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Nov; 26,1946.
‘R. B. cams Em»
2,411,501
PHOTOGRAPHIC MATERIAL
Filled Dec. 6,- 1944
34D
500
40D
500
.
-
'"280
"W
iii/7:311 _
540
400
4
500
j
e00
-.
--"100
780‘
ma
W2
340
4,00 .
‘
500
600
"200
780
_____7”1;7§: 6
my
Roland?enwwd (Joni/1w
'
MZLZGPINVENTORS
BY
fy?m,
.
v ATTORMYY
‘
Patented Nov. 26, ‘1946
i
'
A
2,411,507
UNITED STATES PATENT OFFICE
2,411,507
PHOTOGBAPHIC MATERIAL
Ronald Bernard Collins, llford‘, and John Miller,
. Nottingham, England, assignors to Ilford Lim
ited; Ilford, England, a British company
Application December 6, 1944, Serial No. 566,823
In Great Britain December 20, 1943
(01. 95-7) '
12 Claims.
2
1.
V
The groups R11, R2 and R4 are preferably lower
This invention relates to photographic mate—
rials and particularly to the manufacture of dye
alkyl radicles, i. e. radicles containing-not more
sensitised photographic silver halide emulsions.
hydroxy lower-alkyl‘radicles, and the group R3,
Photographic silver halide emulsions have a
certain natural sensitivity-to light‘, but- this is re
' alkyl radicle, e. g. methyl or ethyl. These groups
than ll'carbon atoms, e- g. methyl or ethyl, or '
when not hydrogen, is also preferably a lower
stricted to a short range of - wavelengths in the
may, however, be higher alkyl radicles, or may be
aralkyl radicles such as benzyl or naphthyl
ultra-violet and/or blue regions of the spectrum.
The e?ect of incorporating a sensitising dye is to
impart to the emulsion sensitivity to light of other
wavelengths, It has been known for some time
methyl.
'
The residues D1, D2 and D3 may be selected
‘ from the residues of thiazoles, oxazoles, selena
that the effect of incorporating in'theemulsion,
soles and their polycyclic homologues such as'
together with a sensitising dye, a second sub
those of the benzene, naphthalene, acenaphthene
stance (which may or may not itself be a sensi
and anthracene series, pyridine and its polycyclic
tiser) sometimes imparts anadditional sensitivity
homologues, such as ‘quinoline and a- and p
to the emulsion beyond that which can be re
garded as the simple additive effector the sepa~
naphthaquinolines, lepidines, indolenines, dia
rate substances. Combinations of sensitising dye
and another substance which give this latter re
sult are known as supersensitising combinations.
zoles (e. g. thio-Mr-diazele) ,_ oxazolines, thiazo
Zines, such as pyrimidines and quinazolines, dia
lines and selenazolines,
The polycyclic com
. pounds of these series mayalso be substituted in
The present invention is concerned with super-_ “ ‘ the carbocyclic rings with one or more groups,
~ sensitising combinations.‘
According to the in
such as alkyl, aryl, amino, hydroxy, alkoxyand'
methylene-'dicxy groups, or by halogen atoms,“
I vention, photographic: silverhalide emulsions are
supersensitised by incorporating in.
emulsion
The acid radicle A may be, for example, ch10.
,_ ride, bromide, iodide, alkyl vsulphate, alkyl-p
a combination of a sensitising'dyestuirof the
toluene sulphonate or perchlorate.
In the case of the compound of general For
mula II, the groups'Xand Y, where ester groups,
are preferably lower alkyl esters. Where the
.
ov group X is alkyl, aryl or aralkyl it may be, for
example, methyl, ethyl or .a higher alkylgroup,
where R1 and R2 are the same or different and
benzyl, ‘naphthyl-methyl, phenyl' or'fnaphthyl.
are-alkyl or aralkyl groups ‘or substitutedgroups
of this type, R3 is hydrogen for'an, alkyLoraralkyl
Where it is an acyl group it is preferably a resi
due of a lower fatty acid, e. g. acetic or propionic
and are residues of heterocyclic nitrogen nuclei I 3.'acid. Where X and Y together-form the resi
due of a 5-membered‘keto-methylene ring this
‘of the classes common in cyanine dyes, A‘ is an '
‘ may be, for example, a pyrazolone, thiopyrazo
acid radicle, andn 1s nought or one, and a com
lone, rhodanine, indandione 'or hydantoin nu
pound of the general Formula II:
-
group, and Di and D2 are the same or di?erent
'19 cleus.
The following are examples of speci?c com
in
‘
~
-
Y pounds which maybe employed according to this
I invention, the compounds being lettered to facili
I
where D3 is the residue of a :heterocyclic nitro
tate ' subsequent reference:
gen’ ring (which may be the'same. or different
Dyestuffs of general Formula I
from D1 or D2) , R4 is an alkyl, aralkyl or substi
tuted group of this type, X is‘ a carboxyl, carbox- 4
ylic ester, acyl or nitrile group, and Y is a car
bocyanine iodide."
I . boxyl, carboxylic ‘ester, nitrile 0r acrylic ester
group, or Xand Y togethenformthe residue of a
5-memb'ere'd 'keto-methylene ring, and his nought
orone.
'
"
I‘
"
“
'
The above terms, as used-in the present speci
?cation and claims, have the following meaning:
Nltrile means '
‘
‘chloride.
,
‘
nineiodide.
.
.
.
,
G. 3.9-diethyl-3'-methyl - 4.4’ - dichlor-thiacar
bocyanine iodide;
I
v
where
.C. 3.3’-diethyl-g9-methyl --thiacarbocyanine bro
n.‘ mide,
‘3.3L9-ti‘iethyl _: 4.5 14*.54 'clibenzthiacarbocya-l'
cyanine iodide.
(H).
.LCEN
.
- E». 3.3’.Q-triethyl-oxacarbocyanine iodide.
' 5; F. ‘3.3’-dimethyl-9-ethy1-4.¢l'—dichlor - thiacarbo
Carboxyl means
-(:0 OH
Carboxylic ester means —-8 0
>
Acyl means
~
B. 3.3’.9-triethyl-5.5’~dichloro - thiacarbocyanine
‘ Acrylic ester,
.._QCH;VCH__C 0 O R .
is a hydrocarbon radical.vv f __ >
'
.
3.3’-diethyl-9-methyl - 4.4’ - dichlor-thiacar
bocyanine iodide. ,
_
-'
.
-
.
2,411,507
4
I. 3.3'-methyl-9.4.4’-trimethyl - thiacarbocyanine
iodide.
W. 4.2’ (3' methyl-dihydrobenzthiazolyl) -1-phen
yl-3-methyl-5-pyrazolone having the formula:
J. iodide.
3.3'4.4'-tetramethyl-Q-ethyI-thiaoarbocyanine
K. 3.3'-diethy1-9-methyl-5.6.5'.6'-bis-dioxymeth
ylene-thiacarbooyanine iodide.
L. 3.3'-diethyl-9-methyl-5.6.5‘.6’ - tetramethoxy
thiacarbocyanine iodide
M. 3.3’-diethyl~9-methy1~selenacarbocyanine io
dide.
X. 2.2'-(3' methyl-dihydrobenzthlazolyl) 1.3-in
dandione having the formula:
dide.
O. 1.3'-dimethyl-10-ethyl-2 -
nine iodide.
1?CuHi
10
N. 3.3'-dlmethyl-9-ethyl-selenacarbocyanine i0
quinothiacarbocya
Compounds of general Formula II
15
1?. Ethyl-3-methyl-dihyclrobenzthiazolyl-Z-cyan
acetate having the formula:
OH:
S
\czo/
N/
20I Y. 3-methyl-dihydrobenzthiazolyl-Z-acetone di
CN
carboxylate having the formula:
\C O O C2155
|
CH:
25
Q, 3-methyl-dihydrobenzthiazolyl-2-ac‘eto acetic
ester having the formula:
#1113
-
Z. 3-methy1-5.6.-dimethoxy dihydrobenathiazolyl
30
R. 3-ethyl-dihydrobenzthiazolyl-Z-ethyl
acetate having the formula:
2-cyanacetic ethyl ester having the formula:
35
CH3
cyan
ZA. 3-Inethyl-dihydrobenzthiazolyl-2-glutaoonic
' diethylester having the formula:
S
\ C=C/
N/
ON
40
\C O O CzHs
I
Call!
CH:
S. _ 3-methvl-dihydro-benzoxazolyl-2-ethy1 cyan
'23. 2-dicyanmethylene-3-methyl-dihydrobenz
acetate having the formula:
'
‘ thiazole having the formula:
o
\M/
>
\N/
ON
50
\o 00 01H.
ON
I
OH:
T. 3-methyl-4:5-benzbenzthiazole-2-ethyl cyan
CH:
55
ZC. 3-methyl—dihydrobenzselenazolyl-2-ethy1 cy
anacetate having the formula:
acetate having the formula:
Se
/
60
/
IIICH3
or:
\C O 0 02115
ZD. l-ethyl-dihydroquinolylidene-2-malonic eth'
yl ester having the formula:
V. 3-methyl-dihydrobenzthiazolyl-2-malonic eth
yl ester having the formula:
'0 o 0 02115
02H:
(be:
COOCZHF,
The optimum quantity of the dyestuif of gen
eral Formula I to be in corporated in the emulsion
will generally be of th e order of 5 to 50 cc.’ of a,
‘ 1 in 2000 solution of the dyestuff per litre- of‘
2,411,507
line) and 1b (dotted line). Fig. 2 shows the spec
tral 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 (dot
emulsion. The optimum quantity of the com
pound of general Formula II will generally fall
within the same range, but in many cases opti
mum results are obtained where the quantity of
such compound is somewhat greater than the
quantity of dyestuff used.’
The following examples illustrate the inven
ted 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
tion. In these examples the emulsions contain
ing the dyestuff of general Formula I and com
pound of general Formula II were tested for speed
to daylight and to “red” light. This latter ?gure
was obtained, by exposing the emulsions to white
light passing through a ?lter. which cuts off all
radiation of wavelengths less than 600 ma. , The
increase'in'the “red speed” shown by the super
sensitised emulsions in comparison with emul
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 col
loids for the emulsion may be employed, for
example polyvinyl alcohol, polyvinyl acetals, far
hydrolysed cellulose esters and the like.
sions containing only the dyestuffs of general
Formula I affords a measure of the supersensitis
What we claim is:
1. Silver halide photographic emulsions con
20 taining
a sensitizing‘ dyestuff of the general
' ing 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 supersensitis 25
ing compound were incorporated in a gelatin
silver iodobromide emulsion containing about 6.5
where R1 and R2 are each selected from the
group consisting of alkyl and aralkyl groups, R3
gms. of silver halide (calculated as silver) per
litre of emulsion, during the manufacture of the
is selected from the group consisting of the_
emulsion, and the resulting emulsion was coated 30 hydrogen atom, alkyl and aralkyl groups, D1 and
D2 are each selected from the group consisting
on glass and the speed values referred to above
of residues of heterocyclic nitrogen nuclei, A is
were determined. The results are set out in the
an acid radicle and n is selected from the group
following table:
'
consisting of nought and one, and a compound
‘I
Quantity
of the, general formula:
Quantity of
i9‘mm
“31 a 1 c'0m- 0°?i—‘p°““1d
ormu a
agile
0'
11n_cc;b€[§ g‘oumi
{if II1i_n
clrisdooi'
II
solution
in
mum I
emulsion
emulsion
15
A
A
15,
15'
None
P '
Q -'
7
28
22
A'
22
_T
B.
22
None,
B
22
P ,
,
22
'
~
None
__________ ._
2-2
. R
22
S
B
22
T
C
22
None
C
22
'13
D
22
None
22
P
E
22
None
E
22
P
K
15
None
K
15
P
K
15
None
K
15
Z
107
105
145
where D3 is selected from the same- class‘ as D1
and D2, R4 is selected from the same class as R1
15
and R2, X is selected from-the class consisting
of the carboxyl, carboxylic ester, acyl and nitrile
23
24
J 38
60
- groups, and atoms which with-Y form the residue
50
~- ' 78
of a 5-membered keto-methylene ring, and Y
I45
50
32
180
I 60
4
145
55
32 '
160
' 58
__________ __
135
15
155
19
134
49
155
80
110
11
135
19
120
17
'
D
92
165
____________ . .
B
40
135
15
______ ..
30
None
Redd
spee
Speed
__________ _ .
. A
B
in
per litre of
A
B
-
ormu a
solution
per litre of
'
14
.......... __
55
.......... _.
28
__________ _ _
30
__________ ._
30
170
330
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
50 S-membered keto-methylene
ring, and n is
selected fromythe group consisting of nought
and'oner,
*160
45
_
' 6
‘ 93'
v
. 68
'
'
,
2. Silver halide photographic emulsions con
taining a sensitizing dyestuff of the general
55
formula:
.
V
-
'
I
' The speed values given in the foregoing table
are substantially linearly related, i. e. are in
R1
direct proportion. It will be apparent from the
60
data given in the foregoing table, that the super;
sensitising combinations of this invention in
manycases not only impart an increased sensi
tivity to the emulsion in the sensitising region of
the'dyestuf‘f of Formula I, but actually effect an 65
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 sensi
tivity of the emulsion.
R:
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 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:
-
70'
These effects are illus
trated by the accompanyingdrawing which shows
spectral sensitivity curves for the emulsions of
certain of the foregoing examples.
7
whereDa is selected. fromthe same, class, asDi
R4. is; selected. fromathe sameaclass‘ as
In the drawing Fig. 1 shows thespectral sensi
and
tivitycurve- oi the emulsions. oiv Examples: is (full 75
2,411,507
' 8
B1 and R2, X is selected from the class consisting
of the carboxyl, carboxylic ester, acyl and nitrile
taining a sensitising dyestu? which is a com~
pound of the general formula:
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 11.
is
selected from the group consisting of nought
and one.
10 where R1 and R2 are each selected from the
group consisting of alkyl and aralkyl groups-R3
3. Silver halide photographic emulsions con
taining a sensitizing dyestuff of the general
is selected from the group consisting of the hy
formula:
drogen atom and alkyl and aralkyl groups, M1
and M2 are each the residue of a thiazole'nu
15 cleus and A is an acid radicle, and a compound
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
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 car
an acid radicle and n is selected from the group
consisting of nought and one, and a compound
of the general formula:
boxyl, carboxylic ester, acyl and nitrile groups
and atoms which with ‘Y form the residue of a
5-membered keto-methylene ring, and Y is se
lected from the group consisting of carboxyl, car
3O boxylic ester, nitrile and acrylic ester groups and
atoms which with X form the residue of a 5
where D; is a residue of an azole nucleus, R4 is
selected from the same class as R1 and R2, X is
membered keto-methylene ring.
selected from the class consisting of the carboxyl,
carboxylic ester, acyl and nitrile groups and
taining a sensitising dyestuff which is a com
pound of the general formula:
6. Silver halide photographic emulsions con
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 40
keto-methylene ring, and n is selected from the
group consisting of nought and one.
where R1 and R2 are each selected from the group‘
4. Silver halide photographic emulsions con
consisting of alkyl and aralkyl groups, R3 is se_-,
taining a sensitising dyestu? of the general
lected from the group consisting of the hydro_-;
formula:
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: '
I
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 hydro
gen atom, alkyl and aralkyl groups, D1 and D2
4
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
where M3 is a residue of a, benzthiazole nucleus,’
R4 is selected from the same class as R1 and R2,
X is selected from the class consisting of the
general formula:
carboxyl, carboxylic ester, acyl and nitrile groups
and atoms which with Y form the residue of a
60 5-membered keto-methylene ring, and Y is se
lected from the group consisting of carboxyl, car
boxylic ester, nitrile and acrylic ester groups and
atoms which with X form the residue of a 5
where D3 is a residue of an azole nucleus, R4 is
selected from the same class as R1 and R2, X is 65
membered keto-methylene ring.
selected from the class consisting of the carboXyl,
carboxylic ester, acyl and nitrile groups and
taining a, sensitising dyestu? which is a ‘com
7. Silver halide photographic emulsions con
pound of the general formula:
2
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 70
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 2' halide - photographic emulsions Icon
75
where R1 and R2 are. each ‘lower alkyl groups,
R3 is aloweralkyl group,.l\/IJL-and-M2;a1Te cathihe
a
' 2,411,507,
.
1'0
-
10. Silver halidephotographic emulsions con
residue of a‘thiazole nucleus and A is an acid
radicle, and a compound of the general formula:
taining a sensitising dyestu? which is a com
pound of the general formula:
-
R4
where M: is a residue of a thiazole nucleus, R4
where R1 and R2 are each lower alkyl groups, R3
'is a lower alkyl group, X is selected from the 10, is a lower alkyl group, M1 and M2 are each the
class consisting of the carboxyl, carboxylicester,
residue of a thiazole nucleus and A is an acid
acyl and nitrile groups and atoms which with Y
form the residue of a 5-membered keto-methyl
radicle, and a compound of the general formula:
ene 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-methyl
ene ring.
8. Silver halide photographic emulsions con
Y
.
whereMa is a residue of a thiazole- nucleus, R4
is ‘a lower ‘alkyl group, ‘X is a carboxylic ester
taining a sensitising dyestuff which is a com-‘ 20
group, and Y is a nitrile group.
pound of the general formula:
7
11. Silver halide photographic emulsions con
taining' a sensitising dyestuff which is a com
pound of the general formula:
R\
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 for- _
mula:
'
’,s
'
X
Lia: \G=>C/
\N/ -\Y
is
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 for
mula:
where M3 is a residue of a benzthiazole nucleus,
R4 is a lower alkyl group, X is selected from the
class consisting of the carboxyl, carboxylic ester, 40
where M3 is a residue of a benzthiazole nucleus,
acyl and nitrile groups and atoms which with Y
R4, is a lower alkyl group, X is a carboxylic ester
form the residue of a S-membered keto-methyl
group, and Y is selected from the group consist
ene ring, and Y is selected from the group con
ing of carboxyl, carboxylic ester, nitrile and
sisting of carboxyl, carboxylic ester, nitrile and
acrylic ester groups and atoms which with X
form the residue of a 5-membered keto-methyl
acrylic ester groups and atoms which with X
form the residue of a 5-membered keto-methyl
ene ring.
ene ring.
,
.
12. Silver halide photographic emulsions con
9. Silver halide photographic emulsions con
taining asensitising dyestuff which is a com
taining a sensitising dyestuffv which is a com
pound of the general formula: '
pound of the general formula:
where R1 and R2 are each lower alkylgroups, R3
'is a lower alkyl group, M1 and‘ M2 are each the
residue of a thiazole nucleus and A is an acid
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
R1
radicle, and a compound of the general formula:
of a thiazole nucleus, R4
where M: is a residue
is a lower alkyl group, X is a carboxylic ester
group, and Y is selected from the group consist
B2
A
radicle, and a compound of the general formula:
60
65
7
ing of carboxyl, carboxylic ester, nitrile and
acrylic ester groups and atoms which with X form 70
the residue of a 5-membered keto-methylene
ring.
where M3 is a residue of a benzthiazole nucleus,
R4 is a lower alkyl group, X is a carboxylic ester
group, and Y is a nitrile group.
RONALD BERNARD COLLINS.
JOHN MILLER.
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