U.S. patent number 3,713,832 [Application Number 04/841,717] was granted by the patent office on 1973-01-30 for solarization type silver halide emulsion containing a halogenated hydroxyphthalein sensitizing dye and a desensitizing compound.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Masanao Hinata, Masao Sawahara, Keisuke Shiba.
United States Patent |
3,713,832 |
Shiba , et al. |
January 30, 1973 |
SOLARIZATION TYPE SILVER HALIDE EMULSION CONTAINING A HALOGENATED
HYDROXYPHTHALEIN SENSITIZING DYE AND A DESENSITIZING COMPOUND
Abstract
A direct positive silver halide photographic emulsion
illustrates improved qualities when it contains at least one dye
represented by the following general formula: ##SPC1## And at least
one desensitizing compound represented by either of the following
two general formulas: ##SPC2## X.sub.1, x.sub.2, x.sub.3, x.sub.4,
or X.sub.5 can be hydrogen atom or a halogen atom, q can be 1, 2, 3
or 4, M can be a hydrogen atom, an alkali metal, NH.sub.4 or an
alkaline earth metal, Y represents non-metallic atoms necessary to
complete a heterocyclic ring, R can be an alkyl group or a
substituted alkyl group, a, b, and r can be 1 or 2, and X
represents an anion.
Inventors: |
Shiba; Keisuke (Kangawa,
JA), Hinata; Masanao (Kangawa, JA),
Sawahara; Masao (Kangawa, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Minami, Ashigara-shi, Kanagawa, JA)
|
Family
ID: |
12841604 |
Appl.
No.: |
04/841,717 |
Filed: |
July 15, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Jul 15, 1968 [JA] |
|
|
43/49815 |
|
Current U.S.
Class: |
430/606; 430/570;
430/594; 430/598; 430/940 |
Current CPC
Class: |
G03C
1/48523 (20130101); G03C 1/4853 (20130101); Y10S
430/141 (20130101) |
Current International
Class: |
G03C
1/485 (20060101); G03c 001/36 () |
Field of
Search: |
;96/101,64,139 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Brown; J. Travis
Assistant Examiner: Louie, Jr.; Won H.
Claims
We claim:
1. A direct positive silver halide photographic emulsion which has
been previously fogged to maximum density containing at least one
dye represented by the following general Formula (I): ##SPC7##
in which X.sub.1, X.sub.2, X.sub.3, X.sub.4 and X.sub.5 represent,
respectively, a member selected from the group consisting of
hydrogen atoms or halogen atoms, q represents 1, 2, 3 or 4, and M
represents a member selected from the group consisting of a
hydrogen atom, an alkali metal, NH.sub.4 or an alkaline earth
metal; and at least one desensitizing compound represented by the
following general Formula (II):
in which Y represents non-metallic atoms necessary for completing a
heterocyclic ring, R represents an alkyl group or a substituted
alkyl group, a, b, and r represent 1 or 2, and X represents an
anion; or at least one desensitizing compound represented by
general Formula (III):
in which Y, r and b have the same meaning as in general Formula
(II).
2. The direct positive silver halide photographic emulsion claimed
in claim 1, wherein the halogen atoms in X.sub.1, X.sub.2, X.sub.3,
X.sub.4 and X.sub.5 of the general Formula (I) are selected from
the group consisting of chlorine, bromine and iodine.
3. The direct positive silver halide photographic emulsion claimed
in claim 1, wherein said heterocyclic rings containing Y in general
Formula II are selected from the group consisting of thiazolines,
thiazoles, benzothiazoles, naphthothiazoles, oxazoles,
benzoxazoles, naphthoxazoles, benzoselenazoles, naphthoselenazoles,
benzimidazoles, 2-quinolines, 4-quinolines and indolenines.
4. The direct positive silver halide photographic emulsion claimed
in claim 1, wherein said alkyl group in R of the general Formula II
is a methyl or ethyl group.
5. The direct positive silver halide photographic emulsion claimed
in claim 1, wherein said substituted alkyl group in R of the
general Formula II is selected from the group consisting of
2-hydroxyethyl, 2-methoxyethyl, carboxymethyl, 2-carboxyethyl,
2-sulfoethy, 3-sulfopropyl or carboethoxymethyl group.
6. The direct positive silver halide photographic emulsion claimed
in claim 1, wherein the proportion, by weight, of said dye
represented by general formula I to said desensitizing compound
represented by general Formula II or III is from 1:10 to 10:1.
7. The process which comprises coating am emulsion as recited in
claim 1 onto a support and thereafter imagewise exposing said
emulsion; and developing said exposed emulsion to form a silver
image in the unexposed areas of the emulsion.
8. The direct positive silver halide photographic emulsion of claim
1, wherein said dye represented by general Formula I is present in
an amount of from 10 to 150 mg/Kg of emulsion.
9. The direct positive silver halide photographic emulsion of claim
1, wherein said dye represented by general Formula I is present in
an amount of from 20 to 100 mg/Kg of emulsion.
10. The direct positive silver halide photographic emulsion of
claim 1, wherein said dye represented by general Formula I is a
member selected from the group consisting of ##SPC8##
11. The direct positive silver halide photographic emulsion of
claim 1, wherein said desensitizing compound represented by general
Formula II is a member selected from the group consisting of
##SPC9##
12. The direct positive silver halide photographic emulsion of
claim 1, wherein said desensitizing compound represented by general
Formula III is a member selected from the group consisting of
##SPC10##
13. The process of claim 7, wherein said dye is present in an
amount of from 10 to 150 mg/Kg of emulsion.
14. The process of claim 7, wherein said dye is present in an
amount of from 20 to 100 mg/Kg of emulsion.
15. The process of claim 7, wherein the proportion, by weight, of
said dye to said compounds is within the range of from 1:10 to
10:1.
16. A direct positive silver halide photographic emulsion when has
been previously fogged to maximum density containing
a. at least one dye selected from the group consisting of
##SPC11##
b. at least one desensitizing compound selected from the group
consisting of ##SPC12##
or
c. at least one desensitizing compound selected from the group
consisting of ##SPC13##
said dye being present in an amount of from 20 to 100 mg/Kg of
emulsion,
and
the proportion, by weight, of said dye to said desensitizing
compound ranging from 1:10 to 10:1.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a silver halide photographic emulsion, in
particular to a previously fogged silver halide photographic
emulsion used for direct positive materials.
2. Description of the Prior Art:
It is well known that a sensitizing dye can be added to a
previously fogged silver halide photographic emulsion capable of
directly giving a positive image by exposing and developing,
whereby said silver halide emulsion is spectrally sensitized and,
consequently, the total sensitivity is raised. It is also well
known that the contrast of an image varies with the type of
sensitizing dye added to the emulsion and the quantity thereof,
even though the total sensitivity of the emulsion is raised.
Generally, by increasing the amount of a sensitizing dye which is
added to a direct positive silver halide photographic emulsion, the
total sensitivity thereof is markedly raised, but, in many cases, a
satisfactory image is not obtained, mainly due to lowering of the
maximum density (D.sub.max) and contrast.
We have made various studies on such problems and have found that a
halogen-substituted hydroxyphthalein dye represented by the
following general Formula (I) is excellent as a dye capable of
raising the total sensitivity while keeping a predetermined maximum
density and contrast:
GENERAL FORMULA (I) ##SPC3##
in which X.sub.1, X.sub.2, X.sub.3, X.sub.4 and X.sub.5 represent,
respectively, hydrogen atoms or halogen atoms, q represents 1, 2, 3
or 4 and M represents a hydrogen atom, an alkali metal such as Na
or K, NH.sub.4 or an alkaline earth metal such as 1/2 Ca.
When a sensitizing dye is added to a direct positive silver halide
photographic emulsion, furthermore, the total sensitivity thereof
is raised. However, in some cases, "re-reversal" is enlarged,
hardly resulting in a satisfactory white color.
The term "re-reversal" describes the phenomenon that, as shown by
the dotted curve of the characteristic curve in FIG. 1, if a direct
positive photographic emulsion showing solarization is given a
sufficient amount of exposure, the density eventually ceases and
then shows a new upward trend (see C. E. Kenneth Mees; "The Theory
of the Photographic Process," Revised Edition, pages 243 and 244,
1942).
This "re-reversal", dependent upon the process of preparting the
silver halide photographic emulsion, is particularly large when the
emulsion is sensitized with the halogen-substituted
hydroxyphthalein dye represented by the foregoing general Formula
(I). Accordingly, it is hard to use this dye in a practical
process.
It is the principal object of the invention to provide a direct
positive silver halide photographic emulsion having high
sensitivity, which has a low minimum density without "re-reversal"
while holding a predetermined maximum density and a high
contrast.
SUMMARY OF THE INVENTION
The present invention provides additives to a direct positive
silver halide photographic emulsion which provide high sensitivity,
low minimum density and a lack of "re-reversal" while providing a
predetermined maximum density and high contrast.
The additives comprise at least one dye represented by the
following general Formula (I): ##SPC4## in which X.sub.1, X.sub.2,
X.sub.3, X.sub.4 and X.sub.5 represent, respectively, a member
selected from the group consisting of hydrogen atoms or halogen
atoms, q represents 1, 2, 3 or 4, and M represents a member
selected from the group consisting of a hydrogen atom, an alkali
metal, NH.sub.4 or an alkaline earth metal; and at least one
desensitizing compound represented by the following general Formula
(II):
in which Y represents non-metallic atoms necessary for completing a
heterocycylic ring, R represents an alkyl group or a substituted
alkyl group, a, b, and r represent 1 or 2, and X represent an
anion; or at least one desensitizing compound represented by
general Formula (III):
in which Y, r and b have the same meaning as in general Formula
(II).
The present invention thus provides a direct positive silver halide
photographic emulsion with high sensitivity, low minimum density,
no re-reversal and a predetermined maximum density and high
contrast.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are plots of density versus light sensitivity (log
E).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The heretofore mentioned object can be accomplished by
incorporating a desensitizing compound represented by the following
general Formula (II) or general Formula (III) in a direct positive
silver halide photographic emulsion, sensitized with the
halogen-substituted hydroxyphthalein dye represented by the
foregoing general Formula (I):
GENERAL FORMULA (II)
in which Y represents non-metallic atoms necessary for completing a
heterocyclic ring such as thiazolines, thiazoles, benzothiazoles,
naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles,
benzoselenazoles, naphthoselenazoles, benzimidazoles, 2-quinolines,
4-quinolines and indolenines, R represents an alkyl group one to
four carbon atoms such as a methyl or ethyl group, or a substituted
alkyl group one to four carbon atoms such as 2-hydroxyethyl,
2-methoxyethyl, carboxymethyl 2-carboxyethyl, 2-sulfoethyl,
3-sulfo-propyl or carboethoxymethyl group, X represents an anion
such as a halide, toluenesulfonate or a perchlorate ion and a, b
and r represent 1 or 2; and
GENERAL FORMULA (III)
in which Y, r and b have the same meaning as in General Formula
(II). Examples of the compound represented by General Formula (I)
are as follows: ##SPC5##
The dyes represented by the foregoing general Formula(I) are well
known and sold.
Examples of the compound represented by General Formula (II) and
(III) are as follows: ##SPC6##
The desensitizing compounds represented by the foregoing general
Formulas (II) and (III) are well-known, and are capable of lowering
the minimum density (D.sub.min) of a direct positive silver halide
photographic emulsion, as disclosed in U.S. Pat. No. 2,541,472.
It is surprising that the dye of general Formula (I), according to
the invention, has an excellent action for sensitizing a direct
positive halide photographic emulsion, since it has either no
sensitizing effect on an ordinary negative emulsion or a much lower
sensitizing effect than a cyanine sensitizing dye or merocyanine
sensitizing dye.
The direct positive silver halide photographic emulsion, sensitized
with the dye represented by the general Formula (I) has such
features that the sensitivity is high, the maximum density
(D.sub.max) is not substantially lowered and the contrast is not
lowered. However, its "re-reversal" and minimum density (D.sub.min)
are so high that it cannot be put to practical use.
Further, when the desensitizing compound represented by the general
Formula (II) or (III) is added to an ordinary negative photographic
emulsion sensitized by a spectral sensitizing dye, the spectral
sensitizing action of the dye fades away, and the whole sensitivity
thereof lowers.
It has now been found that the foregoing disadvantage of a direct
positive silver halide photographic emulsion sensitized with the
dye represented by the general Formula (I) can be overcome by the
coexistence of the desensitizing compound represented by the
general Formula (II) or (III) in said emulsion. Ordinarily, the dye
represented by the general Formula (I) and the desensitizing
compound represented by the general Formula (II) or (III) are added
to an emulsion, preferably in the form of a solution. As suitable
solvents, there can be used water, methyl alcohol and ethyl
alcohol.
The amount of the dye represented by general Formula (I) which is
added to a silver halide photographic emulsion for direct positives
is effectively 10-150 mg., particularly 20-100 mg per kg of the
emulsion, while the amount of the desensitizing compound
represented by the general Formula (II) or (III) which is added is
effectively 10-150 mg, particularly 20-100 mg per kg of the
emulsion, the proportion by weight of the dye compound (I) and
desensitizing compound (II) or (III) being preferably 1:10 to
10:1.
Illustrative of the silver halides of the invention are silver
chloride, silver bromide, silver chlorobromide, silver
chloroiodide, silver iodobromide and silver chloroiodobromide.
The silver halide photographic emulsion for direct positives used
in the invention is fogged to a maximum density by light or by the
addition of a chemical fogging agent. Such a chemical fogging agent
must fog silver halide without affecting the emulsion. Thiourea
dioxide, stannous chloride, formaldehyde or hydrazine are usually
used as a chemical fogging agent.
After the fogging operation, a solution of the dye represented by
the general Formula (I) and a solution of the desensitizing
compound represented by general Formula (II) or (III) are added to
the emulsion (with adequate agitation), and the emulsion is then
coated onto a support member. The dye represented by the general
Formula (I) and the desensitizing compound represented by the
general Formula (II) or (III) may be added to the emulsion in any
optional sequence, or along with ordinary additives such as coating
aids and hardening agents. Suitable supports are, for example, a
glass sheet, cellulose derivative film, synthetic resin film or
baryta paper.
The following examples are given in order to illustrate the
invention in detail without limiting the same.
EXAMPLE 1
A silver chloroiodide (iodide 1.3 mol percent, chloride 98.7 mol
percent) emulsion was fogged with hydrazine dihydrochloride and,
its pH and pAg were respectively adjusted to 5.6 and 6.7. To the
emulsion were added, while stirring adequately, the dye represented
by the general Formula (I) and then the desensitizing compound
represented by the general Formula (II). The emulsion was then
coated onto a cellulose triacetate base. For comparison, only the
dye of general Formula (I) was added to the emulsion and coated
onto a base. After drying, the resulting photographic materials
were exposed by means of a sensitometer through a step wedge.
The thus exposed materials were developed with a developing
solution having the following composition.
Formula of developer Metol 4 g. Hydroquinone 10 g. Anhydrous sodium
sulfite 60 g. Anhydrous sodium carbonate 2.5 g. Water to 1,000
ml.
A direct positive image, after being developed, was fixed with a
fixing solution containing sodium thiosulfate, washed with water
and dried. Measurement of the optical density was carried out by
the use of a densitometer. The results are tabulated below.
---------------------------------------------------------------------------
TABLE 1
Compound Compound of of general general White formula I formula II
Sensi- Test (mg/kg (mg/kg tivity Max. Min. No. emuls.) emuls.) (log
E) density density
---------------------------------------------------------------------------
1 1.80 2.3 0.07 2 I-10(62.5mg) 0.38 2.3 0.15 3 I-10( ")
II-6(59.0mg) 0.66 2.2 0.08 4 I-10( ") II-6(118mg) 1.03 2.2 0.07 5
I-6(55.5mg) 0.82 2.3 0.34 6 I-6( ") II-6(59.0mg) 1.23 2.3 0.15 7
I-6( ") II-6(118mg) 1.43 2.3 0.10 8 I-12(73.5mg) 0.87 2.3 0.11 9
I-12( ") II-6(59.0mg) 1.39 2.3 0.07 10 I-12( ") II-6(118mg) 1.44
2.3 0.07
__________________________________________________________________________
The "re-reversal" effect is shown in FIG. 2 in which the numerals
2, 3 and 4 correspond to Test Numbers in Table 1. It is evident
therefrom that the "re-reversal" is lowered by adding the
desensitizing compound represented by general Formula (II) or
(III).
EXAMPLE 2
A silver chloroiodobromide (bromide 2.4 mol percent, iodide 1.3 mol
percent, chloride 96.3 mole percent) emulsion was fogged with
hydrazine dihydrochloride, and its pH and pAg were adjusted to 5.6
and 6.7, respectively. To the emulsion were added the dye
represented by the general Formula (I), while stirring adequately,
and then the desensitizing compound represented by the general
Formula (II) or (III), while stirring adequately. The emulsion was
then applied to a cellulose triacetate base. For comparison, only
the dye represented by general Formula (I) was added to the
foregoing fogged emulsion and coated onto a base. After drying, the
resulting photographic materials were exposed and developed in the
same manner to Example 1, thereby obtaining the results shown in
Table 2.
---------------------------------------------------------------------------
TABLE 2
Compound Compound of of general general White formula I formula II
Sensi- Test (mg/kg (mg/kg tivity Max. Min. No. emuls.) emuls.) (log
E) density density
---------------------------------------------------------------------------
1 1.67 2.2 0.06 2 I-10(125mg) 0.08 2.1 0.14 3 I-10( ") II-3(55 mg).
0.38 2.0 0.08 4 I-10( ") II-3(110mg) 0.77 2.0 0.07 5 I-6(110mg)
0.73 2.1 0.32 6 I-6( ") II-4(55mg) 1.14 2.1 0.15 7 I-6( ")
II-4(110mg) 1.34 2.0 0.11 8 I-12(37mg) 0.65 2.2 0.09 9 I-12( ")
II-5(54mg) 1.20 2.1 0.07 10 I-12( ") II-5(108mg) 1.25 2.1 0.07
__________________________________________________________________________
* * * * *