US3481742A

US3481742A - Silver halide photographic emulsion

Info

Publication number: US3481742A
Application number: US469304A
Authority: US
Inventors: Yahachi Terashima; Yukio Yasuda; Tadao Sakai
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1964-07-11
Filing date: 1965-07-02
Publication date: 1969-12-02
Anticipated expiration: 1986-12-02
Also published as: DE1472899A1; BE666666A; GB1118965A

Description

United States Patent ,481,742 SILVER HALIDE PHOTOGRAPHIC EMULSION Yahachi Terashima, Yukio Yasuda, and Tadao Sakai, Kanagawa-ken, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa-ken, Japan, a corporation of Japan No Drawing. Filed'July 2, 1965, Ser. No. 469,304 Claims priority, application Japan, July 11, 1964, 39/319,675 Int. Cl. G03c 1/28, 1/12 US. Cl. 96-104 7 Claims ABSTRACT OF THE DISCLOSURE A silver halide photographic emulsion Containing a methine dye and a compound shown -by the general formula R-i'I-Ri onto o- I wherein R represents an alkyl group having 8 to 18 carbon atoms; R represents a member selected from the class consisting of CH COOH and (CH CH O) H; R represents a member selected from the class consisting of CH COOH and (CH CH O),,H; and p and q each represents 0 or a positive integer, p+q being however 1 to 18.

' The present invention relates to a silver halide photographic emulsion optically sensitized with a polymethine dye'. U silver halide photographic emulsion has generally an intrinsic sensitivity to a blue wave length range in avisible spectrum but by incorporating a polymethine dye in the photographic emulsion, the emulsion can be endowed with a photosensitivity to a green wave length range as well as toa red wave length range, which is generally known as sensitization. In particular, a high color sensitivity is required in a so-called panchromatic black and white photographic film, sensitized to visual wave length region or in a multi-layered color photographic material consisting of silver halide emulsion layers each having blue', green and red sensitivity in visual wave length region. A polymethine dye which is adsorbed on a silver halide emulsion and gives a color sensitivity to its silver halide emulsion is known as optical sensitizer and a polymethine dye is generally considered to be different from a chemical sensitizer which increases the intrinsic sensitivity of a silver halide emulsion.

However, an optical sensitizer cannot always give satisfactory color sensitivity to silver halide emulsions. The color sensitivity of a silver halide emulsion may be increased incidentally by increasing the intrinsic sensitivity of the silver halide emulsion but the color sensitivity of the emulsion can be also increased by increasing the color sensitizing efiiciency of a polymethine dye for the silver halide emulsion having the same intrinsic sensitivity. In color photographic materials, in particular, it is preferable to increase the color sensitivity by increasing the color sensitizing efficiency to silver halide photographic emulsions having same intrinsic sensitivity. It is well known that a super sensitizer is used together with an optical sensitizer to increase the color sensitizing efficiency (of, C. E. K. Mees, The Theory of the Photographic Process; pages 474-477 (1954), MacMillan Co.). However, a high color sensitizing efliciency is not always obtained by the use of conventional super sensitizer together with various polymethine dyes. Most conventional super sensitizers are usually effective only when they are used together with polymethine dyes having specific chemical structures. Further, the use of conventional super sensitizers gives undesirable additive photosensitive spectrum ranges to the color sensitizing sensitivity range of a silver halide photographic emulsion containing a polymethine dye or the use of a conventional super sensitizer together with a polymethine dye increases the formation of fogs of a silver halide photographic emulsion. These properties of such conventional super sensitizers are very inconvenient for the production of photographic materials.

Therefore, an object of this invention is to provide a silver halide photographic emulsion optically sensitized with a polymethine dye and a specific super sensitizer without being accompanied with the above-mentioned faults.

Another object of this invention is to provide a high optical sensitizer that can be used effectively with polymethine dyes to increase the color sensitivity of a silver halide photographic emulsion without increasing the formation of fogs.

In accordance with the present invention, a silver halide photographic emulsion is incorporated with a methine dye and a compound shown by the gen ifll formula OHBCOO'" (I) wherein R represents an alkyl group having 8 to 18 carbon atoms; R represents and p and q each represents 0 or a positive integer but p-l-q is 1-18. (If p or q is 0, R or R respectively, each represents CH COOH.) To increase, the color sensitivity of the silver halide photographic emulsion.

Compound (I) in this invention is very effective for increasing the color sensitivity of a silver halide photographic emulsion when used with a polymethine dye. Further, the use of compound (I) of this invention does not give a tendency to giving undesirable photosensitive spectrum range to the silver halide photographic emulsion and gives little tendency to increasing the formation of fog,

Typical examples of polymethine dyes which can be effectively used with compound (I) of this invention for increasing the color sensitivity of a silver halide photographic emulsion are shown by the following general Formulas II to V.

wherein R and R each represents an alkyl group (such as methyl, ethyl, propyl, and butyl groups) or a substituted alkyl group (such as B-hydroxyethyl, fl-acetoxyethyl, B-sulfoethyl, 'y-sulfopropyl, 6-sulfobutyl, carboxyethyl, ,8- sulfoethyl oxyethyl, allyl, butylsulfate, and benzyl groups); L L and L each represents a methine group (such as =CH, =C(CH =C(OCOCH 2 5) 2 5) 2- e 5) =C(C H and =C(C H COOH); n represents 1 or 2; 121 represents a positive integer of 1 to 3; Z represents an atomic group necessary for forming 5- or 6-membered heterocyclic ring, for example,

thiazoles (such as, thiazole, 4-methyl thiazole,

S-methyl thiazole,

5-phenyl thiazole,

4,5-dimethyl thiazole,

and 4- 2-thieny1) -thiazle benzothiazoles (such as, benzothiazole, 4-chloro benzothiazole,

S-chloro benzothiazole,

6-chloro benzothiazole,

7-chloro benzothiazole,

4-methyl benzothiazole,

S-methyl benzothiazole,

6-methoxy benzothiazole,

S-ethoxy benzothiazole,

6-ethoxy benzothiazole, 4,5,6,7-tetrahydroxy benzothiazole, 5,6-dimethoxy benzothiazole, -hydroxy benzothiazole,

4-phenyl benzothiazole,

5-phenyl benzothiazole,

6-phenyl benzothiazole,

and 5,6-diphenyl benzothiazole), naphthothiazoles (such as, a-naphthothiazole, li-naphthothiazole,

and S-methoxy-fl-naphthothiazole), oxazoles (such as, 4-methyl oxazole, S-methyl oxazole,

and 4-pheny1 oxazole), benzoxazoles (such as, benzoxazole, S-chloro benzoxazole,

6-chloro benzoxazole,

4 S-hydroxy benzoxazole, 6-hydroxy benzoxazole, S-methoxy benzoxazole, 5-phenyl benzoxazole, 5,6-diphenyl benzoxazole, and S-bromobenzoxazole) selenazoles (such as, 4-methyl selenazole and 4-phenyl selenazole), benzoselenazoles (such as, benzoselenazole, S-ethyl benzoselenazole, S-chloro benzoselenazole and S-methoxy benzoselenazole), naphthoselenazoles (such as, a-naphthoselenazole and fl-naphthoselenazole), naphthoxazole (such as, u-naphthoxazole and fl-naphthoxazole), thiazolines (such as, thiazoline, 4-methy1 thiazoline, 4-hydroXymethyl-4-methyl thiazoline, 4-acetoxymethyl-4-methyl thiazoline, and 4-acetoXymethyl-4-methyl thiazoline), oxazolines (such as, oxazoline and 4-acetoxymethyl-4-methyl oxazoline), selenazolines, 2-quin0lines (such as, 2-quinoline, 6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline. 6-chloro-2-quinoline, S-chloro-Z-quinoline, 5-ethoxy-2-quinoline, 6-ethoxy-2-quinoline, and 6-hydroxy-2-quinoline), 4-qu1'nolines (such as, 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-quinoline, and 8-methyl-4-quin01ine), 3,3-dialkyl indolenines (such as, 3,3-dimethyl indolenine), and

benzimidazoles (such as, l-ethyl benzimidazole, l-phenyl benzimidazole, 1-ethyl-S-chlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-hydroxyethyl-5,6-dichlorobenzimidazole, and 1-ethyl-5-cyanobenzimidazole);

Z represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring, for example, thiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles, selenazoles, benzoselenazoles, naphthoselenazoles, naphthoxazoles, thiazolines, 2-quinolines, and benzimidazoles; d represents a positive integer of 1 to 3; at least one of P and Q represents an organic substitutent such as CN and COOR (R represents an alkyl group) or P and Q may be closed to form a heterocyclic ring, such as,

pyrazoles (such as, l-phenyl-3-rnethyl-5-pyrazolone and l-phenyl-S-pyrazolone),

iso-oxazolines,

oxyindoles,

2,4,6-triketohexahydropyrimidines (such as, barbiturlc acid and 1-ethy1-2-thiobarbituric acid),

2-thio-2,4-thiazolidinediones (such as, 3-ethyl0-danine X represents a Br, 1-, SCN 0r C10; anion;

4-thiazolidones (such as, Z-ethyI-mercapto-4-thiazolinone,

and 2-alkylphenylamino-4-thiazolinone),

2-imino-2,4-oxazolidinediones,

2,4-imidazolidinediones (such as, 2,4-imidazolidinedione and 3-cthyl-2,4-imidazolinedione),

2-thio-2,4-imidazolidinediones (such as, 2-thio-3-ethyl 2,4-imidazolidinedione and 1,3-diethyl-2-thio-2,4-imidazolidinedione),

and S-imidazolinones;

and Y and Y each represents an atomic group such as, S, O--, -Se, and N(R necessary for forming a S-membered heterocyclic ring, such as, 4-oxazolidine, 5-oxazolidine, 4-thiazolidinone, S-thiazolidinone, 4-imidazolidinone, and the like. 1

By incorporating the above-mentioned compound (I) of this invention together with one or more polymethine dyes shown by the above general Formulas II, III, IV and V in a silver halide photographic emulsion, the color sensitizing sensitivity of the emulsion can be effectively increased. 1

The increase of the color sensitivity of a silver halide photographic emulsion with the compound (I) of this invention shall be clearly distinguished from the sensitization with polyalkyleneoxide derivatives disclosed by Japanese publication No. 6,475/56. The polyalkyleneoxide derivataives shown by the patent can serve for only increasing the intrinsic sensitivity of a silver halide photographic emulsion but they cannot increase particularly only the color' sensitivity. On the other hand, compound of this invention can, when it is used with a polymethine dye, increase remarkably the 'color sensitivity of a silver halide photographic emulsion without or with slightly giving influences on the intrinsic sensitivity of the silver halide emulsion containing a polymethine dye.

The increase of the color sensitivity of a silver halide emulsion with the compound (I) of this invention is far superior to the increase of sensitivity of a silver halide photographic emulsion with a cationic surface active agent of a quaternary ammonium salt form disclosed by U.S. Patents 2,271,623 and 2,334,864. That is, the cationic surfaceactive agent shown by the US. patents increases mainly the intrinsic sensitivity of a silver halide photographic emulsion. In a silver halide photographic emulsion in which a polymethine dye is incorporated, there is a tendency that the relative sensitivity in a long wave length side is highly increased. However, the addition of-such a cation surface active agent is accompanied with the marked formation of fogs and, in particular, reduces the stability of photographic sensitive materials for preservation. On the other hand, the use of compound (I) of this invention give no infiuencesjor slightly weak influences, if any, on the intrinsic sensitivity of a silver halide emulsion and increases ,iefiectively only the color] sensitivity of the silver halide emulsion. Further, by the use of compound (I) of this invention, fog formation is, not almost increased and the stability ofphotographic sensitive materialsmade by the silver halide photographic emulsion for preservation are not eifected. Inthese points, the compound (I) of this invention is far superior to the cationic surface active agent disclosed by the US. patents. As the silver halide photographic emulsion of which the color sensitizing sensitivity can be increased with compound (I) of this invention may be applied to silver chloride, silver bromochloride, silver bromide, silver bromoiodide, or silver iodochloride formedin gelatin, a derivative of gelatin, polyvinyl alcohol, a water-soluble cellulose derivative, agar agar, zein, or ahydrophilic colloid of a hydrophillic synthetic or natural resin. I

Compound (I) of this invention may be used as a form of intermolecular salt or may be used as an inorganic acid added salt as well as a double salt form. Compound (I) or a salt of the compound may be added in a silver halide photographic emulsion as an aqueous solution, an alcohol solution, or a solution in other solvent. The addition may be effectively done in any steps of the production of the silver halide photographic emulsion. However, greater effects can be obtained by adding the compound (I) in the silver halide photographic emulsion before adding a polymethine dye in the emulsion or as a mixture with a polymethine dye. In particular, in case where a water-soluble coupler or a dispersion of oil-soluble coupler is incorporated in a silver halide photographic mulsion in the production of color photographic materials, it is necessary to add the compound (I) in the emulsion before the addition of the coupler. The addition of compound (I) from 0.05 g. to 20 g. is especially effective to obtain increase in color sensitivity.

The silver halide photographic emulsion to be incorporated with compound (I) and polymethine dye of this invention may be chemically sensitized with one or more chemical sensitizers, such as, a sulfur-containing sensitizer, e.g., allyl thiourea and allyl isothiourea, a reducing sensitizer, e.-g., imino-aminomethane sulfinic acid, a noble metal sensitizer, e.g., a salt of gold, platinum, and pallasium or a complex salt thereof, and a sensitizer of a polyalkylene derivative, e.g., a condensation product of cetyl alcohol and polyalkylene oxide and a condensation product of nonyl phenol and poyalkylene oxide.

In the case of manufacturing the silver halide photographic emulsion the color sensitivity of which is increased with compound (I) of this invention, there may be added an anti-fogging agent, a stabilizer, a color-toning agent, a hardening agent, a wetting agent, a plasticizer, a developing promoter, an irradiation preventing dye, a surface active agent for coating, a fluorescent agent, a ultraviolet ray absorbing dye, a filter dye, and a coupler.

The practical examples of compound (I) of this invention are as follows:

CHzCOO' (Io) CHzCHzOH 'ntnowfi omomon orncoon H25C12-1G-CHzCOOH CH2COO- ngoou-u-ongongon These compounds may be synthesized by the process described in Kogyo Kagaku Zassi, vol. 60, pages 104- (1957).

EXAMPLE 1 before being added with the polymethine dye and after letting alone for 30 minutes at 40 C. was applied on a film support followed by drying. A set of thus prepared samples were subjected to sensitometric exposure through a blue filter transmitting light of about 430 Nm. and another set of the samples were subjected to sensitometric exposure through a red filter transmitting light having a wave length longer than 600 Nm. These samples were then developed in a usual black and white developing solution containing methol and hydroquinone. Thus obtained photographic materials were examined about fogs and reactive sensitivity, which are shown in the following table.

TABLE 1 Blue Red exposure exposure Polymethine dye and eompd. (1) relative relative (g-lml. of AgX) sens. sns. Fog

(1) Dye (a), 0.37 100 100 0.17 (2) Dye (a), 0.37+compd. (Ia), 5.50 110 158 0.18 (3) Dye (a), 0.37+compd. (1b), 5 50 105 151 0.19 (4) Dye (a), 0.37+compd. (1c), 5 50 98 123 0. 17 (5) Dye (a), 0.37+compd. (Id), 5 5 100 123 0.17 (6) Dye (a), 0.37+compd. (1e), 5.50-- 93 162 0.17 (7) Dye (a), 0.37+compd. (If), 5.50 107 135 0. 17 (8) Dye (a), 0.37+crnpd. (Ib), 5.50 100 125 0.17

where dye (a) was CH2CI'I2OCOCII3 CHzCHzOCOCH EXAMPLE 2 A silver iodobromide gelatin emulsion as in Example 1 was added with a methanol solution of compound (I) and a polymethine dye shown by Formula 11, let alone for 60 minutes at 40 C., and after being added with a stabilizer, a hardening agent, and 20 parts of a aqueous solution of 1-hydroxy-4-sulfo-4-N-octadecyl-2-naphthoamide, applied on a film support followed by drying. The film was then subjected to sensitometric exposure as in Example 1, color-developed using N,N-diethyl aminoaniline, and subjected to usual bleaching and fixing treatments to form a cyan color image. Thus obtained films were examined about fogs and relative sensitivities,

the results of which are shown in the following table.

TABLE 2 Blue Red exposure exposure Polymethine dye and compd. (1) relative relative (g./mo1 AgX) sens. sens. Fog

(1) Dye (b), 0.50 100 100 0. 21 (2) Dye (b), 0.50+cornpd. (If), 1.40-... 98 123 0. 22 (3) Dye (b), 0.50+oompd. (II), 5.50 93 135 0.22

(4) Dye (c), 0.50 100 100 0. 17 (5) Dye (0), 050+ cornpd. (Id), 2.50 98 151 0. 17

(6) Dye (d), 0.30; dye (e), 0.10 100 100 0. 18 (7) Dye (d), 0.30; dye (e), 0.10-j-(Id), 2.50 100 174 0.18

where dye (b) was C=CHG==CHC 01 CHzCH-CHzO CH3 CHaCHCHzO CH3 0 0 11 80 0 O HeSOaNa 8 dye (c) was s C H /s 2 5 C=CH( 3=OHO Br i 1 CH3 CH3 dye (d) was 2 5 L C=CH( I=OHC Bri U C2115 CgHs and dye (e) was S S CzHs \O=OH(|J=CHC/ Brorno OCH3 N f (E2H4OH CzHqOH EXAMPLE 3 Silver bromochloride gelatin emulsion which had been prepared in accordance with a conventional method were added with the polymethine dyes shown by Formulas II, III, IV and V and, after letting alone for 30 minutes at 35 C., applied on film supports followed by drying.

While, same emulsions were added with compound (I) together with the polymethine dyes of the Formulas II, III, IV and V and after letting alone under the same conditions, applied on film supports followed by drying. Thus prepared samples were subjected to sensitometric exposure through a yellow filter absorbing light of wave length shorter than 500 Nm., and then treated with a black and white developing solution containing methol and hydroquinone. Thus obtained films were examined about fogs and relative sensitivities, the results of which are shown below.

TABLE 3 Yellow exposure sensi- Polymethine dye and compd. (I) (g./mol AgX) tivity Fog (1) Dye (f), 0.30 0. 09 (2) Dye (f), 0.30+cornpd. (If), 3.50 155 0. 10

(3) Dye (g), 0.30 100 0. 08 (4) Dye (g), 0.30+compd. (If), 3.50 141 0.13

(5) Dye (h), 0.30 100 0. 08 (6) Dye (h), 0.30+compd. (10,350.- 0.14

(7) Dye (e), 0.30 100 0. 16 (8) Dye (e), 0.30+compd. (11), 3.50 0.18

(9) Dye (i), 0.30 100 0. 08 (10) Dye (i), 0.30+compd. (If), 3.50.- 138 0. 12

(11) Dye (j), 0.30-l-compd. (II), 3.50.. 100 0.10 (12) Dye (j), 0.30+compd. (If), 3.50 132 0. 12

(13) Dye (k), 0.30+compd. (If), 3.50 100 0.13 (14) Dye (k), 0.30+eornpd. (If), 3.50 141 0.20

15) Dye 1 0.30 100 0.08 (16) Dye (l), 0.30+compd. (If), 3.50-. 126 0. 09

(17) Dye (m), 0.30 100 0. 09 (18) Dye (m), 0.30+cornpd. (II), 3.50 141 0. 12

where dye (f) was OH? I- r r 01H 02H! dye (g) was own-011:0. x

dye (j) was CzHs (k) was Hat-cam. I

dye (l) was CH3 I EXAMPLE 4 The silver bromochloride gelatin emulsion as in Example 3 was added with 0.25 g./mol AgX of 9-ethyl-5,5'- diphenyl-3,3'-bis-sulfobutyl oxacarboxycyanine pyridinium salt, let alone for 30 minutes at 35 C., and added with a stabilizer and a hardening agent. The emulsion was then further added with 30 g./mol AgX of 1-(4-phenoxy- 3-sulfophenyl)-3-heptadecyl-5-pyrazone and applied on a film support followed by drying.

In this case, before adding the polymethine dye, a set of the emulsion was added with 1-2 g./mol AgX of compound (If) and another set of the emulsion was added with 1-2 g./mol AgX of dodecyl-trimethyl ammonium bromide.

A set of these samples were subjected to sensitometry exposure through a blue filter transmitting light of about 430 Nm. and another set of the samples were subjected to sensitometry exposure through a green filter transmitting light of about 550 Nm. and then they were colordeveloped using N,N-diethylamino aniline to form a magenta color image. The samples were then examined about fogs and relative sensitivities. The results are shown in the following table.

TABLE 4 Blue Green exposure exposure relative relative sensisensi- Additive (g./mol AgX) tivity tivity Fog None 100 0. 09 Cornpd. (II), 1.0... 102 138 0.09 Compd. (If), 2.0... 114 0.09 Dodecyltrimethyl ammonium bromide, 10 129 138 0.12 Dodeoyltrimethyl ammonium bromide, 2.0. 140 140 0. 24

EXAMPLE 5 A mixture of g. of a 0.06% methanol solution of the polymethine dye (11) shown below and 2.5 to 80 g. of a 2% methanol solution of compound (If) was added in 1 kg. of an emulsion containing 0.85 mol of silver iodobromide and chemically sensitized with a sulfur-containing sensitizer and a gold salt-containing sensitizer by a conventional method and, after letting alone for 30 minutes at 40 C., the emulsion was added with a usual stabilizer, a hardening agent, and then 200 parts of an aqueous 5% solution of 1-hydroxy-4-sulfo-N-octadecyl- 2-naphthamide as a coupler.

The prepared coating solution was coated upon a film support and dried. The coated sample Was exposed and developed as in Example 2. The results for detecting the fog and the relative sensitivity are shown in Table 5.

' olmsoiuficam EXAMPLE 6 Into 1 kg. of an emulsion containing 0.15 mol of silver chlorobromide prepared by a conventional method was added a mixture of 30 g. of a methanol solution of 0.1% of 9-ethyl-5,5'-diphenyl-3,3'-bis-sulfobutyl oxacarbocyanine-pyridinium salt and 15 to 150 g. of a 2% methanol solution of compound (Ib) and then the emulsion was added with 7 g. of l-(4-phenoxy-3-sulfophenyl)-3-heptadecyl-5-pyrazolone as a coupler. The emulsion was, after letting alone for 30 minutes at 35 C., coated upon a film support and dried. The values of fog and relative sensitivity obtained by testing as in Example 4 are shown in Table 6.

What is claimed is:

1. A gelatino-silver halide photographic emulsion containing a methine dye and a compound having the general Formula I:

R1 n-f r rq omooowherein in Formula I R represents an alkyl group having 8 to 18 carbon atoms; R represents(CH CH O) H; R represents (CH CH O) H, p and q each represents a cardinal number including 0, and p-l-q equals 1 to 18, provided that when p is zero R is CH COOH and when q is zero R is -CH COOH, said methine dye having a general formula selected from the group consisting of:

wherein in Formulas II and III L L and L each represents a methine group, n is an integer of from 1 to 2, m is an integer of from 1 to 3, X is an anion selected from the group consisting of Br', 1*, SCN- and C10 Z and Z are each selected from the class consisting of atomic groups necessary for forming heterocyclic rings having 5 to 6 members, a is an integer of from 1 to 3, P and Q taken together are the atomic groups necessary for forming heterocyclic rings having 5 members and containing in the ring 3 carbon atoms, one nitrogen atom and one of nitrogen, sulfur and oxygen atoms and R and R are each selected from the class consisting of alkyl groups, allyl groups and substituted alkyl groups, said substituents being selected from the class consisting of hydroxy, acetoxy, sulfo, carboxy, alkoxy, sulfate and phenyl groups.

2. The emulsion as claimed in claim 1 wherein said emulsion contains the compound shown by the general Formula I in an amount of about 0.05 g. to 20 g. per 1 mol of silver halide.

3. The emulsion as claimed in claim 1, wherein said methine dye has the formula wherein R and R are each selected from the class consisting of alkyl groups, allyl groups, and substituted alkyl groups; said substituents being selected from the class consisting of hydroxy, acetoxy, sulfo, carboxy, alkoxy, sulfate and phenyl groups; L L and L each represents a methine group; ,X is an anion selected from the class 12 consisting of BF, 1*, SCN- and C10 Z and Z are each selected from the class consisting of atomic groups necesary for forming heterocyclic rings having 5 to 6 members; It is an integer from 1 to 2; and m is an integer from 1 to 3, v

4. The emulsion as claimed in claim 1, wherein said methine dye has the formula rzi 1 P R1 1'-I oH=oH n-1-o:(L, L,)d 1=o 'Q wherein R is selected from the group consisting of alkyl groups, allkyl groups andsubstituted alkyl groups," said substituents being selected from the classconsisting of hydroxy, acetoxy, sulfo, carboxy, alkoxy', sulfate and phenyl groups; L and L each represents a methine group; Z is selected from the class consisting of atomic groups necessary for forming 'heterocyclic rings-having from 5 to 6 members; P and Q taken together are the atomic groups necessary for forming heterocyclicrings having 5 members and containing in the ring 3carbon atoms, one nitrogen atom and one of nitrogen, sulfur and oxygen atoms; 21 is in integer from 1 to 2, and d is an integer from 1 to 3.

5. The emulsion as claimed in claim 1, wherein said compound shown by the Formula I is:

(CHzCHzQ) H H C l I(CHzOH;O) H

CHnCOO' wherein p+q is 18.

6. The emulsion as claimed in claim 1, wherein said compound shown by the Formula I is:

(CHzCHzOhH H,,o,2 fi oHzoH,o),H

wherein p-l-q is 10.

- 7. The emulsion as claimed in claim 1, wherein said compound shown by the Formula I is:

zC zOhH Hi5c,ifi cH1cHio)qH 0111000- wherein p+q is 5.

References Cited UNITED STATES PATENTS 2,271,623 2/1942 Carroll 96104 3,113,026 12/1963 Sprung 96107 I. TRAVIS BROWN, Primary Examiner Us. '01; X.R.