the nuclear material of
The surface of the core particles is dipped and then dried.
The presence of low-molecular compounds containing fluorine in
it can. Further, the surface of the group I particles or the group II particles is constituted.
The polymer has a monomer unit having a fluorine atom
It is preferably a homopolymer or a copolymer. In the copolymer, the unit containing fluorine atoms is 10% by weight.
The above is preferable, and 30% by weight or more is more preferable.
Good Examples of the monomer unit having a fluorine atom include
Alkyl vinyl ethers each having a fluorine atom,
Ruquilisopropenyl ethers, alkylcarbonyl
Oxyethylenes, styrenes, alkylstyrenes,
Acrylic acid esters, methacrylic acid esters,
Rylamides, methacrylamides, acrylic acid, meta
Monomers derived from acrylic acid and olefin
Units are mentioned. Alkyl vinyl ethers having fluorine atoms and fluorine
From alkylisopropenyl ethers containing elementary atoms
Preferred examples of the derived monomer unit are the following group A
And an alkylcarbo having a fluorine atom.
Preference for monomer units derived from nyloxyethylenes
Examples of new ones include those of the following group B.
Styrenes with a child and alkyls with a fluorine atom
With preferred monomer units derived from styrenes
Include those of the following group C, which has a fluorine atom.
Acrylic esters and methacrylic acid containing fluorine atoms
Preferred examples of the acid esters are those of the following group D
And acrylamides having a fluorine atom and
Derived from methacrylamides containing fluorine atoms
Preferable monomer units include those of the following group E.
Acrylic acid having a fluorine atom and a fluorine atom
Of monomer units derived from methacrylic acid having
Examples of the new ones include those of the following group F.
Preference of monomeric units derived from child-bearing olefins
Examples of the new group include those of the following G group. Group AGroup BGroup CGroup DGroup EGroup FG groupWhere R₁, R_Two, R₅~ R₇, R₁₁, R₁₂, R
₁₅, R₁₈, R₂₀, R₂₁, R₂₃And R₂₄Is each
Hydrogen atom, fluorine atom, R_Three, R_Thirteen, R₁₇as well as
R₂₂Are each a hydrogen atom, a fluorine atom, or a fluorine atom.
The optionally substituted methyl group is represented by R_FourAnd R₁₄Is each
An alkyl group which may be substituted with a fluorine atom is represented by R
₈~ R₁₀And R₂₅Are hydrogen atom, fluorine atom or
Chlorine atom, R₁₈And R₁₉Are hydrogen atom and alk
Group or aryl group,¹ _f▼ is replaced by a fluorine atom
The alkyl group² _f▼ is a fluorine atom or fluorine
An alkyl group substituted with an atom is represented by R₂₆Is a hydrogen atom,
Alkyl which may be substituted with fluorine atom or fluorine atom
A kill group, m is an integer of 0 to 5, and m is 2
When ~ 5 each ▲ R² _f▼ may be the same or different. Also, R₁~ R_FourAt least one of R₁₁~ R₁₄of
At least one, R₂₀~ R₂₂At least one of
And R₂₃~ R₂₆At least one of
A group having a fluorine atom, and when m is 0, R₈~ R
₁₀At least one of them is a fluorine atom. The unit of group A will be described in more detail. R_FourMay be linear or branched and has 1 to 15 carbon atoms
Is preferred. In addition, substituents other than fluorine atom (
Including, the same hereinafter), and as the substituent,
For example, alkyloxy group, alkyloxycarbonyl group
(Preferably having 2 to 11 carbon atoms), carboxyl
Group, carboxyalkoxy and the like. R_FourA preferred group as the group is the formula (CH_Two) N (CF_Two) MX
(Here, m is an integer of 1 to 10 and n is an integer of 0 to 2.
X is H, F orRepresents ) Is a group represented by. Specific examples of the units of group A include the following.
Be done. A-1m: 2 to 12 n: 1 to 10 A-2n: 1 to 11 A-3A-4A-5A-6A-7A-8m: 0 to 2 n: 1 to 3 A-9A-10A-11n: 2-12 A-12A-13A-14n: 0 to 2 Y₁: F, CF_Three Y^Two: F, Cl, CmF_Twon₊₁ m; 1-10 A-15The unit of group B will be described in more detail. ▲ R¹ _fThe alkyl group of ▼ may be linear or branched and has a carbon number of
Those having 1 to 10 are preferable and may have a substituent. Examples of the unit of group B include the following. B-1B-2B-3The unit of group C will be described. ▲ R² _fThe alkyl group of ▼ may be linear or branched and has a carbon number of
The thing of 1-3 is preferable and you may have a substituent.
Examples of the substituent include a hydroxyl group. Specific examples of the units of the C group are as follows.
Can be mentioned. C-1C-2C-3C-4C-5C-6C-7C-8C-9C-10C-11C-12The group D will be described in more detail. R₁₄Even if substituted with a fluorine atom represented by
A good alkyl group may be linear, branched or cyclic, and is preferred.
More preferably, it has 1 to 10 carbon atoms,
It may be substituted by a substituent, and as these groups
Is, for example, a hydroxy group, a halogen atom (eg ClBr)
Etc.) and the like. In addition, this alkyl group has a carbon chain
A linking group such as an oxo group or a thio group may be interposed between
Yes. The following are specific examples of the monomer unit of group D.
Can be mentioned. D-1D-2D-3(N = 2 to 9) D-4n = 1 to 10 D-5(N = 2 to 9) D-6(N = 2 to 8) D-7D-8D-9(N = 2 to 8) D-10(N = 2 to 8) D-11D-12n = 1 to 10 D-13n = 3 to 7 D-14n = 1 to 4 D-15D-16D-17n: 2 to 4 D-18D-19D-20D-21D-22m, n: 0-3 D-23D-24D-25Specific examples of units of group E include the following.
It E-1E-2Specific examples of the monomer unit of group F are as follows.
You can F-1F-2The unit of the G group will be described in more detail. R₂₆Is an alkyl group which may be substituted with a fluorine atom
In the case of, even if it further has a substituent (for example, a hydroxyl group)
Good. Specific examples of the monomer unit of group G are as follows.
One of them is. G-1 -CH_Two-CFH-G-2-CH_Two-CF_Two-G-3-CF_Two-CFH-G-4 -CF_Two-CF_Two-G-5-CF_Two-CFCl-G-6-CF_Two-CHCl-G-7G-8G-9G-10G-11G-12G-13G-14G-15G-16G-17G-18As a unit unit having a fluorine atom other than groups A to G,
The following are listed. The above-mentioned polymer is a monomer other than a monomer unit having a fluorine atom.
It may have a body unit. Examples of the monomer unit include
For example, mono having at least one ethylenic double bond
Examples include units formed from mers. As the monomer
For example, ethylene, propylene, 1-butene, iso
Butene, vinyl chloride, vinylidene chloride, 2-methylbute
Olefins such as amines; 1,1,4,4-tetramethyl
Diolefins such as butadiene; vinyl acetate, acetic acid
Olefin alcohol esters such as ril; methylmeth
Tacrylate, ethyl methacrylate, cyclohexyl
Methacrylate, methyl acrylate, butyl acryl
, Olefinic carboxylic acids such as ethyl acrylate
Esters; methyl vinyl ether, ethyl vinyl ether
Olefin ethers such as ether; acrylonitri
Vinyl, methyl vinyl ketone, ethyl vinyl ketone
Nylketones; divinylbenzene, allyl acrylate
Tomato, allyl methacrylate, 1,3-butylene diacrylate
Rate, 1,3-butylene dimethacrylate, diethyl
Glycol diacrylate, diethylene glycol di
Methacrylate, vinyl acrylate, vinyl methacrylate
Rate, triethylene glycol diacrylate, tri
Ethylene glycol dimethacrylate, ethylene diac
Relate, ethylene dimethacrylate, 1,6-hexa
Diacrylate, 1,6-hexanedimethacrylate
Having two or more ethylenically unsaturated double bonds such as
, Acrylic acid, methacrylic acid, maleic acid, maleic
Ethylenically unsaturated bond such as acid half ester, itaconic acid
And those having an alkali solubilizing group.
Wear. Specific examples of polymers having a monomer unit having a fluorine atom
The following may be mentioned. P-1P-2(Molar ratio 20:40:40) P-3(Molar ratio 25:30:45) P-4(Molar ratio 30:30:40) P-5(Molar ratio 35:65) P-6(Molar ratio 60:40) P-7(Molar ratio 35:65) P-8(Molar ratio 70:30) P-9(Molar ratio 50:50) P-10(Molar ratio 50:50) P-11(Molar ratio 60:40) P-12(Molar ratio 50:50) n: 0-2 X: F, CF_Three P-13(Molar ratio 50:50) 1: 0.1 m: 0-10 However, when l = 0, m ≠ 0 P-14(Molar ratio 80:20) P-15(Molar ratio 80:20) P-16(Molar ratio 10:40:50) P-17(Molar ratio 15:35:50) P-18(Molar ratio 20:30:50) P-19(Molar ratio 60:40) P-20(Molar ratio 50:50) P-21(Molar ratio 70:30) P-22(Molar ratio 40:60) P-23(Molar ratio 60:10:30) P-24(Molar ratio 70:30) P-25(Molar ratio 50:10:40) P-26(Molar ratio 40:20:40) P-27(Molar ratio 30:10:60) P-28(Molar ratio 50:50) P-29(Molar ratio 40:60) P-30(Molar ratio 50:20:30) P-31(Molar ratio 60:40) P-32(Molar ratio 40:10:50) P-33(Molar ratio 40:20:40) P-34(Ibid. 50:50) P-35(Ibid. 60:40) P-36(Ibid. 60:40) P-37(Ibid. 70:30) P-38(Ibid. 80:20) P-39(Molar ratio 40:60) P-40(Dit. 40:60) P-41(Ibid. 60:40) P-42(Ibid. 50:50) P-43(Ibid. 50:50) P-44(Dit. 40:60) P-45(10:50:50) P-46(Ibid. 30:20:50) P-47(Same 20:50:30) P-48(Same 30:20:50) P-49(Ibid. 40:10:50) P-50(Same 30:30:40) P-51(Ibid. 40:20:40) P-52(Ibid. 20:20:60) P-53(Same time 20:30:50) P-54(Ibid. 20:20:60) P-55(Same 30:30:40) P-56(Same 30:30:40) P-57(Ibid. 20:10:70) P-58(Dit. 40:60) P-59(Dit. 60:40) P-60(Ibid. 30:70) P-61(10:50:50) P-62(Same 30:20:50) P-63(Dit. 40:10:50) P-64(10:50:50) P-65(Same time 20:30:50) P-66P-67P-68P-69P-70P-71P-72P-73(Ibid. 80:20) P-74(Same 10:30:60) P-75(Ibid. 15:10:75) P-76(Dit. 40:60) P-77P-78(5:25:70) P-79(Ibid. 30:70) P-80(Ibid. 25:75) P-81(10:50) P-82(Same 30:30:40) P-83(Ibid. 40:30:30) P-84(10:50) P-85(10:50:50) P-86P-87P-88(Ibid. 40:10:50) P-89(Same 30:10:60) P-90(Same 30:30:40) P-91P-92P-93(Ibid. 30:70) P-94(Ibid. 25:55:20) P-95(Dit. 60:40) P-96(Ibid. 70:30) P-97(15:25:60) P-98(10:50:50) P-99(Ibid. 70:30) P-100(10:50:50) P-101(Dit. 40:60) P-102(Ibid. 50:50) P-103(10:20:70) P-104(Ibid. 20:80) P-105(10:40:60) P-106(Ibid. 70:30) P-107(Ibid. 80:20) P-108(Same 10:30:60) P-109(Same 30:70) P-110(Ibid. 70:30) P-111(Ibid. 75:25) P-112(Ibid. 25:75) P-113(10:50) P-114(Dit. 60:40) P-115(Weight ratio 50:50) P-116(Ibid. 46:54) P-117(Ibid. 57:43) P-118(Ibid. 55:45) P-119(Ibid. 25:75) P-120(Dit. 40:60) P-121(Ibid. 55:45) P-122(Ibid. 54:46) P-123(Dit. 40:60) P-124(Ibid. 56:44) P-125(Ibid. 55:45) P-126(Ibid. 45:55) P-127(Ibid. 55:45) P-128(10:50:50) P-129(10:50) P-130(Ibid. 43:57) P-131(Ibid. 35:65) P-132(Ibid. 50:50) P-133(Ibid. 35:65) P-134(Ibid. 35:65) P-135(Ibid. 45:55) P-136(10:50:50) P-137(Ibid. 33:67) P-138(Ibid. 40:60) P-139(Ibid. 25:75) P-140(Ibid. 25:75) P-141(Ibid. 25:75) P-142(Ibid. 30:70) PP-143(Id. 55:45) Among the above-mentioned polymers, the image quality of the image obtained by the light-sensitive material is improved.
Considering image quality such as sharpness, alkali solubilizing group (preferred
20 to 90 moles of monomer unit having a carboxyl group)
%, More preferably 20 to 70 mol%. The above-mentioned polymers are all known solution polymerizations, bulk polymerizations, and suspension polymerizations.
It can be easily synthesized by a method such as suspension polymerization. An example
For example, in solution polymerization, generally, a suitable solvent (for example, ethanol) is used.
2 kinds of suitable concentration in methanol, methanol, etc.)
Is a mixture of 3 types of monomers (usually 40
Two types of concentration less than or equal to% by weight, preferably 10-25% by weight
Is a mixture of three types of monomers) a polymerization initiator (for example, peracid
Of benzoyl chloride, azobisisobutyronitrile, etc.)
Under a suitable temperature (eg 40-120 ℃, preferably 50-100
The copolymerization reaction is carried out by heating to (° C.). So
After that, pour the reaction mixture into a medium such as water.
Unreacted by letting the product settle and then drying.
The reaction mixture is separated off. In addition, an alkali may be used in advance in the synthesis of the above polymer.
It is not always necessary to polymerize using a monomer having a solubilizing group.
After obtaining a polymer having no such group, the polymer is not essential.
The reaction may produce an alkali-solubilizing group. For example, P-1 to P-4 are based on Japanese Patent Publication No. 45-26303.
As a monomer,
After obtaining the polymer using kill fluorovinyl ether,
Can generate carboxyl groups by hydrolysis
It For P-5 to P-8 and P-11, etc., refer to Japanese Patent Publication No. 58-5908.
Perfluoroallyl fluorosulfate
It can be obtained by hydrolyzing the coalesced product, or Journal of
 the American Chemical Society, Vol100, 1948 (1978
Years) and polyolefins in the presence of oxygen.
After fluorinating to obtain a -COF group, it may be converted into a -COOH group. P-12 is a sulfamo, as described in JP-A-53-141188.
HNO polymer having an yl group₂Can be reduced by
P-13 is a polymer as described in JP-A-54-83982.
It is obtained by oxidizing the chlorosulfonyl group of. As described in JP-A-54-32189, P-13 is a black compound in the polymer.
Obtained by adding olefinic carboxylic acid to the sulfonyl group
You can Furthermore, P-15 is a fluorinated polyolefin.
It can be obtained by graft polymerization of carboxylic acid. Polymer P-79 and the like are added as described in JP-B-45-26303.
Preference is given to reacting under pressure. In addition, polymers P-80 and P
-110, P-111, etc. are British Patent No. 1023717
Of Polymer Science: Polymer Letters
Diction (Journal of Polymer Science: Polymer Let
ters Editition) Vol, 18, PP201〜209 (1980 etc.
Like above, after obtaining the polymer without fluorine atom in advance,
It can be produced by a molecular reaction. For producing particles using the fluoropolymer according to the present invention
Various methods can be used. For example, the surface of the particles made of the above-mentioned nuclear material should be
To produce particles coated with coalescence, particles of nuclear material were
Immersion treatment in fluoropolymer solution that does not dissolve substances
And dry or plasma with fluorine-containing monomer
By the method of grafting on the surface of the nuclear material by polymerization,
A fluoropolymer can be present on the surface of the. When no nuclear material is used, for example, fluorine-containing
An organic solvent solution of the polymer is added to an aqueous surfactant solution (gelatin
(May contain hydrophilic colloid)
The solvent was removed from the resulting emulsion under reduced pressure.
After that, the polymer particles may be separated by centrifugation. Further, fine particles may be formed by pulverizing means. Also heavy
From the emulsion obtained by the combined reaction by centrifugation
It is also possible to obtain particles immediately. Further, the matting agent particles of the present invention should be made into particles in advance.
Is not essential, and the polymer is a low boiling organic solvent such as acetic acid.
Ethyl acetate, butanol-containing ethyl acetate (butanol, 50 fold
Less than%), butanol-containing methanol (butanol 50
(Less than wt%), a solution of the hydrophilic colloid,
For example, disperse in an aqueous gelatin solution under rapid stirring.
To form particles and use this dispersion as a coating liquid
You may stay. The photosensitive material referred to in the present invention is a support used for the photosensitive material.
Undercoated, one or more layers on the support
The upper photo-constituent layer (including packing layer) was applied
Halogen on photographic material and support as intermediate products
Silver halide emulsion layer, subbing layer, intermediate layer, filter layer, hazel
Coating layer such as anti-static layer, protective layer, packing layer, etc.
Including all things such as photosensitive materials as finished products
The present invention is for general black and white, special black and white, color
Suitable for various finished products and intermediate products for printing, printing, X-ray, etc.
Can be used. With the matting agent of the present invention in the present invention, the outer surface is matted.
The outer layer that has been converted into a coated layer is one of the layers coated on the support.
Including an outermost layer of the optical material and adjoining from the outermost layer
A non-photosensitive layer provided as a photosensitive halogen
At least one of the silver halide emulsion layer side and the back surface layer side
And a photosensitive silver halide emulsion layer is provided on both sides of the support.
When it ’s on both sides,
Good. When the outer layer is the back layer, the outer layer and the support are
There may be no coating layer between them, or only the undercoat layer
Good. The surface of such an outer layer side is roughened by the matting agent of the present invention.
For example, at least one of the outer layers (preferably
Is the outermost layer) and the matting agent is contained in the coating composition.
It may be applied and dried. Alternatively
Spray the matting agent alone to the outermost layer of the outer layer, or
The outer layer is a mixture of a coating agent and a binder such as gelatin.
After supercoating as an upper layer, it may be dried. The photographic material of the present invention includes the following aspects. At least one layer of photosensitive silver halide milk on one side of a support
The agent layer and the outer layer of the present invention as a protective layer on the layer
And the matting agent of the present invention is contained in the coating composition for the uppermost layer of the layer.
A mode in which the outer surface is matted after being applied. At least two non-photosensitive parent layers as the back layer of the photosensitive material
The present invention has an aqueous colloidal layer, and the uppermost coating composition has the present invention.
The matte agent is included in the coating and the back surface layer is matted.
Aspect. A particularly preferred embodiment of the present invention is the matting agent of the present invention.
The surface of the protective layer provided on the photosensitive layer side is matte.
It is what is converted. The film thickness of the outermost layer according to the present invention is a
0.1 to 3 μm, especially 0.5 to 3 μm is preferable when using
If the binder is cellulose diacetate,
When using a high-molecular compound, 0.01 to 3 μm, especially 0.1
03 to 1 μm is preferable. The total thickness of the outer layer according to the present invention is preferably 0.2
˜5 μm, and particularly preferably 0.7 to 4 μm. The outer layer of the present invention is on the back layer side even when it is on the photosensitive layer side.
Also in the case, a known composition other than the matting agent of the present invention is used.
Can be taken. Preferred embodiments of the invention include the following. (1) At least one layer of photosensitivity on at least one side of the support
A silver halide emulsion layer and at least two layers above the layer
A hydrophilic colloid layer having a non-photosensitive hydrophilic colloid layer
At least one layer of the hydrophilic colloid layer contains oil droplets.
The outer surface of is matted with the matting agent of the present invention
Photosensitive material (the above oil droplets are described in Japanese Patent Publication No. 57-9053)
It has the same contents as Y. ). (2) Photosensitive halogenation of at least one layer on one side of the support
Has a silver emulsion layer and has at least two non-photosensitive layers on the other side
Layer and the outer surface of the non-photosensitive layer is the matting agent of the present invention.
In the present invention, the surface of the outermost layer of the outermost layer is "matting agent".
"More roughened" is due to the presence of the matting agent.
Means that the surface of the outermost layer is roughened. That is, the protrusions on the outermost layer surface are made of the matting agent material.
If the matting agent is exposed on the surface of the protrusions,
The matte agent surface is the outermost layer material (the outermost layer other than the matte agent).
(Particulate matter) wrapped around the composition may project on the surface of the outermost layer.
By, the surface of the protrusion is composed of the outermost layer material.
It is also included in the case. In the present invention, the average particle size of the matting agent is preferably 0.
1 to 10 μm, more preferably 0.5 to 8 μm
However, if it is mixed with the binder of the outermost layer,
Greater than dry film thickness (where there is no protrusion due to matting agent)
It is preferable that the dry film thickness is less than that in terms of antistatic effect.
Also, the particle size of the matting agent of the present invention is twice or more, further 2.5 times or more.
It is particularly preferable that it is large. The amount of the matting agent applied is for the purpose of improving the matting effect.
, The more effective it is, 10 mg / m²The above is preferable, and
20 mg / m²Above 50 mg / m²The above is preferable. Also transparent
Considering the effect on the image quality and the sharpness of the image,
500 mg / m²The following is preferred, especially 200 mg / m²Be less than
Is preferred, but the above-mentioned fluorine atom and alkali-solubilizing group
In the case of particles containing a polymer having
Especially 400 mg / m because of good solubility in the process²Below
Preferably there is. The matting agent according to the present invention is used as a mixture with another matting agent.
The mat according to the present invention can be
It is preferable to use a smaller amount than the agent. The fluorine-based surfactant used in the present invention is, for example,
National Patent Nos. 1,330,356, 1,524631 and U.S. Patent 3,58
No. 9,906, No. 3,666,478, Japanese Patent Publication No. 52-26687, Japanese Patent Laid-Open No.
Compounds described in 49-46733, 51-32322, etc.
And preferably has at least one 3 to 30 carbon atoms
A hydrocarbon chain and at least one hydrophilic group (eg
On group, nonion group, cation group, betaine group)
And the hydrocarbon chain has at least one fluorine atom
Is a compound substituted by. A preferred fluorosurfactant is represented by the following general formula
It is something. Rf-XY In the formula, Rf is at least one (preferably at least 3).
Hydrocarbon chains substituted by fluorine atoms (in a straight chain
May be branched or cyclic) and X is a simple bond.
Or represents a divalent group, and Y represents a hydrophilic group. The divalent group represented by X is, for example, an aliphatic hydrocarbon.
Group, aromatic hydrocarbon group, heterocyclic group (aromatic hydrocarbon group
May be condensed), -O-, -CO-, -SO₂-, -NR- (here
And R is a hydrogen atom or preferably an alkyl group having 1 to 5 carbon atoms.
Group represented by the formula (1), and a combination of these groups.
Be done. Further, the hydrocarbon chain represented by R above is represented by X above.
Also included are those interrupted by a divalent group. Examples of the hydrophilic group represented by Y include hydrophilic anio.
Group, hydrophilic nonionic group, hydrophilic cationic group, hydrophilic group
An example is a tine group. The following are preferred as the hydrophilic anion group.Here, M is a hydrogen atom, an alkali metal atom, or ammonium.
Groups (eg ammonium, dimethylammonium, die
Tananol ammonium, pyridinium, morpholinium
And R may be substituted by a fluorine atom.
Represents a hydrocarbon chain. Preferred as the hydrophilic nonionic group(Where R₁And R_TwoIs a hydrogen atom or a methyl group, R
_ThreeIs a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
m represents an integer of 5 to 20. ) Is a group represented by. Examples of hydrophilic cationic groups includeIs mentioned. R here_Four~ R₆Has 1 to 5 carbon atoms
Represents an alkyl group, which is bonded to each other to form a heterocycle.
Good. X₁ ⁻Represents a halogen ion. The following are preferred as hydrophilic betaine groups.
ItR_FourAnd R₅Represents an alkyl group having 1 to 5 carbon atoms
But R_FourAnd R₅May combine with each other to form a heterocycle. X_TwoRepresents an alkylene group having 1 to 5 carbon atoms. Typical examples of the fluorine-based active surfactant according to the present invention are shown below.
An example is given. (Exemplified compound) 1 CF₃-(CF₂)₂-COOH 2 H- (CF₂)₆-COOH 3 H- (CF₂)_Ten-COOH 4567 CF₃-(CF₂)₆-COONH_Four 89 CF₃-(CF₂)₇-SO₃Na 10111213 14 151617181920 CF₃-(CF₂)₇-SO₃Na 2122 CF₃-(CF₂)₂-COO-CH₂-CH₂-CH₂-SO₃Na 23twenty four 25 H- (CF₂)₆-CH₂-O-CH₂-CH₂-CH₂-SO₃Na 26 H- (CF₂)₆CH₂-OOC-CH₂-CH₂-SO₃Na 27 CF₃-(CF₂)₆-CH₂-O-CH₂-CH₂-CH₂-SO₃Na 28 H- (CF₂)₈-CH₂-O-CH₂-CH₂-CH₂-SO₃Na 29 H- (CF₂)_Ten-CH₂-O-CH₂-CH₂-CH₂-SO₃Na 30 H- (CF₂)_Ten-COO-CH₂-CH₂-CH₂-SO₃Na 3132333435 H- (CF₂)₃-CH₂-OSO₃Na 36 H- (CF₂)₆-CH₂-OSO₃Na 37 H- (CF₂)₆-CONH-CH₂-CH₂-O-SO₃Na 38394041424344 F₃C- (CF₂)₂-CH₂O (-CH₂CH₂O)_FiveH 45 F₃C- (CF₂)₂-COO (-CH₂CH₂O)₇-CH₃ 46474849 C₇F₁₅-CONH-C₂H₆-N (CH₃)₃・ I  50The amount of the fluorine-based surfactant used in the present invention is
0.1 to 100 mg / m²Demon
Is suitable, preferably 1.5 to 50 mg / m²In the range of
It The effect of the present invention is to provide a fluorine-containing matting agent and a foam used in the outermost layer.
The ratio of the matting agent to the total amount of fluorine-containing surfactant is 85
Played when the content is not less than 95% by weight. this
When the ratio is lower than 85% by weight, antistatic storability,
Also, the deterioration of the coating property will increase, and if it exceeds 95% by weight,
The antistatic storability, coatability and adhesion resistance deteriorate. The photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material.
The silver halide emulsion used in the case of
Silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and salt
Any of the silver halide etc. used in ordinary silver halide emulsions
Can be used. The silver halide grains used in the silver halide emulsion are acid
Obtained by either sex method, neutral method or ammonia method
But it's okay. The particles may be grown at one time, or seed particles
It may be grown after making. How to make seed particles and
The growth method may be the same or different. A silver halide emulsion has the same halide and silver ions.
Even if mixed occasionally, in the liquid in which one exists, the other
May be mixed. Also, the critical growth of silver halide crystals
Mix the halide and silver ions while considering the speed.
Sequentially adjust while controlling pH and / or pAg in the pot
It may be generated by adding it at times. By this method
Halogen with a regular crystal form and a nearly uniform grain size
Silver halide grains are obtained. Use the conversion method after growth
The halogen composition of the particles may be changed. The silver halide emulsion may contain a halogen
With a silver halide solvent, the grain size of the silver halide grains,
Control particle shape, particle size distribution and particle growth rate.
Can be trolled. The silver halide grains can be formed by the process and / or formation of grains.
In the process of lengthening, cadmium salt, zinc salt, lead salt, tariu
Rhodium salt, iridium salt (including complex salt), rhodium salt (complex salt)
At least) and iron salts (including complex salts)
Also using one kind of metal ions, and
Alternatively, it is possible to add these metal elements to the particle surface.
Inside the particles by placing it in an appropriate reducing atmosphere.
Reduction sensitizing nuclei can be imparted to the surface and / or grain surface. After the growth of silver halide grains, the silver halide emulsion is
Unnecessary salts may be removed or
You can leave it alone. When removing the salts,
Research Disclosure R
Abbreviated as D).
You can Silver halide grains have uniform halogenation within the grains.
Even if it has a silver composition distribution, the inside of the grain and the surface layer
Even for core / shell grains having different silver halide compositions
Good. A latent image is mainly formed on the surface of silver halide grains.
Such particles may be
It may be particles that are formed. Silver halide grains are like cubes, octahedra and tetradecahedra.
It may have a regular crystal form, or it may be spherical or plate-shaped.
It may have an irregular crystal form. These grains
Use any ratio of {100} faces to {111} in the child
it can. Also, it may have a composite form of these crystal forms
Alternatively, particles of various crystal shapes may be mixed. Silver halide emulsions have any grain size distribution
May be used. Emulsions with a wide grain size distribution
Disperse emulsion) may be used, and the grain size distribution
Narrow emulsion (called monodisperse emulsion. Monodisperse milk here
An agent is the standard deviation of the particle size distribution divided by the average particle size.
The value is 0.20 or less. Here the particle size is spherical
In the case of silver halide, the diameter should be
In the case of particles, the projected image is converted into a circle image of the same area.
Indicates the diameter of the mushroom. ) May be used alone or in combination of several kinds.
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. Silver halide emulsions are two or more types of halogen
The silver halide emulsion may be mixed and used. The silver halide emulsion can be chemically sensitized by a conventional method.
Wear. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold and other noble metal compounds
It can be used alone or in combination. Silver halide emulsions are sensitizing dyes in the photographic industry.
Optically enhance the desired wavelength range using known dyes.
I can feel it. The sensitizing dyes may be used alone, but two or more kinds
You may use in combination. With sensitizing dye
A dye that does not have a spectral sensitizing effect, or visible light
Is a compound that does not absorb light, and the sensitizing action of the sensitizing dye
A strengthening supersensitizer may be contained in the emulsion. As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dye, complex merocyanine dye, holopolar
-Cyanine dye, hemicyanine dye, styryl dye and
And hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, it prevents fog during photographic processing or reduces photographic performance.
End of chemical ripening during chemical ripening for the purpose of keeping the temperature constant
Time and / or after completion of chemical ripening, the silver halide emulsion is
By the time it is applied, the antifoggant or safety agent in the photographic industry
Compounds known as excipients can be added. With a binder (or protective colloid) for silver halide emulsions
For this reason, it is advantageous to use gelatin.
Derivatives, graft polymers of gelatin and other macromolecules,
Other proteins, sugar derivatives, cellulose derivatives, single
Hydrophilicity of synthetic hydrophilic polymer such as ruby or copolymer
Colloids can also be used. Photographic emulsion layer of the light-sensitive material of the present invention, other hydrophilic colloid
The coating layer crosslinks the binder (or protective colloid) molecules.
Use of one or more hardeners that enhance the film strength
Can be hardened. Hardener hardens in the processing liquid
Amount to harden the light-sensitive material to the extent that it is not necessary to add an agent
Can be added, but adding a hardening agent to the processing liquid
Is also possible. The silver halide emulsion layer and / or other hydrophilic co-layer of the light-sensitive material
A plasticizer can be added to the Lloyd layer to increase flexibility.
It Preferred plasticizers are described in A of RD17643, Section XII.
It is a compound. The size of the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material
Water insoluble or sparingly soluble for the purpose of improving stability
Including a dispersion (latex) of synthetic polymer
You can In color photographic light-sensitive materials, the emulsion layer contains color development.
In the processing, an aromatic primary amine developer (for example, p-
Phenylenediamine derivatives and aminophenol derivatives
Etc.) to form a dye.
Dye forming couplers are used. The dye-forming coupler
Absorbs the light in the light-sensitive spectrum of the emulsion layer for each emulsion layer.
It is usually chosen so that the dye that collects is formed.
In the blue-sensitive emulsion layer, the yellow dye-forming coupler
Magenta dye forming couplers are used in the sensitive emulsion layer
A cyan dye-forming coupler is used in the agent layer. However
However, depending on the purpose, it can be used differently from the above combinations.
A silver halide color photographic light-sensitive material may be prepared. These dye-forming couplers are called ballast groups in the molecule.
Has a group with 8 or more carbon atoms that makes the coupler non-diffusing
Is desirable. Also, these dye-forming couplers consist of one molecule
4 molecules of silver ions are reduced to form the dye
Even if it is necessary to have 4 equivalence, 2 molecules of silver ion
It may be either dimeric, which only needs to be reduced. Pigment
Forming coupler for coupling with oxidized form of developing agent
Therefore, development inhibitor, development accelerator, bleaching accelerator, developer,
Silver halide solvent, toning agent, hardener, fog agent, fog
Such as inhibitors, chemical sensitizers, spectral sensitizers, and desensitizers
Included are compounds that release photographically useful fragments.
Be done. Among these, release the development inhibitor with development,
DIR is a coupler that improves image sharpness and image graininess.
Called a coupler. Developer instead of DIR coupler
Coupling reaction with the oxidant of the compound produces a colorless compound
At the same time, a DIR compound which releases a development inhibitor may be used.
Yes. DIR couplers and DIR compounds used are coupling
And the inhibitor is directly bonded to the
Coupled to the coupling position, and the coupling reaction
Intramolecular nucleophilic reaction in the group dissociated by
It was also attached so that the inhibitor could be released by a transfer reaction, etc.
(Timing DIR Coupler, and Timing DIR Compound
Referred to as). In addition, the inhibitor is also diffusible after withdrawal.
Depending on the application, those that are not so diffuse
They can be used alone or in combination. Aromatic first class
Coupling reaction with the oxidant of amine developer
Colorless couplers that do not form elements (also called competing couplers)
Can also be used in combination with a dye-forming coupler. As a yellow dye-forming coupler, a known acylacetate can be used.
Toanilide type couplers can be preferably used.
Of these, benzoylacetanilides and pivalo
Ilacetanilide compounds are advantageous. Examples of magenta dye-forming couplers include 5-pi
Razolone couplers, pyrazolobenzimidazole couplers
Puller, open-chain acylacetonitrile coupler, indah
Do not use zolone couplers with the couplers of the present invention.
You can Cyan dye-forming couplers include phenol or
Futor couplers are commonly used. Dye formation without the need for adsorption on the silver halide crystal surface
Coupler, DIR coupler, DIR compound, image stabilizer, color balance
Anti-blurring agent, UV absorber, fluorescent whitening agent, etc.
Of solid compounds, solid dispersion method, latex dispersion method, oil-in-water type
It can be dispersed using various methods such as emulsion dispersion method.
This depends on the chemical structure of hydrophobic compounds such as couplers.
Therefore, it can be appropriately selected. Oil-in-water emulsion dispersion method
Is a conventionally known one in which a hydrophobic additive such as a coupler is dispersed.
The method can be applied and is usually a high-boiling organic substance with a boiling point of about 150 ° C
Low boiling point and / or water-soluble organic solvent, if necessary
Dissolve in a combined use with a hydrophilic binder such as an aqueous gelatin solution.
Stirrer, homogenizer, using a surfactant in the
Colloid mill, flowgit mixer, ultrasonic device, etc.
After emulsifying and dispersing using a dispersing means, the desired hydrophilicity
It may be added to the colloidal solution. After dispersion or at the same time as dispersion
A step of removing the low boiling point organic solvent may be added to. As a high boiling point solvent, a solvent that does not react with the oxidant of the developing agent.
Nole derivative, phthalic acid alkyl ester, phosphoric acid
Steal, citrate, benzoate, alk
Lamide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a boiling point of 150 ° C or higher is used. With or without a high boiling solvent
Organic solvents can be used. Low boiling, virtually water-insoluble organic
As the solvent, ethyl acetate, propyl acetate,
Butyl acetate, butanol, chloroform, tetrachloride
Carbon, nitromethane, nitroethane, benzene, etc.
In addition, water-soluble organic solvents include acetone and methyl iso
Butyl ketone, β-ethoxyethyl acetate, methoki
Ciglycol acetate, methanol, ethanol,
Cetonitrile, dioxane, dimethylformamide, di
Methyl sulfoxide, hexamethylphosphoric amine
De, diethylene glycol monophenyl ether,
For example, noxyethanol and the like can be mentioned. Dye forming coupler, DIR coupler, DIR compound, image stabilization
Agents, antifoggants, UV absorbers, optical brighteners, etc.
When having an acid group such as rubic acid and sulfonic acid
Is introduced into the hydrophilic colloid as an alkaline aqueous solution.
You can also do it. Hydrophobic compounds may be used alone or in combination with high boiling solvents.
Dissolved in different solvents and dispersed in water using mechanical or ultrasonic waves
As an auxiliary agent for dispersion, an anionic surfactant,
Nonionic surfactant, cationic surfactant and amphoteric field
A surface active agent can be used. Emulsion layers of light-sensitive material (same color-sensitive layers and / or different layers)
In the color sensitive layer), the oxidant of the developing agent or the electron transfer agent
When it moves, color turbidity occurs, sharpness deteriorates, graininess
Use anti-foggant to prevent conspicuousness
be able to. The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer is provided between adjacent emulsion layers and contained in the intermediate layer.
Good. An image stabilizer to prevent deterioration of dye images
Can be used. Compounds that can be preferably used
The product is as described in RD17643, item VIII J. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials
Turnip caused by discharge caused by material being charged due to friction, etc.
UV absorption to prevent deterioration of image and image by UV
You may include the agent. Magenta dye formation by formalin during storage of light-sensitive materials
To prevent the deterioration of couplers etc.
A phosphorus scavenger can be used. Dye, UV absorber, etc. are added to the hydrophilic colloid layer of the photosensitive material.
When included, they may include cationic polymers, etc.
It may be mordanted with a mordant. Silver halide emulsion layer of photosensitive material and / or other hydrophilic
Change the developability of development accelerator, development retarder, etc.
A compound to be compounded and a bleaching accelerator can be added. Development accelerator
Compounds that can be preferably used as RD17643
And the development retarder is 1
The compound is described in Item XXI, Item E of 7643. Development acceleration
Black and white developing agents for other purposes, and / or their precursors
May be used. The emulsion layer of the light-sensitive material increases sensitivity, increases contrast,
Is a polyalkylene oxide or its adduct for the purpose of promoting development.
Ether, ester, amine derivative, thioetherification
Compounds, thiomorpholines, quaternary ammonium compounds,
Including retan derivative, urea derivative, imidazole derivative, etc.
It doesn't matter. The light-sensitive material emphasizes the whiteness of the white background and
Optical brighteners can be used for the purpose of making the coloring inconspicuous.
Wear. A compound that can be preferably used as an optical brightener
The compound is described in item V of RD17643. The photosensitive material includes a filter layer, an antihalation layer, and
Auxiliary layers such as anti-radiation layer can be provided
It In these layers and / or emulsion layers, during development processing
Contains dyes that may be bleached or bleached from the light-sensitive material.
You may be allowed to have it. Such dyes include oxono
Dye, hemioxonol dye, styryl dye, melodie
Examples include anine dyes, cyanine dyes, azo dyes, etc.
it can. Lubricants may be added to the photosensitive material to reduce sliding friction.
Wear. Photographic emulsion layer and / or other hydrophilic colloid layer of light-sensitive material
Includes coating property improvement, antistatic property, slip property improvement, emulsion dispersion,
Prevention of adhesion, improvement of photographic properties (development acceleration, hardening, sensitization, etc.)
Various interfaces other than fluorine-based surfactants for the purpose of
Activators can be used. The support used in the light-sensitive material of the present invention includes α-olefin.
In polymer (eg polyethylene, polypropylene,
Paper, laminated with ethylene / butene copolymer)
Flexible reflective support such as synthetic paper, cellulose acetate, nitric acid cell
Loin, polystyrene, polyvinyl chloride, polyethylene
Half of terephthalate, polycarbonate, polyamide, etc.
Films made of synthetic or synthetic polymers and these films
Flexible support with glass reflective layer on glass, metal, ceramic
Includes vessels. The hydrophilic colloid layer of the light-sensitive material may be the surface of the support, if necessary.
Directly after corona discharge, ultraviolet irradiation, flame treatment, etc.
Adhesion, antistatic property, dimensional stability in contact with or on the surface of support
Property, wear resistance, hardness, antihalation property, friction characteristics,
And / or one or more layers below to improve other properties
It may be applied via a coating layer. When coating photosensitive material, increase viscosity to improve coatability
Agents may be used. Also, for example, like hardeners,
Because it is fast, if it is added to the coating solution beforehand, it will gel before coating.
For those that cause
It is preferable to mix them just before coating by using a mixer or the like. As a coating method, it is possible to coat two or more layers at the same time.
Extrusion coating and curtain
Is particularly useful, but for some purposes it is a bucket.
Coating is also used. Also, the coating speed can be selected arbitrarily.
it can. The light-sensitive material of the present invention is an emulsion constituting the light-sensitive material of the present invention.
Using electromagnetic waves in the spectral region where the layer is sensitive
Can be exposed. As a light source, natural light (sunlight), tangs
Ten electric lights, fluorescent lamps, mercury lamps, xenon arc lamps, carbon lamps
Lamp, xenon flash lamp, cathode ray tube flyings
Pot, various laser light, light emitting diode light, electron beam,
Emission from phosphors excited by X-rays, γ-rays, α-rays, etc.
Any known light source can be used, such as emitted light
It The exposure time is from 1 millisecond to 1 second which is usually used in cameras.
The exposure time is of course less than 1 microsecond, for example
100 nanoseconds to 1 microphone using a polar tube or xenon flashlight
It is also possible to use exposure for a second, longer than 1 second
Exposure is also possible. Even if the exposure is continuously performed,
It may be performed in the gap. Any known method is used for the development processing of the light-sensitive material of the present invention.
You can This development process is a silver image depending on the purpose.
Process (black and white development process) or form a color image
It may be any of the developing treatments. If inversion method
When printing, perform the black and white negative development process first, and then
Bath with white exposure or with fog
And color development processing. In addition, the color in the photosensitive material
After the exposure, a black and white development process is performed to record
A silver color that creates an image and uses this as a bleaching catalyst to bleach dyes.
Unbleached may be used. Each processing step usually involves immersing the photosensitive material in the processing solution.
However, other methods such as spraying the treatment liquid
Spray method to supply, contact with carrier impregnated with treatment liquid
Web system for viscous processing, viscous development processing
A method or the like may be used. To obtain a silver image using the light-sensitive material of the present invention, after exposure, black
Perform white development processing. Black-and-white development process includes development process, fixing process, and water washing process.
A physical process is performed. After the development process, the stop process is performed.
Or when performing the stabilization process after the fixing process,
The water washing process step may be omitted. Also the developing agent
Or its precursor is built into the photosensitive material
You may perform a process only with an alkaline solution. As a developer
A development processing step using a developing solution may be performed. Black and white developers used for black and white development are generally known.
Black-and-white first development used for processing color photographic light-sensitive materials
For processing so-called liquids or black and white photographic light-sensitive materials
It is used and is generally added to black and white developers.
Various additives can be contained. 1-phenyl-3-pyrazolid as a typical additive
Developing agents such as amine, metol and hydroquinone,
Preservatives such as sulfates, sodium hydroxide, sodium carbonate
Bromide, an accelerator consisting of alkali such as um and potassium carbonate
Potassium, 2-methylbenzimidazole, methylben
Inorganic or organic inhibitors such as tuthiazole, po
Water softeners such as phosphonates, traces of iodide and merca
A surface overdevelopment inhibitor composed of a compound
it can. Silver halide fixing agent used in fixing solution in fixing process
Halogenated as used in normal fixing processing
A compound that reacts with silver to form a water-soluble complex salt, for example,
Potassium thiosulfate, sodium thiosulfate, thiosulfate
Thiosulfates such as monium, potassium thiocyanate, thiocyanate
Such as sodium cyanate and ammonium thiocyanate
Substitutes include thiocyanate, thiourea, and thioether.
It is a table. These fixing agents are 5 g
Used in an amount that can be solved, but generally 70 g to 250 g
Use with /. The fixer contains boric acid, borax, sodium hydroxide, and hydroxide.
Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate
Lithium, potassium bicarbonate, acetic acid, sodium acetate, hydroxide
Various pH buffering agents such as ammonium chloride, etc.
It can be contained in combination with the above. Furthermore,
Contain various optical brighteners, defoamers or surfactants
You can also close it. Also, hydroxylamine, hydra
Preservatives such as bisulfite adducts of gin and aldehyde compounds,
Organic chelating agents such as aminopolycarboxylic acids or ni
Stabilizers such as tro-alcohol and nitrate, methanol, dime
Organic solvents such as tylsulfamide and dimethylsulfoxide
Etc. can be appropriately contained. The fixer is used at a pH of 3.0 or higher, but generally pH 4.5 or higher.
Used at pH 10 or lower, preferably pH 5 or higher and pH 9.5 or lower
It is used, and the most preferable pH is 6 or more and 9 or less.
Is processed in. The processing temperature is below 80 ℃,
It is preferably used at 55 ° C or lower. To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing is a color development processing
Process, bleaching process, fixing process, washing process
If necessary, perform a stabilization process, but use a bleaching solution.
1-bath bleaching instead of physical processing and processing using fixer
A bleach-fixing treatment step can also be carried out using the landing liquid.
However, color development, bleaching and fixing can be performed in one bath.
Monobath processing process using 1 bath development bleach-fixing solution
You can In combination with these treatment steps, the pre-dural treatment step,
Performs neutralization process, stop-fixing process, post-hardening process, etc.
May be. Instead of the color development process in these processes
Contains a color developing agent or its precursor in the material.
Activator for which development processing is performed with an activator solution
The beta treatment process may be performed or its mono-bus treatment
Activator treatment can be applied to. these
A typical process is shown below during the process. (These processes
As the final process, washing process, washing process and stability
One of the chemical treatment steps is performed. ) ・ Color development processing step-bleaching processing step-fixing processing step-Color development processing step-bleach fixing processing step-Pre-hardening processing step-color development processing step-stop fixing processing step
Process-washing process-bleaching process-fixing process-washing
Processing step-Post-hardening processing step-Color development processing step-Water washing processing step-Supplementary color development processing
Process-Stopping process-Bleaching process-Fixing process-Activator process-Bleaching process-Activator process-Bleaching process-Fixing process
・ Monobath treatment process The treatment liquid temperature is usually selected in the range of 10 ℃ to 65 ℃.
The temperature may exceed ℃. Preferably at 25 ° C to 45 ° C
It is processed. Color developing solutions are generally alkaline water containing a color developing agent.
It consists of a solution. Color developing agent is aromatic primary amine color
A developing agent, aminophenol-based and p-phenylene
And diamine-based derivatives are included. These color developing agents
Can be used as salts of organic and inorganic acids, for example
For example, salt machine acid, sulfate, p-toluenesulfonate, sulfite
Use salt, oxalate, benzene sulfonate, etc.
You can These compounds are generally preferred for Color Developer 1.
The concentration is about 0.1 to 15 g, more preferably 1 to 15 g.
Use in degrees. Examples of the aminophenol-based developer include o-a
Minophenol, p-aminophenol, 5-amino-
2-hydroxytoluene, 2-amino-3-hydroxy
Toluene, 2-hydroxy-3-amino-1,4-dime
Cylbenzene and the like are included. Particularly useful primary aromatic amine color developing agents are N, N
A dialkyl-p-pheninediamine compound,
Alkyl group and phenyl group may be substituted or not
May not be replaced. Among them, especially useful
As an example of compound, N, N-dimethyl-p-phenylenedia
Min hydrochloride, N-methyl-p-phenylenediamine hydrochloride
Salt, N, N-diethyl-p-phenylenediamine hydrochloric acid
Salt, 2-amino-5- (N-ethyl-N-dodecylami)
No) Toluene, N-ethyl-N-β-methanesulfone
Midoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoanili
4-amino-3-methyl-N, N-diethylanili
4-amino-N- (2-methoxyethyl) -N-E
Cyl-3-methylaniline-p-toluenesulfonate
Etc. can be mentioned. The above color developing agents may be used alone or in combination of two or more kinds.
You may use it. Furthermore, the color developing agents are color
It may be incorporated in the photographic material. In this case, halogenation
Use silver color photographic light-sensitive material with alkali instead of color developer.
It is also possible to treat with a solution (activator solution). The color developer is an alkaline agent commonly used in developers, for example
For example, sodium hydroxide, potassium hydroxide, ammonium hydroxide
Ni, sodium carbonate, potassium carbonate, sodium sulfate
, Sodium metaborate, borax, etc.
In addition, various additives such as benzyl alcohol, ha
Alkali metal rogenides, such as potassium bromide, or salts
Potassium iodide, etc., or as a development regulator, for example,
Hydroxylamine or sulfite as preservatives such as diacid
An acid salt or the like may be contained. Furthermore, various antifoaming agents and surface active agents
Agent, also methanol, dimethylformamide or di-
Properly contain organic solvents such as methyl sulfoxide
be able to. The pH of the color developer is usually 7 or more, preferably about 9 to
It is 13. Further, it is essential for the color developing solution used in the light-sensitive material of the present invention.
If necessary, use diethylhydroxyamid as an antioxidant.
, Tetronic acid, tetronimide, 2-anilinoethano
Alcohol, dihydroxyacetone, secondary aromatic alcohol,
Hydroxamic acid, pentose or hexose, pyroga
Contains roll-1,3-dimethyl ether, etc.
Good. In the color developer, various types of sequestering agents can be used as sequestering agents.
A rate agent can be used in combination. For example, the chelate
As an agent, ethylenediaminetetraacetic acid, diethylenetriamid
Aminopolycarboxylic acids such as pentaacetic acid, 1-hydroxyethyl
Organic phosphonic acids such as cylidene-1,1-diphosphonic acid,
Aminotri (methylenephosphonic acid) or ethylenedi
Aminopolyphosphonic acid such as amine tetraphosphoric acid, citric acid
Acid or oxycarboxylic acid such as gluconic acid, 2-phos
Phonophenone such as honobtan-1,2,4-tricarboxylic acid
Carboxylic acid, tripolyphosphoric acid or hexametaphosphoric acid
And polyhydroxy compounds such as polyphosphoric acid, etc.
It As mentioned above, the bleaching process is the same as the fixing process.
It may be performed or may be performed individually. As a bleach
Is a metal complex salt of an organic acid such as polycarboxylic acid.
Organics such as acids, aminopolycarboxylic acids or oxalic acid, citric acid
Acid that is coordinated with metal ions such as iron, cobalt, and copper
Is used. Most preferred organic of the above organic acids
As the acid, polycarboxylic acid or aminopolycarboxylic acid
Is mentioned. Specific examples of these include ethylene diami
Tetraacetic acid, diethylenetriaminepentaacetic acid, ethyl
Diamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nit
Lilotriacetic acid, cyclohexanediaminetetraacetic acid, a
Minodiacetic acid, dihydroxyethylglycine citric acid (also
Is tartaric acid), ethyl ether diamine tetraacetic acid, gly
Coal ether diamine tetraacetic acid, ethylenediamine
Tetrapropionic acid, phenylenediamine tetraacetic acid, etc.
Can be mentioned. These polycarboxylic acids are alkali metal salts, ammonium
It may be a sodium salt or a water-soluble amine salt. These bleaching agents are preferably 5-450 g /, more preferably
It should be used at 20 to 250 g /. In addition to the bleaching agents described above, the bleaching solution should be preserved as necessary.
It is possible to use a liquid having a composition containing sulfite as an agent.
Wear. In addition, the bleaching solution is ethylenediaminetetraacetic acid iron (II
I) Complex bleach containing halo, such as ammonium bromide
It may be a liquid composed of a large amount of genide.
Yes. Examples of the halide include ammonium bromide
Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide
Um, potassium bromide, sodium iodide, potassium iodide,
Ammonium iodide or the like can also be used. The bleaching solution includes JP-A-46-280, JP-B-45-8506 and 46-
556, Belgian Patent 770,910, Japanese Patent Publication No. 45-8836, 5
3-9854, JP-A-54-71634 and JP-A-49-42349, etc.
Various known bleaching accelerators can be added. The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0 and most preferred
Specifically, it is 5.0 to 7.0. It is recommended to use a fixer having a commonly used composition.
it can. As a fixing agent, it can be used for normal fixing process.
A compound that reacts with silver halide to form a water-soluble complex salt
Compounds such as potassium thiosulfate, sodium thiosulfate
Thiosulfate such as ammonium thiosulfate, thiocyanate
Potassium acid salt, sodium thiocyanate, thiocyanic acid
Thiocyanates such as ammonium, thiourea, thioe
Ether is a typical example. These fixatives
It is used in an amount of 5 g / or more, which can be dissolved.
Use at 70-250g /. The fixing agent is a part of it.
Can be contained in the bleaching solution, and conversely
Parts may also be included in the fixer. The bleaching solution and fixing solution are boric acid, borax, sodium hydroxide.
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
Various pH buffers such as ammonium and ammonium hydroxide
Rui can be contained in combination of two or more
It Furthermore, various optical brighteners, antifoaming agents or interfaces
An activator can also be included. Also, hydroxyl
Bisulfite addition of amine, hydrazine and aldehyde compounds
Preservatives for substances, organic chelates such as aminopolycarboxylic acids
Agents or stabilizers such as nitro alcohol and nitrates, water
Hardeners such as soluble aluminum salts, methanol, dime
Organic solvents such as tylsulfamide and dimethylsulfoxide
Etc. can be appropriately contained. The fixer is used at pH 3.0 or higher, but generally 4.5-10.
Used, preferably used at 5-9.5, most preferred
It is 6 to 9. As the bleaching agent used in the bleach-fixing solution,
The metal complex salts of organic acids described above can be mentioned as
The compound and the concentration in the processing solution should be the same as the above bleaching process.
It is the same as in. In addition to the bleaching agents mentioned above, the bleach-fix solution contains silver halide
Contains a binder and, if necessary, sulfite as a preservative.
A liquid of the composition having is applied. Also, ethylenediamine
Iron (III) tetraacetate complex salt bleaching agent and silver halide fixing described above
Add a small amount of other halide such as ammonium bromide
A bleach-fix solution consisting of the added composition, or vice versa
Is it a composition containing a large amount of halide such as monium?
It is also possible to use a special bleach-fixing solution consisting of The above
As halides, in addition to ammonium bromide, water chloride
Acid, hydrobromic acid, lithium bromide, sodium bromide, odor
Potassium iodide, sodium iodide, potassium iodide, ammonium iodide
Monium or the like can also be used. Silver halide fixing that can be included in bleach-fixing solutions
Examples of the fixing agent include the fixing agents described in the fixing processing step.
You can Fixing agent concentration and bleach-fixing solution
For the pH buffer and other additives that can
This is the same as in the deposition process. The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5,
It is also preferably 6.5 to 8.5.

【Example】

Hereinafter, the present invention will be described more specifically with reference to Examples.
The present invention is not limited to this. Example 1 300 g of gelatin per mol of silver halide, and
As a yellow coupler, α-pivaloyl-α- (1-
Benzyl-2,4-dioxyimidazolin-3-yl)
2-Chloro-5 [γ- (2,4-tert-aminophenoxy) butyramide] acetanilide containing 2.5 × 30 ^-2 mol of blue-sensitive silver iodobromide for color (silver iodide 7 mol%)
An emulsion was prepared. Table 1 for protective layer with this emulsion
Matting agent polymer particles shown in Table 1 (average particle size 2 μm), Table 1
A gelatin solution containing the fluorosurfactant described in 1. was prepared, and an emulsion layer and a protective layer were sequentially coated from a support on a cellulose triacetate film support having an undercoat layer by a slide hopper method to obtain a sample. . The thickness of the protective layer was 1 μm. Each sample was examined for antistatic property, adhesion resistance and coating property. The antistatic property is 23 after leaving each sample in an atmosphere of 55 ° C for 3 days.
After controlling the temperature for 2 hours in an atmosphere of ℃, 20% RH (RH represents relative humidity. The same applies hereinafter), the emulsion surface side is rubbed with a neoprene rubber roller and a Delrin (formaldehyde polymer manufactured by DuPont) roller, and the following treatment is performed. After the process, the generation of static marks was examined. Treatment process Temperature Treatment time (1) Current image …… 38 ℃ 3 minutes 15 seconds (2) Bleaching …… 38 ℃ 4 minutes 30 seconds (3) Fixing …… 38 ℃ 4 minutes 20 seconds (4) Washing with water… ... 38 ° C for 3 minutes and 15 seconds (5) Stabilization ... 38 ° C for 1 minute and 5 seconds The composition of each of the developing solution, the bleaching solution, the fixing solution and the stabilizing solution is as follows. Developer (pH = 10.05) Hydroxylamine sulfate 2.5g 4-Amino-3-methyl-N- (β-hydroxyethyl) -aniline sulfate 4.56g Diethylenetriaminehexaacetic acid 4.75g K ₂ CO ₃ 30.3g Sodium sulfite 4g Water In addition, it is set to 1. Bleach (pH = 5.70) Ammonium bromide 173 g 80% acetic acid 20 ml EDTA FeNH ₄ 103 g EDTA 27 g Add water to make 1. Fixer (pH = 6.50) Ammonium thiosulfate 800 ml Sodium sulfite 4.6 g Sodium bisulfite 5.0 g Add water to make 1. Stabilizer (pH = 7.30) 40% formalin 6.6 ml 50% polyoxyethylated lauryl alcohol 0.6 ml Add water to make 1. Evaluation of the degree of occurrence of static marks A: No generation of static marks was observed at all B: Some generation of static marks was observed C: Generation of static marks was considerably observed D: Generation of static marks was observed It was carried out in four stages, which can be seen on almost the entire surface. To check the storage stability of antistatic property, each raw sample was stored in an atmosphere of 40 ° C and 80% RH for 7 days, and then stored at 23 ° C and 20%.
It was stored under an atmosphere of% RH. Then, in the same manner as above, after leaving it in the atmosphere of 55 ℃ for 3 days, 23 ℃,
After controlling the temperature for 2 hours in an atmosphere of 20% RH, the emulsion surface side was rubbed with a neoprene rubber roller and a Delrin (formaldehyde polymer made by DuPont) roller, and after the treatment in the above treatment step, generation of static marks was examined. Adhesion resistance: Cut the coated sample after drying into two pieces each having a size of 5 cm, and keep them at 40 ° C and 80 ° C without touching each other.
After storing for 2 days in an atmosphere of% RH, contact the protective layers of each sample, apply a load of 1 kg, and store in an atmosphere of 40 ° C, 80% RH, and then peel the sample to determine the area of the adhesive part. The adhesiveness was measured. The results are shown in Table 1. The evaluation criteria were the following methods. A Area of bonded part 0 to 20% B 〃 21 to 40% C 〃 41 to 60% D 〃 61 to 80% E 〃 81% or more Applicability is for the sample coated with the above protective layer at a speed of 100 m / min. The occurrence of coating unevenness was visually evaluated. ×: Uneven coating △: Medium ◯: Small It can be seen from Table 1 that the samples of the present invention are excellent in coating properties, adhesion resistance and antistatic storability. Further, when the alkali-soluble matting agent P-11 was used as the fluorine-containing matting agent, the sharpness of the obtained image was particularly excellent. Example 2 35 g of gelatin and 100 g of silver iodobromide (3 g / kg of emulsion)
Silver iodobromide gelatin high-sensitivity X-ray emulsion containing 1 mol% of silver iodide) was subjected to gold sensitization and sulfur sensitization during the second ripening, and then 4-hydroxy- 6-
Methyl-1,3,3a7-tetrazaindene compound, glyoxal as a hardener, and saponin as a coating aid were added, and a dry film thickness of 7 μm was obtained on a polyethylene terephthalate film support having a thickness of 175 μm which was subjected to an undercoating treatment. Sample No. 15 to No. 15 and No. 15 to No.
Got 20. (Protective Layer Composition) Gelatin 0.5 g Di-2-ethylhexyl sodium sulfosuccinate 0.01 g Glyoxal 0.01 g In addition to the above, the matting agent (average particle size 3 μm) and the fluorosurfactant described in Table 2. Then, in the same manner as in Example 1, the coating property, the adhesion resistance and the antistatic property were measured. The results are shown in Table 2. From the results of Table 2, the sample of the present invention shows that the coating property, the adhesion resistance,
It is also found that the antistatic property is excellent in storage stability.

EFFECT OF THE INVENTION The photographic light-sensitive material of the present invention has excellent antistatic properties, adhesion resistance and coating properties, and maintains good antistatic properties even during storage.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-60-210613 (JP, A) JP-A-60-80845 (JP, A) JP-A-58-62650 (JP, A) JP-A-54- 158222 (JP, A) JP 50-160034 (JP, A) JP 46-7781 (JP, A)

Claims (1)

[Claims] 1. A photographic light-sensitive material in which at least one surface is roughened with a fluorine-containing matting agent, and the outermost layer constituting the surface contains a fluorine-containing surfactant. A photographic light-sensitive material characterized in that the ratio of the matting agent to the total amount of the surfactant is 85% by weight or more and 95% by weight or less.