DE2038199A1 - Fine grain, high speed photosensitive material - Google Patents

Description

DR. E. WIEGAND DIPL.-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MDNCHEN HAMBURG

July 31, 1970

TELEPHONE: 55547 «8000 MD NCH EN 15, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 40006/70 - Dr.Ko / G

fuji Photo Film Co., Ltd., Ashigara-Kamigun, Kanagawa, Japan

Fine-grained ·· liclite sensitive ·· high-speed material

The invention is concerned with and relates to photosensitive materials for black-and-white photography especially fine-grained light-sensitive high-speed screen materials for black-and-white photography, in which two or more light-sensitive silver halide emulsion layers are superposed on a support are absorbed, each of which contains one or more non-diffusing color couplers and each of which is spectrally sensitized so that they have sensitivity over a considerably wide range of the verifiable spectrum.

gelatin silver halide photographic films have conventionally been used for high-speed black and white camera films. on the other hand have been used in low speed photosensitive materials such as those used for printing, office copying and printing

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reproductions are used, In lttsttr time the materialita uattr Aawtndung von Iliohtailbereubetansen, at · spielaweiae photolelttndt Subftansen, photoeepfinilica « Poljatrt, Vtelcularfilat odtr Diaaovtrbindentn ei sets, wl «known let ·

Dita · neuan light-sensitive materials are la the latter case is cheaper and easier and quicker Processing accessible, however, due to their low lepfindlichiteit not for a · practical use ale Kamerafilae vamandet «ground. The previous light-sensitive layers made of oil-coated silver halide, wherein fine silver halide separates in gelatin aind, aind However, especially considering the last one Anatiegea the price for silver expensive, since egg © usually ■ indeatena approx. 70 ag dea expensive Silbera to 100 approx ent * hold aüaeen, among other things, the aaxial density necessary for good sound reproduction is shown, whereby only the H'-Ufte de · silver · la eohileSliob. The silver image that has been obtained is left behind, while the other halftones have lost their fixation goes·

The task of the invention is therefore to produce «Division of a ·· fine-grained photograph! Eoheη high-speed materiala for the Schwari-und-feia-Photograuhle.

line next · task «the invention beats in the her hand» «Division of a cheap Sahwar» -and-f «1 & -las» raiii ·· β, with d «a a" small "amount" of silver halide is necessary ·

line next «task« of the invention beateht in tinea photographic fiIa that is used in ordinary laaeras can be obtained, giving the photographer useful negatives from which fine-grain black and white prints can be obtained.

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Further objects will emerge from the following description of the invention.

Ia the scope of the invention was now a method for Production of new photosensitive layers for Black and white kaaerafilae with a finer grain and get a faster rate than it does on the previous subject were possible «where a negative image was made exclusively of metallic silver due to the Reduction of silver halide grains was obtained by the decomposition solution, the above-mentioned minia & l necessary amount of silver to about 1/3 to 1/4 can be reduced and the cost of the film thereby can be reduced quite considerably

To further explain the invention, the following description is used in conjunction with the enclosed Drawings, with FIGS. 1 and 2 greatly enlarged cross-sections of FIG. Execution forms of the fine-grained high speed photosensitive materials according to of the invention.

Bas photosensitive material according to the charge consists of * white or more silver halide emulsion layers »1, 2 and 3« where the speed of the silver halide grains ♦ is different in different eeulaion layers · Each layer contains a color-forming coupler 9, the structure shown below and the molar ratio of silver halide »coupler in each layer are appropriately selected.

The silver halide emulsions stranded with a stabilizer such as 4-Hydrojqr-6 ~ methyl ~ 1.3 _t 3a, 7-tetrasainden, a hardener such as chrome alum, an auxiliary agent such as saponin and the like are uniformly on a softened1-

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gene carrier 8, for example made of glass, cellulose triacetate or polyethylene terephthalate, the silver halide emulsions spectrally to the same region of the spectrum by infrared sensitizers, panchromatic or orthochromatic optical sensitizing dyes such as they are familiar in the field, e.g. Moes and James, The Theory of the Photographic Process, J. Edition 1966, Chapters 11 and 12, which have the desired spectral sensitivity properties so that they 'im Not only in contrast to the usual blue sensitive, yellow color forming layers of color negative films for the blue light area to which the silver halide is sensitive, but also for the green light area and / or Red light range of the visible spectrum are sensitive «This light-sensitive material can also be a Antihalation layer 5 »an intermediate layer 6 and one Protective layer 7 contained in accordance with known methods.

FIGS. 1 and 2 serve to explain the invention without limiting it.

As color-forming couplers for the new light-sensitive materials according to the invention, benzoylacetanilide, its substituted derivatives and similar compounds as known to those skilled in the art are, for example Mees and James, ibid, chapter 17, used, and in numerous In some cases, the main spectral absorption of the dye obtained therefrom by color development consists mainly in the visible wavelength range Spectrum, whereby the maximum absorption peak of this is preferably in the range of 400 - 530 nm *

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These color-forming couplers can either be obtained from dam non-diffusing type, due to the installation of ballast groups, with, for example, 12 to 18 carbon atoms in the chain, or equivalents thereof, and they can also in the aqueous photographic gelatin emulsion by introducing hydrophilic groups such as -GOOH or -SO ^ H solubilized, or of the nondiffusion type, dissolved in a solvent, usually esters such as triphenyl phosphate, Tricresyl phosphate, dibutyl phthalate and dioctyl phthalate, for example, Mees and James, ibid. P.393 and U.S. Patent 2,322,027. These couplers are often used in a mixture of two or more couplers is used, so that the solubility of the coupler and the spectral absorption properties of the color image formed by the color development be improved.

Examples of the former are;

5 ~ (p-Octadecanamidbenzoylacetamido) isophthalic acid,

5-Garboxy-2-methoxy- (4'-octadecinylsuccinmonoaaid) benzoylacetanilide,

2- (N-methyl-N-octadecyl-amino) -5-carboxy- (4-methoxybenzoyl) -acetanilide,

2- (N-methyl-N-octadecyl-amino) -5-sulfo- (4-methoxybenzoyl) -acetanilide.

Examples of the latter type are: ^ -Benzoylacetamide-N-butyl-N-octylbenzamide, Benzoylaceto- (2-methoxy-5-dodecyl03 {ycarbonyl) anilide, Benioylaceto-2-chloro-5- (2-methylhexyloxycarbonyl) anilide.

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In addition, other Kuptlex · containing a dye with a spectral absorption in the longer "normal length range of the spectrum are used according to the invention, for example cyanoacetyldeiivate, difchio-1,3-diketones, Oxythiazolyl-5-acetonitrile and 1-phenyl-5-pyrazolidone.

The photosensitive materials obtained in the present invention can of course with ordinary black and white developers developed after exposure, but preferably color development after exposure, in particular a color negative development, for example according to the Fuji Film CN-Ή-type process or the Subjected to Kodak C-22 process. In this case, the couplers listed above react with the oxidation product of the aromatic primary amino color developing agent and give a color image according to the amount of exposure (Mees and James, ibid, chapter 17).

As a large number of color development laboratories If the plan is only for the time being, consumers will receive the above light-sensitive materials easily and correctly color-developed in a short time after exposure.

With the above photosensitive layers, the usual color negative treatment becomes the silver image completely removed during the bleaching stage and only the color negative image remains

The new properties of this color image consist in the following four aspects:

1) The grain of the negative color image is much finer than that of the silver negative image, which in ordinary black-and-white development the choice of the molar ratio of silver halide to coupling

QRiQINAt INSPECTED

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lar to a suitable value in each emulsion layer, for example 40 in the high-speed report 1 of Figures 1 and 20 in the low speed sublayer and by appropriate choice of the thickness of each emulsion layer.

P.) A positive image can easily be obtained from the negative color image by printing the latter on an ordinary black-and-white blue-sensitive or blue-green-sensitive printing paper, positive films and other various light-sensitive materials having a spectral sensitivity in the range of 500 to 5>!? 0 nm will. (

3) The spectral absorption of the color image can be easily to a certain extent by changing the structure of the coupler or by using two or more couplers with different spectral absorption properties in admixture can be varied so that dl «absorption for the spectral Sensitivity properties of a special to the Printing sensitive material used must be met.

4) Under the conditions of practice, the amount of lift of silver halide grains necessary to give the same maximum density of the HD curve is, in most cases, only 1/3 to 1/4 that of ordinary black and white Films, as is also demonstrated by the following examples. i

The particularly valuable advantage is listed above under 1). With the usual Schwaxs-und-Weiß films leads to a coarsening of the silver halide grains Purpose of increasing the photographic sensitivity deterioration in the grain of the negative negative image finally obtained, while in the case of the light-sensitive materials according to the invention, the grain size of the color image obtained by the color development, which is composed of color images of

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two or more layers is built up, not simply pro- / proportional to the size of the silver halide grains or the The grain size of the silver image obtained therefrom is so that a fine grain negative can be obtained despite the high speed. Sas means that the present light-sensitive materials surprisingly two have opposite properties, i.e. high speed and fine grain, which are most favorable for camera films are.

As also mentioned above under 4), the necessary amount of winding of the silver can be largely reduced are compared with ordinary high-speed negative photosensitive materials for black and white photography, and the requirements for the spectral absorption properties of the developed color image are not as sharp as in the case of ordinary color negative files. As a result, the manufacturing cost of the photosensitive materials becomes quite significant as a whole the choice of very cheap color-forming couplers is reduced and consumers can get cheap fine-grained and high-quality ones Get black-and-white images available at high speed, even if the Koatenaofcieg due to the necessary color development instead of just black-and-white development.

Furthermore, the invention is advantageous with regard to the recovery of the valuable silver content, since the total · silver present in the photosensitive material is dissolved in the color developing baths and then recovered and regenerated, in contrast to the case the usual black and white films.

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Since iaa get according to the method of the invention, e yellow color negative image not ho aichtbar under the usual gränen or robes Sieherheitelichtern for ^Dunkelr: mme lat, and this is inconvenient for the production of printing, a small amount of a for forming a color image in magenta or cyan color suitable coupler, e.g., Meee and James, ibid., Chapter 17, can be used in conjunction with the yellowing coupler if necessary to overcome this disadvantage.

The following examples serve to further illustrate the dex invention without limiting it.

example 1

a) A solution of 44.6 g of the yellow-forming coupler 4-benzoylaoetamide-N-butyl-N-ootylbenzamide in 30 ml of dibutyl phthalate and 45.0 al of ethyl acetate were added to 150 ml of an aqueous gelatin solution of 10 wt .- ^, which with 300 ml of a 10% aqueous solution of Ifatriuadodeoylbenzenesulfonat was forbidden, added. The whole room was given several times through a colloid mill. In this way a very stable and very fine emulsion was recovered which was composed of 1,000 g of a fine-grained gelatin-silver halide emulsion for low speed containing 1 mole of silver halide composed of 5 mole percent silver iodide and 95 mole percent silver broaid and 30 g gelatin. and the above-old a "sulfur" sensitizer and a Goldsensibllieator been digested to achieve the maxi bask speed was 'added to dea * obtained mixture, then 100 al of a 0.1% solution in methanol of anhydro-5f5'"6 _t 6 '-tebrachior-1,1 * - diethyl-3,3'-di (4-sulfobutyl) -benzimidasolcarbocyanin-hydroxyd and 80 ml of a 0.025% solution in methanol of anhydro-

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OWQINAt

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1.1 ^l -dL- (4-sulfobutyl) -2,2'-cyanine hydroxide alo optical j .'msibLiialer dyes, 15 ml of an aqueous solution of 4-hydroxy-o-methyl-1,3,3a, 7-tetraziilnden as a SfcabLlioator, ie as an anti-formation agent, 1, i> ml of a 10% aqueous solution of chrome alum as a hardener and 1 ml of a 6% aqueous solution of S-aponin added as a coating aid and the resulting mixture uniformly on a Cellulose triacetate / ilmgrunila, drawn on and then dried, so that a dry emulsion layer with a thickness of 2.4 microns was obtained. The molar ratio of silver halide to color copper is 10 (mol%).

b) To a coarse Grelatine silver Halo ^ snidemulsion f ^r ir high speed, the 1 mole of silver halide from 5 mol% silver iodide and 95 mol% of silver bromide and 200 g of gelatin, and was digested with a Schwefelsensibllisator and a gold sensitizer to achieve maximum speed , 1/3 of the weight of the above emulsion, which contained the yellow coupler according to a), the sensitizing dye, stabilizer, hardener and coating aid according to a), was added and the total painting was applied to layer a to a dry thickness of 2.6 microns, whereupon a protective gelatin layer approximately 1 micron thick continued to be pulled. The molar ratio of silver halide to color coupler was 30 (mol-tf).

c) Black-and-white negative file used as a control for high speed was applied in a similar manner by applying a mixture of the same gelatin-silver halide emulsion for high speed, of the sensitizer dye, Stabilizer, hardener and coating aid

QlttÖJNAL! NSPECTEO

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by means of gemHIi b), but the emulsion that the yellow-forming coupler was omitted a Celluloaea ^ etatfilmgrund base with subsequent Drying to obtain a dry emulsion layer; π recovered to a thickness of 14 microns, -uie same Protective layer as in b) was then applied to this. The speed and dryness of the layers a) and b) were chosen so that the print density of the yellow image of the superimposed films from a) + b), such as when treated with the Kodak C-22 procedure Fuji Bromide No. 3 »a black-and-ftei'i printing paper for Magnification obtained was the same as the printing density of the syllable image c) as obtained by development during 7 minutes with the developer Kodak D-7 & was obtained. The amount of silver drawn and the photographic Properties are listed in Table I and the grit values according to Selwayn (G-Aert) in Table II.

Table I.

Amount of silver / a Filaatary relati-

ke ve speed

Layered film according to the

Invention from a) + b) 2.87 g 6 μ

Black and white ne gat iv-
film o) for high speed (control) 8.45 g 15/1

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Table II

Print density 0.46 0.90 1.25 1.53 1.83

Stacked one on top of the other

Film according to the invention

from a) + b) 0.42 0.53 0.46 0.25 0.12

Black-and-white negative film for high speed (control) 0.68 0.74 · 0.8? 0.87 0.79

Sa results from the above values that the Film according to the invention from layers a) and b) has practically the same speed and a far better one Coefficients of the Selwayn grain when used only of a third has drawn silver, like film c) according to the state of the art

Example 2

a) To 1 kg of a fine-grain silver iodobromide emulsion for medium speed with a content of 9.8% by weight W gelatin and 2.4% by weight silver as silver halide (6 mol% silver iodide), 80 ml of a 0.05% -igen solution in methanol of 3 »3 ^l -diethyl-9-methylthiacarbocyanine bromide and 3.0 ml of a 0.1% solution in methanol of 3» 3i9-triethyl-5t5'-diphenyl-oxaoarbocyanine rhodanide ale optical sensitizer dyes, 10 ml a 1% aqueous solution of 4-hydroxy-6-methyl-1,3T3a »7-tetrazaindene old? Anti-scouring agent, 200 ml of a 10% -lgen alkaline aqueous solution of 5- (p-Cctadecanamidobe2Uioylacetamid) i8O-

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phthalic acid as a yellow-forming copper, a hardener and a coating agent added and the total mixture on an oellulose triacetate film base drawn up and then dried to give 1.02 g of silver per square meter. The molar ratio of silver halide to color coupler is 6.3 (mol%).

b) To a Silbet iodobromide emulsion for high speed »The 8% by weight of gelatin and silver halide accordingly 3 wt .-% silver (silver iodide 4 mol%) contained, became 70 ml of a 10% aqueous alkaline solution of the ge! forming coupler listed above and the The above-mentioned spectral sensitizing dyes, stabilizers, hardeners and coating auxiliaries were added and the total mixture on the layer a) drawn so that 1.08 g of silver per square meter were obtained, whereupon one Ordinary gelatin protective layer with about 1 / Iikrön then peeled off became. The molar ratio of silver halide to color coupler is 18 (mol%).

The speeds of the two emulsions and the thicknesses of layers a) and b) were chosen so that the Printing density of the color image from the superimposed films a) + b), obtained by processing according to Fuji Film CN-1 ^ - process on Berona No. 3 »a black-round-Welß printing paper for enlargement, the same as the printing density of one by developing for 8 minutes with the developer Kodak D-76 obtained silver image on the printing paper listed above.

The amount of silver drawn up and the photographic properties of the superimposed films according to the invention and the black-and-white film for Control are in Table III and the grit values according to

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ORIGINAL INSPECTED

A t β "j

- 14 -

.ielwayn (G-value) and listed in Table IV.

Table III

ο Amount of silver / jn- Strength Relative Ge

ijspeed

') bereiii £ iu.ler _b ^% e campers

Film according to the invention .2,10 7 u

6.70 16 u

for Hociligeachwindiglrelt (KontruLio)

Table IY

DruikiljLte 0.42 0.78 1.13 57

h mder - ^ iai; or »

forth FlLm $ em & x ier 0.42 0.57 0.50 0.46

Invention;

for Hochg38.ihwindJ.g- 0.48 0.59 0.74 0.78

ability (K ^ nf; role)

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Claims (5)

Alol ^J 199 Patent sprints rl, ¹ fine-grain, light-sensitive high-speed! • ei. ^ material fir ° ".h.varz-und-Weiil-riiütü, rnphie, characterized in that on a door" ibsreinandor lying .-. VQi ode: nehr photiache GelHtine-.lilborh -lOi-oni-I-aariloionsschiahton «e.jebenenf Ils zummnen rait v.eit.ren Hilfanchichton aui'ceaogen ainl, whereby, jeda .lilborh- lo < _: onidf .nulsionsacliicht? inen oi-ίΧ 'inen oi-ίΧ' more nichtliffuniiorende color couplers Jie to form a Färb "iurch Umaoüzur ^ with ' which are capable of oxidation product, irivrlron / rainoftirbentwiclclungsmlttela, un-i every bilberhalo-kenide emulsion is spectrally sensitized to practically the same region of the spectrum from the dex group of blue and green, blue and red, and blue-green and red eats. 2. Photosensitive time. rial according to claim 1, characterized in that the photographic geography-silver halide ionic objects diverge from any other speed on the carrier ii. aar Fo] [50 are arranged that the Emulaionfisihlcht juii; Höli ^ rer (tescJiwindif <lceit further away from de «Tr-igor an, e jr'.c''ü · iist» λ 3 · Light-sensitive material according to claim 1 or 2, characterized in that silver halide emulsions with a different molar ratio of silver to color coupler are applied to the support in eXc sequence _t that the emulsion layer with; ^ röüeroci Molr.r'.cr; i ^: iltnie further tntXernt attached by the wearer. BAD OB (OfNAi. 80S / Ί Λ 2 4 2U38199 4. Photosensitive material according to claim 1 to 3t characterized in that the silver halide emulsions at least one non-diffusing yellow coupler each contain· 5. Photosensitive material according to claim 4, characterized characterized in that the silver halide emulsion contains a non-diffusing yellow coupler, magenta coupler and / or Contains cyan yellow coupler. 109809 / 'U2