Spectral sensitization of photographic emulsions
United States Patent [191
[11]
4,326,023
DeSeyn
[45]
Apr. 20, 1982
[54] SPECTRAL SENSITIZATION OF PHOTOGRAPHIC EMULSIONS
[75] Inventor:
of the spectrum with a combination of three sensitizing
dyes. The dyes have the generic structural formulae:
Mary K. DeSeyn, Rochester, NY.
[73] Assignee: Eastman Kodak Company, Rochester, NY.
[21] Appl. No.2 723,418 [22] Filed:
Sep. 15, 1976
[51]
Int. Cl.3 .............................................. .. G03C 1/14
[52]
US. Cl. . . . . . .
[58]
Field of Search ................ .. 96/124, 137; 430/574,
. . . . . . .. 430/550; 430/574;
430/588 430/588, 550
[56]
References Cited U.S. PATENT DOCUMENTS 3,463,640 8/1969 3,907,575 9/1975 3,922,170 11/1975 3,967,967 7/1976
Ficken et al. ....................... .. Shiba et a]. ......................... .. Shiba et al. ..................... .. Hinata et al. ....................... ..
96/ 124 96/124 96/124 96/ 124
Primary Examiner—J. Travis Brown Attorney, Agent, or Firm—Joshua G. Levitt
[57]
ABSTRACT
Photographic emulsions are sensitized to the red region
11 Claims, No‘ Drawings
4,326,023
1
SPECTRAL SENSITIZATION’OF PHOVTOGRAPHIC EMULSIONS This application relates to photographic emulsions
y'Rli'and Rg'are, independently, alkyl or acid substituted
and elements. In a particular aspect it relates to a photo graphic emulsion which is sensitized to the red region of
alkyl, provided at least one of R1 and R2 is acid substituted alkyl;
the electromagnetic spectrum with a particular combi nation of dyes.
'
'
(1 is hydrogen, or
-' _
aand R1 together, are ethylene or propylene; G is hydrogen; G1 is hydrogen,» halogen or alkoxy;
Schwan et al US. Pat; No. 3,672,898 relates to multi
color photographic elements which produce good ac ceptable color rendition upon exposure to any of a vari
- G2 is hydrogen or alkoxy; or
ety of common illuminants, such as daylight, tungsten light sources and ?uorescent light ‘sources. This is ac
G and: Gyor Gland G2: are the atoms necessary to complete a fused benzene ring;
complished by adjusting the spectral, sensitivity of the
G3 is alkyl, alkoxy,v aryl, halogen or styry1;-and ‘G4 is hydrogen,‘ alkyl or halogen;
emulsions employed in the elements. One, way in which
this adjustment is accomplished is by employing combi
II; a dye having the structural formula:
nations of dyes to sensitize the various emulsion layers so that sensitivities of the individual layersconform to
20
idealized curve shapes of relative log sensitivity. Suit able dyes, and combinations thereof, for use in the red sensitive layer, are described in columns 19-21 ofsaid US. Pat. No. 3,672,898.
'
62
I have found that certain combinations of dyes are
particularly advantageous for sensitizing photographic where: R is methyl or ethyl,
emulsions to the red region of the electromagnetic spec trum. When such combinations are ‘employed, one or
R1 and R2 are, independently, alkyl, hydroxyalkyl, or
more of the following advantages are obtained: (a) There is an improvement in speed compared with corn
acid-substituted alkyl, provided at least one of R1 and R2 is acid-substituted alkyl or hydroxyalkyl; and
binations of dyes heretofore employed. (b) There is
G1ahd G2 are, independently, hydrogen, halogen, alkyl,
obtained a relative log sensitivity curve "having a broader peak and an improved curve shape. (0) Fewer
dyes are required than previously had been employed. The photographic vemulsions _of- my invention are
35 .
aryl'or alkoxy, provided that at least one of G1 and G1 is a substituent other than hydrogen; and III. a dye having the structural formula:
particularly advantageous as the red sensitive layer in the photographic elements described in US. Pat. No. 3,672,898. In addition, they are advantageously em ployed as the red sensitive layer in other multicolor photographic elements, or as the sole photosensitive layer in non-multicolor elements. In accordance with my invention there is provided a
photographic silver halide emulsion sensitized‘to the region of the electromagnetic spectrum between 590 and 640 nanometers with a dye from each of the follow
ing groups I, II and III: I. a dye having the structural formula:
where:
,
~
'
.
.
R is methyl, ethyl or a negatively charged ketomethyl ene residue which forms an allopolarcyanine dye; and R1 and R2 are each, independently, alkyl or acid-sub
Y
>=mp=cn~ .-
R] liq
Z,
IR
I
stituted alkyl;
>
and dyes I, II, and'III have associated an anion or a
cation, if necessary, to neutralize the charge on the dye 55 molecule.
_ " R2
As used in this speci?cation, the following de?nitions ' apply to the substituent in the structural formulae. The
alkyl and alkoxy groups typically contain 1 to 6 carbon , atomsand preferably are straight chain alkyl and alkoxy '60 ‘groups of l to 4 carbon atoms. Particularly preferred ‘ alkyl and alkoxy groups are methyl, ethyl, methoxy,
where: Y is selenium or sulfur; Z is oxygen or
and etho'xy. The hydroxyalkyl groups typically contain ,1 to 6 carbon atoms and preferably are hydroxypropyl and hydroxybutyl. The acid-substituted alkyl groups 65 typically'contain’ l to 6'carbon atoms and preferably are
R is methyl or ethyl when Z is oxygen, and R is hydrogen when Z is
’
acid-substituted ethyl, propyl and butyl. Representative acid substituents include carboxy, sulfo, sulfoalkoxy, sulfato, thiosulfato, and phosphono. Particularly pre
4,326,023
3
ferred acid-substituted alkyl groups are carboxyalkyl of 2 to 4 carbon atoms and sulfoalkyl of 2 to 4 carbon atoms. The aryl groups typically contain 6 to 10 carbon atoms. Preferred aryl are phenyl, and substituted
sulfoalkyl.’
ene residues which form allopolarcyanine dyes contain
10
5-one and indan-l,3-dione.
-
In a preferred embodiment of my invention the dyes have the structural formulae 1, II, and III shown above ' wherein: in formula I, Y is sulfur, Z is oxygen, R is
ethyl, R1 and R2 are alkyl or sulfoalkyl, provided that at least one of R1 and R2 is sulfoalkyl, is hydrogen, G is hydrogen, G1 and G2 are hydrogen or alkoxy, G3 is alkyl or aryl and G4 is hydrogen; in formula II, R is methyl or ethyl, R1 and R2 are alkyl, hydroxyalkyl or
I
1
'
structural formulae 1, II, and III wherein: in formula I Y is sulfur, Z is oxygen, R is ethyl, R1 and R2 are sulfoal kyl, a is hydrogen, G is hydrogen, G1 and G2 are alk oxy, G3 is phenyl and G4 is hydrogen; in formula II, R is ethyl, R1 and R2 are hydroxyalkyl and G1 and G2 are alkoxy; and in formula III, R is ethyl and R1 and R2 are
the moiety
Preferred ketomethylene compounds include 1,3-chro
'
Particularly preferred are dyes having the above
phenyl. The preferred halogen is chlorine. Ketomethyl
mandione (4-hydroxycoumarin), 3H-naphtho[2,l-b]py ran-l,3-(2I-I)-dione, 2~pyrazolin-5-one, 2-isoxazolin
4
formula III, R is methyl or ethyl and R1 and R2 are
sulfoalkyl. In Tables I, II, and III which follow, representative dyes having structural formulae I, II, and III, respec
- _tively, are described. In these tables, the following ab
breviations are employed: 3-SB for 3-sulfobutyl, 4-SB for‘ 4-sulfobutyl, 3-SP for 3-sulfopr0pyl, 3-HOPr for 3-hydroxypropyl, 2-HO Et for 2-hydroxyethyl, 2-C Et for 2-carboxyethyl and 3-C Pr for 3-carboxypropyl. Other abbreviations employ standard chemical sym bols. Many of these dyes are zwitterionic compounds and hence do not have ions associated with them. Some are anionic and have associated cations, while others are cationic and have associated anions. The ions are indi cated where they are associated with the dye and are necessary to neutralize the charge on the dye molecule.
OCH 3
4,326,023
5
6
’ 'v ‘TABLE I-continued G;
Y i ‘v I
G1
rlq G
‘
Z
G4
>Ca'-CIZ=CHA< R
$
R]
G3
R2
Y 40. s
Z N—C2H5
R H
R1 3-SP9
(1 H
R1‘ G G1 3-5139 —CH=CH—-CH=CH—
G2 H
G3~ Cl
G4 C1
Ions Natl?
41. s
N-isoC3I-I7
H
C2H5
H
3-589 —CH=CH—CH=CH-
H
C1
C1
-
TABLE II S
15
S
typical photographic addenda incorporated therein as G]
Q >=CH_(I:=CH_< N.
'
R
1- CH3
R
3
l
I
R1
R2
described in paragraphs III, IV, V, VI, VII, XI, and XII
G2
of this PLI publication. The emulsions of this invention can be employed to provide silver images or they can be
20 employed to provide dye images, the latter typically in
R1
R2
G1
G2
1°“
a multilayer, multicolor photographic element. When
3-5P9
3-SP9
OCH:
OCH;
Nae
employed in a multilayer multicolor photographic dye
2' CZHs
CH3
35129
H
OCH3
_
3.
CH3
4-5139
H
C6H5
—
3539 C4I-I9
CZHS 3-SP9
C1 OCH3
C1 OCH3
__ -
6- 6H;
3-H0 Pr 3-H0 Pr OCH:
OCHs
Bre
are describedin paragraph XII of the above PLI publi
7. CH3
2-C Et
9
CH3
CH3
_
cation‘
3_ CH3
4.559
iiggEet
OCH3
OCH3
Nae
C1H5
4_ CZHS 5. C2H5
.
' image the element can have incorporated in associa .
images are well known to those skilled in the art.
The following examples are included for a further understanding of this invention. In the following examples the controls are a four dye
5
>=CH—C=CH—< l0-4/mole Ag.
R1
R2
They are identi?ed below.
R1 3_SP9
R2 3_SP9
Ions Na@
‘ 3-s1=e
3~SP9
(cz?shNer
CZHS
CZHS
_
40 I
osXyoe
‘
Dye And Level Of Concentration Controls
I-l
I-40
111-2
x
A
1.21
1.51
0.171
0.328
B C
1.21 0.870
1.51 1.08
0.153 0.153
0.328 0.240
2
1121*
1:22
21:
3:22
‘Group derived from l,3-Bis-(2-methoxyethyDbarbituric acid
N
’.
The emulsions can be employed to provide negative
'
IIK ,
,. '
30 images or positive images. Processes for obtaining such
TABLE III S
’.
25 tlon with the present emulsion, a color forming coupler, typlcally a cyan dye formlng coupler. Sultable couplers
45
N
CH3O(CHZ)Z/ \u/ \(CH2)2—OCH3 % 50
S
.
‘
5
While the relative proportions of the dyes and the
ratio dye towide silverlimits halide which isupon employed can be variedofwithin depending the particular dyes employed, the particular silver halide emulsion employed, the curve shape desired, and the like, partic- 55
Q >=CH-
[11]
4,326,023
DeSeyn
[45]
Apr. 20, 1982
[54] SPECTRAL SENSITIZATION OF PHOTOGRAPHIC EMULSIONS
[75] Inventor:
of the spectrum with a combination of three sensitizing
dyes. The dyes have the generic structural formulae:
Mary K. DeSeyn, Rochester, NY.
[73] Assignee: Eastman Kodak Company, Rochester, NY.
[21] Appl. No.2 723,418 [22] Filed:
Sep. 15, 1976
[51]
Int. Cl.3 .............................................. .. G03C 1/14
[52]
US. Cl. . . . . . .
[58]
Field of Search ................ .. 96/124, 137; 430/574,
. . . . . . .. 430/550; 430/574;
430/588 430/588, 550
[56]
References Cited U.S. PATENT DOCUMENTS 3,463,640 8/1969 3,907,575 9/1975 3,922,170 11/1975 3,967,967 7/1976
Ficken et al. ....................... .. Shiba et a]. ......................... .. Shiba et al. ..................... .. Hinata et al. ....................... ..
96/ 124 96/124 96/124 96/ 124
Primary Examiner—J. Travis Brown Attorney, Agent, or Firm—Joshua G. Levitt
[57]
ABSTRACT
Photographic emulsions are sensitized to the red region
11 Claims, No‘ Drawings
4,326,023
1
SPECTRAL SENSITIZATION’OF PHOVTOGRAPHIC EMULSIONS This application relates to photographic emulsions
y'Rli'and Rg'are, independently, alkyl or acid substituted
and elements. In a particular aspect it relates to a photo graphic emulsion which is sensitized to the red region of
alkyl, provided at least one of R1 and R2 is acid substituted alkyl;
the electromagnetic spectrum with a particular combi nation of dyes.
'
'
(1 is hydrogen, or
-' _
aand R1 together, are ethylene or propylene; G is hydrogen; G1 is hydrogen,» halogen or alkoxy;
Schwan et al US. Pat; No. 3,672,898 relates to multi
color photographic elements which produce good ac ceptable color rendition upon exposure to any of a vari
- G2 is hydrogen or alkoxy; or
ety of common illuminants, such as daylight, tungsten light sources and ?uorescent light ‘sources. This is ac
G and: Gyor Gland G2: are the atoms necessary to complete a fused benzene ring;
complished by adjusting the spectral, sensitivity of the
G3 is alkyl, alkoxy,v aryl, halogen or styry1;-and ‘G4 is hydrogen,‘ alkyl or halogen;
emulsions employed in the elements. One, way in which
this adjustment is accomplished is by employing combi
II; a dye having the structural formula:
nations of dyes to sensitize the various emulsion layers so that sensitivities of the individual layersconform to
20
idealized curve shapes of relative log sensitivity. Suit able dyes, and combinations thereof, for use in the red sensitive layer, are described in columns 19-21 ofsaid US. Pat. No. 3,672,898.
'
62
I have found that certain combinations of dyes are
particularly advantageous for sensitizing photographic where: R is methyl or ethyl,
emulsions to the red region of the electromagnetic spec trum. When such combinations are ‘employed, one or
R1 and R2 are, independently, alkyl, hydroxyalkyl, or
more of the following advantages are obtained: (a) There is an improvement in speed compared with corn
acid-substituted alkyl, provided at least one of R1 and R2 is acid-substituted alkyl or hydroxyalkyl; and
binations of dyes heretofore employed. (b) There is
G1ahd G2 are, independently, hydrogen, halogen, alkyl,
obtained a relative log sensitivity curve "having a broader peak and an improved curve shape. (0) Fewer
dyes are required than previously had been employed. The photographic vemulsions _of- my invention are
35 .
aryl'or alkoxy, provided that at least one of G1 and G1 is a substituent other than hydrogen; and III. a dye having the structural formula:
particularly advantageous as the red sensitive layer in the photographic elements described in US. Pat. No. 3,672,898. In addition, they are advantageously em ployed as the red sensitive layer in other multicolor photographic elements, or as the sole photosensitive layer in non-multicolor elements. In accordance with my invention there is provided a
photographic silver halide emulsion sensitized‘to the region of the electromagnetic spectrum between 590 and 640 nanometers with a dye from each of the follow
ing groups I, II and III: I. a dye having the structural formula:
where:
,
~
'
.
.
R is methyl, ethyl or a negatively charged ketomethyl ene residue which forms an allopolarcyanine dye; and R1 and R2 are each, independently, alkyl or acid-sub
Y
>=mp=cn~ .-
R] liq
Z,
IR
I
stituted alkyl;
>
and dyes I, II, and'III have associated an anion or a
cation, if necessary, to neutralize the charge on the dye 55 molecule.
_ " R2
As used in this speci?cation, the following de?nitions ' apply to the substituent in the structural formulae. The
alkyl and alkoxy groups typically contain 1 to 6 carbon , atomsand preferably are straight chain alkyl and alkoxy '60 ‘groups of l to 4 carbon atoms. Particularly preferred ‘ alkyl and alkoxy groups are methyl, ethyl, methoxy,
where: Y is selenium or sulfur; Z is oxygen or
and etho'xy. The hydroxyalkyl groups typically contain ,1 to 6 carbon atoms and preferably are hydroxypropyl and hydroxybutyl. The acid-substituted alkyl groups 65 typically'contain’ l to 6'carbon atoms and preferably are
R is methyl or ethyl when Z is oxygen, and R is hydrogen when Z is
’
acid-substituted ethyl, propyl and butyl. Representative acid substituents include carboxy, sulfo, sulfoalkoxy, sulfato, thiosulfato, and phosphono. Particularly pre
4,326,023
3
ferred acid-substituted alkyl groups are carboxyalkyl of 2 to 4 carbon atoms and sulfoalkyl of 2 to 4 carbon atoms. The aryl groups typically contain 6 to 10 carbon atoms. Preferred aryl are phenyl, and substituted
sulfoalkyl.’
ene residues which form allopolarcyanine dyes contain
10
5-one and indan-l,3-dione.
-
In a preferred embodiment of my invention the dyes have the structural formulae 1, II, and III shown above ' wherein: in formula I, Y is sulfur, Z is oxygen, R is
ethyl, R1 and R2 are alkyl or sulfoalkyl, provided that at least one of R1 and R2 is sulfoalkyl, is hydrogen, G is hydrogen, G1 and G2 are hydrogen or alkoxy, G3 is alkyl or aryl and G4 is hydrogen; in formula II, R is methyl or ethyl, R1 and R2 are alkyl, hydroxyalkyl or
I
1
'
structural formulae 1, II, and III wherein: in formula I Y is sulfur, Z is oxygen, R is ethyl, R1 and R2 are sulfoal kyl, a is hydrogen, G is hydrogen, G1 and G2 are alk oxy, G3 is phenyl and G4 is hydrogen; in formula II, R is ethyl, R1 and R2 are hydroxyalkyl and G1 and G2 are alkoxy; and in formula III, R is ethyl and R1 and R2 are
the moiety
Preferred ketomethylene compounds include 1,3-chro
'
Particularly preferred are dyes having the above
phenyl. The preferred halogen is chlorine. Ketomethyl
mandione (4-hydroxycoumarin), 3H-naphtho[2,l-b]py ran-l,3-(2I-I)-dione, 2~pyrazolin-5-one, 2-isoxazolin
4
formula III, R is methyl or ethyl and R1 and R2 are
sulfoalkyl. In Tables I, II, and III which follow, representative dyes having structural formulae I, II, and III, respec
- _tively, are described. In these tables, the following ab
breviations are employed: 3-SB for 3-sulfobutyl, 4-SB for‘ 4-sulfobutyl, 3-SP for 3-sulfopr0pyl, 3-HOPr for 3-hydroxypropyl, 2-HO Et for 2-hydroxyethyl, 2-C Et for 2-carboxyethyl and 3-C Pr for 3-carboxypropyl. Other abbreviations employ standard chemical sym bols. Many of these dyes are zwitterionic compounds and hence do not have ions associated with them. Some are anionic and have associated cations, while others are cationic and have associated anions. The ions are indi cated where they are associated with the dye and are necessary to neutralize the charge on the dye molecule.
OCH 3
4,326,023
5
6
’ 'v ‘TABLE I-continued G;
Y i ‘v I
G1
rlq G
‘
Z
G4
>Ca'-CIZ=CHA< R
$
R]
G3
R2
Y 40. s
Z N—C2H5
R H
R1 3-SP9
(1 H
R1‘ G G1 3-5139 —CH=CH—-CH=CH—
G2 H
G3~ Cl
G4 C1
Ions Natl?
41. s
N-isoC3I-I7
H
C2H5
H
3-589 —CH=CH—CH=CH-
H
C1
C1
-
TABLE II S
15
S
typical photographic addenda incorporated therein as G]
Q >=CH_(I:=CH_< N.
'
R
1- CH3
R
3
l
I
R1
R2
described in paragraphs III, IV, V, VI, VII, XI, and XII
G2
of this PLI publication. The emulsions of this invention can be employed to provide silver images or they can be
20 employed to provide dye images, the latter typically in
R1
R2
G1
G2
1°“
a multilayer, multicolor photographic element. When
3-5P9
3-SP9
OCH:
OCH;
Nae
employed in a multilayer multicolor photographic dye
2' CZHs
CH3
35129
H
OCH3
_
3.
CH3
4-5139
H
C6H5
—
3539 C4I-I9
CZHS 3-SP9
C1 OCH3
C1 OCH3
__ -
6- 6H;
3-H0 Pr 3-H0 Pr OCH:
OCHs
Bre
are describedin paragraph XII of the above PLI publi
7. CH3
2-C Et
9
CH3
CH3
_
cation‘
3_ CH3
4.559
iiggEet
OCH3
OCH3
Nae
C1H5
4_ CZHS 5. C2H5
.
' image the element can have incorporated in associa .
images are well known to those skilled in the art.
The following examples are included for a further understanding of this invention. In the following examples the controls are a four dye
5
>=CH—C=CH—< l0-4/mole Ag.
R1
R2
They are identi?ed below.
R1 3_SP9
R2 3_SP9
Ions Na@
‘ 3-s1=e
3~SP9
(cz?shNer
CZHS
CZHS
_
40 I
osXyoe
‘
Dye And Level Of Concentration Controls
I-l
I-40
111-2
x
A
1.21
1.51
0.171
0.328
B C
1.21 0.870
1.51 1.08
0.153 0.153
0.328 0.240
2
1121*
1:22
21:
3:22
‘Group derived from l,3-Bis-(2-methoxyethyDbarbituric acid
N
’.
The emulsions can be employed to provide negative
'
IIK ,
,. '
30 images or positive images. Processes for obtaining such
TABLE III S
’.
25 tlon with the present emulsion, a color forming coupler, typlcally a cyan dye formlng coupler. Sultable couplers
45
N
CH3O(CHZ)Z/ \u/ \(CH2)2—OCH3 % 50
S
.
‘
5
While the relative proportions of the dyes and the
ratio dye towide silverlimits halide which isupon employed can be variedofwithin depending the particular dyes employed, the particular silver halide emulsion employed, the curve shape desired, and the like, partic- 55
Q >=CH-
