JPS6311934A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To speed up coating and to reduce layer thickness by incorporating a hydrophilic colloid and a high-molecular compd. having a sulfonate group, sulfate group or carboxylic group at the side chain and having 0.4-1.5 ultimate viscosity thereof into a titled material and coating the same on a base in a 80-300m/min range. CONSTITUTION:This photosensitive material has at least one photosensitive silver halide emulsion layer on the base. The material prepd. by incorporating the hydrophilic colloid and the high-molecular compd. having the sulfonate group, sulfate group or carboxylic group at the side chain and having 0.4-1.5 ultimate viscosity ([eta]0.1N NaCl 30 deg.C) therein is coated in the 80-300m/min range on at least the lowermost layer at the time of coating the silver halide emulsion layer or the other hydrophilic colloidal layer on the base. The simultaneous coating of the multiple layers, the coating at the higher speed and the coating of the thinner layers are thereby attained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a silver halide photographic material. More specifically, the present invention relates to a method for rapidly coating a photographic constituent layer coating liquid comprising a hydrophilic colloid liquid containing gelatin or a gelatin derivative.

(Technical background) Generally, photographic materials use cellulose ester, polyethylene terreslate, polycarbonate,
Synthetic polymer films such as glass, paper, or paper coated with polyethylene are used, and silver halide photographic emulsion layers are applied directly or via an undercoat layer to these supports. A surface protective layer is coated on the photographic emulsion layer to prevent the material from scratching due to scratches or processing with surfaces of the same or different types. Also coating layers consisting of gelatin or other hydrophilic colloids or vinyl polymer latices, such as antihalation layers, containing additives such as dyes, antistatic agents, hardeners, color-forming couplers, antihalation agents, etc. Middle layer, filter! 4. Anti-static etc. are applied.

In recent years, the coating methods for each layer constituting such photographic materials have undergone remarkable technical changes and become more complex. is becoming extremely difficult.

For example, in order to save labor during coating, each coating layer is applied every 7 layers.
Instead of a coating method that involves coating, setting, and drying, a so-called multilayer simultaneous coating method, in which multiple layers are coated simultaneously, has been put into practice.

When coating with such a multi-layer simultaneous coating method, the coating solution for each layer is continuously coated almost simultaneously, so the coating solution h and the coating layer (immediately after coating) are coated uniformly and in a thin layer at high speed without being mixed. You can apply it! This is more difficult than the method of coating and drying each #.

Normally, when applying a coating liquid to a continuously running web, the amount of coating liquid t per unit area of the web (hereinafter referred to as "@cloth amount")
That's what it means. It is known that the rougher the surface of the web or the higher the running speed of the web, the more difficult it is to start uniform coating. In other words, as the coating becomes thinner and the coating speed increases, it becomes difficult to start uniform coating, and the coating liquid is not applied to the web immediately after coating starts, resulting in slight induction. It was usual for the coating solution to be applied to the web only after passing through the section. Moreover, even when the coating liquid is applied to the web after passing through this induction zone t5, the coating film near the line connecting the points where the coating liquid is first applied to the web (hereinafter referred to as the "application start line") is different from the one shown in FIG. Approximately compared to a steady coating film of! 0-/l)
He was known to be a thick-skinned person in charge of D.

If the coating amount is further reduced or the web running speed is increased, the coating liquid may be applied unevenly to the web, or
In some cases, it was even not applied at all.

Many studies have been conducted on the causes of such troubles at the start of coating from various aspects, but the current state of affairs is that there are still many that can be considered as established theories, and in general, coating should not be continued until the web is sufficiently wet. It is difficult for the liquid to adhere to the web,
Alternatively, it is explained that coating does not start until the coating liquid can eliminate the air layer entrained in the web by itself, but these explanations do not fully explain such phenomena. I couldn't do it.

This is because the cause is not clear.

At present, there is no solution that can completely eliminate the troubles that occur when starting coating.

However, if this problem at the start of coating is not resolved, the thickly coated film near the coating start line may dry, and the thickly coated area may be only a small part of the entire coat. However, there is a serious problem in that it requires a long drying process, which is not only extremely uneconomical, but also makes it difficult to apply and cannot be manufactured. I couldn't respond to the recent 4-layer talk.

On the other hand, with the simultaneous multilayer coating, high speed coating, and thin layer coating,
Spun fabric g (hereinafter referred to as
It is simply called "coating liquid." ) has become a problem in that it cannot be applied uniformly on the web, which is so-called uneven coating.

Such coating unevenness becomes more obvious as the amount of coating per unit area of the support is smaller, or the speed of the support is faster, and the thinner and faster the tamping coating becomes. It is recognized that

One way to solve such problems is to
It is well known that physical properties such as surface tension and viscosity of various coating liquids are important, and various surfactants and thickeners have been proposed for this purpose.

However, in recent years, it has been difficult to achieve simultaneous multilayer coating, high speed coating, and thin layer coating.

(Objective of the Invention) The first object of the present invention is to eliminate such troubles that occur at the start of coating, prevent thick coating of the coating near the coating start line, and prevent unnecessary increase in drying load. Another object of the present invention is to provide a method for producing a photosensitive material that enables faster coating and thinner layers.

A first object of the present invention is to provide a method for producing a photographic material without the risk of coating unevenness.

(Structure of the Invention) These objects of the present invention are to provide a method for producing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support. When applying the colloid layer, at least the bottom layer contains a hydrophilic colloid and a sulfonic acid group or sulfate ester group in the side chain.
It has a carmenic acid group, and its intrinsic viscosity ([w]o, t
NactJ.

It has been found that 0C) can be achieved by containing a polymer compound of O, a to i, z and applying it at a rate ranging from ram/min to 300 ml/min.

In the present invention, at least one sulfonic acid group in the side chain,
Examples of polymeric compounds having sulfuric acid ester groups and carboxylic acid groups include vinylbenzenesulfonic acid, co-acrylamide-comethylpropanesulfonic acid, acrylic acid, methacrylic acid, maleic acid, halfester of maleic acid, and vinylbenzene carboxylic acid. -8O3M1 in the side chain
-O803M1-COOM (M is a hydrogen atom, ammonium, alkali metal) or the like means a polymerization of monomers having groups such as -O803M1-COOM (M is a hydrogen atom, ammonium, or an alkali metal) or a copolymer of these monomers with other monomers copolymerizable with them.

Particularly preferred comonomers for forming the copolymer are monomers having a sulfonic acid group, sulfuric acid ester group, or carboxylic acid group in the side chain of the present invention, such as vinylbenzenesulfonic acid (Na salt). Acrylic acid (Na salt),
λ-acrylamide-comethylpronognesulfoic acid (Nap)-methacrylic acid (Na salt). The copolymerization ratio in this case is not particularly limited.

When forming a copolymer with a monomer other than the monomer forming the polymeric substance of the present invention, examples of comonomers include butyl acrylate, butyl methacrylate, styrene,
Examples include acrylamide, N-vinylpyrrolidone, and the like. The copolymerization ratio in the case of stiffness is not particularly limited, but the monomer of the present invention having a sulfonic acid group, sulfuric acid ester group, or carboxylic acid group in the side chain is used! It is preferable to contain more than 0 moles.

Particularly preferred among these polymers or copolymers are polyvinylbenzene sulfonate, poly(,2-acrylamido-comethylprononesulfonate), and polyacrylate.

These polymers or copolymers C used in the present invention are as follows:
Polymer) is structurally the same as conventionally known polymers, but its characteristic feature is that the intrinsic viscosity [η] of the polymer is O6u~/,j(0,/N N
aαJ o ℃).

Especially preferably [η]=o, j-/, J.

Generally, when a water-soluble polymer is added to a photographic coating solution for the purpose of thickening, a polymer with a high average molecular weight is used, which has a stronger thickening effect and allows a target viscosity to be obtained with a small amount of use. For this reason, the average molecular weight usually exceeds 700,000-/DO in many cases. In this case, the limiting viscosity [η] is generally 2
．． 0 to 80.0 (0./N NaQ!jo°C
). However, as a result of extensive research, it was surprisingly found that as the average molecular weight of the water-soluble thickening polymer decreases, the coating speed at which coating unevenness occurs increases.

This phenomenon occurs when the intrinsic viscosity [η] of the polymer is 1. j(0°/N
It was found that this becomes noticeable from NaαJ o °C or lower, and as the value further decreases, high-speed coating can be stably achieved. However, the intrinsic viscosity is extremely low [”η]==O, u(
When the amount was less than 0,/N NaCIJooC), the thickening effect of the polymer was significantly weakened, making it impossible to obtain the target viscosity and making it impossible to apply.

An example of the method for measuring the limiting viscosity in the present invention is shown below.

Viscometer: Utsuberohde viscometer C Rigosha automatic viscometer Ty
pe VMC-or, 2) Temperature: 30 IC Solvent: 0. /NNacI! Concentration: 14.0.7j, Oobu, 0. j scratch(wt
/vol) The relative viscosity, specific viscosity, and reduced viscosity of the polymer solution at each of the above concentrations are determined, and the limiting viscosity is determined from the intercept when the plot of the reduced viscosity and the polymer solution concentration is arranged from # degree to θ.

These polymers used in the present invention can be easily synthesized by conventional methods. The intrinsic viscosity can be freely controlled by adjusting the amount of initiator, concentration of 7mer, type of solvent, temperature, etc.

For example, as the amount of polymerization initiator increases, the intrinsic viscosity tends to decrease; as the monomer concentration increases, the intrinsic viscosity tends to increase; and as the reaction temperature increases, the intrinsic viscosity tends to decrease. There is.

Therefore, by appropriately controlling these factors, a polymer having the desired intrinsic viscosity can be obtained.

A synthesis example is shown below.

[Synthesis example]

62 with thermometer, stirrer, cooling pipe sN2 introduction pipe
! l Tulo flask, sodium styrene sulfonate (
Add 1,200 ml of distilled water and stir to dissolve. After dissolution tN-H
Add Cl// in solution PH.

Make ovcv@. Raise the temperature to bring the internal temperature to too high, then add the initiator potassium persulfate and 7309 to distilled water.
Add the solution dissolved in nl and add ro0c while introducing N2.
The mixture was stirred for u hours and further for 00C1 hour.

The pH of the polymerization solution was 2.6. /N-NaOH in PH7. OK prepared.

The polymer had [η]=o, rj.

The coating solution to which the polymer used in the present invention is added may be added to all coating solutions, but in the case of simultaneous multilayer coating, it is necessary to add it to at least the bottom 1i1 coating solution.

In the present invention, the addition t of such polymer is an amount that can control the required viscosity of each coating solution, but generally it is 0.0/~80.0 with respect to the hydrophilic colloid (solid).
Weight range.

The gelatin used as the hydrophilic colloid in the present invention includes lime-treated gelatin, acid-treated gelatin, and Bull gelatin.
, Soc, Sci, Phot, Japan.

Enzyme-treated gelatin and other gelatin derivatives such as those described in IqA&) may also be used.

Examples of the photographic coating layer using gelatin as a binder in the present invention include a silver halide emulsion layer, a surface protective layer, a filter layer, an intermediate layer, an antihalation 111 static prevention layer, an undercoat layer, and a backing layer. Can be done.

Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

Silver iodobromide containing silver iodide in a molar range of IO to 20, and silver chlorobromide containing silver bromide in a molar range of IO to 80 molar are preferred. There are no limitations on the crystal form, cap structure, grain size, grain size distribution, etc. of the silver halide grains. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or l-particulate. The grains may be tabular grains having a thickness of 0.2 microns or less, a diameter of at least 0.6 microns, and an average aspect ratio of 5 or more, as described in Research Disclosure Coco J311.

The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding, and various crystal structures may be used. It may also consist of a mixture of particles in crystalline form. Further, it may be one in which the a-image is mainly formed on the surface of the particle, or one in which it is formed internally.

The grain size of the silver halide may be fine grains of 0.17 microns or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. .

These silver halide grains can be produced by known methods commonly used in the art.

The silver halide emulsion is subjected to conventional chemical sensitization, that is,
Sensitization can be achieved by sulfur sensitization, noble metal sensitization, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. As dyes that can be advantageously used in the present invention, methine dyes and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol can be used in combination of ah, iWi, or more.

In the present invention, the poorly water-soluble photographic additives include, for example, oil-soluble color couplers, antioxidants used to prevent color fogging or color mixing, and fading prevention agents (such as alkylhydroquinones, alkylphenols, chromans, etc.). , coumarons, l, hardeners, oil-soluble filter dyes, oil-soluble ultraviolet absorbers, DIR compounds, DIR hydroquinones, colorless DIR compounds, etc.), developers, dye developers, DrlR compounds, DI) R coupler, etc. can be used.

Among the oil-soluble color couplers, benzoylacetanilide-based, pivaloylacetanilide-based, pyrazolone-based, cyanoacetyl-based, phenol-based, and naphthol-based compounds can be used.

Examples of high-boiling organic solvents used in the present invention include phthalic acid alkyl ester C dibutyl phthalate, dioctyl phthalate, etc., phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate)
, citric acid esters (eg, acetyl tributyl citrate), benzoic acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl laurylamide), and the like.

In addition, the hydrophilic colloid coating solution used in the present invention may contain stabilizers, hardeners, dyes, matting agents, photosensitive silver halide particles, other surfactants, polymer latex, fluorescent brighteners, and others. Various additives useful in photographic materials can be included.

Regarding the above additives, product licensing
Index Magazine Vol. 92, pp. 807-80 (Li 7/year/
J Month), Research Disclosure/jt/tλ
(January 2007), 176173 (January 2017)
(Kozuki).

The hydrophilic organic colloid coating layer containing gelatin containing the polymer of the present invention may contain a silver halide emulsion or may contain no silver halide emulsion at all.

As the coating method in the present invention, both single-layer and simultaneous multi-layer coating methods are effective; however, when performing simultaneous multi-layer coating, the polymer of the present invention may be added to all coating solutions; When added to at least the bottom layer, K significantly increases the coating speed, allowing coating to be performed in a range of 7 minutes per ROM to 1 minute per 300 ml.

When applying simultaneous multilayer coating, US Patent Co., 7t/.

Hopper application described in μ17, same J! It is possible to follow the curtain coating method described in Or, ri≠7, and other coating methods as described in Research Disclosure/76 μg (Li 7, December 2013).

〔Example〕

Comparative examples and examples are listed below in order to make the effects of the present invention even clearer.

The viscosity was measured at 300C in the case of the intrinsic viscosity, and at μo°C in the case of the coating liquid.

Comparative example 1 One thickness! By varying the running speed of a web made of polyethylene-coated baryta paper with a width of Oμ and a width of JOtm, the coating solutions shown in Table 7 were coated in two layers using a bead coating method, with Solution I in the lower layer and Solution II in the upper layer. The minimum amount of coating liquid that can be applied simultaneously and uniformly applied across the entire width of the web at the start of coating is 6! When the running speed of the web was determined to be σ/yn2, it was found to be r Om/min. In addition, a 60 cm long induction zone occurred, and the coating film near the coating start line was compared to the normal area! ! The regret was also thick.

Table 1 Note) [μ] = Intrinsic viscosity (0, /N NaαJO°C) Example-7 Comparative example Sodium〕C1〕=/,
0 (o, /N NaQ!! Jo °C) and the liquids ① and ② were prepared to a predetermined viscosity. Other than that, two-layer simultaneous coating was carried out in exactly the same manner as in Comparative Example 1, and at the start of coating, the minimum coating liquid 1 that could achieve uniform coating over the entire width of the web was t, tCc/m2. When we calculated the running speed of a web like this, we found that tp t
m/min. In addition, no induction zone was observed or thick coating near the coating start line was observed.

EXAMPLE A photographic support was prepared by coating a gelatin subbing layer on a cellulose triacetate film (1 thickness: 33 μm). The coating liquid shown in Table 1 was applied onto this support using the slide bead method.
3rd simultaneous coating was performed at a coating speed of rOmZ. However, as a thickener, the intrinsic viscosity of poly[sodium p-styrene sulfonate] [η] (o, /N Naα3o0c
), [η]='o, 4tt; ["η]=o, q3,
[η]=/, Ge, [η]=2.7, [η)=7. o, and by changing the amount of thickener added so that the viscosity of liquids I, II, and III becomes OCP.
II. Solution (■) was prepared. In addition, the coating amount of liquids ■, ■, and ■ is 20Cc/m2.20CC/m2, /jC, respectively.
C/m2.

Table 2 Application properties were evaluated by observing the dried surface with the naked eye using transmitted light. The results are shown in Table 3.

Table 3 As is clear from Table 3, [η] of the thickener poly[sodium p-styrene sulfonate] is o, 4Aj80. ?
No uneven coating was observed when using the coatings of J,/, and the like.

On the other hand, when a material with [η] of 2.7.7.0 was used, the occurrence of unevenness in the tube fabric was clearly observed.

Example 3 (1; Preparation of silver halide emulsion for upper emulsion layer Formation of silver iodobromide (silver iodide) spherical grains in the presence of ammonia by double jet method with average grain size /
, θμ), chlorauric acid salt and thiosulfuric acid salt +7 μm).

After chemical sensitization, anhydro-!
,! '-dichloro-2-ethyl-3.3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt, potassium iodide, weight average molecular 'Ir (MW
) to, ooo polyacrylamide, antifoggant,
A coating solution for the upper emulsion layer was prepared by adding coating aids and the like.

The specific gravity of the coating liquid is /, /70. Silver/gelatin weight ratio Bt
, 3o, the weight ratio of polyacrylamide/gelatin is o,
It was i, t.

'21 Preparation of tabular silver halide grain emulsion Add gelatin and 301?1 potassium bromide JP to water/l, and add silver nitrate aqueous solution (j9 as silver nitrate) and potassium iodide in a container kept at 6 o''C while stirring. A potassium bromide aqueous solution containing 0./!f was added over 7 minutes using the double jet method.Aqueous silver nitrate solution (as silver nitrate/μ!9) and potassium bromide iodide, co?
An aqueous solution of potassium bromide containing was added using a double jet method.

At this time, the addition flow rate was accelerated so that the flow rate at the end of addition became the same as at the start of addition.

After the addition was completed, soluble salts were removed by a sedimentation method at 3!0C, and the temperature was raised to .mu.o.degree. C., and 33t of gelatin was additionally twisted to adjust the pH to 6.7. The resulting emulsion had tabular grains with a projected area of %-b of 80.91 .mu.m and an average thickness of .theta./3 r.mu.m, and a silver iodide content of 3 molar width. This emulsion was chemically sensitized using a combination of gold and sulfur sensitization to obtain an emulsion of tabular silver iodobromide grains.

Polyacrylamide and poly(sodium p-styrene sulfonate ξ) with [η]=/0 were added to the resulting emulsion to prepare a coating solution for a layer containing tabular silver halide grains.

What is the specific gravity of the coating liquid? ,/J! , silver/gelatin weight ratio is /,
! 01 Polyacrylamide/gelatin weight ratio is θ, l!
Met. Poly[sodium p-styrene sulfonate]
The amount added was 7 parts by weight relative to gelatin.

(3) Ready-made gelatin and poly[sodium p-styrene sulfonate] for surface protective layer coating solution
([μ]=/, 0), polymethyl methacrylate particles (average particle size J, 4 μ) as a matting agent, saponin, JP-A-Shoj! -203≠Compound example-7 in the specification of No. 33
An 80% aqueous gelatin solution was prepared consisting of the 12≠-dichloro-3-humano(roxyS-)riazine salt described as This was used as a coating solution for a surface protective layer.

(4) Preparation of photographic material An emulsion layer containing tabular silver halide grains, an upper emulsion layer and a surface protective layer are formed in this order on a subbed polyethylene terephthalate film support having a thickness of 180 μm.
It was coated and dried by a coextrusion coating method. At this time, the viscosity of the coating solution is <t o cp, and the coating amount is OCX:, /m2.2 DCC/m2, / j
cX:, 7m2" Chb, m cloth speed ih om7 minutes.

A photographic material was prepared by applying the above three layers in the same order to the other side of the support. The coating properties were good on both sides.

Example -μ On a cellulose nine triacetate film support with a base coat,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

Composition of photosensitive layer C) The coating amount is the amount expressed in units of 97 m2 of silver for silver halide and colloidal silver, and the amount expressed in units of tim2 for couplers, additives and gelatin.
The sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation agent) Black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.2 gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・／, 3 colored coupler C-/
・・・・・・・・・・・・・・・0.01 Ultraviolet absorber UV-t ・・・・・・・・・・・・・・・・・・
...0. / Same as above U■-2・・・・・・・・・・・・
・・・・・・・・・O、Co-dispersed oil Oil −/
・・・・・・・・・・・・・・・・・・0.0/Same as above Qil-co ・・・・・・・・・・・・・・・・・・
...0.01st -r@ (intermediate layer) Fine grain silver bromide (average grain size 0.07μ)...l1.0. /J Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・0 Colored Coupler C-2・Old・Old・・・・0.02 Dispersion Oil 0il-/・Old・・・...... Old...
...0. /Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide comol ratio, average grain size 0.Jμ)
・・Silver O1μ gelatin ・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Old・・・・・・・・・Ol
Sensitizing dye... Old... Old... /, 0X80-' Sensitizing dye ■... Old...
...Old...Mountain... J, O x 80"-'sensitizing dye■
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・lX80-5 Coupler C-3・・・・・・
・・・・・・・・・・・・・・・・・・・・・o, o coupler C-μ... group... old... for use...
o, ot coupler C-t ・Old...Old...
・・・・・・・・・o, o da coupler C-2・・・・
・・・・・・・・・・・・・Ih・・o, o3 dispersion oil 0th −/ ・Ih・・・・・1 group・0. O.J.
Same as above Oil-J... Group... Old...
...0.0/Coder layer C second red-sensitive emulsion layer) Silver iodobromide emulsion C silver iodide! Molar size, average particle size 0. Jμ)・・・・・・・・・・・・・・・
・・・・・・0.7 Sensitizing dye I ・・・・・・・・・・・・
・・・・・・・・・Old・・・・River/X/0”-'
Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
Ih...lX80-'Increase g color int ・Use・
・・Old・Old・old・・・／
-・0.2≠Coupler C-μ・・・・・・・Old Old Old・・・Old・・o, −μ force i Ra-C−r ・Old...
...dan...old...old...o, op caffler-C-2
・・・・・・・Old・・Gan・・Ih・・o, o≠Dispersed oil 0il−/・・・・・・・・Ih・Gan・・
0. /J-fnOil -J ・・・・・・Ih
...Old...0.02nd! Layer (Third red-sensitive emulsion #) Silver iodobromide emulsion (silver iodide 80 mol width, average grain size o, 7μ)
・・Silver／、0 Seratin・Old・・・For the group・・・・・・
...Ih.../,.

Sensitizing dye processing ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・／ X / 0-'m color sense in
・Old...Ih...Old...J
X / 0-' s-enhancing dye m・Ih・group・・・Ih
......lX80-5 force i ra C-6...
・Old...Old・l1...Old...o, or i-ra-C-7
・Old・・・・Dan・・・・・・Old Old・Old・・o, 1 dispersion oil 0il−/・・Dan・・Old・・・Dan・
0.01 Same as above O eye-2・・・・・・・・・・Ih・・
・・・Oth layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／、0 compound Cp d -A・・1 group・・old・old・・
・0.03 dispersion oil Oil -/ ・Old...
・・・・・・・・・・・・o, or 71st-(first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide μmolar ratio, average grain size 0.Jμ)...・・・・・・Old・Old・
・0. JO sensitizing dye■ ・・・・・・・・・・・・・・・
...Old...River...j X/o-'sensitizing dye■...
・o, 3xio-'sensitizing dye■ ・・・・・・・・・・
・・・・・・・・・・・・・・・Old...Ko xio"-'
Gelatin ・・・・・・・・・・・・ Old・・・・・・
Old・・・・・・・・・・・・・・0 Coupler C-ta・Old−・Old−・・−−−−−−−・・−・−・・・−o
, Kokara-C-!・Old・・・・・・Old・Kawa・Old・0.03 Coupler C-t・・・・・・・
...Dan...Old...0. OJ dispersion oil 0il-/ ・・・・・・・・・・・・・・・・Ih
...o,! Rth layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! molar ratio, average grain size O0!μ)... Old... Old...
・o,p sensitizing dye■ ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・! ×80-' Sensitizing dye■ ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・CoX/0-'sensitizing dye■ ・・・・
・・・・・・・・・・・・・・・・・・・・・0. JXl
o"-'Coupler C-9... Old...
Old...old...0.21 coupler C-/...
...Used old group...0.03fyl'5-C
-80・・・・・・・・・・・・Use・o,
ol! Coupler C-t・・・・・・・・・Use・
・・・・・・・・・・・・0.0/Dispersion oil Oil −/
・・・・・・Old・・・・・・・・・・・・θ
, -9th r @ (No. 1 green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide grain size, average grain size 0.7 μ) ・・・・・・・・・・・・・・・ Silver o , rj gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・1.
0 Sensitizing dye■・・・・・・・・・・・・・・・・
...J,! x/(f4 sensitizing dye■...
・・・・・・・・・・・・・・・・・・／、μX8
0”-4 force P5-C-// ・・・・・・Old・Mark・
...Dan 0.0/Coupler C-/Co...
・・Old・・・・Old・・・・0.03 Coupler C-
/J ・・・・・・・・・・・・・・・・・・・・・
・・・O, CoO coupler C-/ ・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.0.2 coupler c-it ・Mountain・・・・・・・・・・Dan・・・・
...0.02 Dispersion oil Oil -/ ...
・・Old・・・・・・・・・O,,2O Dispersion oil O
il-J ・・・・・・・・・・・・・・・・・・
・・・o, oj io io (yellow filter single layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／、J Yellow colloidal silver ・・・・・・・・・・・・・・・・・・・・・
......0.0 as compound Cpd-B...
・・・・・・・・・・・・・・・・・・・・・・・・0
．． / Dispersion oil 0il-i・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.3 1st i M (
@ / Blue-sensitive emulsion #) Monodisperse silver iodobromide emulsion (silver iodide μmole, average grain size 0.3
μ)・・・・・・・・・・・・・・・・・・ Silver O
,4L gelatin ・・・・・・・・・・・・－・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・／, 0
Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・-X80-'Coupler c-iu
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・O, Ta coupler C-t ・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 0.07 Dispersion oil 0il-/・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.2 1st-# (Blue-sensitive emulsion layer) Silver iodobromide (Silver iodide lO molten, average grain size 1.tμ)・・・・・・・・・・・・・・・・・・
...Silver 0. Yo gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・O0≦sensitizing dye■ ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・1X80' Coupler C-/l・・・・・・・・・・・・・・・・・・・・・・
......0. -! Dispersion oil 0il-/・・
・・・・・・・・・・・・・・・・・・0.07 7th
3 layers (1st protective layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. Ultraviolet absorber UV-/・・・・・・・・・・・・・・・
・・・・・・0.7M upper UV-2・・・・・・・・・
・・・・・・・・・・・・O, Co-dispersion oil 0il-
/ ・・・・・・・・・・・・・・・・・・・l),
01 Same as above 0il-2・・・・・・・・・・・・・・・
...0.01 1st ≠ layer (protective layer) Fine grain silver bromide (average grain size 0407μ) ......
・・・0.2 gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・O,
<at polymethyl methacrylate particles (diameter 1.!μ)・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. Co-hardening agent) 1-, / ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・O, U formaldehyde gas venter 8-/ ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・O0j Formaldehyde Kabe/Jar S-J ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・O0! In each layer, in addition to the above components, poly[sodium p-styrene sulfonate] [η]=1. O was added to give the viscosity shown in Table 1, and KJ% surfactant (sodium dodecylbenzenesulfonate) was added as a coating aid. When a photosensitive material was prepared by repeating multilayer simultaneous coating and drying μ times using the coating liquids prepared as described above in the combinations shown in Table μ, the coated surface condition was good.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below: Table μ z / y = 7 / j (weight ratio) U■-2 Oi! -/ Tricresyl phosphate Oil- Dibutyl cophthalate Oil -J His(2-ethylhersyl) phthalate α -J -J -r H3C-C-CI(3 H2 C(CH3)3 C-I C-ta α m=2! m'=2! moJowt, about koo, oo.

C-/J α C-/μ Cpd-AoH pa -B H H RIg dye Extra-dye dye and sensitizing dye■ (CH2)3SO3Na Sensitizing dye■ Sensitizing dye■ 2H5 Sensitizing dye■ Sensitizing dye■ Sensitizing Dye ■ -t C) 12=CH-302-CH2-CONH-CH2C
H2=CH5O2-CH2C0NH-CH2S-/S-
2 Using a tungsten light source for this photographic element and adjusting the color temperature to 4#000K with a filter, the ICMS exposure was set to 3.
After that, development processing was performed at 3r 0c according to the following processing steps. As a result of development, it was confirmed that it exhibited good photographic properties.

Color development 3 minutes/! Bleach for 6 minutes and 30 seconds Wash with water
λ min 80 seconds Fixing μ min 20 seconds Washing 3 min/! Stable for 1 min oj seconds The composition of the treatment liquid used in each process was as follows.

Color developer diethylenetriaminepentaacetic acid /, 0fl-hydroxyethylidene-7゜l-diphosphonic acid J, Of sodium sulfite μ, ot Potassium carbonate
3o, op potassium bromide
1. noon? potassium iodide
/, J~hydroxylamine sulfate [;, 4'?
≠-(N-ethyl-N-β- and droxyethylamine)-2 monomethylaniline sulfate μ,! ? Add water /, 01 pH 80.0 Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt ioo, or ethylenediaminetetraacetic acid disodium salt io, or ammonium bromide /60.0? Ammonium nitrate 80.0? add water
/, DipH6,0 Fixer ethylenediaminetetraacetic acid disodium salt /, Of sodium sulfite μ, 09 Ammonium thiosulfate aqueous solution (7 o’clock) tyz, o Sodium bisulfite da, But add water
/, 04pHJ, j Stabilized liquid formalin (a04) ko, 0rt
l, if IJ oxyethylene-p-monononylphenyl ether (average degree of polymerization 80) 0.3 is added with water /, O6 Example-! A color photosensitive material was prepared by coating the following photosensitive layers consisting of the first layer to the seventh layer on a paper support fully laminated on both sides with polyethylene. The polyethylene on the side coated with the first layer contains titanium dioxide and traces of ultramarine blue.

(Light Ii! Configuration) Each component (corresponding numbers indicate the coating amount expressed in units of 97 FF12, and for silver halide, the coating amount is expressed in terms of silver.

1st layer (blue sensitive layer) Silver chlorobromide emulsion (80 moles of silver bromide)
Silver 0. JO yellow color (it)・・・・・・・・・
・・・・・・・・・・・・0.70 Same as above solvent (TNP)
・・・・・・・・・・・・・・・・・・・・・・・・0
．． /! Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／, 20th 2nd
1 @ (Intermediate r4p) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.90 Ge-t-octylhydroquinone・・・0.0! l1iFJ
Up? l [(DBP)...Old...Old use...
0.80 3rd layer (green r-) Silver chlorobromide emulsion ... group ... old river ... old ... silver o
, 4Aj (brominating agent 70 moles 4) Magenta coupler (side dish)・・・・・・・・・・・・・・・
...0.31fil top solvent (TOP) ...
...1 Old... Old... o, up anti-fading agent (
+3i dinnerμ)・Old・・・・・・0.0180.80 Gelatin・・・・・・・・・・・・1 Old・・・・・・・・・
・Old.../, 00th layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (appetizer! Hari/嘗7) ・・・・・・・・・・・・0.0 Otsu 80.2680 .2
JSI Top Solvent (TNP)・・・・・・・・・Group・・Old・Seal・・・・・／、Co□Ceratin・Old・Dan・・Old・Dan・・Old・・・・・・・・・・・River.../, 30th! Layer C redness~) Silver chlorobromide emulsion (y% silver chloride 7 cyan coupler c rump/yellowness)......θ.
, 280. Cocoupler solvent (TNP/DBP)-”・・・・・・--0.8080
．． 20 Gelatin...1 Old...Old...River...
Old...Old...o. Layer (UV-absorbing intermediate layer) Ultraviolet absorber (Aoj/Yu-t/Buttocks 7) ・・・・・・・・・・・・0.0bu80. Ko! 80. Ko! Draining solvent (DBP) ・・・・・・・・・・・・・・・
...Dan...0.20 gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、! No. 711i (Protective layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1. ! Here, D.B.
P represents dibutyl phthalate, TOP#i) su(n-octyl phosphate), TNPij) su(n-nonyl phosphate), and compounds (+7) to (tatami) are shown below by chemical structural formulas.

(Nursing) α (÷3) H H (Chi 4t) (bones C Sobu) c buttocks 7) C4He(t) (Nyi t) C blue) The following color range was used as a spectral sensitizer in each emulsion layer.

Blue sensitive emulsion II! :≠-(j-chloro-2-[!-chloro3C≠-sulfonatobutyl) Benzothiazoline-2-indenemethylcou-3-benzothiazolio)butanesulfonate triethylammonium salt (coX80' mol per mol of silver halide) Green Sensitive emulsion layer; J,! '-G(r-sulfopropyl)
-z,z'-diphenyl-2-ethyloxacarbocyanine sodium salt C #) per mole of silver halide,! X80-'mol) Red-sensitive emulsion layer: J,! '-G(r-sulfopropyl)
-Termethyl-thiadicarbocyanine sodium salt (co, ! x 80 moles per mole of silver halide) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; 5OsK 5OaK Also, first layer ~
The seventh layer contains poly[sodium p-styrene sulfonate] ([η] = 0.5) with a viscosity shown in Table 3.
) was added.

Multi-layer simultaneous coating and drying were repeated twice using the coating solution prepared as described above in the combinations shown in the table @j to form a photosensitive material (
Sample 1O7) was prepared.

In the next step, add poly[sodium p-styrene sulfonate].
Samples were prepared in exactly the same manner except that η] = λ, j. Sample 80/ had good coating properties, but sample 70.7 had uneven coating. These samples were subjected to gradation exposure for sensitometry using an enlarger (Fuji Color Head T09, manufactured by FF Photo Film Co., Ltd.), and then subjected to a printing process using the following processing steps. Sample 801
Sample No. 1 showed good photographic properties.

Processing process Temperature Time Developer 33
°C 3, z minute bleach-fix solution 33 °C 1,3 minutes water washing λt~3t0c 3. o component developer nitrilotriic acid ff11jNa 2. Of benzyl alcohol /! dDiethylene glycol 80ml1Na2SO3a,
o? KBr O,! t-hydroxylamine E#e salt 3. oyhiro-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate-", 05PNa2
CO3 (/water salt) 30? Add water
(pH/θ, /) bleach-fix ammonium thiosulfate (rpwt4) itop N
a 2503/! S
'NH,i[Fe(EDTA):l r
r9EDTA @, 2Na
u? Adding water to make it liter (pH increase) Patent applicant: Fuji Photo Film Co., Ltd. 1, Incident display
Showa t2 long-awaited tirr'y No. 2, name of invention
Manufacturing method of silver halide photographic light-sensitive material 3, relationship with the amendment person case Patent applicant contact information 〒80
6 2-26-30-4, Nishi-Azabu, Toshi-ku, Tokyo, Subject of the amendment: ``Detailed explanation of the invention'' column 5 of the specification, Contents of the amendment The description of the ``Detailed explanation of the invention'' section of the specification is as follows. Correct the standard.

1) No. 1! page 80th line ``J that is difficult to apply “Even application became difficult.” and correct it.

2) Number 73 on page 73 "Acryloamide" "Acrylamide" and correct it.

3) Page 1r≠line Before “bead application” "slide" Insert.

4) Replace the second page with a separate sheet.

Claims (1)

[Scope of Claims] A method for producing a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, during coating of the silver halide emulsion layer or other hydrophilic colloid layer. has a hydrophilic colloid and a sulfonic acid group, sulfuric acid ester group, or carboxylic acid group in the side chain in at least the bottom layer of
1. A method for producing a silver halide photographic light-sensitive material, comprising the steps of: containing a polymer compound having a molecular weight of 0.4 to 1.5 and coating the material at a rate of 80 m/min to 300 m/min.