JPS6336238A - Silver halide photographic sensitive material having improved coatings trouble - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of preventing generation of a mat ping, and reducing coating stripes by incorporating a specific (co)polymer, a fluorine contg. surface active agent and a mat agent to a surface layer of the photographic sensitive material. CONSTITUTION:The surface layer of the photographic sensitive material contains a polymer and/or a copolymer having a repeating unit shown by formula I or II, (for example, the copolymer shown by formula III, X:Y=50:50) and the fluorine contg. surface active agent (for example, the compd. shown by formula IV) and the mat agent (for example, SiO2). In formulas I and II, R1 and R2 are each H, halogen, atom, hydroxy, carboxyl, 1-6C alkyl, or alkoxy carbonyl etc., R3 and R4 are each hydroxy or carboxyl group. Thus, a white spot so called the mat pin and the coating trouble such as the coating stripes of the titled material can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material in which coating failures such as the occurrence of matte pins in the surface layer of the silver halide light-sensitive material are improved.

[Conventional technology]

In general, a highly hydrophilic substance such as gelatin is used as a binder for silver halide layer formation in silver halide photographic materials (hereinafter sometimes simply referred to as photographic materials). For example, when the photosensitive material is stored under high-temperature conditions, the adhesiveness of the surface layer increases, causing a so-called sagging phenomenon, which can damage the photographic material.

Furthermore, the surface layers of photographic materials come into contact with each other during handling during the manufacturing process of photographic materials, or, for example, due to contact with other photographic materials during the exposure process or contact with the equipment itself, The surface layer of the photosensitive material is easily damaged.

As one of the means for preventing such physical damage to photographic light-sensitive materials, a method of adding a matting agent to the surface layer of the photographic light-sensitive material to make it matte is widely known.

Therefore, the above-mentioned matting agent is usually added to one or both of the outermost layers of a photographic light-sensitive material, such as the outermost protective layer or non-photosensitive back layer, to make the surface matte. At the very least, damage to the surface layer due to contact between photographic light-sensitive materials or contact between photographic light-sensitive materials and an exposure device or the like is reduced or prevented.

However, when a matting agent is added to the outermost layer, if the content is too high, the matting agent will embed into the adjacent photosensitive silver halide emulsion layer, resulting in so-called pine I.
・White spots called pins may occur, which may reduce the maximum image density of the photographic light-sensitive material. In addition, when the present invention is used as a photosensitive material for plate making, it is necessary to open the matte pins during proofreading.
This results in a decrease in plate-making work efficiency.

Furthermore, since the matting agent used for the above purpose is hydrophobic in terms of radiation, it is not easy to disperse it in a hydrophilic colloid such as gelatin used in photographic sensitization.
If a fine particulate matting agent is added alone, the matting agents will aggregate with each other. For example, if a protective film solution containing a matting agent that remains poorly dispersed is used, it may be difficult to mix it with a coating solution containing a silver halide emulsion. If multi-layer coating is performed at the same time, a trailing failure will occur, and a uniform coating layer will not be obtained.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a silver halide photographic material that prevents the occurrence of matte pins and has a matte effect without coating failure.

[Structure of the invention]

As a result of various studies, the present inventors have found that in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an outermost layer on at least one side of a support, the outermost layer has the following general properties. The above object can be achieved by a silver halide photographic light-sensitive material containing a pomopolymer and/or copolymer having a repeating unit represented by formula [IA] or (TB), a fluorine-based surfactant, and a matting agent. I found out.

General formula CIA, 3 R5 -CI(2-C- ■ General formula (IB) -CIl-CI- 1h R.

(However, in the above general formulas [IA] and (IB), R+ and R2
is a hydrogen atom, a halogen atom, a hydroxy group, a carboxyl group, an alkoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a sulfoalkyl group or a pyrrolidone R3 and R4 each represent a hydroxy group or a carboxyl group. ) That is, according to the present invention, when a dispersion obtained by containing both the polymer represented by the above general formula and a fluorosurfactant and dispersing a matting agent is used, it is possible to use a dispersion obtained by dispersing a matting agent in a hydrophilic binder. Even when a large amount of matting agent is used to maximize the matting effect, a certain matting agent can be well dispersed, and even when a large amount of the matting agent is used to maximize the matting effect, there is no pin formation or coating failure, and the hydrophilic agent has a good matting effect. It has been found that a single layer of binder is obtained.

In this specification, a silver halide photographic light-sensitive material is one in which at least one photosensitive silver halide emulsion layer is formed on at least one side of a support, and usually a silver halide emulsion layer is formed on at least one side of a support. It may consist of a layer and a non-photosensitive layer (for example, a base layer, an intermediate layer, a protective layer, etc.). Further, a plurality of silver halide emulsion layers may be formed with a non-photosensitive layer interposed therebetween.

When a silver halide emulsion layer is formed on only one side of the support, the other side of the support is usually a non-photosensitive layer (
For example, a backing layer) may be formed.

The outermost layer refers to the outermost layer of the layers constituting the silver halide photographic light-sensitive material, and usually the side on which the silver halide emulsion layer is provided is a protective layer. However, any material that can substantially function as the outermost surface layer is sufficient; for example, a thinner coating layer may be formed on the outermost layer, or a laminate layer may be formed; If it functions as the outermost layer of a photographic light-sensitive material, it is included in the outermost layer referred to herein.

(On the side where the silver halide emulsion layer is not provided, a non-photosensitive back layer, such as a layer called a backing layer, may be formed.) A matting agent is the outermost layer of a silver halide photographic light-sensitive material. It is used to prevent scratches, prevent physical damage to the outermost layer, and improve writability.

The matting agent dispersion liquid refers to a liquid in which such a matting agent is dispersed.

The protective film liquid is a coating liquid for forming a protective layer.

The present invention will be explained in more detail below. First, specific examples of pomopolymers and copolymers represented by the above general formulas (TA) and [IB) include homopolymers such as acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoargyl methacrylate, and glycidyl. acrylate, glycidyl methacrylate,
Mention may be made of polymers such as hydroxyalkyl acrylates, hydroxyalkyl methacrylates, pyrrolidone, alkoxyalkyl acrylates, styrene, vinylidene chloride, maleic anhydride, and itaconic acid. As the copolymer, a copolymer obtained by copolymerizing a combination of the monomers exemplified as forming the above-mentioned homopolymer can be exemplified. For example, (a) C1h + CH2Cl1'h□C112C1l→-yX: Y=5
0:50COOCzH5C00II M=1
60,000 (b) (:ll+CIIzCOOI1 (-CH2-C-)y-(-C1lz-C-)y-x:
y=98:2COOCJs C0OHM #40,000(
c) C00t+(d)
CL■ (-Cll 2 C1l→-X-+CI+2-CH→
-7x: y=30 near 0COOCtH+ q OC
OCH3M #200,000 (e)
Cll +CH2Ctl +A-CHz C→-y
x:y=50:50COOC5l19 Cj!
M#400,000 (f) CH, 1 M#300,000 can be mentioned. Particularly preferred polymers include styrene-maleic acid copolymers and polyvinylpyrrolidone.

The above polymer according to the present invention can be synthesized by a conventional polymerization reaction. Is it used in this polymerization reaction? As the medium, for example, acetone, methanol, isopropanol, methyl ethyl ketone tetrahydrofuran, dimethylformamide, benzene, or a mixed solvent thereof can be used. In addition, as a polymerization initiator for the polymerization reaction, ordinary radical polymerization catalysts such as azoisobutyronitrile and hendiyl peroxide can be effectively used, and the amount is 0.5 to 2.0% by weight based on the monomer. used.

There is no particular restriction on the molecular weight of the homopolymer and copolymer, but it is usually preferably about 10@-3 to 10@6, more preferably from 10@4 to 5.times.10@5.

In addition, the fluorine-based surfactant used in the present invention has a hydrophobic part and a hydrophilic part in its molecule,
There is no particular limitation as long as the solution exhibits a decrease in surface tension.

As fluorosurfactants particularly preferably used in the present invention, compounds represented by the following general formulas [A) to (nE] can be mentioned.

General formula (UA) (However, in the above general formula (IIA), R12 has 1 carbon atom
~32 alkyl groups, such as methyl, ethyl, propyl, hexyl, nonyl, dodecyl, hexadecyl, etc., and these groups are substituted with at least one fluorine atom. n represents an integer of 1 to 3, and nl represents an integer of 0 to 4. ) General formula (IIB) R++ OCOC1+2 ■ RI4 0GOCIl RI5 General formula (nc) R160COCH2 Rat OCOCR R+ll0COCtl RI9 (However, the above general formula (I[B), (R1, in IICI.

R14+ RI6+ R17 and R+a are each a linear or branched alkyl group having 1 to 32 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, nonyl group,
It does not represent a decyl group, a dodecyl group, an octadecyl group, etc., but may be a cyclic alkyl group, and these groups are substituted with at least one fluorine atom. Also R I3+
RIf R16+ R+7 and R11+ each represent an aryl group, such as a phenyl group, a naphthyl group, etc., and these groups are substituted with at least one fluorine atom.

Furthermore, RI5 and RI9 represent an acid group such as a carboxylad group, a sulfonate group or a phosphoric acid group, and these groups may be substituted with at least one fluorine atom. ) General formula CIID) (However, in the above general formula (, IID), Rgo represents a saturated or unsaturated straight chain or branched alkyl group having 1 to 32 carbon atoms. For example, as a saturated alkyl group, a methyl group , ethyl group, butyl group, isobutyl group, hexyl group, dodecyl group, octadecyl group, etc., and unsaturated alkyl groups include, for example, allyl group, butenyl group, octenyl group, etc.These saturated and unsaturated alkyl groups The group is substituted with few (both are substituted with one fluorine atom.R2
and R3 represents an integer of 1 to 3. Moreover, R4 represents an integer from 0 to 6. ) In the general formula (HA) (the above general formula CUE), Y is a sulfur atom, a selenium atom,
represents an oxygen atom, a nitrogen atom, or an R2 group □ N- (where R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group), and R21 is represented by the above general formula CIIA) It represents a group having the same meaning as the group represented by R12 or an atomyl group substituted with at least one fluorine atom (eg, phenyl group, naphthyl group, etc.). Further, Z represents an atomic group necessary to form a 5- or 6-membered heterocycle, examples of which include a thiazole ring, a selenazole ring, an oxazole ring,
Examples include an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a pyrimidine ring, and a triazine ring.

The above heterocycle may further have a substituent such as an alkyl group or an aryl group, and these substituents may be substituted with a fluorine atom. ) Next, the above general formula (UA)
Specific examples of the fluorosurfactants represented by (TIE) are shown in (TI-1,) to (TI-39), but the compounds that can be used in the present invention are limited to these exemplified compounds. It's not a thing.

(Exemplary compounds) CF3 CF3 (IT-4) (IT-9) CF2O(CF3)2CF2CF(CF3) CH2
00CCH2■ ChC(CF+)zcFzcF(CF3) ChzO
OCCH5O3eCFa(CF2)++OOCCI
5O3eCF 3 (CF 2) I JOCCll5
Ozθ(II-12) CFa(CFz)soOccHz ■ CI'+ (CF2) 500cctl SO3”(
U-13) CF3 (CF2) 3CF (C1!F5) CF200CC
H2CF3 (CF,) 3CF (C2F4)CF2
00C-Cll5(hθ(I[-15) (II-19) CF3(CF2)7 00CCH□ ■ Ch(CFz)7 00CCH CF3 (CF2) 7 00C-CI+ 503θ
CF2=CF CF2 (■-23) (II14) CF3 ([16) (IT-27) H-(CFZ)6C1+, -0
-C00CHz-3O3e(n -28) H(
CF2)ecH2-0-CH2CI+2-3O3θNa
03SCHC00CIIz(CFzCFz)3H■ CH2C00C5HI I(iso) (■-31) NaQsS C;H-COOCth(CFzCFz)
31tCI2 COOCHgCC00CH C21(5 NaOsS co C00CHz(CFzCPz)
ttlCH2C00CJt(n) (■”4)NaO*S CI C00CH7(CF2C
F2) Jl CH□C00CI! 3 (■-35)NaOsS ClIC0OCH2CFZC
F2□Cl12COOCI. +(21(n) (■-37)NaO3S CHC00C)Iz(CF2
CF2) Jl CIl□C00CJ+q(iso) (■”8)NaOsS ClIC0OCII...FZ
CF2)2BCl1zCOOC! +3(n) (■-3”)NaOsS-cll-COOCIlz(C
Fz)aHCI□-CO'OC)+2(CF2)611
Next, we will discuss matting agents. Examples of matting agents used in the present invention include silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, diatomaceous earth,
Inorganic compounds such as polymethyl methacrylate,
Examples include fine particles of organic compounds such as cellulose acetate propionate, starch, and the like. Preferred are fine particulate materials of silicon dioxide or polymethylmethacrylate-1. In particular, silicon dioxide improves adhesion resistance,
Furthermore, it is suitable for roughening the surface of the outermost layer using a matting agent, and is the most suitable matting agent for exerting the effects of the present invention.

The above matting agent usually has a particle size of 0.01 μm or more, for example.
Although a particle size of 10 μm can be arbitrarily selected, the preferred particle size is in the range of 0.1 μm to 5 μm. There are no particular restrictions on the mixing ratio with the hydrophilic binder, but
In order to significantly exhibit the effects of the present invention, for example, 0.00% of the binder forming the outermost layer (usually a protective layer)
3% to 30% by weight is preferred, particularly preferably 0.
3% to 10% by weight is desirable.

A preferred method for dispersing the matting agent in the present invention is to add the matting agent to an aqueous solution of a fluorosurfactant represented by the general formula [■A] to (+'lE), and add it to a static mixer. , Matton-Gorlin mixer, ultrasonic dispersion machine, pipeline homomixer, etc. A homopolymer and/or copolymer having a repeating unit represented by the above general formula (IA) or (TB) is gradually added to the matting agent dispersion obtained in this way, and thereby the above general formula [IA] or A dispersion of a homopolymer and/or copolymer having a repeating unit represented by [IB), a fluorosurfactant, and a matting agent is prepared.

When preparing the matting agent dispersion, a surfactant other than the fluorosurfactant may be used in combination for dispersion.

The temperature of the dispersion during preparation is, for example, 15° to 100°.
The dispersion method involved in the method can preferably prepare a uniform dispersion of the matting agent at a temperature ranging from room temperature to 50°C. Furthermore, according to the above dispersion method, the stagnation storage property after dispersion is also good.

The silver halide used in the photographic material of the present invention includes:
Any of those used in ordinary silver halide photographic emulsions such as silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver chloride are included. In particular, when the material is used as a photosensitive material exposed in a bright room using a printer using a metal halide or high-pressure mercury lamp as a light source, silver chlorobromide containing 70 mol% or more of silver chloride is preferable as the silver halide composition. These silver halides may be coarse grained or fine grained,
Various methods, such as U.S. Patent No. 2.592.250;
Same No. 3,276.877, Same No. 3.31.7.322
No. 2.222゜264, No. 3,320,06
9, No. 3,206, 31.3, or "Journal of Photographic Science (J, Photo, Set,) J Volume 12, No. 5 (September and October issue) ), 1964, pp. 242-251.

It is also possible to mix and use silver halides prepared by different methods.

The silver halide contained in the silver halide emulsion layer used in the present invention has an average grain size of 0.05 to 1.5 μm, preferably 0.1 to 0.0 μm, although it is not limited to this.
5 μm and at least 75%, more preferably 80% or more of the total number of particles is 0.5 to 1.5 times the average particle size, most preferably 0.6 to 1.5 μm.
It is desirable to include silver halide having four times the grain size.

According to a most preferred embodiment of the present invention, the above silver halide has an average grain size of 0.10 to 0.4 μm, and more than 80% of the total grains have an average grain size of 0.6 to 0.4 μm.
Silver iodobromide, silver bromide, silver chlorobromide, or silver chloroiodobromide having a grain size of 1.4 times.

Further, the silver halide grains preferably contain iridium, rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, and 10-8 to 10-2 mol per 1 mol of silver halide in the crystal grains,
In particular, it is suitable to contain 10-6 to 10-4 mol. Further, it may be a surface latent image type or an internal latent image type. Additionally, silver halides prepared by a variety of different methods may be mixed. The crystal shape may be hexahedral, octahedral, or spherical without any limitations.

Further, tetrazolium salts represented by the following general formulas (I[IA,), t[[B) and (IITC] may be contained in these silver halide crystal grains.

General formula CI[IA] General formula (IB) General formula (ITIC) (However, the above general formulas (IIfA), (IIrB), (I
C) Medium, R:+++ R33+ R3ar R:lS+
R3s+ R, lq+ R4° and R41 each represent an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an alkenyl group (e.g. vinyl group, allyl group, propenyl group, etc.), an aryl group (e.g. Phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group,
a group selected from α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (e.g. thiazolyl group, benzothiazolyl group, oxacyl group, pyrimidinyl group, pyridyl group, etc.) Each of these may be a group that forms a metal chelate or a complex.

R3□, Rff6 and Rff? are allyl group, phenyl group which may have a substituent, naphthyl group which may have substituent, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group), respectively. , mercaptoethyl group, etc.), hydroxyl group, carboxyl group or its salt, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.)
, represents a group selected from an amino group (e.g. amino group, ethylamino group, anilino group, etc.), a mercapto group, a nitro group, or a hydrogen atom, D represents a divalent aromatic group, and E
represents a group selected from alkylene group, arylene group, and aralalkylene group, Xθ represents an anion, and n is 1
or represents an integer of 2. However, when the compound forms an inner salt, n is 1. ) Next, the general formula (II[A,
), (IIIB) or (IIIC) as shown below (III-1).
-(III-34), but compounds that can be used in carrying out the present invention are not limited to these exemplified compounds.

Exemplary compounds: (III-1) 2-(benzothiazol-2-yl)-3-phenyl-5-dodecyl-2H-tetrazolium chloride, (III-2) 2.3-diphenyl-5-(4- -octyloxyphenyl)-2H-tetrazolium bromide, (III-3) 2,3.5-)diphenyl-2H-
Tetrazolium bromide, (III-4) 2,3.5-1-li (p-carboxyethylphenyl)-2H-tetrazolium sulfate, (I[r-5> 2-(benzothiazol-2-yl)-3 -phenyl-5-(o-chlorophenyl)-2
H-tetrazolium chloride, (III-6) 2.3-diphenyl-2H-tetrazolium sulfate, (I[l-7) 2.3-diphenyl-5-methyl-
2H-tetrazolium bromide, (m-8) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-te] lazolium sulfate, (III-9) 2.3-diphenyl-5-ethyl −
2H-tetrazolium bromide, (lII-10) 2.3-diphenyl-5-n-hexyl-2H-tetrazolium chloride, (III-11> 5-cyano-2,3-diphenyl-2H-tetrazolium chloride, ( IIl-12) 2-(benzothiazole-2-
yl)-5-phenyl-3-(4-)lyl)-2H-tetrazolium bromide, (III-13) 2-(benzothiazole-2-
(III-14) 5-ethoxycarbonyl-2,
3-di(3-nitrophenyl-2H-tetrazolium chloride, (III-15) 5-acetyl-2,3-di(p
-ethoxyphenyl)-2H-tetrazolium sulfate, (III-16) 2.5-diphenyl-3-(p-
) Lyl)-2H-tetrazolium bromide, (III-
17) 2.5-diphenyl-3-(p-iodophenyl)-2H-tetrazolium sulfate (III-18) 2.3-diphenyl-5-(p-
diphenyl)-2H-tetrazolium sulfate, (III
-19) 5-(p-bromophenyl)-2-phenyl-3-(2,4,6-)lychlorphenyl)-2H
-Tetrazolium chloride, (III-20) 3-
(p-hydroxyphenyl)-5-(p-nitrophenyl)-2-phenyl-2H-tetrazolium bromide, (Illil) 5-(3,4-dimethoxyphenyl)-3-(2-ethoxyphenyl)-2- (4-methoxyphenyl)-2H-tetrazolium chloride, (nu-22) 5-(4-cyanophenyl) -
2,3-diphenyl-2H-te) lazolium bromide, (1-23) 3-(p-acetamidophenyl)
-2,5-diphenyl-2H-tetrazolium bromide, (1-24) 5-acetyl-2,3-diphenyl-2H-tetrazolium sulfate, (Iff-25) 5-(furur-2-yl)-2,
3-diphenyl-2H-tetrazolium chloride, (II
I-26) 5-(thieno-2-yl)-2,3
-diphenyl-2H-tetrazolium chloride, (III
-27) 2,3-diphenyl-5-(pyrido-4-
yl-2H-tetrazolium chloride, (m-28)
2.3-diphenyl-5-(quinol-2-yl)-
2H-tetrazolium bromide, (1-29) 2.3-diphenyl-5-(benzoxazol-2-yl)-2H-tetrazolium sulfate, (Tll-30) 2.3. 5-1-(p-ethylphenyl)-2H-tetrazolium bromide, (IH-31) 2,3.5-)(p-allylphenyl)-2H-tetrazolium chloride, (III-32) 2. 3. 5-1-li (p-hydroxyethyloxyethoxyphenyl)-2H-te]
・Razolium sulfate, (III-33)2,3.5-)ri(p-dodecylphenyl)-2H-tetrazolium sulfate, (rff
-3/l) 2,3.5-)li(p-benzylphenyll-2H-tetrazolium chloride, the silver halide being added to the hydrophilic colloid layer, is particularly advantageously used in the present invention) The hydrophilic colloid is gelatin. Examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid,
Hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat.
Phenylcarbamyl gelatin, acylated seratin, phthalated gelatin as described in the specifications of No. 753, or U.S. Patent Nos. 2,548,520 and 2
, 83L767, styrene acrylate, acrylic ester, methacrylic acid,
Examples include gelatin graft-polymerized with a polymerizable monomer having an ethylene group such as methacrylic acid ester, and these hydrophilic colloids can be used in layers that do not contain silver halide, such as antihalation layers and protective layers. , it can also be applied to intermediate layers, etc.

The silver halide photographic light-sensitive material of the present invention is formed by coating a hydrophilic colloid layer containing the above-mentioned silver halide on a suitable photographic support. Supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. Films and the like are typically included, and these supports are appropriately selected depending on the intended use of the silver halide photographic material.

As described above, the silver halide photographic material of the present invention is formed by coating at least one emulsion layer containing silver halide on a support. Furthermore, a homopolymer and/or copolymer having a repeating unit represented by the general formula [IA] or CI B), a fluorine-based surfactant, and a matting agent are further contained on the side of the silver halide emulsion layer. It has an outermost layer. This outermost layer is preferably formed as a protective layer with a moderate thickness, i.e. preferably 0.1
It is desirable that the gelatin protective layer be formed by coating as a gelatin protective layer with a thickness of 1 to 10 μm, particularly preferably 0.8 to 2 μm.

In the present invention, the hydrophilic colloid used to form the silver halide emulsion layer and the outermost layer may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, and Stabilizers, ultraviolet absorbers, anti-stain agents, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusters, in addition to those mentioned above. Also, various matting agents and the like can be used within the range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those which can be particularly preferably used in the present invention include, for example, thickeners or plasticizers as described in U.S. Pat.
Publication No. 39, West German Application Publication No. L904,604, Japanese Unexamined Patent Publication No. 48-63715, Japanese Patent Publication No. 45-1546
Publication No. 2, Belgian Patent No. 762,833, US Patent Box 3, 767, 410, Hergiy Patent No. 558,
Substances described in each specification of No. 143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based, Various hardeners and ultraviolet absorbers such as isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, and acyloyl-based agents include, for example, U.S. Patent Box 3,
253.92] and British Patent No. 1,309.349, particularly 1-(2'-
Hydroxy-5-tertiary butylphenyl)hencytriazole, 2-(2'-hydroxy-3',5'-di-3
butylphenyl)hencytriazole, 2- (2'
-Hydroxy-3'-tertiary butyl-5'butylphenyl)-5-chlorobenzotriazole, i(2''-hydroxy-3',5'-di-tertiary butylphenyl)-5-
Examples of dyes include U.S. Pat. No. 2,072,908, German Patent No. 107,990, and U.S. Pat. No. 3,048.
, 487, US Pat. No. 515,998, and the like can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, or the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photographic materials include, for example, US Pat. No. 548.532. No. 1.
, 216.389, specifications of U.S. Patent No. 3,026,202, and U.S. Pat.
-26,580, 4.3-17.922, 43
-17,926, 43-13,166, 48-
Anionic, cationic, It is possible to use nonionic or amphoteric compounds.

In addition, as an antistatic agent, for example, Japanese Patent Publication No. 46-2415
No. 9, JP-A No. 48-89979, specifications of U.S. Pat.
No. 0, No. 4B-90391, Special Publication No. 46-241.5
No. 9, No. 46-39312, No. 48-43809,
Compounds described in various publications such as JP-A No. 47-33627 can be mentioned.

The developer that can be used in the present invention is not limited to either squirrel or rabbit use.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example-1 Three types of matting agent dispersions (1) and (2) are shown below.

(3) was produced 8 times.

Matting agent Buuki Rattan U-Kun 1ri Silicon dioxide as a matting agent (average particle size 2.5 μm)
1 kg was dispersed in 10 ρ of pure water to prepare a 10% by weight matting agent dispersion (1).

Preparation of matting agent dispersion (2) Silicon dioxide as matting agent (average particle size 2.5 μm)
1 kg to 4% by weight of the copolymer exemplified compound (e)
It was added to aqueous solution 1β and dispersed for 60 minutes by ultrasonic dispersion to prepare a matting agent dispersion (2).

rmdan clarification solution (3) Weekly 1 kg of silicon dioxide (average particle size 2.5 μm) as a matting agent to 101 1% by weight aqueous solution of exemplified compound ■-11
was added, and dispersion was continued for 60 minutes at room temperature using an ultrasonic dispersion method. A 4% by weight aqueous solution 11 of copolymer exemplified compound (e) was added, and ultrasonic dispersion was continued again for 60 minutes to form a matting agent dispersion. (3) was prepared.

The above matting agent dispersions (1) and (2) are comparative dispersions other than the present invention, and the matting agent dispersion (3) is a matting agent dispersion according to the present invention.

Preparation of Halodef 1m Hole Coating Solution Next, a silver halide emulsion coating solution was prepared as follows. That is, a silver chlorobromide gelatin emulsion containing 38 mol % of silver bromide was prepared by a simultaneous mixing method at 65° C. over 70 minutes. The emulsion thus prepared was desalted and redispersed, with an average grain size of 0.
．． A monodisperse emulsion of 25 μm was obtained.

To this emulsion were added 1.15 mg of citric acid, 700 mg of potassium bromide, 1.0 mg of sodium thiosulfate, and 14 mg of chloroauric acid in 1 mole of AgX, and the mixture was heated at 60°C to
Chemically aged for 5 minutes. To this chemically ripened emulsion, 5 ml of a 0.5% solution of 1-phenyl-5-mercaptotetrazole was added as an antifoggant, and 1% of 6-methyl-4-hydroxy-1,3,3a,7-titrazaindene was added as a stabilizer. 130ml of solution, 400ml of sensitizing dye of the following formula
g, in addition to 20% Merckzabonin solution 20 as a spreading agent.
m 12 and further copolymer exemplified compound (e)
30g of was added.

(Sensitizing dye) On the other hand, as a protective film solution for photographic light-sensitive materials, 8 cc of 0.6% sodium-2,6-dichloro-1,3,5-) riazine oleate was added to an aqueous solution of 500 g of inert gelatin.
．． 40 cc of 5% formalin was added, and the above-mentioned matting agent dispersions (1,), (2) and (3) were added thereto so that each contained 3% by weight based on the weight of gelatin in terms of matting agent. Three types of protective film liquid (a), (b),
(c) was prepared.

Sample Preparation The protective film solutions (a), (b), and (c) containing the silver halide emulsion coating solution and matting agent prepared above were coated on a polyethylene terephthalate support that had been subjected to a subbing process at a coating speed. 100 m/n+in and the emulsion layer has a silver content of 4.0
g/m, and the amount of gelatin in the protective layer was 1.2 g/M.
It was created.

Study Results The three types of samples mentioned above were developed using a developing solution and a fixing solution having the following compositions, and matte pins were studied.The results are shown in Table 1.

(Developer formulation) (Fixer formulation) (Composition A) (Composition) When using the fixer, dissolve the above composition A and then the composition in 500 ml of water, and II! It was finished and used. The pH of this fixer was approximately 4.3.

Processing conditions are development condition 38°Cl2O seconds, fixing condition 25
℃, 20 seconds, washing condition 20℃, 20 seconds, drying condition 50℃
.

It is 20 seconds.

” If there is a pinhole in the 1 table, 1. oocn! The number of pinholes per hit was observed and counted using a looper with a magnification of 0.

As is clear from Table 1, the occurrence of matte pins is significantly reduced in the present invention sample-3, which has a protective layer containing an effectively dispersed matting agent. In sample 1, which had a protective layer dispersed only with water, matte pins were significantly generated, and in sample 1, which had a protective layer in which a matting agent was dispersed in the presence of only a copolymer.
Although the occurrence of matte pins was suppressed to some extent in Example No. 2, it cannot be said that the occurrence of matte pins was sufficiently prevented compared to the present invention.

Example 2 Four types of matting agent dispersions (4) to (7) were prepared as described below.

7) ready-made silicon dioxide as a matting agent (average particle size 3
．． 5μ mark"g was added, and dispersion was continued for 60 minutes at room temperature using an ultrasonic dispersion method.
A 4% by weight aqueous solution 1β of e) was added, and ultrasonic dispersion was continued again for 60 minutes to prepare a matting agent dispersion (4).

(Formula-A) CI+3(CI+□)3 CH(CJs)CHz
OOCCtlz" CH3(CHz)i CH(CJs)CHz OO
CCH5O3N.

Preparation of matting agent dispersion (5) Add 1 kg of silicon dioxide (average particle size 3.5 μm) as a matting agent to 1% by weight aqueous solution 101 of exemplary compound ■-26.
A matting agent dispersion (5) was prepared in the same manner as the matting agent dispersion (4) with respect to the copolymer to be contained and the dispersion method.

Preparation of matting agent dispersion (6) 1% by weight aqueous solution of exemplary compound ll-15 107! In addition, silicon dioxide (average particle size 3.5 μm) L as a matting agent
kg, and for the rest, add a matting agent dispersion (
A matting agent dispersion (6) was prepared in the same manner as in 4).

4 days Preparation of matting agent dispersion (7) 1 k of silicon dioxide (average particle size 3.5 μm) as a matting agent was added to 101 of a 1% by weight aqueous solution of exemplary compound ■-30.
g, and for the rest, use the matting agent dispersion (4)
A matting agent dispersion (7) was prepared in the same manner as above.

The matting agent dispersion liquid (4) is a comparative dispersion liquid other than the present invention, and the matting agent dispersion liquids (5), (6), and (7) are dispersion liquids according to the present invention. The type of agent used has been changed.

Preparation of silver halide emulsion coating solution and protective film solution Next, Examples-
A silver halide emulsion coating solution and four types of protective film solutions were prepared in the same manner as in Example 1.

Sample Preparation and Experimental Results Both of the above coating solutions were applied in the same manner as in Example 1, and Sample 4. Sample-5, sample-6, and sample-7 were created.

Further, the development process was performed in the same manner as in Example-1, and the matte pin was examined. The results of the study are shown in Table 2 below.

According to Table 2 above, Sample-5, Sample-6, Sample-
It can be seen that in Sample No. 7, the amount of matte pins generated was significantly reduced compared to the comparative sample.

It was also revealed that there was no significant change in the number of matte pins generated even when the type of fluorosurfactant was changed.

Example-3 Six types of dispersions (8) to (13) were prepared as described below.

(2) Preparation of a 51 mo dispersion 40) 1% by weight aqueous solution of a surfactant represented by the following (formula-B) 10 I! 1 kg of silicon dioxide (average particle size 4.0 μm) as a matting agent was added to the mixture, and dispersion was continued for 60 minutes at room temperature using an ultrasonic dispersion method. was added thereto, and the ultrasonic dispersion method was continued again for 60 minutes to prepare a matting agent dispersion (8).

(Formula-B) 1 kg of silicon dioxide (average particle size 4.0 μm) as a matting agent is added to 10 A of a 1% by weight aqueous solution of Exemplified Compound ■-35.
A matting agent dispersion (9) was prepared in the same manner as the matting agent dispersion (8) except that a matting agent dispersion (9) was added.

Preparation of Matte Division Solution (10) Silicon dioxide (average particle size 4.08 m) as a matting agent was added to 1ON of a 2% aqueous solution of exemplary compound Tl-35 (average particle size 4.08 m).
g, and for the rest, matting agent dispersion (8)
A matting agent dispersion (10) was prepared in the same manner as above.

A matting agent dispersion liquid (11) was prepared by adding 1 kg of diatom ± (average particle size 4.0 μm) as a matting agent to 10A of the % aqueous solution, and otherwise in the same manner as the matting agent dispersion liquid (8). .

Preparation of matting agent dispersion 12) Add diatom ± (average particle size 4.0 μl 11) as a matting agent to 1% by weight aqueous solution 101 of Exemplary Compound 1-35.
kg, and for the rest, add matting agent dispersion (8 kg).
) A matting agent dispersion (12) was prepared in the same manner as in Example 1.

Preparation of matting agent dispersion (13) Add 1 kg of 2 wt % aqueous solution of Exemplary Compound ■-35 to 10 A of 2% by weight aqueous solution of diatom ± (average particle size 4.0 μm) as a matting agent.
A matting agent dispersion (13) was prepared in the same manner as in the matting agent dispersion <8) except that a matting agent dispersion (13) was added.

The above-mentioned matting agent dispersions (8) and (11) are dispersions outside the scope of the present invention because they do not use a fluorosurfactant.

The above-mentioned matting agent dispersions (9) and (10) are the matting agent dispersions according to the present invention, each of which uses silica as the matting agent, and the above-mentioned matting agent dispersions (1, 2).

(13) is a dispersion liquid according to the present invention, and diatomaceous earth is used as a matting agent.

Next, a silver halide emulsion coating solution and six types of protective films were prepared in the same manner as in Example 1, and coating was performed in the same manner as in Example 1. Samples No. 11, Sample-12, and Sample-13 were prepared and developed in the same manner as in Example 1. Thereafter, as in Example 1, the matte pin was not examined, and the test results are shown in Table 3 below.

As shown in Table 3 above, even if the matting agent is diatomaceous earth instead of silica and the amount of fluorine-based surfactant is changed, the number of matting pins is almost the same as when the matting agent is silica. Moreover, it can be seen that the matte pin has been greatly improved.

Example 4 Preparation of Eie Kozuki Dispersion (14) A matting agent dispersion was prepared in exactly the same manner as the matting agent dispersion (4) of Example 2.

Preparation of matting agent dispersion (15) A matting agent dispersion was prepared in exactly the same manner as matting agent dispersion (5) in Example-2.

Preparation of matting agent dispersion (16) A matting agent dispersion (16) was prepared in exactly the same manner as matting agent dispersion (6) in Example-2.

Preparation of matting agent dispersion liquid (17) A matting agent dispersion liquid (17) was prepared in exactly the same manner as the matting agent dispersion liquid (7) of Example-2.

An emulsion (containing 65 mol % silver chloride per mol silver) was prepared. That is, an aqueous solution of silver nitrate and an aqueous solution containing sodium chloride and potassium bromide were continuously added to an aqueous gelatin solution at 40°C for 80 minutes with stirring to obtain an average particle size of 0.
Silver chlorobromide emulsion grains of 32 μm were formed.

The emulsion thus prepared was desalted and redispersed to obtain a monodispersed emulsion with an average grain size of 0.32 μm. This emulsion contains AgX
150 mg of citric acid, 300 mg of potassium bromide, 5 mg of chloroauric acid and 15 mg of sodium periosulfate were added to 1 mole, and the mixture was chemically aged at 60°C for 80 minutes.

This chemically ripened emulsion was added with 2-methyl-4- as a stabilizer.
150 cc of a 1% solution of hydroxy-L 3,3a,7-chitrazaindene compound and an aqueous gelatin solution were added.

Furthermore, as an ortho-sensitizing dye, the following compound was added to 150 m
g was added.

(Sensitizing dye) Next, 30 In of 20% saponin aqueous solution was added as a coating aid.
Then, 1.0 g/rrf of the latex polymer used in Example-1 was added, and 2 g of copolymer exemplified compound (e) was added as a thickener. 40 chloride salt of the compound
mg/n (added to give a final concentration of 11 per mole of silver halide to obtain a coating solution for a silver halide photographic light-sensitive material.

Protective film Higashiq Koushige Next, a coating solution for a protective film for emulsion was prepared according to the following procedure.

That is, add 10 A of pure water to 1 kg of gelatin, and after swelling, add 40
It was heated to 0.degree. C., divided into four parts, and matting agent dispersions (14) to (17) were added to each of these four parts.

The emulsion coating solution prepared above and the coating solution for the protective film were combined on a 100 μm thick polyethylene terrestrial base support with a silver content of 4.0 μm.
g/po, gelatin is 1. ．． 9 g/nf, and gelatin for the protective film was applied in an amount of 1.1 g/m. Coating conditions are coating speed 100 m/min, lapse rate wet bulb 24
It was ℃. At the time of coating the protective film, 50 ml of a 3.5% formaldehyde hardening agent solution was added to the protective film coating solution to harden the film. Samples-14 to 17 were created in this way.

The above test sample was processed in an automatic developing machine with a developing tank capacity of 40 ρ using a developer having the following formulation and the fixer of Example 1. After that, we conducted a study on matte pins, and the results are shown in Table 4.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fix at 30℃ for 30 seconds
Wash with water for 20 seconds, room temperature 2
0 seconds (developer composition) (silk) When using the developer, the above composition A was melted in the order of composition A and composition 11 in pure water 500 mβ and used.

According to Table 4 above, the pine trees 1 to 1 dispersed according to the present invention
Sample-15° Sample-16 with a protective film layer containing the agent
, Comparing Sample-17 with Sample-14 As can be seen by comparing the number of pinholes with Sample-14, even in the system with tetrazolium salt added, the one in which the fluorine-based surfactant, matting agent, and polymer were dispersed, was compared to the comparative sample. It is clear that the number of matte pins has decreased significantly. Furthermore, even if the type of fluorosurfactant is changed, the mat pin does not change.

Example 5 Using the sample prepared in Example 2, coating failures were investigated. The results are shown in Table 5.

Margin below.

The evaluation of coating streaks at 2° was made on a five-point scale, with 5 being the highest (no streaks at all) and 1 being the lowest.

As can be seen from the above results, those dispersed using a fluorine-based surfactant are also superior in terms of coating failure.

Furthermore, it can be seen that there is no deterioration in performance even when the type changes.

〔Effect of the invention〕

As described in detail, according to the present invention, it is possible to obtain a silver halide photographic material that prevents the occurrence of matte pins and has a matte effect without coating failure.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and an outermost layer on at least one side of a support, in which the outermost layer has the following general formula [I
A silver halide photographic material comprising a homopolymer and/or copolymer having the repeating unit represented by A] or [IB], a fluorine-based surfactant, and a matting agent. General formula [I A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the above general formulas [I A] and [I B], R_1 and R_2 represents a hydrogen atom, a halogen atom, a hydroxy group, a carboxyl group, an alkoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a sulfoalkyl group, or a pyrrolidone group, and R_3 and R_4 represent a hydroxy group or a carboxyl group. 2. The outermost layer is a homopolymer and/or copolymer having a repeating unit represented by the general formula [I A] or [I B] obtained by adding and dispersing a matting agent in an aqueous fluorosurfactant solution. The halogenated compound according to claim 1, characterized in that a protective film solution obtained by adding a matting agent dispersion obtained by adding and continuing dispersion to an aqueous gelatin solution is applied. Silver photosensitive material.