US2411507A

US2411507A - Photographic material

Info

Publication number: US2411507A
Application number: US566823A
Authority: US
Inventors: Collins Ronald Bernard; Miller John
Original assignee: Ilford Ltd
Current assignee: Ilford Imaging UK Ltd
Priority date: 1943-12-20
Filing date: 1944-12-06
Publication date: 1946-11-26
Anticipated expiration: 1963-11-26

Description

Nov 26,19 6. R. B. cams Em 2,411,501

PHOTOGRAPHIC MATERIAL Fi led Dec. 6, 1944 34D 40D iii/7: 11

Rolandflenwwd (Joni/1w MZLZGPINVENTORS BY fy v ATTORMYY Patented Nov. 26, 1946 UNITED STATES PATENT OFFICE PHOTOGBAPHIC MATERIAL Ronald Bernard Collins, llford, and John Miller, Nottingham, England, assignors to Ilford Limited; Ilford, England, a British company Application December 6, 1944, Serial No. 566,823 In Great Britain December 20, 1943 This invention relates to photographic mate rials and particularly to the manufacture of dyesensitised photographic silver halide emulsions. Photographic silver halide emulsions have a certain natural sensitivity-to light, butthis is restricted to a short range of wavelengths in the The present invention is concerned with supersensitising combinations. I vention, photographic: silverhalide emulsions are According to the insupersensitised by incorporating in emulsion a combination of a sensitising'dyestuirof the where R1 and R2 are the same or different and are-alkyl or aralkyl groups or substitutedgroups of this type, R3 is hydrogen for'an alkyLoraralkyl group, and Di and D2 are the same or difierent and are residues of heterocyclic nitrogen nuclei I of the classes common in cyanine dyes, A is an acid radicle, andn 1s nought or one, and a compound of the general Formula II:

in I

where D3 is the residue of a :heterocyclic nitrogen ring (which may be the'same. or different from D1 or D2) R4 is an alkyl, aralkyl or substituted group of this type, X is a carboxyl, carbox- 4 ylic ester, acyl or nitrile group, and Y is a car- I boxyl, carboxylic ester, nitrile 0r acrylic ester group, or Xand Y togethenformthe residue of a 5-memb'ere'd 'keto-methylene ring, and hi nought orone. I The above terms, as used-in the present specification and claims, have the following meaning:

Carboxyl means -(:0 OH Carboxylic ester means -8 0 Acyl means (H).

Nltrile means .LC I Acrylic ester, QCH;VCH C 0 O R where is a hydrocarbon radical. f

12 Claims.

2 V The groups R11, R2 and R4 are preferably lower alkyl radicles, i. e. radicles containing-not more than l'carbon atoms, eg. methyl or ethyl, or

hydroxy lower-alkylradicles, and the group R3, when not hydrogen, is also preferably a lower alkyl radicle, e. g. methyl or ethyl. These groups may, however, be higher alkyl radicles, or may be aralkyl radicles such as benzyl or naphthylmethyl.

The residues D1, D2 and D3 may be selected from the residues of thiazoles, oxazoles, selenasoles and their polycyclic homologues such as' those of the benzene, naphthalene, acenaphthene and anthracene series, pyridine and its polycyclic homologues, such as quinoline and aand pnaphthaquinolines, lepidines, indolenines, dia- Zines, such as pyrimidines and quinazolines, diazoles (e. g. thio-Mr-diazele) oxazolines, thiazolines and selenazolines, The polycyclic compounds of these series mayalso be substituted in the carbocyclic rings with one or more groups,

such as alkyl, aryl, amino, hydroxy, alkoxyand' methylene-'dicxy groups, or by halogen atoms,

The acid radicle A may be, for example, ch10.- ride, bromide, iodide, alkyl sulphate, alkyl-ptoluene sulphonate or perchlorate.

In the case of the compound of general Formula II, the groups'Xand Y, where ester groups, are preferably lower alkyl esters.

example, methyl, ethyl or .a higher alkylgroup, benzyl, naphthyl-methyl, phenyl' or'fnaphthyl. Where it is an acyl group it is preferably a residue of a lower fatty acid, e. g. acetic or propionic .'acid. Where X and Y together-form the residue of a 5-memberedketo-methylene ring this may be, for example, a pyrazolone, thiopyrazolone, rhodanine, indandione 'or hydantoin nucleus.

' 9 The following are examples of specific com- Y pounds which maybe employed according to this I invention, the compounds being lettered to facilitate subsequent reference:

Dyestuffs of general Formula I bocyanine iodide." B. 3.3.9-triethyl-5.5-dichloro thiacarbocyanine chloride.

.C. 3.3-diethyl- 9-methyl --thiacarbocyanine bromide,

n. 3.3L9-tiiethyl 4.5 14*.54 'clibenzthiacarbocyanineiodide. E. 3.3.Q-triethyl-oxacarbocyanine iodide.

' F. 3.3-dimethyl-9-ethy1-4.l'dichlor thiacarbocyanine iodide. G. 3.9-diethyl-3'-methyl 4.4 dichlor-thiacarbocyanine iodide;

3.3-diethyl-9-methyl 4.4 dichlor-thiacarbocyanine iodide.

Where the o group X is alkyl, aryl or aralkyl it may be, for

Compounds of general Formula II 1?. Ethyl-3-methyl-dihyclrobenzthiazolyl-Z-cyanacetate havin the formula:

CN N/ C O O C2155 quinothiacarbocya- Q, 3-methyl-dihydrobenzthiazolyl-2-aceto acetic ester having the formula:

R. 3-ethyl-dihydrobenzthiazolyl-Z-ethyl acetate having the formula:

ON C=C N/ C O O CzHs I Call S. 3-methvl-dihydro-benzoxazolyl-2-ethy1 cyanacetate having the formula:

ON o 01H.

T. 3-methyl-4:5-benzbenzthiazole-2-ethyl cyanacetate having the formula:

cyan- V. 3-methyl-dihydrobenzthiazolyl-2-malonic ethyl ester having the formula:

4 W. 4.2 (3' methyl-dihydrobenzthiazolyl) -1-phenyl-3-methyl-5-pyrazolone having the formula:

CuH

X. 2.2'-(3' methyl-dihydrobenzthlazolyl) 1.3-indandione having the formula:

I Y. 3-methyl-dihydrobenzthiazolyl-Z-acetone dicarboxylate having the formula:

Z. 3-methy1-5.6.-dimethoxy dihydrobenathiazolyl- 2-cyanacetic ethyl ester having the formula:

ZA. 3-Inethyl-dihydrobenzthiazolyl-2-glutaoonic diethylester having the formula:

'23. 2-dicyanmethylene-3-methyl-dihydrobenzthiazole having the formula:

CH: ZC. 3-methyldihydrobenzselenazolyl-2-ethy1 cyanacetate having the III CH3 formula:

ZD. l-ethyl-dihydroquinolylidene-2-malonic eth' yl ester having the formula:

COOC HF,

02H: The optimum quantity of the dyestuif of general Formula I to be in will generally be of th 1 in 2000 solution of corporated in the emulsion e order of 5 to 50 cc. of a, the dyestuff per litreof emulsion. The optimum quantity of the compound of general Formula II will generally fall within the same range, but in many cases optimum results are obtained where the quantity of such compound is somewhat greater than the quantity of dyestuff used.

The following examples illustrate the invention. In these examples the emulsions containing the dyestuff of general Formula I and compound of general Formula II were tested for speed to daylight and to red light. This latter figure was obtained, by exposing the emulsions to white light passing through a filter. which cuts off all radiation of wavelengths less than 600 m The increase'in'the red speed shown by the supersensitised emulsions in comparison with emulsions containing only the dyestuffs of general Formula I affords a measure of the supersensitising eifect obtained.

Examples In these examples the compounds of Formulae I and II are referred to by the letters given to them above.

The combinations of dyestuif and supersensitising compound were incorporated in a gelatin silver iodobromide emulsion containing about 6.5 gms. of silver halide (calculated as silver) per litre of emulsion, during the manufacture of the emulsion, and the resulting emulsion was coated on glass and the speed values referred to above were determined. The results are set out in the following table:

Quantity Quantity of i 31 1 c ?i 1 mm a '0mormu a gi 11n cc;b[ g oumi {if II1i n clrisdooi' Redd in ormu a in spee mum I solution II solution Speed per litre of per litre of emulsion emulsion A None 92 15 A 15 P 7 107 23 A 15' Q 28 105 24 A 22 None 145 J 38 A' 22 T 15 170 60 B. 22 None 135 50 B 22 P 30 165 78 B 22 None I45 50 B 2-2 R 32 180 I 60 B 22 S 4 145 55 B 22 T 32 160 58 C 22 None 135 15 C 22 '1 14 155 19 D 22 None 134 49 D 22 P 55 155 80 E 22 None 110 11 E 22 P 28 135 19 K 15 None 120 17 K 15 P 30 330 *160 K 15 None 45 6 K 15 Z 30 93' v 68 The speed values given in the foregoing table are substantially linearly related, i. e. are in direct proportion. It will be apparent from the data given in the foregoing table that the super sensitising combinations of this invention in manycases not only impart an increased sensitivity to the emulsion in the sensitising region of the dyestuff of Formula I, but actually effect an increase in the overall sensitivity oi'the emulsion as shown by the generally increased daylight speed. Moreover, the inclusion of the compounds of Formula II frequently produces a marked change in the distribution of the spectral sensitivity of the emulsion. These effects are illustrated by the accompanyingdrawing which shows spectral sensitivity curves for the emulsions of certain of the foregoing examples. 7

In the drawing Fig. 1 shows thespectral sensitivitycurveoi the emulsions. oiv Examples: is (full line) and 1b (dotted line). Fig. 2 shows the spectral sensitivity curve of the emulsion of Examples 3a (full line) and 3b (dotted line). Fig. 3 shows the spectral sensitivity curve of the emulsion of Examples 6a (full line) and 6b (dotted line). Fig. 4 shows the spectral sensitivity curve of the emulsion of Examples 7a (full line) and 7b (dotted line). Fig. 5 shows the spectral sensitivity curve of the emulsion of Examples 8a (full line) and 8b (dotted line). Fig. 6 shows the spectral sensitivity curve of the emulsion of Examples 9a (full line) and 9b- (dotted line).

While this invention is of particular value in connection with the supersensitizing. of silver halide emulsions in gelatin, other binding colloids for the emulsion may be employed, for example polyvinyl alcohol, polyvinyl acetals, farhydrolysed cellulose esters and the like.

What we claim is:

1. Silver halide photographic emulsions containing a sensitizing dyestuff of the general where R1 and R2 are each selected from the group consisting of alkyl and aralkyl groups, R3 is selected from hydrogen atom, alkyl and aralkyl groups, D1 and D2 are each selected from the group consisting of residues of heterocyclic nitrogen nuclei, A is an acid radicle and n is selected from the group consisting of nought and one, and a compound of the general formula:

where D3 is selected from the sameclass as D1 and D2, R4 is selected from the same class as R1 and R2, X is selected from-the class consisting of the carboxyl, carboxylic ester, acyl and nitrile groups, and atoms which with-Y form the residue of a 5-membered keto-methylene ring, and Y is selected from the group consisting of carboxyl,

carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a S-membered keto-methylene ring, and n is selected from the group consisting of nought and'oner 2. Silver halide photographic emulsions containing a sensitizing dyestuff of the general formula: V I

R1 R: A

whereDa is selected. fromthe same, class, asDi and R4. is; selected. from the same class as the group consisting of the and one.

3. Silver halide photographic emulsions containing a sensitizing dyestuff of the general formula:

R1 R2 A where R1 and R2 are each selected from the group consisting of alkyl and aralkyl groups, R3 is selected from the group consisting of the hydrogen atom, alkyl and aralkyl groups, D1 and D2 are each selected from the group consisting of residues of heterocyclic nitrogen nuclei, A, is an acid radicle and n is selected from the group consisting of nought and one, and a compound of the general formula:

where D; is a residue of an azole nucleus, R4 is selected from the same class as R1 and R2, X is selected from the class consisting of the carboxyl, carboxylic ester, acyl and nitrile groups and atoms which with Y form the residue of a 5- membered keto-methylene ring, and Y is selected from the group consisting of carboxyl, carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a 5-membered keto-methylene ring, and n is selected from the group consisting of nought and one.

4. Silver halide photographic emulsions containing a sensitising dyestufi of the general formula:

where R1 and R2 are each selected from the group consisting of alkyl and aralkyl groups, R3 is selected from the group consisting of the hydrogen atom, alkyl and aralkyl groups, D1 and D2 are each the residues of azole nuclei, A is an acid radicle and n is selected from the group consisting of nought and one, and a compound of the general formula:

wher D3 is a residue of an azole nucleus, R4 is selected from the same class as R1 and R2, X is selected from the class consisting of the carboXyl, carboxylic ester, acyl and nitrile groups and atoms which with Y form the residue of a 5- membered keto-methylene ring, and Y is selected from the group consisting of carboxyl, carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a 5-membered keto-methylene ring, and n is selected from the group consisting of nought and one; 7

l 5. Silver halide photographic emulsions con- 8 taining a sensitising dyestufi which is a compound of the general formula:

where R1 and R2 are each selected from the group consisting of alkyl and aralkyl groups-R3 is selected from the group consisting of the hydrogen atom and alkyl and aralkyl groups, M1 and M2 are each the residue of a thiazole'nucleus and A is an acid radicle, and a compound of the general formula:

where M; is a residue of a thiazole nucleus, R4 is selected from the same class as R1 and R2, X is selected from the class consisting of the carboxyl, carboxylic ester, acyl and nitrile groups and atoms which with Y form the residue of a 5-membered keto-methylene ring, and Y is selected from the group consisting of carboxyl, carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a 5- membered keto-methylene ring.

6. Silver halide photographic emulsions containing a sensitising dyestuff which is a compound of the general formula:

where R1 and R2 are each selected from the group consisting of alkyl and aralkyl groups, R3 is se lected from the group consistin of the hydro gen atom and alkyl and aralkyl groups, M1 and M2 are each the residue of a benzthiazole nucleus and A is an acid radicle, and a compound of the general formula:

where M3 is a residue of a, benzthiazole nucleus,

where R1 and R2 are. each lower alkyl groups, R3 is aloweralkyl group,.l\/ JL-and-M2;a1Te cathihe 'is a lower alkyl group,

'is a lower alkyl group,

residue of athiazole nucleus and A is an acid radicle, and a compound of the general formula:

where M: is a residue of a thiazole nucleus, R4 X is selected from the class consisting of the carboxyl, carboxylicester, acyl and nitrile groups and atoms which with Y form the residue of a -membered keto-methylene ring, and Y is selected from the group con-, sisting of carboxyl, carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a 5-membered keto-methylene ring.

8. Silver halide photographic emulsions containing a sensitising pound of the general formula:

where R1 and R2 are each lower alkyl groups, R3 is a lower alkyl group, M1 and M2 are each the residue of a benzthiazole nucleus and A is an acid radicle, and a compound of the general formula:

,s X i where R1 and R2 are each lower alkylgroups, R3 M1 and M2 are each the residue of a thiazole nucleus and A is an acid radicle, and a compound of the general formula:

ring.

where M: is a residue dyestuff which is a com- 7 group, and

10. Silver halidephotographic emulsions containing a sensitising dyestufi which is a compound of the general formula:

where R1 and R2 are each lower alkyl groups, R3 is a lower alkyl group, M1 and M2 are each the residue of a thiazole nucleus and A is an acid radicle, and a compound of the general formula:

where R1 and R2 are each lower alkyl groups, R3

is a lower alkyl group, M1 and M2 are each the residue of a benzthiazole nucleus and A is an acid radicle, and a compound of the general formula:

where M3 is a residue of a benzthiazole nucleus, R4, is a lower alkyl group, X is a carboxylic ester group, and Y is selected from the group consisting of carboxyl, carboxylic ester, nitrile and acrylic ester groups and atoms which with X form the residue of a 5-membered keto-methylene ring.

12. Silver halide photographic emulsions containing a sensitising dyestuff which is a compound of the general formula:

R1 B2 A where R1 and R2 are each lower alkyl groups, R; is a lower alkyl group, M1 and M2 are each the residue of a benzthiazole nucleus and A is an acid radicle, and a compound of the general formula:

where M3 is a residue of a benzthiazole nucleus, R4 is a lower alkyl group, X is a carboxylic ester Y is a nitrile group.

RONALD BERNARD COLLINS. JOHN MILLER.