JPS63218950A - Silver halide photographic sensitive material containing novel surfactant - Google Patents

Abstract

PURPOSE:To improve the coatability of hydrophilic colloid on a base, film properties and photographic characteristics by incorporating a specific surfactant into hydrophilic colloidal layers. CONSTITUTION:This photosensitive material has at least one hydrophilic colloidal layers on the base. At least one layer of the hydrophilic colloidal layers contain the surfactant having a polyoxazoline chain and hydrocarbon group consisting of >=4C at the terminal of the polyoxazoline chain. The photographic sensitive material which has the high-speed coatability of the hydrophilic colloid contg. an emulsion and polymer latex, is improved in the properties of the coated film formed thereof and has the sufficiently assured photographic characteristics is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material containing a novel surfactant.

[Background of the invention]

Generally, a photographic light-sensitive material has a plurality of photographic constituent layers containing hydrophilic colloids provided on a support. These photographic constituent layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer, and a surface protective layer. Therefore, when manufacturing photographic materials, hydrophilic layers such as gelatin are often added to the support. Multiple different photographic constituent layers containing sexual colloids may be coated in layers simultaneously, and in this case, the coating solution is coated in a thin layer uniformly and at high speed without causing coating failures such as repelling. required to do so. In order to satisfy this requirement, surfactants have conventionally been added to coating solutions.
969, Japanese Patent Application Laid-open No. 51-3219, and Belgian Patent No. 708347, Belgian Patent No. 723690, etc. The surfactant is not only used as a coating aid, but also as an organic solvent for hydrophobic photographic additives such as couplers, ultraviolet absorbers, and fluorescent brighteners, or for hydrophobic synthetic polymers such as acrylic esters ( It is also used as a dispersant when applying a hydrophilic colloid liquid containing a dispersion of polymer latex (hereinafter referred to as polymer latex).

However, surfactants used in photographic materials require photographic properties such as photographic sensitivity, fog, and gradation, and rapid processing properties such as speed of development (i.e., good wetting on the film surface). However, many of the surfactants conventionally used as coating aids for hydrophilic colloid liquids, etc. have a negative effect on wettability. Moreover, as a dispersant for photographic additives, it has a high viscosity and generates a lot of bubbles, cissing, etc. (which is not preferable).

Particularly when adding a polymer latex to a hydrophilic colloid layer to improve the physical properties of the film, e.g.
．． As described in the specification of No. 386, Japanese Patent Publication No. 57-9051, and Japanese Patent Application Laid-open No. 57-200031, etc.
It is necessary to consider the scratch strength, dimensional stability, flexibility, etc. of the hydrophilic colloid layer, and in this case, the polymer latex tends to aggregate in gelatin, which always affects the dispersion stability and eventually the spreadability. There were concerns and it was not completely satisfactory. Therefore, when a surfactant is added to a photographic coating solution, uniform coating of the photographic coating solution cannot be obtained, and development unevenness occurs during development, and there has been a desire to improve this problem.

[Purpose of the invention]

The present invention has been made to solve the above-mentioned problems, and has excellent coating properties of a hydrophilic colloid to a support, and even if the colloid contains polymer latex, it can be uniformly coated without agglomeration. The object of the present invention is to provide a silver halide photographic material which can be dispersed to improve the physical properties of the film and which has excellent photographic properties such as sensitivity and fog. In particular, it is an object of the present invention to provide a silver halide photographic material with good halftone dot quality in a photosensitive material for printing.

[Structure and operation of the invention]

The present invention provides a silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer on a support, in which at least one of the hydrophilic colloid layers has a polyoxazoline chain and a carbon group at the end of the polyoxazoline chain. The above object could be achieved by a silver halide photographic material containing a surfactant having the above-mentioned hydrocarbon group.

In the present invention, at least one of the hydrophilic colloid layers contains a surfactant having a polyoxazoline chain and a hydrocarbon group having 4 or more carbon atoms at the end of the polyoxazoline chain. The polyoxazoline chain is a bonded chain obtained by ring-opening polymerization of oxazoline.

The surfactant is not particularly limited as long as it has the above structure, but when carrying out the present invention, it has the following general formula (1
) are preferably used.

General formula (I) R' −+ NClllCH2 ÷ "R1 where R, R'
, R' is a group having an alkyl group, alkenyl group, or aryl group having 1 to 22 carbon atoms, and either R' or R'' has an alkyl group, alkenyl group, or aryl group having 4 or more carbon atoms. Among these substituents, those substituted with fluorine are also included in the present invention.

Further, n represents an integer of 1 to 50.

Further, when carrying out the present invention, among the above general formulas (I), those represented by the following general formulas (n) and (II[) are more preferable.

General formula (n) C;0 General formula (III) S Rt +NCHzCHz→-NH-C-CHzOCOR
yC=OR& In the above general formulas (1) and (II), Rt, Rt and R1 represent any substituent of an alkyl group, alkenyl group or aryl group having 1 to 22 carbon atoms,
R2, R1+ R5 and R6 represent the above-mentioned substituents and also represent a hydrogen atom. However, R,, R, do not become hydrogen atoms at the same time.

Further, the hydrogen atoms bonded to the carbon atoms of each substituent represented by R3 to R7 include those substituted with fluorine atoms.

Examples of the surfactant expressed by the above general formula are shown below.
The present invention is not limited to the following compounds.

(1) (n) CJ9NH+ CIhCEIz
N+r-CH3CI.

(2) (n)CsH,7NH+CHIC)1.
N+r-CH3I CriO CH2 (3) (n)Cs■+JH+CHzCHJ+r
-CH3C;0 CH.

(4) (n)C+ &Hff3NH+ CHzCH
J +T-CHs0M0 Hs (5)' (n)CsH+JH-(-CHzGH
zN-+T-CH3 blind C=0 CH3 (6) (It)C+zHzsNH-(-CHz
CHJ +r-CH3■ CI.

(7) (n)CJ+sNH-(-CHzCHJ+
T-CHsC=0 Js (8) (n)C+zHzsNH+CHzCHz
N-)-v-CHsC;0 Js CH3C-0 Police CI.

(10) ((n)CsH+t)J+CHzCH
zN−+T−CHsC=0 1h CH.

■ CH3C=0 Hs CH3C=0 ■ Hs CH.

C1l+I C=0 Js (14) (n)CaF+? NH+CHtCH
! N+-T-CH2CH3 (15) (n)CaF+JH+CHzCHz
N-)-r-CH:1■zns (16) (n)CsF l? NH+CH
zCHtN +r-CH3C! 0 ■ CH3 C=0 HI C=0 ■ C,, H9 The above surfactant according to the present invention can be used, for example, in “ring-opening polymerization (1
), (n) J Takeo Saegusa (Kagaku Doujin, 1971)
and [Block and Graft Polymerization
iza-tion) by J.R.J., Ceresa (Jalm
It can be easily synthesized by the method described in Wily & Sows, 1973).

The surfactant of the present invention can be added in an amount of 0.01 to 50 g per 1 kg of various photographic coating solutions, but usually 0.0 g to 50 g per kg of various photographic coating solutions.
5 to 5 g is preferred. As for the addition method, it is preferable to add the compound by dissolving it in water, methanol, or other hydrophilic solvent.

The surfactant of the present invention is used as a coating aid in the coating solution of any of the hydrophilic colloid layers, such as the undercoat layer, intermediate layer, photosensitive layer, and surface protective layer, which are photographic constituent layers constituting the silver halide photographic light-sensitive material. The hydrophilic colloid layer may be a photosensitive layer or a non-photosensitive layer.

The surfactant of the present invention is suitable as a dispersant for incorporating lipophilic substances such as couplers, alkylhydroquinones, ultraviolet absorbers, and sensitizing dyes into photographic materials.

The lipophilic substance can be used directly as a coating solution by finely and stably dispersing a solution dissolved in a poorly water-soluble organic solvent with a high boiling point in a hydrophilic colloid aqueous solution in the presence of the surfactant of the present invention, or by directly using the solution as a coating solution. Furthermore, it can be used by being added to coating solutions such as photographic emulsions.

Even when the surfactant of the present invention is added to a photographic emulsion in a large amount, there is no risk of inhibiting photographic properties (or in combination with other anionic, cationic, nonionic, or amphoteric type surfactants). You can also.

In this case, the surfactant can be optionally added to the plurality of hydrophilic colloid layers, whether in the same layer or in different layers. Other surfactants that can be used in combination include, for example, those described in Ryohei Oda and Hiroshi Teramura, Synthesis of Surfactants and Their Applications (Maki Shoten 1964 edition).

The surfactants of the present invention can be preferably used in hydrophilic colloids containing polymer latexes. Polymer latex can be easily produced by redispersing a polymer obtained by emulsion polymerization, solution polymerization, or bulk polymerization, and among these polymerization methods, emulsion polymerization is preferred.

In this emulsion polymerization method, the reaction temperature is 20 to 180'C1, preferably 40 to 100t', and water and
~50% by weight of a hydrophobic vinyl monomer, 0.05-5% by weight of a polymerization initiator based on the monomer, and 0.1-20% by weight of a polymerization initiator.
This can be done using % by weight emulsifier.

During this emulsion polymerization, the surfactant of the present invention can be present as a dispersion stabilizer, and the polymerization initiator, concentration, reaction temperature, reaction time, etc. can be varied widely and arbitrarily depending on the purpose. can do.

The surfactant of the present invention to be present during polymerization can be used in the entire amount added to the photographic coating solution.

Further, it is preferable to use an emulsifier in view of the stability over time of the resulting polymer latex, compatibility with hydrophilic colloids, etc.

When polymerizing the polymer latex, other anionic, cationic, amphoteric, or nonionic surfactants or emulsifiers such as water-soluble polymers can be used in place of or in combination with the surfactant of the present invention. .

Examples of polymerization initiators used in the polymerization of polymer latex include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, and 4,4'-azobis-
Sodium 4-cyanovalerate, 2,2'-azobis(2
-amidinopropane) water-soluble azo compounds such as hydrochloride salts,
Hydrogen peroxide can be used.

The molecular weight of the polymer latex in carrying out the present invention is preferably 2,000 to i, ooo, ooo, more preferably 5.000 to 500,000, and the particle size is preferably 0.01 to 1 μm, more preferably is 0.01
~0.5 μm.

The monomer used to obtain the polymer latex is not particularly limited as long as it is a polymerizable ethylenic monomer, but hydrophobic vinyl monomers are preferred. Examples of hydrophobic vinyl esters include acrylic esters,
Preferred are methacrylic acid ester, vinyl acetate, styrene, vinyl chloride, vinylidene chloride, butadiene, and the like.

The content of the polymer latex used in carrying out the present invention is preferably 80% by weight or less, more preferably 5% by weight based on the hydrophilic colloid, and the coating amount is 0.01 to 1 rrr per hydrophilic colloid layer. The amount is preferably 5.0 g, more preferably 0.1 to 1.0 g.

As the hydrophilic colloid forming the hydrophilic colloid layer in the present invention, in addition to gelatin, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as polyacrylamide, etc. can be used alone or in combination.

Water-insoluble polymers such as polyalkyl acrylates or polyalkyl methacrylates may also be dispersed in the hydrophilic colloid.

As the silver halide used in carrying out the present invention, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be arbitrarily selected and used. .

In addition, silver halide photographic emulsions include direct positive photographic emulsions that have silver halide grains whose surfaces have been fogged with light, reducing substances, noble metal salts, etc., and internal latent photographic emulsions that produce positive images by surface development. Type photographic emulsions can be used.

Silver halide emulsions that have been chemically sensitized with a sulfur compound, selenium compound, noble metal compound, etc. or spectrally sensitized with a sensitizing dye are preferably used.

The coating liquid for forming the photographic constituent layer when carrying out the present invention is as follows:
The physical properties of the coating film can be improved by inorganic hardeners such as chromium alum, chromium acetate, etc., and organic hardeners such as formaldehyde, mucochromic acid, active halogen compounds, active vinyl compounds, ethyleneimide compounds, etc. .

In addition, when carrying out the present invention, various emulsion stabilizers such as azaindene compounds and phenylmercaptotetrazole,
It can contain antifoggants, etc., and various other additives required to obtain photographic materials, such as surface-modifying detergents such as silicone, fluorine-containing compounds, and fatty acid esters, and various additives for color photographic materials. Those containing color couplers, filter dyes, dyes such as anti-irradiation dyes, plasticizers, etc. to improve photographic properties are used.

The silver halide photographic material according to the present invention includes a black-and-white silver halide photographic material (for example, a black-and-white sensitive material for X-ray, a black-and-white sensitive material for printing, etc.), a multilayer color photographic material (for example, a color reversal film, It can be applied to various photographic materials such as color negative film, color positive film, etc.).

The support of the present invention may be made of any material as long as it can support the photographic constituent layers, such as plastic films such as cellulose ester, polycarbonate, and polyethylene terephthalate, paper, or glass.

〔Example〕

The present invention will be explained below based on the following examples, but the present invention is not limited to the following examples.

Incidentally, the % display indicates weight % unless otherwise specified.

Example 1 A high-sensitivity high-contrast emulsion containing 6% gelatin and 6% silver iodobromide (silver iodide 1.5 mol%) was prepared, and 0.01 g of sodium dodecylbenzenesulfonate according to the present invention was added to this photographic emulsion. Exemplary compound (6) is added at 0.01 to 1 kg per 1 kg of emulsion.
Added as a 2% aqueous solution with varying amounts within a range of 2.5 g,
Samples with different amounts of addition were prepared as shown in Table 1 below, and some of them contained polyethyl acrylate latex 150.
g (20% solids by weight) was added. Each of these emulsions was coated on a cellulose triacetate support having an undercoat layer and dried.

By adding exemplified compound (6) as shown in Table 1,
It can be seen that the number of repellents is greatly reduced.

Furthermore, from Table 1, it can be seen that even if polymer latex is contained, the number of cissing decreases significantly as the amount of exemplary compound (6) added increases. Furthermore, even with high-sensitivity, high-contrast emulsions, there was no or very little occurrence of capri, and good photographic properties could be obtained.

Example 2 Negative photographic emulsion containing 7% gelatin and 8% silver iodobromide (silver iodide 7 mol%) per kg 0.15 g of urisaponin and polyoxyethylene nonylphenyl ether (polyoxyethylene chain length: 15 ) 0.06 g of each of compounds (4), (6) and (8) shown in Table 2 below per 1 kg of 7% gelatin aqueous solution.
A dispersion liquid containing 0g of the above was prepared.

Next, the above photographic emulsion and dispersion were simultaneously coated onto the undercoated triacetyl cellulose support using a multilayer coating method so that the dry film thicknesses became 5 μm and 1 μm, respectively, cooled and set, and then dried to form Samples 11h19-25. It was created. The surface protective layer of the obtained sample was inspected, and the number of repellency points of each coating solution was counted. Further, a commercially available phenidone-hydroquinone developer was dropped onto each sample placed horizontally, and the contact angle was measured using a contact angle measuring device (Goniometer Model 0-1 manufactured by Elma). Incidentally, the larger the contact angle value, the more likely it is that when a photographic film is immersed in a developer, the film will become wet, bubbles will adhere to it, and uneven development will occur. Therefore, the smaller the contact angle value, the better the development.

Table 2 [*Sensitivity; The reciprocal of the exposure amount at an optical density of 1.50 fog is calculated, and the relative sensitivity is shown with the blank (sample size 19) set as 100.

As is clear from Table 2 above, the sample NFL according to the present invention
Samples Nos. 20 to 22 have small contact angles, and almost no repellency is observed. On the other hand, in comparative sample N124.23 in which the anionic surfactants sodium lauryl sulfate and sodium dodecylbenzenesulfonate were added, although the number of repellents decreased, the contact angle of the developer dropped on the film surface was large, and the developer It can be seen that the wetting condition is poor and uneven development occurs. In addition, polyoxyethylene nonylphenyl ether (n
It can be seen that the comparative sample No. 25 to which 10) was added had a large number of repellents during application.

Furthermore, when each of the above samples was developed with a commercially available developer, as shown in Table 2, both sensitivity and capri of the present invention samples 11h20~
It can be seen that Sample No. 22 is comparable to Comparative Samples Nos. 23 to 25, which are conventional products, and is good.

Example 3 An antihalation layer containing a water-soluble magenta dye, gelatin, and an ethyl acrylate polymer prepared according to the following formulation (1) is pre-coated on one side of a polyethylene terephthalate support having subbing layers on both sides. . On the other hand, 4
．． 5% by weight gelatin and 19.5 mol% silver bromide, 80
3-carboxymethyl-
5-[2-(3-ethylthiazolinidene)ethylidene] rhodanine, 4-hydroxy-1,3,3a, 7-chitrazaindene, mucochloric acid, polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and N -(γ-diethylaminopropyl)-N'-phenylurea was added in the usual amount, divided into two equal parts, one part was further divided into four equal parts, and the mixture was prepared according to the following recipe (1) or 4). 200-mg per 1 kg of emulsion was added to the dispersion of ethyl acrylate polymer and mixed with thorough stirring to prepare four types of emulsions. Each of the prepared emulsions used as emulsions was coated on the side of the support opposite to the antihalation layer at a ratio of 55±5 silver per 100 cd.

Prescription (1) 3 kg of ethyl acrylate in 121 g of distilled water, 10 g of the exemplary compound (8) according to the present invention as a dispersant, 10 g of dextran sulfate, and 2 g of propylene glycol.
Add and stir at 500 to 800 rpm to emulsify. Next, 0.15 g of potassium persulfate as a polymerization initiator was added, and while stirring, the mixture was heated and maintained at 90 to 100° C. to conduct a reaction for 6 hours.

After the reaction, steam distillation was carried out for 1 hour to remove some residual monomer and obtain the desired stable aqueous dispersion of ethyl acrylate polymer. The particle size of the solid vinyl polymer in these dispersions was distributed in the range of about 0.02 to 0.1 μm, and most of the particles were spherical particles with a size of about 0.05 g.

Formulation (2) A dispersion was prepared in the same manner as in Formulation (1) using the following nanoionic surfactant (a) in place of Exemplified Compound (8).

(a) Prescription (3) The following nanionic surfactant (
A dispersion was prepared according to recipe (1) using b).

Surfactant (b) CJ+qCOO (CHzCHtOh-H
8), 1 kg each of the above surfactants (a) and (b)
A coating solution prepared by adding 100 μm to an aqueous gelatin solution was applied in the combinations shown in Table 3 below to a dry film thickness of 1 μm to form a protective layer, thereby preparing samples Nos. 26 to 33.

Each of these samples was exposed to light using a tungsten light source through a 150-line magenta contact screen on the area of each sample, and without passing through the screen on the remaining area A, and then exposed using the developer shown in Table 4 below. Development processing was carried out using (1) and (2) at a development temperature of 25° C. and a development time of 2 minutes.

After the development process, the photographic sensitivity was measured and the halftone quality was observed using an optical microscope with a magnification of 100, and the results shown in Table 5 below were obtained.

The following margins;; 1...2y... °゛7U・' Table 4 Developer prescription In Table 5 above, sensitivity, gamma, fog, halftone quality,
The stability and scratch strength of latex were determined as follows:
The following evaluation was performed.

■LJL: Same as Table 1.

■ Gamma: The light range (log E) required to change the image density from 1.0 to 2.0 is expressed as a reciprocal number.

■ Latex: Add 0.29 and 0.65 g of KNOx to Polymer Latex 40- and evaluate the state of aggregation after standing for 3 hours (visual judgment) A: No change B: Cloudy C: Coagulated matter D Niss slurry
The halftone dots were observed and visually graded into A-D.

A: Excellent B: Practically acceptable C: Poor D: Very poor ■ ILIL skin: After developing, fixing, and washing with water in the above processing steps, the film surface was pulled with a weighted metal needle while immersed in washing water. By scratching, the minimum weight of the metal needle that caused scratches was determined (scratching strength).

As is clear from Table 5 above, the number of photosensitive material samples containing the exemplified metal article and polymer latex of the present invention is 26.29.
gives almost the same sensitivity in both developers (1) and (2) having different ionic strengths, indicating that the dependence on the developer is small. In addition, sample 11h26 using polymer latex emulsion polymerized using the exemplary compound of the present invention.
As the results show, is stable in the presence of electrolytes,
By adding it, excellent scratch strength can be obtained, and there is almost no change in sensitivity. On the other hand, it can be seen that the stability of the polymer latex of the comparative sample is inferior, the halftone quality of the lithographic development is also inferior (see comparative sample 11m27.28), and the scratch strength is also low (comparative sample 1).
1i127.28).

Example 4 Next, layers having the following composition were successively formed on a triacetyl cellulose film support to prepare a multilayer color photographic material.

First layer; antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Gelatin 2.2 g/tr? 2nd N; Intermediate N(Il,) Gelatin layer comprising an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2g/n (3rd N; low sensitivity red-sensitive silver halide emulsion layer (RL-1) average grain size (F) 0.30+ljmSAgI 6 mol%
Monodispersed emulsion (emulsion ■) consisting of Brl containing 1.8 g of silver coated/sensitizing dye ■...6 x 10-' mole sensitization per mole of silver Dye ■・・・・・・ 1.0% per mole of silver. OX 10-'Morsian coupler (C-1)...0.06 mol per 1 mol of silver Colored cyan coupler (CC-1)... 1 silver
0.003 mol DIR compound (D-1)...0.0015 mol DIR compound per mol silver? I(D-2)...0.002 mol gelatin per 1 mol silver 1.4 g/rd 4th layer; High sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size (r) 0.5 μm, monodispersed emulsion (emulsion ■) consisting of AgBr1 containing 7.0 mol% Agl... Silver coating amount 1.3 g/rd Sensitizing dye I... 3 x 10-' mole sensitizing dye per mole of silver 1.0 x 10'' moles cyan coupler (C-1) per mole of silver... 1 mole of silver 0.02 against
Mol colored cyan coupler (CC-1)・・・Silver 1
0.0015 mol to mole DIR compound (D-2) 0.001 mol to silver 1 mol Gelatin 1.0 g/i No. 5N; Intermediate layer (1, L,) No. 21i Same as gelatin layer.

Gelatin 1.0 g/n 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion - ■... Coated silver amount 1.5 g/n?
Sensitizing dye■...2.5 x 10-' mol sensitizing dye■ per 1 mol of silver
...... 1.2 x 10-' moles per mole of silver Magenta coupler (M-1) ...... 0.2 x 10-' moles per mole of silver
05 mol Colored magenta coupler (CM-1) 0.009 mol per mol of silver DIR compound (D-1) 0.0010 mol per mol of silver DIR compound (D-3) 0.0030 mol to 1 mol of gelatin 2.0 g/7th resistant layer; Highly sensitive green-sensitive silver halide emulsion layer (GH-1) Milk Agent - ■... Coated silver amount 1.4 g/rrr Sensitizing dye ■... 1.5 x 10-' mol sensitizing dye ■ per 1 mole of silver
...... 1.0 x 10-5 mole magenta coupler per mole of silver (M-1>...0.020 per mole of silver
Mol color magenta coupler (CM-1)...
0.002 mol per mol of silver DIR compound (D-3)... o, ooio mol gelatin per mol of silver 1.8 g/n? 8th layer: Yellow filter single layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.5 g/rd No. 9N; Low sensitivity blue-sensitive silver halide emulsion layer (BL-1) Average grain size 0.48 μm, AgBr containing 16 mol% Ag
Consists of 1.

Monodisperse emulsion (emulsion ■)... Silver coating amount 0.9 g/rd Sensitizing dye ■... 1.3 x 10-' mol yellow coupler (Y-1) per 1 mol silver )・・・・・・0.29 mol to 1 mol of silver 1.9 g/rd of gelatin 10th layer; Highly sensitive blue-sensitive silver halide emulsion layer (BH-average grain size 0.8 μm, Agl 15 mol% AgB containing
Monodisperse emulsion consisting of r1 (emulsion ■)... Silver coating 10.5 g/rrr Sensitizing dye V... 1.5 g/rrr per mole of silver. OX 10-' mole Yellow coupler (Y-1)...0.08 per mole of silver
Mol DIR compound (D-2)... 0.0015 mol gelatin 1.6 g/rrf for 1 mol silver 111: 1st protection N (Pro-1) Silver iodobromide (Agl 1 mol % average particle size 0.07μm
)...Gelatin layer containing silver coating amount 0.5g/rrr ultraviolet absorbers (U'V-1) and (tlV-2).

Gelatin 1.2g/r+ (12N; 2nd protection 71 (Pro-2) Polymethyl methacrylate particles (diameter 1.5 μm) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm) C11F1?5OJCHtCOONa C,H.

-・-・・-----1-・10■/d Exemplary compound (1
4) Gelatin layer containing -・・・・−111−・3■/d and formalin scavenger (HS-1) Gelatin 1.2 g / rrr In addition to the above composition, each layer also contained , gelatin hardener (H-
1), polyethyl acrylate latex, exemplary compound (3) according to the present invention, and surfactant (SA-1) were added.

Back 1st layer Stearic acid ・・−・−・・−・20■
/d diacetyl cellulose ------・----1----10 curvature/d2Cβθ ----Ig/rrf Back 2nd layer Diacetyl cellulose -------1 ...-50■/d Stearic acid-----10■/d Silica matte agent---50■/po (average particle size 3μ) However, magenta coupler (M-1) is exemplified compound (3)
And it was.

The compounds contained in each of the above layers are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide! Dye 11; Anhydro-9-ethyl-3,3'-di (3-sulfopropyl)-4°5.4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; Anhydro-5,5'-diphenyl −
9-ethyl-3,3'-di(3-sulfopropyl)oxacarpocyanine hydroxide sensitizing dye ■; Anhydro 9-1: thyl-3,3'-di(3-sulfopropyl)-5°6. 5',6'-Dibenzoxacarbocyanine hydroxide sensitizing dye ■; Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine 0 Summer I C-1 H M-I 0■ 0H V-1 V-2 to 2Hs H5-I SA-11,.

−6−°. 1゜II2. . . □2 Comparative sample 11h33 was also prepared in the same manner as sample 11h32, except that sodium dodecylbenzenesulfonate was used instead of the exemplified compound used as a surfactant when preparing sample Na32.

Among the samples 32 and 33 thus obtained, the sample 32 according to the present invention had good coating properties with the emulsion etc. on the support, as shown in the above example, and was formed completely smooth. As shown in Table 6, no hajikimura was formed. On the other hand, comparative sample magnet 33 showed the same results as those shown in Table 1, and was inferior in coatability.

Next, the sample 11m32.33 was exposed to white light for 7 degrees, and then subjected to the following development treatment, and the results are shown in Table 6 below.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer> 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1-2 sulfate 2. 0g Anhydrous potassium carbonate 37.3g Sodium bromide 1.3g Nitrilotriacetic acid
Trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 11.

Bleaching solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10. Ow11 water was added to make the solution 11, and the pH was adjusted to 6.0 using ammonia water.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 11
and adjust the pH to 6.0 using acetic acid.

Stabilizer> Formalin (37% aqueous solution) 1.5 m
g Conidax (manufactured by Konishiroku Photo Industry ■) 7.5d Add water to make 1N.

Table 6 As is clear from Table 6 above, sample Kan 32 of the present invention showed better results in both sensitivity and fog than comparative sample 11kL33, and the multilayer color photographic material also showed the same results as the above examples. It was found that it shows.

〔Effect of the invention〕

As described above, according to the present invention, the hydrophilic colloid containing the emulsion and polymer latex has excellent high-speed coating properties (for example, 70 m/min or more), and the physical properties of the formed coating film are improved, and the photographic properties are improved. It is possible to provide a silver halide photographic material with a sufficient amount of silver halide. In particular, it is possible to provide a silver halide photographic material with good halftone dot quality in a photosensitive material for printing.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Toru Takatsuki Procedural principal author (spontaneous)
(July 1, 1986, Case Description 2, Title of Invention: Silver Halide Photographic Light-sensitive Material Containing a Novel Surfactant 3, Relationship with the Amendment Person Case: Address of Patent Applicant: Tokyo Shinjuku-ku Nishi-Shinjuku 1-26-2 Name
Name (127) Roku Konishi Photo Industry Co., Ltd. 4, Agent Address 11-9 Niban-cho, Chiyoda-ku, Tokyo 102 FAX 03 (221) 1924 1) In the specification, "Carbon" on the last line of page 6 "having a carbon number of 1 to 22" is corrected to "having a carbon number of 1 to 22".

2) On page 15, line 7, "5% by weight" is corrected to "5% by weight or more."

3) Correct "mucochromic acid" on page 16, line 13 of the same page to "mucochloric acid."

4) "Nanionic" on page 25, line 18 and page 26, line 4 are corrected to "nonionic."

5) Amend Table 3 on page 27 as attached.

that's all

Claims (1)

[Claims] In a silver halide photographic material comprising at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers has a polyoxazoline chain and a carbonized polyoxazoline chain having 4 or more carbon atoms at the terminal end thereof. A silver halide photographic material comprising a surfactant having a hydrogen group.