US3795519A - Photographic materials containing mordants - Google Patents

Abstract

A PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT HAVING THEREON A HYDROPHILIC COLLOID LAYER CONTAINING A POLYMER OF AN ADDITION PRODUCT OF BISACRYLAMIDE AND A SECONDARY DIAMINE OR THE QUATERNARY SALT THEREOF, AND A WATER-SOLUBLE ACIDIC DYE IS DISCLOSED.

Description

United States Patent 3,795,519 PHOTOGRAPHIC MATERIALS CONTAINING MORDANTS Takushi Miyazako, Tatsuya Tajima, Hirotetu Kato, Tadayoshi Kokubu, Tsutomu Nishiua, and Nobuo Tsuji, Minami-ashigara, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed July 24, 1972, Ser. No. 274,373 Claims priority, application Japan, July 30, 1971, 46/57,276 Int. Cl. G03c 1/84 U.S. Cl. 96-84 A 12 Claims ABSTRACT OF THE DISCLOSURE A photographic material comprising a support having thereon a hydrophilic colloid layer containing a polymer of an addition product of bisacrylamide and a secondary diamine or the quaternary salt thereof, and a water-soluble acidic dye is disclosed.

BACKGROUND OF THE INVENTION 1) Field of the invention This invention relates to mordants for use in colored layers in photographic materials.

(2) Description of the prior art It is well known to provide colored layers for the purpose of light filtering or light absorbing. The position of the colored layer in the photographic material depends upon its purpose. The colored layer may be coated as the outermost layer when overall filtering is required, between layers when selective filtering is required or next to the support for antihalation purposes.

These layers often contain organic dyes, but these dyes often exert a deleterious effect on the light-sensitive layers used in the photographic material. Therefore, it is important to prevent these dyes from diffusing into adjacent layers.

As a means to prevent this diffusion, a method of converting a fairly soluble dye into an insoluble complex using a mordant is well known. For example, an acid dye can be mordanted with a high molecular weight compound having a basic group. By the way, where light filtering or light absorbing layers are used in photographic materials, it is necessary that these layers be bleached during the photographic processing. For example, the dye must be released from the mordant and discharged from the layer by immersing the photographic material in an alkaline solution, such as a photographic developer solution.

Processes utilizing mordants, such as are described above, are disclosed in a great number of patents, e.g., British Pats. Nos. 786,592, 906,083 and 1,162,214; U.S. Pat. No. 3,445,231; German Pats. OLS 1,914,361 and 1,914,362, etc.

However, in the processes which have been proposed so far, the dye is not sufficiently discharged in many cases which results in the color remaining. In addition, a considerable amount of thiosulfate ions are absorbed from an acidic fixing solution due to the mordanting action of the mordant to acidic compounds, the mordant remaining in the layer, and this results in reducing the stability of the image formed on the material.

An object of the present invention is to provide compounds which can be used as mordants for acidic dyes whose mordanting action is markedly reduced due to the action of alkaline solutions.

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SUMMARY OF THE INVENTION The present invention provides photographic materials comprising a support having thereon a hydrophilic colloid layer containing an addition polymer of bisacrylamide and a secondary diamine, or the quaternary salt thereof, and a water-soluble acidic dye.

DETAILED DESCRIPTION OF THE INVENTION The addition polymer of bisacrylamide and a secondary diamine used as the mordant in the invention is a polymer, of repeating units, in which an amino group of the secondary diamine is added to the terminal unsaturated double bond of the bisacrylamide. The nitrogen atom of this amino group of the secondary diamine exists as a tertiary amine in the polymer, and the term quaternary salt thereof as used herein means the con version of such a tertiary amine to the quaternary salt.

The term bisacrylamide, which is used as the starting material for the mordants in accordance with the present invention, includes compounds represented by the following General Formula I:

wherein R and R which may be the same or different, each represents a hydrogen atom, a methyl, an ethyl or a propyl group, and A represents an alkylene group having from 1 to 6 carbon atoms, which may be substituted with a methyl or an ethyl group.

Specific examples of the compounds represented by the General Formula I are illustrated hereinafter.

CH2=C H C O NH CHQNHC O CH=CHI CH1=CHC O NHCHzCHqNHC O C H=CH3 CHg=OHC O NH (CH1) sNHC 0 C H=CH1 CHz=CHC O NHCHCHzNHC O CH=CHI II-I3 CI-Iz=C C O NHCHINHO O C=CHI CH: 1H:

CH1=C CONH (CH2) tNH C O C=CH C Ha CH -C C O NHCHINHC O CH=CH1 CH =C C ONH (CH1) :NHC O C=CH1 CH; CH1=C C O NHCHg) CHINHC O C=CH CH3 CH3 CH;

CH: CH2=C C ONHCHn CHINHO O CH=CH2 3H1 J a The other starting material, the secondary diamine, includes piperazine, (C to C alkyl-substituted piperazine and N,N'-di-(C to C )alkylethylenediamine. As specific compounds, there are illustrated piperazine, 2,5-dimethylpiperazine, N,N'-dimethylethylenediamine, N,N-diethylethylenediamine and the like.

The polymer can readily be synthesized by heating the bis-acrylamide and the secondary diamine in water. The quaternary salt thereof also can be synthesized readily 3 in any conventional mannner, i.e., by the reaction of an alkyl halide (e.g., ethyl bromide, butyl bromide, etc.) or an alkylsulfate (e.g., diethyl sulfate, etc.) with the tertiary amine group of the polymer.

Specific processes for synthesizing these polymers are illustrated hereinafter. The intrinsic viscosity of the resulting polymer is that measured in a 1% sodium chloride aqueous solution at a temperature of 30 C.

SYNTHESIS EXAMPLE 1 CIIzCH: C O NHCHaNH C O CHaCHzN CHa-CH: J

SYNTHESIS EXAMPLE 2 In the same manner as described in Synthesis Example 1, there was obtained 20 g. (91% yield) of a polymer using 15.4 g. (0.1 mol) of methylenebisacrylamide and 17.5 g. (0.09 mol) of piperazine 6H O. The resulting polymer had an intrinsic viscosity of 0.15.

SYNTHESIS EXAMPLE 3 In the same manner as described in Synthesis Example 1, there was obtained 22 g. (86% yield) of a polymer using 18.2 g. (0.1 mol) of methylenebismethacrylamide and 19.4 g. (0.1 mol) of piperazine 6H O. The resulting polymer had an intrinsic viscosity of 0.52.

SYNTHESIS EXAMPLE 4 In the same manner as described in Synthesis Example 1, there was obtained 21 g. (82% yield) of a polymer using 18.2 g. (0.1 mol) of methylenebismethacrylamide and 17.5 g. (0.09 mol) of piperazine 6H O. The resulting polymer had an intrinsic viscosity of 0.124.

SYNTHESIS EXAMPLE 5 In the same manner as described in Synthesis Example 1, there was obtained 23 g. (85% yield) of a polymer using 15.4 g. (0.1 mol) of methylenebisacrylamide and 11.6 g. (0.1 mol) of N,N-diethylethylenediamine. The resulting polymer had an intrinsic viscosity of 0.63.

SYNTHESIS EXAMPLE 6 In the same manner as described in Synthesis Example 1 there was obtained 23 g. (86% yield) of a polymer using 15.4 g. (0.1 mol) of methylenebisacrylamide and 11.4 g. (0.1 mol) of 2,5-dimethylpiperazine. The resulting polymer had an intrinsic viscosity of 0.48.

SYNTHESIS EXAMPLE 7 10 grams of the polymer obtained in Synthesis Example 1 and 6.4 g. of diethyl sulfate were stirred together with 100 ml. of dimethylformamide for 12 hours. Thereafter, the dimethylformamide was removed under reduced pressure, and the residue was placed in a cellophane tube to conduct dialysis overnight, then was lyophilized. Thus, there was obtained 12 g. of a polymer having an intrinsic viscosity of 0.75. The resulting polymer is considered to contain the following repeating units.

L NM

CHF'CH/Q J CHICH:

The mordants in accordance with the present invention have the property that they very rapidly lose their mordanting ability to acidic dyes due to the action of an alkaline solution. Accordingly, they have an important characteristic that, when incorporated in a filter layer or an antihalation layer of a photographic light-sensitive material, the dye mordanted by them can be released easily due to the action of an alkaline photographic processing solution and thus no color remains in the layer.

When the molecular weight of the polymer of the invention is too low, the polymer itself tends to diffuse into the material, whereas, when the molecular weight is too high, compatibility with hydrophilic colloids becomes poor. Therefore, polymers having an intrinsic viscosity of from about 0.01 to 3.0, preferably, about 0.1 to 1.5 is suitable, this intrinsic viscosity being measured at 30 C. using a 1% sodium chloride aqueous solution.

The photographic material of the present invention comprises a support material having thereon at least one hydrophilic colloid layer containing a mordant of the invention, which layer may also contain a light-sensitive silver halide, or, the light-sensitive photographic material may comprise a support having thereon at least one bydrophilic colloid layer containing a mordant of the invention and at least one light-sensitive silver halide emulsion layer. The light-screening or antihalation layers containing the mordant can be prepared by coating an aqueous solution comprising a mordant of the invention, an acidic dye, a hydrophilic colloid binder and a coating aid such as saponin, sodium alkyl benzenesulfonate, polyoxyethylene alkylphenyl ether, etc. on the support or on a photographic layer. In order to improve the strentgh of the light-screening or antihalation layer, compounds such as formaldehyde, mucochloric acid, chlorotriazine derivatives, etc. can also be added as a hardening agent for the colloidal binder. The proportions of mordant, dye, colloidal binder, hardener and coating aid can be varied over a wide range and will depend upon the specific requirements of the photographic material to be produced. The methods used to determine the optimum compositions are well known to those skilled in the art and require no further detailed explanation here.

The support materials include any of those usually used in the field of photography, such as cellulose acetate, cellulose propionate, polyesters, polystyrene, polypropylene, paper or polyethylene-coated paper.

Suitable hydrophilic colloid materials which can be used include gelatin, albumin, collodion, gum arabic, agar-agar, cellulose derivatives (e.g., the alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, etc.), synthetic resins (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, etc.) and others well known in the art.

The dyes that can be effectively mordanted in accordance with the invention are those having at least one acidic group such as a sulfo group or a carboxy group, including for example, the oxonol dyes, the styryl dyes, the azo dyes, the triphenylmethane dyes, the cyanine dyes, or the merocyanine dyes. Specific examples of such dyes are described in US. Pats. Nos. 3,316,091, 3,423,- 207, 3,445,231; British Pats. Nos. 506,385, 906,083, 993,466, 1,034,044, 1,142,697, 1,162,214; French Pat. No. 1,421,679; German Olfenlegungsschrift Nos. 1,472,789, 1,547,999; Belgian Pats. Nos. 689,044 and 697,267. However, the invention is not limited to just those dyes described above and any dye containing one or more sulfo or carboxyl groups can be employed, for example, 2,5- bis(sulfopl1enyl)thiazolo[5,4 d]thiazole, 3 phenyl-2- phenylimino-S-(Z sulfobenzol)-4-thiazolidone and uranine.

Typical examples of suitable dyes are illustrated below.

The silver halide light-sensitive emulsion layers can contain silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc. as the light sensitive material. The silver halide emulsion may be sensitized using any of the sensitizers conventionally used.

The filter layer or antihalation layer containing a mordant of the invention provides an excellent photographic material as will be illustrated in the following examples. The mordant of the invention can also be used for preparing excellent image-receiving layers for use in the dyetransfer process.

The present invention will be illustrated in greater detail by reference to the following examples.

EXAMPLE 1 8 ml. of a 5% aqueous solution of the polymer obtained in Synthesis Example 1 was added to an aqueous solution comprising 50 ml. of water, 5 g. of gelatin, 0.1 g. of saponin and 0.1 g. of mucochloric acid, then 10 ml. of a 2% aqueous solution of each of Dyes 1, 4 and 6 was added thereto. Thereafter, the pH of the solution was adjusted to 6.5 with a 1 N sodium carbonate aqueous solution, and water was added to adjust the total volume to ml.

For comparison, a solution not containing the polymer was prepared in exactly the same manner as described above. Samples were prepared by applying each of these dye containing solutions so obtained to a clear undercoated film base of cellulose triacetate in a dry thickness of 2 microns, then coating thereon a fine-grained silver chlorobromide emulsion containing 40 mol percent of panchromatically and spectrally sensitized silver chloride and g. of gelatin per 1 mol of silver halide in a dry thickness of 2 microns, and further coating thereon a protective layer of gelatin in a dry thickness of 1 micron.

Furthermore, a sample comprising only the emulsion layer and the protective layer was prepared for comparison.

These samples thus prepared were wedge-exposed and were developed and fixed in a conventional manner. Samples containing the dyes were completely bleached.

Comparing the photographic sensitivity of each sample with each other, the sensitivity of the samples containing the dye and the mordant of the invention decreased by about 20% based on the sample containing no dye layer, whereas, the sensitivity of samples containing the dye alone and no mordant of the invention decreased by a ratio of as much as 50%. The sharpness of the image formed was greatly improved in all the samples having the dye layer in comparison with the sharpness of the image samples having no dye layer.

That is, the sharpness can be improved with little decrease in sensitivity using the mordant of the present invention. In the samples containing no mordant, it was observed through examination of the sample with a microscope before processing, that the dye was considerably diffused into the emulsion layer, while no diffusion of the dye was observed in the samples containing the mordant of the invention.

EXAMPLE 2 The same effects as described in Example 1 were observed when ll ml. of a aqueous solution of the polymer obtained in Synthesis Example 2 as a mordant and ml. of a 2% aqueous solution of each of Dyes 2, 4 and 8 were used.

EXAMPLE 3 The same effects as described in Example 1 were obtained when ml. of a 5% aqueous solution of the polymer obtained in Synthesis Example 3 as a mordant and 10 ml. of a 2% aqueous solution of each of Dyes 2, 5 and 8 were used.

EXAMPLE 4 The same effects as described in Example 1 were obtained when 10 ml. of a 5% aqueous solution of the poly mer obtained in Synthesis Example 4 as a mordant and 10, 10 and 8 ml. of a 2% aqueous solution of Dyes 3, 4 and 7, respectively, were used.

EXAMPLE 5 The same effects as described in Example 1 were obtained when 11 ml. of a 5% aqueous solution of the polymer obtained in Synthesis Example 5 as a mordant and 8 ml. of a 2% aqueous solution of each of Dyes 1, 5 and 7 were used.

EXAMPLE 6 The same effects as described in Example 1 were obtained when 10 ml. of a 5% aqueous solution of the poly mer obtained in Synthesis Example 6 as a mordant and 10 ml. of a 2% aqueous solution of each of Dyes 2, 4 and 6 were used.

EXAMPLE 7 The same effects as described in Example 1 were also obtained when 8 ml. of a 5% aqueous solution of the polymer obtained in Synthesis Example 7 as a mordant and 10, 8 and 10 ml. of a 2% aqueous solution of Dyes 2, 5 and 8, respectively, were used.

EXAMPLE 8 8 ml. of a 5% aqueous solution of the polymer obtained in Synthesis Example 1 was added to an aqueous solution comprising 50 ml. of water, 5 g. of gelatin, 0.1 g. of saponin and 0.1 g. of mucochloric acid, then 3 ml. of a 0.1% aqueous solution of Dye 9 was added thereto. Thereafter, the pH of the solution was adjusted to 6.5 with a l N sodium carbonate aqueous solution, and water was added to adjust the total volume to 100 ml.

The resulting dye-containing solution was applied to the red-light sensitive layer of a multilayer type color lightsensitive material in a dry thickness of 1 micron. Then, a green-light sensitive layer, a yellow colloidal silver layer, a blue-light sensitive layer and a protective layer were applied in order. Thus, a multilayer color light-sensitive material was prepared.

For comparison, a sample containing the dye alone and a sample containing neither the dye nor the mordant were also prepared. These samples thus obtained were wedgeexposed and processed in accordance with the standard color reversal processing manner. No dye was observed to remain in any sample.

As the result of the measurement of photographic sensitivity of each sample, it was found that, in the sample containing the mordant of the invention, the undesirable green-light sensitivity of the red-light sensitive layer decreased by 50% based on the sample containing neither the dye nor the mordant while the green light sensitivity of the green-light sensitive layer decreased only by 20%, Whereas, in the sample containing the dye alone, the green-light sensitivity of both the red-light sensitive layer and the green-light sensitive layer decreased by 50%.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A light-sensitive silver halide photographic material comprising a support having thereon a hydrophilic colloid layer containing a polymer of an addition product of bisacrylamide and a secondary diamine or the quaternary salt thereof, and a water-soluble acidic dye.

2. The photographic material as claimed in claim 1, wherein said bisacrylamide is a compound represented by the following general formula;

wherein R and R which may be the same or different, each represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and A represents an alkylene group having from 1 to 6 carbon atoms, said alkylene group being optionally substituted with a methyl group or an ethyl group.

3. The photographic material as claimed in claim 2, wherein said compound is CH1=CH o ONHCHINHC 0 CH=CH1 CH=CHC ONHCHzCI-IQNHC o CH=CH1 CH2=CHC o NmoHmNHc o oH=oH, CHZ=CHC oNfit mcmNno o CH=CH1 CH: 0111:? c o NH(CH:)|NHC o J=orn CH: CH:

om=c c ONHCHzNHG 0 t 3=om CH: CH:

4. The photographic material as claimed in claim 1, wherein said secondary diamine is piperazine, a (C -C alkyl-substituted piperazine or an N,N-di-(C -C )alkylethylenediamine.

5. The photographic material as claimed in claim 4, wherein said (Q-Cflalkyl-substituted piperazine is 2,5- dimethylpiperazine.

6. The photographic material as claimed in claim 4, wherein said N,N'-di-'(C -C.,)alkyl-ethylenediamine is 9 N,N-dirnethylethylenediamine or N,N' diethylethylenediamine.

7. The photographic material as claimed in claim 2, wherein said bisacrylamide compound is methylenebisacrylamide and wherein said secondary diamine is pipermm.

8. The photographic material as claimed in claim 2, wherein said bisacrylamide compound is methylenebismethylacrylamide and wherein said secondary diamine is piperazine.

9. The photographic material as claimed in claim 2, wherein said bisacrylamide compound is methylenebisacrylamide and wherein said secondary diamine is N,N'- diethylethylenediamine.

10. The photographic material as claimed in claim 1, wherein said hydrophilic colloid is gelatin.

11. The photographic material as claimed in claim 1, wherein said water-soluble acidic dye is 12. The light-sensitive photographic material as claimed in claim 1, wherein said support has thereon at least one light-sensitive silver halide emulsion layer.

US. Cl. X.R. 96-84 R, 114