US3502474A

US3502474A - Process for producing photographic light-sensitive elements

Info

Publication number: US3502474A
Application number: US568414A
Authority: US
Inventors: Momotoshi Tsuda; Teruo Kobayashi; Keisuke Shiba
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1965-07-28
Filing date: 1966-07-28
Publication date: 1970-03-24
Anticipated expiration: 1987-03-24
Also published as: BE684714A

Description

United States Patent 3,502,474 PROCESS FOR PRODUCING PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENTS Momotoshi Tsuda, Teruo Kobayashi, and Keisuke Shiha, Ashigara-Kamigun, Kanagawa, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa, Japan No Drawing. Filed July 28, 1966, Ser. No. 568,414 Claims priority, application Japan, July 28, 1965, 40/ 45,503 Int. Cl. G03c 1/84 US. Cl. 96-84 3 Claims ABSTRACT OF THE DISCLOSURE A process for producing photographic light-sensitive elements including applying an emulsion which contains a solution of a water-insoluble oxonol dye having the formula:

where Y and Z are unsubstituted or substituted carbon ring-forming groups or substituted or unsubstituted heterocyclic ring-forming groups. M is hydrogen or HNRRR (where R, -R" and R are hydrogen, lower alkyl or lower hydroxyalkyl) and n is 0, 1 or 2, the oxonol dye solvent can be represented by the formula:

where R is an alkyl group of less than 14 carbon atoms or NCO(CHz)mm where R, and R are lower alkyl and m is a positive integer of less than and R and R are alkyl.

The present invention relates to photography and more particularly to a process for the production of a photographic light-sensitive element having an anti-irradiation effect, an anti-halation effect, and a filter effect.

A photographic light-sensitive element is usually provided with an anti-irradiation layer, an anti-halation' layer and a filter layer for improving the photographic properties and they are colored layers for absorbing harmful reffected light, scattered light and diffused light among the colored lights applied on the light-sensitive element.

However, there is a drawback in such photographic light-sensitive elements in that the coloring materials used in the layer having an anti-irradiation effect, an antihalation layer and a filter layer are frequently diffused or exuded into an adjacent emulsion layer during manufacture of the light-sensitive elements or during storage, which reduces the photographic properties or reduces the effects of these layers. Further, although the coloring matter may not be diffused into the adjacent layer, the mere contact of the coloring matter with the adjacent emulsion layer also frequently injures the photographic properties thereof. The coloring materials used for the above-mentioned purposes are required to have spectral absorption chaacteristics suited for the purpose, to povide high optical densities in coating thicknesses which are as thin as possible, and further to be decolored completely into a colorless state or dissolved out of the layers during the photographic processing steps.

An object of this invention is to provide a process for the production of a photographic light-sensitive element ice having a layer having an anti-irradiation effect, an antihalation effect and a filter effect without being accompanied by the above-mentioned difficulties.

Another object of the present invention is to provide a layer having dispersed therein a colored material for a photographic light-sensitive element, said colored material giving no bad influences on the photographic properties of an adjacent emulsion layer contacted with the layer, having an anti-diffusion property, having the spectral absorption characteristics suited to the purposes of giving the above-mentioned effects, having high optical density in an effective absorption wave length, and being completely de-colored or dissolved out by the developing step.

These objects are accomplished by the present invention as described below.

That is, the oxonol dye having no water-soluble group and represented by the following general formula:

R2 Rr-CON Ra (B) wherein R represents an alkyl group having less than 14 carbon atoms or No0(oH2)ml m where R and R2 represent a lower alkyl group and m is a positive integer less than 10, and R and R represent a lower alkyl group.

The resulting solution is dispersed in a solution containing gelatin, which is then added in an emulsion or a gelatin solution to provide a coating solution and the coating solution is applied to a support to provide a colored layer having an anti-irradiation effect, an anti-halation effect and a filter effect.

The dyes shown in the general Formula A may be incorporated in the layer alone or as a mixture thereof.

The suitable groups Y and Z in the above-mentioned general Formula A are rings having active methylene groups, such as a pyrazolone ring, iso-oxazolone ring, thiobarbituric acid ring, barbituric acid ring, 3-oxythionaphthene ring, 1,3-indandione ring and rhodanine ring. However, oxonol acid dye having a sulfon group or a carboxyl group, which is a water-soluble group, is unsuitable in the present invention.

Among them, the symmetric or antisymmetric oxonol dye having a methyl group at the 3-position of the pyrazolone ring as shown in UK. Patent 506,385 and US. Patent 2,621,125 are slightly dissolved in water although they have no water-soluble group and hence such a dye will diffuse into adjacent emulsion layers and have a bad influence on the photographic properties. However, by using as the dispersing medium for the dye the organic emulsion represented by general Formula B in accordance with this invention, the dye becomes diffusion resistant and has almost no bad influence on the photographic properties. In particular, among the dyes represented by general Formula A, the symmetric or antisymmetric oxonol dye wherein the 3-position of the pyrazclone ring has been substituted with a carboxyalkyl group (ether type) or oxyalkyl group (ether type) are more profitable in the following respect than the above than the above-mentioned symmetric or anti-symmetric dye in which the 3-position of the pyrazolone ring has been substituted with a methyl group as described in UK. Patent 506,385 and U.S. Patent 2,621,125. That is, when comparing both dyes, While employing the same 11 and other factors in the formula, the oxonol dye of the former type has a higher solubility in the organic solvent represented by the general Formula B to be used in the invention than the latter type known dyes, and the absorption maximum of the former oxonol dye is shifted to about 10 to 35 millimicron longer wave length side of the ester type and about 10 to 20 millimicron shorter wave length side in the ether side, by which it can be easily adopted for the desired spectral absortpion characteristics.

The organic solvent having the general Formula B used in the invention has a very good solubility to the dyes shown by general Formula A as compared with conventionally known weak, Water-soluble, organic solvents. It also has an extremely high molar extinction coefficient t the desired optical absorption wave length. Since the organic solvent used in this invention has such properties, the amount of the organic solvent incorporated in photographic elements may be small and a sufficient optical density can be obtained even by a thin film, the dye itself is completely protected from the silver halide particles, and the photographic properties of the photographic element are not injured.

Since the organic solvent having general Formula B used in the present invention has a very strong polarity as well as a proper solubility to water, the use of the solvent makes easy the addition reaction of sulfite ions and the like to the dye having general Formula A. Therefore, this is valuable in the case of de-coloring and dissolving off the dye in the photographic developing process.

The dyes shown by general Formula A used in this invention are illustrated as follows although the dyes are magenta color (colored layer by the invention) cyan c0101 The organic solvents shown by general Formula B used in this invention are illustrated as follows but the solvents should not be limited to these examples by any means:

Solvent (a) 0211 H 0 C O N Solvent (b) 02H:

HzaCn-C O N G2Hs Solvent (0) CH H 5 0 C O N Solvent ((1) H59. C2H5 NC O--(CH2)F'C ON Solvent (e) C411 H2 C1 C 0N EXPERIMENT An excessive amount of the dye was dissolved by heating in a definite amount of water-insoluble organic solvent and, after allowing to stand for 6 days at :5 C., the precipitated crystal of the dye was separated by means of a centrifugal separator, thereafter the solubility of the crystal was measured. The optical density to the desired spectral absorption maximum wave length in the saturated solution is comparatively shown in the following table.

Max. ab- Optical sorpn. wave density in length saturated Dye Organic solvent length (m soln.

Dye (I) Tricresyl phosphate 570 1.0 Dye (I) Dibutyl phthalate. 568 0. 7 Dye (I). Solvent (a) 580 18. 4 Dye (II) Tricresyl phosphate 683 1. 0 Dye (II). Dibutyl phosphate 670 O. 9 Dye (II) Dirnethylethyl phosphate" 680 3. 9 Dye (II) Solvent (a) 685 22. 7 Dye (II) Solvent (b) 680 14. 9 Dye (II) Solvent (c) 670 14. 6 Dye (II). Solvent (d) 685 22. 7 Dye (II)... Solvent (e) 680 14.0

It can be understood, from the above results, that by employing the dye of this invention together with the organic solvent of this invention a colored layer having a high optical density can be formed even if the amount of the organic solvent is small. Forother dyes and organic solvents of this invention, shown above, similar effects are obtained.

The dyes used in this invention may be generally prepared as follows. That is, the symmetric dyes corresponding to the general formula wherein n is 0.1 or 2, may be obtained, as shown in UK. Patent 506,385 and UK. Patent 646,125, by subjecting to a condensation reaction 2 mols of a compound having an active methylene group in the ring with 1 mol of formamidine, malondialdehydedianil, or glutacondialdehydedianil in an alcohol in the presence of a condensing agent, such as triethylamine, diethanolamine, ammonia or pyridine.

Further, the anti-symmetric dyes used in this invention may be prepared as follows, as shown in US. Patent 2,631,125 and UK. Patent 624,462 (pentamethine oxonol dye) and US. Patent 2,611,696 and UK. Patent 663,- 042 (mono-methine oxonol dye and polymethine oxonol dye). That is, 1 mol of the compound having the formula:

is subjected to a condensation reaction with 1 mol of the above-mentioned dianil to provide the intermediate product having the formula:

The condensation reaction may be conducted in a nonpolar solvent such as ligroin or in an alcoholic solvent in the presence of pyridine or triethanolamine. Thereafter, by reacting 1 mol of the intermediate product with 1 mol of the compound having the following formula:

(1) Preparation of Dye 1' Into 200 ml. of an isopropyl alcohol solution containing 46.4 g. (0.2 mol) of 1-phenyl-3-carboxyethyl-5-pyrazolone and 30.3 g. (0.3 mol) of triethylamine was added with stirring 22.2 g. (0.1 mol) of malondialdehydedianil, and resulting mixture was reacted for several hours at about 2080 C., and then allowed to stand for one night to form crystals. The crystals were recovered by filtration and recrystallized by methanol in an amount of 6 ml. per 1 g. of the crystal to provide 55 g. (yield 92%) of Dye I having the melting point of -141 C. The. absorption maximum Wave length of a methanol solution containing 5 ppm. of the Dye I was 562 nm. and the extinction coeflicient thereof was 0.74.

(2) Preparation of Dye I By adding a stoichiometric amount of hydrochloric acid in the methanol solution of Dye I and then water therein, Dye I was obtained in the form of crystals. The melting point of the dye was 162163 C., the absorption maximum wave length of the 5 ppm. methanol solution thereof was 560 nm., and the extinction coefiicient thereof was 0.81.

(3) Preparation of Dye VIII Into 200 ml. of an ethyl alcohol solution containing 61.5 g. (0.2 mol) of 1-(2,4,6-trichlorophenyl)-3-ethoxy- 5-pyrazolone and 40.4 g. (0.4 mol) of triethylamine was added 28.4 g. (0.1 mol) of glutacondialdehydedianilide hydrochloride. The system was reacted for about 10 hours at about 2030 C. or about 1 hour at about 80 C. Thereafter, ligroin was added into the solution of the re action product to completely precipitate the product. The crystals were recrystallized from a mixed solution of an alcohol and ligroin to provide 65 g. of Dye VIII having a melting point of 236 C.238 C. The absorption maximum 'wave length of a methanolic solution of p.p.m. of the dye was 603 nm. and the extinction coefficient thereof was 1.03.

(4) Preparation of Dye IX The intermediate product, S-(w-aniIidO-A-Z:4-pentadieneylidene)-3-ethyl-rhodanine shown by the formula CzHa was prepared in a manner similar to that of UK. Patent 624,462.

That is, the intermediate product was obtained by the reaction of N-ethyl-rhodanine and with equimoles of dialdehyde-dianilide hydrochloride in absolute alcohol with reflux in the presence of triethylamine. By recrystallizing the product from ethanol, purple crystals having a melting point (decomposition) of 199 C., were obtained. Analytical value, found (percent): C, 60.56; H, 5.29; and N, 8.74. Calculated (percent): C, 60.76; H, 5.06; and N, 8.86.

The intermediate product and equimoles of l-phenyl- 3-carboxyethyl-S-pyrazolone were dissolved in pyridine as described in the abovementioned UK. patent, the solution was heated under reflux in the presence of triethylamine, and the product was precipitated with the addition of ether followed by re-crystallization from alcohol to provide a bright green crystal of Dye IX. The absorption maximum wave length of a methanol solution of 5 p.p.m. of the dye was 680 nm. and the extinction coeflicient thereof was 1.1.

(5) Preparation of Dye II The same procedure as in the case of preparing Dye I' was repeated using, in this case, glutacondialdehydedianilide hydrochloride instead of malondialdehyde-diam'l and using diethanolamine instead of triethanolamine to provide Dye II. The melting point of the dye was 118- 120 C., and the absorption maximum wave length of a methanol solution of 5 p.p.m. of the dye was 660 nm., and the extinction coefiicient of it was 1.0.

By treating the Dye II with hydrochloric acid as in Preparation 2, Dye II was obtained. The melting point of the dye was 193 C., the absorption maximum of a methanol solution of 5 p.p.m. of the dye was 658 nm. and the extinction coefficient was 0.98.

Other symmetric dyes, that is, yellow dye (III), red dye (IV), magenta dye (V) and orange red dye (VI) were obtained by using the corresponding compounds. Also, other anti-symmetric dyes, that is, magenta dye (VII) and blue green dye (X) were obtained 'by using the corresponding compounds.

The examples of the preparation of the organic solvents shown by general Formula B are as follows:

(I) Preparation of organic solvent (21), N,N-diethylcaproamide.--A one liter S-necked flask equipped with a thermometer, an agitator, a dropping funnel, and a condensor was placed on a steam bath. In the flask were charged 73 g. (1.0 mol) of diethylamine, 120 g. (1.2 mol) of triethylamine and 500 ml. of acetone and the mixture was stirred at room temperature. Thereafter, 162.5 g. (1.0 mol) of caprylic acid chloride was added dropwise into the system such that the temperature of the y tem was maintained at about 4050 C. After the addition thereof, the system was boiled to complete the reaction.

Then, the product was cooled, poured in iced Water that had been acidified with hydrochloric acid, and extracted with ether. The product was washed with water, dried by anhydrous Glaubers salt and then subjected to vacuum distillation by a conventional method to provide 140 g. (yield 70%) of the organic solvent having a boiling point of 108 C./3 mm. Hg.

(II) Organic solvent (b), N,N-diethyl-lauramide.-The same procedure as in the case of preparing organic solvent (a) was repeated while using g. (1.2 mols) of triethylamine, 73 g. (1.0 mol) of diethylamine, 500 ml. of acetone, and 195.5 g. 1.0 mol) of lauric acid chloride to provide 191 g. (yield 75%) of the organic solvent (b) having the boiling point of 192-194 C./9 mm. Hg.

(III) Preparation of organic solvent (0), N,N-dimethylcapramide.-The same procedure as in the case of preparing organic solvent (a) was repeated using 81.5 g. (1.0 mol) of dimethylamine hydrochloride, 240 g. (2.4 mols) of triethylamine, 500 ml. of acetone, and 162.5 g. (1.0 mol) of caprylic acid chloride while maintaining the reaction temperature below 5 C. to provide 120 g. (yield 70%) of the organic solvent (c) having a boiling point of C./10 mm. Hg.

(IV) Preparation of organic solvent (d), N,N'-tetraethylsebacamide.-The same procedure as in the case of preparing organic solvent (a) was repeated using 146 g. (2.0 mols) of diethylamine, 240 g. (2.4 mols) of triethylamine, 1000 ml. of acetone and 23 g. (1.0 mol) of sebacic acid chloride to provide 310 g. (yield 75 of the solvent having a boiling point of 210-215 C./2 mm. Hg.

(V) Preparation of organic solvent (e), N,N-di butylmyristilamide.The same procedure as in the case of producing organic solvent (a) was repeated using 129 g. (1.0 mol) of di-butylamine, 120 g. (1.2 mols) of triethylamine, 500 ml. of acetone and 246.5 g. 1.0 mol) of myristic acid chloride. The product was then extracted with ether, the extract was decolored by a de-colo-ring carbon, and the ether was distilled 011? at a normal pressure. From the resulting product were removed by distillation under a reduced pressure the fractions less than 120 C./2 mm. Hg to provide 275 g. (yield 81%) of the residue as the objective solvent.

The invention will now be described in detail by the following examples:

EXAMPLE 1 Into 5 ml. of organic solvent (a) was dissolved 0.4 g.

of Dye II or Dye II and the solution was added in 50g. of a 10% gelatin solution. After the addition of a solution of sodium alkylbenzene sulfonate to the solution, the mixture was emulsified by means of a high-speed rotary mixer to provide the emulsified dispersion of Dye II or Dye II;

Into 100 g. of a 70% gelatin solution was added 10 g. of the above-prepared emulsified dispersion of Dye II or Dye II, and the resulting dispersion was applied to a film support followed by drying to provide a film having the anti-halation layer.

By applying to the thus formed anti-halation layer on the support a red-sensitive silver iodo-bromide emulsion containing a cyan coupler and drying, a light-sensitive element was obtained. By microscopic observation, it was confirmed that Dye H orDye II was present only in the anti-halation layer.

The light-sensitive element was edge exposed to red light, developed as usual in a color developing solution mainly consisting of N,N-diethyl-p-aminianiline sulfate, and then subjected to fixing, bleaching and fixing to provide a cyan image. The sharpness of the cyan image was clearly improved as compared with that of a lightsensitive element having no anti-halation layer of this invention, and further, the cyan color of Dye II or Dye II after development was completely de-colored.

9 EXAMPLE 2 Into 5 ml. of organic solvent (c) were dissolved 0.2 g. of Dye VI and 0.3 g. of Dye IX and an emulsified dispersion of Dye VI and Dye IX was prepared in a manner similar to Example 1.

Further, by dissolving 0.5 g. of Dye VIII into 5 ml. of organic solvent (e), an emulsified dispersion of Dye VIII was prepared.

A mixture of 100 g. of a 7% gelatin solution and 20 g. of the emulsified dispersion of Dye VI and Dye IX was applied to a film support and dried to give a film having an anti-halation layer. Further, on the thus formed anti-halation layer was coated a mixture of 100 g. of a red-sensitive silver iodo-bromide emulsion containing a cyan coupler and g. of the emulsified dispersion of Dye VIII followed by drying to provide a red-sensitive emulsion layer.

0n the emulsion layer was coated a 2% gelatin solution containing a hardening agent followed by drying to provide an intermediate layer. On the intermediate layer was coated further a green-sensitive silver iodobromide emulsion followed by dry to provide a light-sensitive element.

The thus obtained light-sensitive element was exposed to red light by using a contact chart for measuring rectangular wave response and then was subjected to processing as in Example 1 to provide a cyan image.

The sharpness of the resulting cyan image was higher than that of a light-sensitive element wherein the emulsion of Dye VIII had not been incorporated in the red-sensitive emulsion, and moreover it was observed that the lightsensitive element of this invention had an irradiation pre venting effect. Further, Dyes VI, IX, and VIH had been completely dissolved out.

EXAMPLE 3 Into 5 ml. of organic solvent (b) was dissolved 0.4 g. of Dye V and the solution was treated as in Example 1 to provide an emulsified dispersion of Dye V.

Instead of the intermediate layer of Example 2 there was employed a magenta-colored intermediate layer that had been formed by applying a mixture of 100 g. of a 2% gelatin and g. of the emulsified dispersion of Dye V.

By a microscopic observation of the raw film, it was confirmed that Dye V in the intermediate layer had not been dispersed in the adjacent emulsion layer.

The resulting light-sensitive layer Was exposed to green light and processed as in Example 1 to provide a magenta image. It was confirmed that the sharpness of the magenta image had been increased by the anti-halation effect of the magenta-colored intermediate layer.

Further, by the filter effect of the colored intermediate layer, the unnecessary green-sensitivity of the red-sensitive emulsion layer was reduced and the color separation between the magenta image and cyan image was improved. Moreover, the stain and recoloring of Dye V after photographic processing were not observed.

EXAMPLE 4.

Into 5 ml. of organic solvent (d) was dissolved 0.4 g. of Dye I or Dye I and the solution was added in 50 g. of a 10% gelatin solution. After the addition of a solution of sodium alkylbenzene sulfonate, the mixture was dispersed by using a high-speed rotary mixer to provide an emulsified dispersion of Dye I or Dye I.

The same results as in Example 3 were obtained by employing the thus prepared emulsified dispersion of Dye I or Dye 1' instead of the emulsified dispersion of Dye V in Example 3.

EXAMPLE 5 Between a panchromatic emulsion layer for black and white photography and a film support was formed the following anti-halation layer. That is, 0.3 g. of Dye X, 0.2 g. of Dye VII, 0.1 g. of Dye IV and 0.2 g. of Dye III were dissolved into 10 ml. of organic solvent (a) and the solution was treated as in Example 1 to provide an emulsified dispersion of the dyes. Then, 20 g. of the thus obtained emulsified dispersion was added into g. of a 0.5% chromium alum solution as a hardening agent, an 0.5% chromium alum solution as a hardening agent, the mixture was applied to a film support and dried to provide the photographic light-sensitive element. The thus formed layer had an excellent anti-halation effect and after developing treatment the dye was de-colored or re moved completely.

What is claimed is:

1. In a process for producing a photographic lightsensitive element comprising applying a film support an emulsion containing a solvent solution of at least one water-insoluble oxonol dye, said oxonol dye being represented by the general formula:

0 r' it o=oH- on=oH).-o 'z I wherein Y and Z each represents a member selected from the group consisting of unsubstituted and substituted carbon ring-forming groups and unsubstituted and substituted heterocyclic ring-forming groups; M represents a member selected from the group consisting of a hydrogen atom and HNR'R"R' .(where Rf, R", and R' each represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group, and a lower hydroxylalkyl group); and n is 0, l, or 2, the improvement which comprises using as the solvent for said oxonol dye an organic solvent selected from the group consisting of those represented by the following general formula:

Rr-CON where R and R each represent a lower alkyl group and sisting of an alkyl group having less than 14 carbon atoms. and

N C O-(CHz) m-- where R and R each represent a lower alkyl group and m is a positive integer less than 10, and R and R each is an alkyl group.

2. A photographic light-sensitive element comprising a film support and a layer formed on said support said layer being produced by drying an emulsion containing the solvent solution of at least one water-insoluble oxonol dye, said oxonol dye being represented by the general formula:

O (l I:

wherein Y and Z each represents a member selected from the group consisting of unsubstituted and substituted carbon ring-forming groups and unsubstituted and substituted heterocyclic ring-forming groups; M represents a member selected from the group consisting of a hydrogen atom and HNR'RR"' (where R, R", and R each represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group, and a lower hydroxylalkyl group); and n is 0, 1, or 2, dissolved in an organic solvent selected from the group consisting of those represented by the following general formula:

/R2 RrCON wherein R is a member selected from the group con- 11 12 sisting of an alkyl group having less than 14 carbon References Cited atoms and UNITED STATES PATENTS 3,220,843 10/1965 Louick 9684 2)m 2,892,712 6/1959 Plambeck 9684 5 2,621,125 12/1952 Van Dormael 9684 where R and R each represents a lower alkyl group and m is 'a positive integer less than 10, and R and R RONALD SMITH Primary Exammer each is an alkyl group.

3. The element of claim 2 wherein said emulsion is a 10 gelatin emulsion. 11733.5