Note: Descriptions are shown in the official language in which they were submitted.
12987Z9
A METHOD OF PROCESSING A SILVER HALIDE
COLOR PHOTOSf~NSI~IVE MATERIAL
- SUBSTANTIALLY E~REE OE~ RINSING
AND A STABILIZING SOLUTION USED THEREFOR
FIELD OF THE INVENTION
This invention relates to a method of processing a
silver halide color photosensitive material without using
any substantial rinsing step an~ also to a non-rinsing
stabilizing solution suitably used therefor, and more
particularly, to a method of processing a novel silver
halide color photosensitive material which is excellent in
storage stability against light in a high temperature and
hi.gh humidity atrnosphere and whose unexposed surface is free
of stains, and a stabilizing solution used therefor.
~ACKGROUND OF TIIE INVENTION
Generally, a silver ha.l.ide color photosensitive
material which has been exposed to light is processed by
developing, bleach-fixing and rinsing steps or developing,
~ !
. .., ~
lZ987Z9
bleaching, rinsing, fixing, rinsing and stabilizing steps
but such Inetho~ ol- processirlg llas encountered the problem
involved in the preservation o~ environments or water
resources which has recently been deemed important.
Therefore, there have been proposed various methods for
reducing the amount of rinsing water which is used in large
quantities. For example, the specification of German Patent
No. 2,920,222 and a technical :Literature entitled "Water
E'low Rate in Immersion-Washing of Motion Picture Film"
(Journal, SMPTE. 64, pages 248-253, May (1955) by S.R.
Goldwasser) are known as showing techniques for reducing the
amount of rinsing water by reverse-flowing the water through a
plurarity of tanks. E~urther, there are described in the
Japanese Laid-open Patent Publications Nos. 57-8543,
58-14834 and 58-134636 methods for processing a
photosensitive material in a stabilized condition without
substantially performing a rinsing step.
However, although all of the above prior art techniques
have been proposed to control the environmental pollution by
reducing the amount of supply of rinsing water, they are
quite insufficient with respect to the time-lasting
preservation of a photographic image and especially, they
have the disadvantage of presenting a high degree of
color fading due to light in a high-temperature and
high-humidity atmosphere. Further, it has been found that
~Z9i 3'7~9
-- 3
the above problem is liable to take place depending
on the variation of processing conditions (mixing
conditions or temperature of the processing bath) due
to the use of a stabilizing agent free of rinsing.
Further, the number of mini-labs has been
increasing and ~hose which have already been
installed throughout the country count about 3,000 in
number as of May, 1985. It is said that about
one-third of them was installed in the past one year
period. Certainly, an unprecedented mini-lab boom!
Most of those mini-labs use a non-rinsing stabilizing
solution because of the requirements of compactness,
pipelessness and simplicity. However, it has been
found that many of the mini-labs have disadvantages
in that when a photosensitive material is processed
by such mini-labs, the stabilizing solution is
enriched to increase the salt density resulting in an
increase in the accumulation of an irradiation-proof
pigment or a sensitizing dye dissolving and flowing
from the photosensitive material with stains
generating on the material.
At the same time, with the recent mini-lab
boom, each company in this field of industry has come
to develop and sell a variety of kinds of automatic
developing machines but the mixing systems for
stabilizing solutions and capacities of such
developing machines are versatile tending to produce
too large differences in mixing capacity among them
and it - - ---------------------
V
12g8729
is the actual circumstances that there are some mini-labs
which are extremely undesirable with respect to the
prevention of s~ains generating on the photosensitive
rnaterial. Above all, such stains are remarkable on the
unexposed section of the photosensitive material and in the
case of color paper, since the unexposed section is white,
even a light stain makes itself a serious defect while in
the case of a negative color film, the exposure-time of the
printer is affected thereby so much as to produce a color
unbalance.
Further, it has been found that in case a color image
is stored, the generation of such stain deteriorates the
durability of the color image especially in a
high-temperature and high-humidity atmosphere.
SUMMA~Y OE TH~ INVENTION
Accordingly, and object ol this invention is to provide
a method of processing a photosensitive material which
method requires substantially no rinsing, is energy saving
and has a small pollution load, and also to provide a
stabili~ing solution used therefor.
Another object of this invention is to provide a method
of processing a photosensitive material which method is
adopted to prevent the lowering of preservation stability of
a colored image at the time of continuous processing,
lZ987~g
especially due to light in a high-temperature and
high-humidity atmosphere by usillg a stabilizing solution
requiring substalltialJy no rinsing, and also to provide such
stabilizing solution.
Still another object ol this invention is to provide a
method of processing a photosensitive material adopted to
prevent the generation of stains on the unexposed section of
the material taking place when Lhe material is
discontinuously processed for a prolonged period of time and
by a small amount of non-rinsing stabilizing solution, and
also to provide such stabilizir,g solution.
A further object of this invention is to provide a
method of processing a photosensitive material which method
controls the generation of bubbles of the stabilizing
solution when the material is conveyed at a high-speed
(e.g., higher than 3 m/min.) during processing, prevents the
bubbles from mixing into other processing solutions thereby
preventing the stabilizing solution from being wasted to no
purpose, and also to provide a non-rinsing stabilizing
solution used for the methocl.
A still further object of this invention is to provide
a method of processing a photosensitive material which is
capable of obtaining a highly-stabilized colored image even
during a high-speecl process (e.g., more than 3
m/min.) in a lab and in any other conditions, and also to
_________
'~
.
,"' ~ .
,''~ .
lZ9872g
- 6 --
provide a stabilizing solution free of rinsing.
An additional object of this invention is to provide a
non-rinsing stabilizing solution which is added with a
chemical compound capable of preventing the generation of
bubbles of the stabilizing solution without reducing the
efficiency of the solution.
DET~ILI:D DESCRIP'l'ION OF THE INVENTION
The method of processing a silver halide color
photosensitive material according to this invention features
that in case the material is processed with a
solution having a fixing capacity and subsequently processed
with a non-rinsing stabilizing solution, substantially without
rinsing process therebetween, the photosensitive ~aterial
contains a high-boiling point organic solvent having a
dielectric constant of 3.5 and higher and that the surface
tension of the non-rinsing stahilizing solution is in the
order of 20-60 dyne/cm..
It has been found that according to a preferred
embodiment of this invention, the above-mentioned
stabilizing solution contains a compound or emulsion type
silicone so that the object of the invention can be
effectively achieved.
Further, it has been found that according to a still
more favorable embodiment of this invention, the effect of
... . .. . .
, 12g87~g
the invention can be better displayed especially when the
silver halide color photosensitive material contains a high
boiling-point organic solvent having a dielectric constant
of 3.5 and higher as shown by the following general formula
[I] or [II].
General formula [I]
~ COOXl
COOR2
wherein Rl and R2 designate an alkyl group and alkenyl
or aryl group, respectively.
~eneral formula 1II]
OR3
\
01~5
wherein R3, R4 ana R5 designate an alkyl group and an
alkenyl or aryl gLoup, respectively.
The non-rinsing stabilizing solution in accordance with
one of the most preferable embodiments of the invention
contains a silicone.
This invention will now be described in further detail.
, _ __ _ _ _ _ _ . . .
12g~7Z9
- 8 -
It has hitherto been known that as described in the
Japanese Patent l~xamined PuhLication No. 49-26262, the
Research Disclosure No. 17431 and the Japanese Laid-open
Patent Publication No. 59-17551, a specific silicone
compound is added to a fina~ processing solution, which is
not a non-rinsin~ stabilizing solution and follows after
fixing and rinsing steps, for the purpose of
preventing the uneven distribution of waterdrops on the
film. However, this invention features that a
photosensitive material containing a high boiling-point
organic solvent having a specitic dielectric constant is
processed with a non-rinsing stabilizing solution having a
specifib surface tension. Particularly, the effect of this
invention can be rnore favorably displayed by adding a
silicone to the non-rinsing stabilizing solution following
the use of a processing solution having a fixing capacity
such as fixation or bleach-fixation, and in this respect,
this invention diEfers from the conventional technique
according to which a silicon compound is added to the final
processing solution which is used as a mere stabilizing bath
after rinsing, for the purpose of preventing the uneven
distribution of waterdrops on the film.
T~le silicone used Eor this invention belong to
organopolysiloxanes which are described, for example, in
"Chemical Encyclopedia," 14th abridged-edition Volume IV,
12987Zg
- ~J
page 872, Kyoritsu Publishing Co., Ltd., September 15,
1972. Further, a preferred siLicone compound is one that is
generally known as an anti-bubbling agent together with
solvents such as specific surface active agents and
alcoholic solvents.
Further, the silicones usecl in this invention are of
oil type, solution type, compound type and emulsion type and
the following compounds may be given as belonging to the
above types of silicone.
(i) Oil type
. FS anti-foam 200 (manufactured by Dow Corning
Corp.)
. L-45 (manufactured by Nihon Unicar Co., Ltd.)
ii) Solution type
. FS Xl)-2889 (manufactured by Dow Corning Corp.)
. FS XD-28g8 (
(iii) Compound type
. FS anti-foam DB-100 (manufactured by Dow Corning
Corp.)
. E'S anti-~oam 544
. FS anti-foam 001
. FS anti-foam 026A
. SAG-47 (manufactured by Nihon Unicar Co., Ltd.)
. SAG-100
. SAG-471
lZ98~7Z5~
- 10 --
. SAG-3300 (
. FZ-328
. FZ-334
. FZ-5604 (
. FZ-5603
(iv) Emulsion type
. FS anti-foam 545 (man~factured by Dow Corning
Corp.)
. FS-anti-foam 013B (
. FS anti-foam AFE
. FS anti-foam DB-31
. FS anti-foam DB-llON (
. FS anti-foam 025
. FS anti-foam 009
. FS anti-foam CE
. FS anti-foam BE
. FZ-336 (Nihon Unicar Co., Ltd.)
. FZ-5205
. SAG-30
. SAG-10 ( '~
. SAG-3310 (
. SAG-3390 (
. SAG-3393 (
. SAG-3395 (
lZ9~'7Z9
-- 1 1 --
. UNISA~
. FZ-3~0
. Anti-foam E-20 (manuEactured by Kao Corp.)
. Anti-foam 90 (manufactured by Dow Corning Corp.)
Of the above types of silicones, the compound and
emulsion type silicones can be favorably used for producing
the effect of this invention. Further, in the case of this
invention, the emulsion type silicones are especially
favorable in view of stability.
It is preferable that each type of silicones of this
invention be used in the range of 1 mg to 1 g of pure
silicone per 1 Q of the non-rinsing stabilizing solution and
more preferably in the range of 3 mg to 200 mg. When
exceeding 1 g, a stain tends to generate on the surface of
the photosensitive material and, when lower than 1 mg, the
effect of the invention tends to reduce.
~ s means Eor adding the silicone of this invention to
the stabilizin~ solution, there are a method of dropping an
undiluted silicone solution continuously or according to
necessity; a method of spraying the silicone solution; a
method of adding the silicone solution to the replenishing
solution or applying it to the photosensitive material; a
method of attaching the silicon solution to the
photosensitive material by addiny the solution to a bath
(prebath) having a fixing capacity; and a method of adding
: ' :
,' ~, ' '
.. i2g~7zg
the silicone solution by coating the solution to the wall
surface o~ a non-rinsing stabili~ation tank and liquating it
bit by bit into the tank.
The surface tension of the non-rinsing stabilizing
solution used ~or the processing according to this invention
is in the order o~ 20-60 dyne/cm when measured at a
temperature of 20C by the general measuring method
described in the literature entitled "Analysis of surface
active agents and testing method" (written by Fumio
Kitahara, Shigeo Hayano and Ichiro Hara and issued by
Kodansha Book Co., Ltd. on May 1, 1982) .
To determine the surface tension of the non-rinsing
stabilizing solution to be in the order of ~0-60 dyne/cm (at
20C), various kinds of agents may be used but the use of a
surface active agent is preferable. Such surface active
agent may be added to the solution in a tank together with a
replenishing solution or may be attached to the
photosensitive material through a prebath. Further, it is
also possible to add the agent to the non-rinsing
s~abilizing solution by liquating it from the photosensitive
material.
Of the surface active agents available for this
invention, compounds expressed by the following general
formulae [IIIJ to [VI] may preferably be used.
~ ~:g~37~
- 13 -
General formula IIII]
R - CH - COA R
R - CH - COOR
wherein either R~ or R7 designates a hydrogen atom and
the other designates a group expressed by the formula SO3M
(wherein M designates a hydrogen atom or monovalent cation,
A1 designates an oxygen atom or a group expressed by the
formula - NRlo - (wherein Rlo designates a hydrogen atom
or an alkyl group having 1-8 carbon atoms and R8 and Rg
designate an alkyl group having 4-16 carbon atoms, provided
that the alkyl yroups expressed by R8 and Rg or Rlo
may be substituted by fluorine atoms.
General formula lIVJ
A~ - 0 - (B)m - Xl
wherein A2 designates a monovalent organic group such as
an alkyl group having 6-20 carbon atoms, preferably 6-12
(for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl or
dodecyl group~ or an aryl group substituted by an alkyl
group having 3-20 carbon atoms and as aryl group, there are
given such groups as phenyl, tolyl, xynyl, biphenyl and
naphthyl of which the phenyl or toryl group is preferable.
As to the position at which the aryl group is bonded to the
alkyl, any of the o-position, m-position and p-position will
lzg8t7z9
- 14 -
do. Further, B designates ethylene oxide or propylene
oxide, m designates an integer in the order of 4-50 and X
designates a hydrogen atom, S03 Y or P03Y2 (wherein Y
designates a hydrogen atom, alkali metal atom (e.g., Na, K
or Li, etc.) or ammonium ion.
General formula IV]
R12 - I 14 X2 Q
Rll~ R12~ R13 and R14 designate a hydrogen
atom, an alkyl group and a phenyl group, respectively, with
the total number of carbon atoms in the order of 3-50.
X2 designates an anion of a halogen atom, hydroxyl group,
sulfonic aciA group, carbonic acid ~roup, ni~ric acid group,
acetic acid group, p-toluensulfonic acid group, etc.
General formula [Vl]
Rl~ R15
~X~Rl 6
(S03M)n (S03M)p
15' R16, R17 and R18 independently represents a
hydrogen atom and an alkyl group, and M is equivalent
~2g~729
- 15 -
to the general formula [III]. n and p designate O or
integers of 1-4 which are values satisfying the formula of
1 ~ n + p < 8.
lZ9~'72~
- 16 -
The following are typical examples of the cheinical
compounds expressed by the general formulae of [III] to [VI].
(Chemical compounds expressed by the general formula [III])
(i) CzH6 .(ii) C4H9
CH2COOCH2CHC6Hl3 C~LCOOCHzCHCIH~
C~COOCH2CHC6HI3 C}ICOOCH 2 CHC~H 9
C2H 6 ¦ C ~H
SO3Na SOsNB
(iii) (iv)
l 4Hg CH2CONHC8H17
CIH2coocH2cHc6Hls CHCOOCH2CHC,~Hg
cHcoocH2cHc6Hla 80~N~
C ~Hg
803K
(v) (vi)
~C4Hg
SO3Na TH2CON~
CHCONHC ID~21
CHCOOCHC 4 H 9
CH2~00CloH2t I C2H6
80~Na
~vii) (viii)
~C~HI3
fH2 CON \ CH 2 COOC 8H ~7
CH z COOC 8H ,7
CH2COOC"HI7
¦ SO~Na
SOgN~
'
.. . . .. . , .. . ,._ _. ,.,. . . .. .... . ~. . _ .. . _ _.. . ,. . ... _. -- ... . ... .. . . .
,,~ , -
i , ';
lZ98729
( ix)
C2~6
CH2COOC6H,2CHCH~
CHC00C 6 H ~2 CHCH 8
0 2H 5
SO3Na
(x)
C;H2C00CH2~CF2CF2 ) 3H
CHcoocl~2~cF2cF2 ) 3H
SO3Na
( x i )
CH2 COOC8F,7
CH C00C 8 F 17
SO ~ N a
(xii)
CH z--COOCH 2--CH--C 4 H g
C2Hs
CH--COOCH 2--CH--C ~ H 9
CzH6
~03Na
~Z98'~;~9
- 18 -
(Chemical compounds expresse~ by the general formula lIV])
(i)
Cl2H25o(c2H~o) ~n}~
ii)
CaH 17o~caH6o) IsH
( iii)
CgHl~O(C~H~O) ~SO3Na
( iv)
CloH2l0(C2H~O) ~sPO3Naz
(v)
C8H,7~3--O(C2H~o) loH
(vi)
C9HI9~3--o(Cz~lJ0) ~ 803Na
(vii)
C6H,3
C6H,a ~ O(C2H~O)P03(NHi)2
12987~
-- 19 --
(viii)
C7H,6
C7H~ o(C3~60)8H
(ix) OSH7
C3H7~0( 2H40) 12 ~Os
C3H7
(x)
c~2H25~o(c3H6o)25H
xi )
OH9
C8H 17~_0( C2H~O) l2H
(xii)
CgHl~--O(C2H~O) loH
(xiii)
C9H19~ O ~ 02H40 t4 SO3Na
CgHl g
(xiv)
C12H250~ 02H40~S03Na
1298~Z9
- 20 -
(Chemical compounds expressed by the general formula [V])
(i)
CH3
e
Cl6H3g-N~CH 3 C L
CH3
(ii)
CH3
C 8H 17--N~CH 2~ CL
CH3
( iii)
C2H6
e
C8HI7~ - c8Hl7 Br
- C2Hs
( iv )
C2H6
C l7H35--CONHCH2CH2~--,N--CH2~ C e
C2H5
~V)
CH3
C ~7 H 95--CONHCH 2 CH2 ~N--CH 2 CH 2 OH NO
CH~
,
lZg8~72g
-- 21 --
(vi)
CH~
C,7H35~N--CH~ Bre
CH~
(vii)
CH3
e
C12~12s--~--CH2~N--CH2CH2H CL
CHa
(viii)
CHa
C " H 23--COOCH 2 CH 2 NHCOCH2 ~N--CH ~ C ,e
CH,
( ix)
CH"
C lz ~ 25 ~3,N--CH2 ~ cLe
CH~
(x)
CHa
C 12 H 25--N~3 ( CH ~ CH2 0~2H C
~CH2 CH2 0~2~I
12g~72~
- 22 -
(Chemical compounds expressed by the general formula [VI])
(i)
SOaN~
0~
( ii)
I,-C~ Hq
NBO3 S ~903Na
( iii)
,~,SO8Na
NaOa 8
( iv)
80 ~Na
NaO8S ~903Na
(v)
OH~ 80~Na
¢~ ,
vi) 803Na
OH~
NaOa~ 903Na
,
- , -
i2~ g
-- 23 --
(vii)
C2H5
SO 9H
SO 3K
( vi i i) ~, OH ~,
SO 3K
( ix)
iC3~7
C3 H7 ,~
- SO3Na
(x)
3 7 iC3H7
C3H7 J~
~0 3Na
12g8~Z9
- 24 -
The effect aimed at by this invention can be achieved
by contro:Lling the surface tension of the stabilizing agent
added with the above-mentioned surface active agent to fall
within the range of ~0 - 60 dyne/cm and especially, a
favorable result can be obtained when the surface tension is
in the range of 25 - S0 dyne/cm.
Further, in the case of this invention, the
photosensitive material is usually processed by the
non-rinsing stabilizing solution and then dried but it is
optional to further rinse the material or processed with a
cleaning solution containing formalin, a surface active
agent, etc
Next, examples of processing steps to which the
processing method of this invention applies will be shown.
Note that in the examples, the letter S designates a
~tabilizing solution and the letter F designates a solution
having a fixing capacity.
(a) Color development , bleach ~ fixation (F) ) S ~ drying
(b) Color development ~ bleach ) rinse ~ fixation (F) , S
cleaning ~ drying
(c) Color development ~ bleach ~ fixation (F) ~ S ,
cleaning ~ drying
(d) Color development , blix (]!') ~ S ~ drying
(e) Color development ) blix (11') ~ S ~ drying
(f) MonoBath color development-blix (F) , S ) drying
12g87~9
- 25 -
(g) Development -~ rinse , reversal ~ color development ,
color correction ~ bleach -~fixation (F) , S ~ cleaning
~ drying
Of course, the processing method according to this
invention is not limited to the above examples but the
examples (b), (c), (e) and ~g) are particularly preferable
for the method according to this invention.
The method according to this invention produces a great
effect when it is applied to a continuous processing (for
continuously processing a photosensitive material while
keeping the processing capacity of the processing solution
constant by replenishing the solution so as to remove
fatigue due to processing). Usually, automatic processors
of various types including hanger-, roll-, sheet- and cine-
types are used Eor continuous processing and this invention
can be preferably used for continuous processing using such
processors. I~urtller, it is desirable that the automatic
processor be provided with a squeege or a blade for
preventing the solution from being brought out from a bath
containing a solution having fixing capacity by the photo-
sensitive material and brougllt into the stabilizing
bath.
The non-rinsing stabilizing solution according to this
invention has a pH in the order of 3 - 9.S and is gifted
with an anti-molding property so that it produces another
i~98'~
- 26 -
effect of removing dirt from the surface oE the
photosensitive material after drying, in addition to the
afore-mentioned ef~ects of the invention.
The term, "photographic processing solutions (each
having a fixing capacity)" given herein means solutions
which are intended for desilvering in the course of
processing a photosensitive material and which include, for
example, a fixing solution, bleaching-fixing solution,
monobath developing-fixing solution, hardening-fixing
solution, monobath developing-bleaching-fixing solution, etc.
The expression, "to process a photosensitive material
with a processing solution having a fixing capacity and to
process the material with a non-rinsing stabilizing solution
without taking any substantial rinsing step" means a process
in which the photosensitive material is subjected to a
stabilizing process immediately after it has been processed
with a processing solution having a fixing capacity instead
of being rinsed. In this case, the processing solution used
for stabilization is called a non-rinsing stabilizing
solution as above-mentioned and a tank for storing such
sol~tion is called a non-rinsing stabilizing bath (or tank)
or merely a stabilizing bath or tank.
However, in case the concentration of a fixing solution
or bleaching-fixing solution in the non-rinsing stabilizing
bath or tank (the foremost stabilizing tank when the bath
12987'Z~
- 27 -
comprises two and more sub-baths or tanks) does no-t exceed
1/2000, the photosensitive material may be subjected to
rinsing, auxiliary rinsing and rinsing promotion processings
for an extremely short time according to a single or
multiple tank counter-current flow system.
As the described above, the processing of a
photosensitive material by the non-rinsing stabilizing
solution is performed after the material is fixed.
As chemical compounds preEerably used with the non-
rinsing stabilizing solution according to this invention are
chelating agents whose chelatinc3 stability constant is 6 and
more to iron ions and these agents can be preferably used
for achieving the objects of this invention.
The term, "a chelating stat~ility constant" herein means
a constant generally known from such literatures as L.G.
Sillen. A.E. Martell, "Stability Constants of Metal-ion
Complexes," and "Organic Sequestering Agents," Wiley (1959).
As the chelating agents of the above type, there are
organic carboxylic acid chelating agents, organic phosphoric
acid chelating agents, inorganic phosphoric acid chelating
agents, polyhydroxy compounds, etc. Note that the
above-mentioned iron ions are ferric ions (Fe3 ).
As the concrete examples of chelating agents having a
chelating stahility constant of 6 and more to iron ions,
there are given the following compounds though not limited
~Z987;~9
- 28 -
thereto. That is, ethylenediaminediorthohydroxyphenyl
acetic acid, diaminopropanetetrac ~Itic acid,
nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid,
dihydroxyethylglisine, ethylenedia minediacetic acid,
iminodiacetic acid, diethylenetriaminepentaacetic acid,
hydroxyethyliminodi- acetic acld, diaminopropanoltetraacetic
acid, trans-cyclohexanediaminetetraacetic acid, grycolether-
diaminetetraacetic acid, ethylenediaminetetrakism-
ethylenephosphoric acid, nitrotrimethylenephosphoric acid,
l-hydroxyethylidene -1, l-diphosphonic acid, 1,
1-diphosphonoethane-2-carboric acid, 2-phosphonobutane-1, 2,
~-tricarboxylic acid, l-hydroxy-l-phosfonopropane-l, 2, 3-
tricarbonic acid, catechol-3, 5 -diphosphonic acid, sodium
pyrrolinate, sodium tetrapolyphosphate and sodium
hexamethaphosphate, and among them, l-hydroxyethylidene-
l,l-diphosphoric acid is most favorably used.
It is preferable that the amount of each of the above
chelating agents be in the order of 0.01 - 50 g per 1 1 of
the non-rinsiny stabilizing solution and more preferably be
in the order of 0.05 - 20 g.
When replenishing amount of the non-rinsing
stabilizing solution is less than 0.5 times that of the
solution carried from the prebath per unit area, the amount
of prebath component stored in the non-rinsing stabilizing
solution increases to lower the preservation stability of
12987Zg
- 2~ -
the photographic color image while, when it is more than 50
times the latter, the effect o~ this invention reduces.
Therefore, it is desirable in the invention to use the
solution in the order of 0.5 - 50 times the latter.
~specially, when the amount of supply of the solution is in
the order of 2 - 30 times that of the prebath solution, a
particularly favorable effect will be produced and it is
most desirable that the solution is applied to the
photosensitive material by 2000 ml per 1 m2 of the
material.
The tank for storing the non-rinsing stabilizing
solution according to this invention may be only one in
number but it is possible to have some two to ten tanks to
produce a more favorable effect. Further, a supply of fresh
non-rinsing stahilizing solution to the exising one may be
made at several portions but it is preferable to supply the
fresh solution into the tank located rearward when viewed
from the direction of the processing line of the
photosensitive rnaterial so that the solution overflows into
the tank just ahead of the first-mentioned tank (including a
case in which the solution flows through a pipe lying below
the liquid level so as to establish communication between
the tanks). More preferably, the non-rinsing stabilizing
solution in more than two tanks is replenished into the last
tank so that the solution overflowing that tank transfers to
i2g~7~
- 30 -
the tank there behind. In this case, a part or the whole of
the overflow of the stabilizing solution next to the
solution having a fixing capacity may be discarded or the
latter solution may be allowed to flow into the former
solution.
As means for imparting an anti-molding property to the
non-rinsing stabilizing solution according to this
invention, there are both mechanical and physical means.
As a concrete example of the mechanical means, there is
a method of adding an anti-molding agent to the non-rinsing
stabilizing solution. Favorable anti-molding agents are
sorbic acid, benzoic acid compounds, phenoL compounds,
thiazole compounds, pyridine compounds, guanidine compounds,
carbonate compounds, morpholine compounds, quantenary
phosphonic compounds, urea compounds, isoaxazole compounds,
propanolamino compounds, sulfanide compounds, pyrronone
compounds and amino-acid compounds.
The above-mentioned benzoic acid compounds include
salicylic acid, hydroxybenzoic acid, and methylester,
ethylester, propylester and decylester as ester compounds of
hydroxybenzoic acid but n-butylester of hydroxybenzoic acid,
isobutylester, propylester and salicylic acid are preferable
and a mixture of the three esters of the above-mentioned
hydroxybenzoic acid is the most favorable.
The phonol compounds may have a halogen atom, nitro
1298~Z~
- 31 -
group, hydroxyl group, carbonic acid group, amino group,
alkyl group (especially of C 1 - 6) or phenyl group as
substituents, and orthophenylphenol, orthoocyclohexaphenol,
nitrophenol, chlorophenol, cresol, glycol, aminophenol and
phenol are preerable.
Thiazol compounds are those having nitrogen and sulfur
atoms in their penta cycle and favorable of them are 1,
2-benzisothiazoline 3-on, 2-methyl-4-isothiazoline 3-on,
2-octyl-4-isothiazoline 3-on, 5-chloro-2-methyl-4-
isothiazoline 3-on and 2-chloro-thiazolyl-benzimidazol.
Pyridine compounds include cyclohexydine,
polyhexamethylenebiguanidine hydrochloride, dodecylguanidine
hydrochloride, etc. of which dodecylguanidine and its salts
are preferable.
Carbamate compounds include methyl-l-(butylcarbamoyl)-
2-benzimidazol carbamate, etc.
Morpholine compounds include 4-(3-nitrobutyl)
morpholine, 4-(3-nitrobutyl) morpholine, 4-(3-nitrobutyl)
morpholine, etc.
Tetraphosphonium compounds include
tetraalkylphosphonium salt, tetraalcoxyphosphonium salt,
etc. and preferable of them is tetraalkylphosphonium salt
and more preferable are tri-phenylnitrophenylphosphonium
chloride and triphenyl nitrophenylphosphonium chloride.
Tetraammoni~m compounds include benzalconium salt,
lZ~8~Z~
- 32 - I
benztnium salt, tetraalkylammonium salt, alkylpyridium salt,
etc. and to be more concrete, they include
dodecyldimethylbenzylammonium chloride, dodecyldimethyl-
ammonium chloride, laurelpyridium chloride, etc.
Urea compounds include N-(3, 4-dichlorophenyl)
-n-(4-chlorphenyl) urea, N-(3-trifluoromethyl)
-N'-(4-chlorophenyl) urea, etc.
Isoxazole compounds include
3-hydroxy-5-methylisoxazole, etc.
Propanolamine compounds include n-propanols and
isopropanols and to be more concrete, they are
DL-2-benzilamino-1-propanol, 3-diethylamino-1-propanol,
2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol,
isopropanolamine, diisopropanolamine,
N,N-dimethylisopropanolamine, etc.
Sulfamide compounds include o-nitrobenzene sulfamide,
p-aminobenzene-sulfamide, fluorosulfamide, 4-chloro-3,
5-dinitrobenzenesulfamide, a-amino-p-truenesulfamide,
sulfanylamide, acetosulfaguanidine, sulfamethyzol,
sul~athiazol, sulfadiazine, sulfameradine, sulfamethadine
æulfaisooxazol, homosulfamine, sulfamidine, sulfaguanidine,
sulfamethysol, sulfapyradine, phtalisosulfathiasol,
succinisulfathiasol, etc.
Amino acid compounds include n-laurel-~-alanine.
129~2~
- 33 -
Further, of the above~mentioned anti-molding agents,
those compounds which are preferably used in this invention
are thiazole compounds, sulfamide compounds, pyronone
compounds, etc.
It is preferable that the amount of addition of the
anti-molding agent to the non-rinsing stabilizing solution
be used in the range of 0.001 - 30 g per 1 Q of the solution
and it is more preferably used in the range of 0.003 g - 5 g.
As the physical means to give an anti-molding property
to the solution, ultraviolet rays may be applied to the
non-rinsing stabilizing solution or a magnetic field may be
caused to pass through the solution.
To subject the non-rinsing stabilizing solution to a
magnetic field in this invention is to cause the solution to
pass through a magnetic field generating between a positive
pole and a negative pole. In this case, the photosensitive
material may or may not be passed through the magnetic field.
The magnetic field used in this invention may be
obtained by using a permanent magnet consisting of
ferromagnetic iron, cobalt and nickel or a coil through
which a DC current flows or any other suitable means for
producing a magnetic field. The magnetic line of force of
the magnetic field may be generated by using a single magnet
or by arranging two magnets of positive and negative
polarities in opposite relationship with each other.
~298729
- 34 -
There are various methods for subjecting the
non-rinsing stabilizing solution of this invention to a
magnetic field. For example, a permanent magnet may be
moved through the stabilizing solution or an externally
arranged permanent magnet is moved (or rotated) or the
non-rinsing stabilizing solution is transferred by agitation
or circulation. As a particularly desirable method, a
permanent magnet may be fixed to a part or the whole of the
outside or inside of a circulation pipe and the stabilizing
solution is circulated through the pipe. In this case, the
permanent magnet may be formed by the pipe itself or it may
be attached to the entire length of the pipe.
In the case of an automatic developer, the above
purpose can be achieved by providing a permanent magnet in
the non-rinsing stabilizing bath but as described
hereinbefore, it is preferable to arrange the magnet in the
circulation system of the stabilizing bath (including
intermediate tanks or other members). Further, in case the
non-rinsing stabilizing process comprises a multistage
stabilizing bath, it is most preferable to subject to a
magnetic field the stabilizing solution in the non-rinsing
stabilizing bath but it is also preferable to subject the
stabilizing solution other than that in the non-rinsing
stabilizing bath nearest the processing solution having a
fixing capacity, to a magnetic field. Alternatively, a
~i :987Z9
~ 35 -
resin lining containing a material capable of generating a
magnetic line oi Eorce may be ayplied to the non-rinsing
stabilizing bath itself, preferably to the internal surface
of the bath, or such lining may be applied to the
circulation system, thereby subjecting the stabilizing
solution to the magnetic field.
Further, the method of applying ultraviolet rays on the
non-rinsing stabilizing solution according to this invention
can be performed by using a commercially available
ultraviolet ray lamp or an ultraviolet ray irradiation
device and in this case, it is preferable for the lamp to
have an output of 5 - 800 W (the tube output) though not
always limited thereto.
According to a preferred embodiment of this invention,
the wavelength of ultrasonic rays of light is in the order
of 220 nm - 350 nrn. Further, as an ultraviolet ray
irradiating method, there is a method in which ultraviolet
rays are irradiated directly from the above-mentioned lamp
or device provided in or outside the non-rinsing stabilizing
bath.
q'he organic solvents used for the photosensitive
material to be processed according to this invention are
chemical compounds each having a dielectric constant of 3.5
and over. They are, for example, esters such as phthalic
acid ester and phosphoric acid ester, organic acid amides,
,. , , . .. , ,.. ,.. , .. . , , .... ~
~9~37æ~t
- 36 -
ketone, hydrocarbon compounds, etc. Preferable high-boiling
point solvents are those haviny a dielectric constant in the
order of 4.0 - ~.5 of which tho~e belonging to phthalic acid
esters or phosphoric acid esters are more preferable.
Further, they may be mixtures of more than two kinds of
compounds provided that they have a dielectric constant of
3.5 and higher. By the way, the dielectric constant
mentioned herein is that measured at 30C.
As phthalic acid esters advantageously used in this
invention include those given hereunder which are expressed
by the following general formula [I].
General formula II]
~COORl
COOR2
wherein Rl and R2 designate an alkyl group and an
alkenyl or aryl group, respectively. However, it is
preferable that the total carbon atom number of the groups
expressed by Rl and R2 be in the range of 2 - 36 and the
range of 6 - 24 is more preferable.
In this invention, the alkyl groups expressed by R
and R2 of the above-mentioned general formula [I] are
those of straight chain or branching, such as butyl groups,
pentyl groups, hexyl groups, heptyl groups, octyl group,
nonyl group, decyl group, undecyl group, dodecyl group,
tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, aryl
lZ98'7Z~
- 37 -
decyl, etc. Further, the aryl groups expressed by Rl and
R2 of the same formula are phenyl and nathtyl groups and
the alkenyl groups expressed thereby are hexenyl, heptenyl
and octadecynyl groups. These alkyl, alkenyl and aryl
groups may have a single or a plurality of substituent
groups. As the substituent groups for the alkyl and alkenyl
groups, there are halogen atoms, alcoxyl, aryl, aryloxy,
alkenyl and alcoxycarbonyl groups, and as substituents for
the aryl group, there are, for example, halogen atoms,
alkyl, alcoxyl, aryl, aryloxy, alkenyl and alcoxylcarbonyl
groups. Two or more of substituent groups may be introduced
into alkenyl or aryl group.
As phosphoric acid esters advantageously used in this
invention, those expressed by the following general formula
[II] may be given.
General formula [II]
/ OR3
\
OR5
wherein R3, R4 and R5 independently designate an
alkyl, an alkenyl or an aryl. However, it is preferable
that the total number of carbon atoms of the groups
expre8sed by R3, R4 and R5 be in the range of 3 - 54.
In this invention, the alkyl groups expressed by
;~
129872~3
- 3~ -
R3, R4 and R5 of the above-mentioned general formula
~II] are straight chain or branching which are, for example,
butyl, pentyl, nexyl, undecyl, dodecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl and nonadecyl
groups.
These alkyl, alkenyl and aryl groups may have a single
or a plurality of substituent groups. It is preferable that
R3, R4 and R5 are alkyl groups which are, for example,
n-butyl, 2-ethylhexyl, n-octyl, 3, 5, 5-trimethylhexyl,
n-nonyl, n-decyl, sec-decyl, sec-dodecyl and t-octyl groups.
As alkenyl groups, there are ethylene, aryl and butene
groups and as aryl groups, there are phenyl, tolyl and xylyl
groups.
The following are examples of high-boiling point
organic solvents according to this invention each of which
has a dielectric constant of 3.5 or more but the invention
is not limited thereto.
~9~37~
- 39 -
A - I A - 2
COOCH3 ~ COOCH3
~ COOCH3 ~ COOC2Hs
A - 3 A - 4
~COOC2Hs ~ COOC3H7
~COOC2H5 ~COOC2Hs
.A ~ 5 A - 6
COOC3H7 ~ COOC4Hg
~ COOC3H7 ~ COOCH3
A - 7 A - 8
~¢oo a ~ Hg ~ ~COOC4Hg
~cooa 2~Is ~ COOC3H7
A - 9 A-l O
COOC4Hg ~ COOCH2CH20CH3
COOC4H9 ~ COOCH2CH200H3
1298';)Z~
-- 40 --
A-- I 1 A--I 2
~COOO IIH23(i) ~COOC 13H27
~cooa 1l H23(i) ~cooc ,3H2?
A--I 3 A~ 1 4
~COO~ ~COOC 12 H25(n)
COO{~ ~COOC 12 H25(n)
A - I 5 A-- 1 6
~ aoo CH 2 CH=CH 2 ~COO C 12 H 25( i)
~¢OOCH20H=aH2 ~ooocl2H25(i)
A-- I 7 A-- I 8
~aooa 6H l3(n) ~aooo gH Ig(n)
~cooa 6 H 13(n) ~ cooa 9 H Ig(n)
A-- I 9
(aH2 ) 3aH3
~COOCH 2 CH ( CH 2 ) 3 CH 3
a2Hs
129~t7Z9
-- 41 --
A--2 0
CH 3 CH 3
OOOCH2 CH2 CHCH2 C--CH 3
~/ CH 3
C~1 3
COOCH2CH2 CHCH2 C--CH3
I I
CH3 CH3
A--2 1 A--2 2
oooc 8Hl7(n) ~cooo loH21(i)
~COOC8Hl7(n)~coOCloH2l(
A--2 3 A--2 4
~COOagHIg(i)~COOO IoH21(~
b ~ coocgHIg(i)~ OOOClOH2l(n)
A--2 5 A-- 2 6
p~OH 3
~O OH3
O=P O~CH 3O = P--O CH 3
\ o~3CH 3 O CH 3
- 42 -
A -27 A -2 8
~ OCH3 / OCH3
O=p - O-c2H5O=P - 0-02H5
OCH3 002Hs
A-29 A- 3 0
~ oC2H5 ~ OC4Hg
o=P - OC2H5O=P\ 002H 5
\ 0 02Hs\ O c2H5
A-3 1 A -3 2
004Hg / 008H~7
O=P - 004HgO=P OC8HI7
\ 004Hg\ OO~H,?
A-33 A -3 4
O-OgHIg(i) C2Hs
O=P-O-OgHIg(i)O-OH2CH(CHg)3CH3
I
O-OgHIg(i)O=P-OOH2CH(CH2)3OH3
0 02Hs
OH2cH(oH2)3oH3
C2~ls
' ' ' ' ` ' ..
lZ~8'729
-- 43 --
A--3 5 A-- 3 6
O--CgHIg(n) O--OI,H23(i)
O=P--OCgHlg(n) O=P--O--CllH23(i)
O--C gH Ig(n) O--C 1l H23(i)
A--3 7 A--3 8
O--CloH2l(i) 0--0l2H25(i)
O = P--O--C lo H21(i)0 = P--O--C ~2 H2s(i)
O--C loH2l(i) -- l2H25(i)
A--3 9
O--C lo H 2l(n)
o=P--o--a lOH2l(n)
~ lo H 21(n)
, ., . , . . , .. .. , ........... , ..... ... , _ _.,. __ . .. ,.. . . . .. .. . ., .... . . .. _ _ ~_ _. ~, ... ~.. ~ . ..
... ,.. ,. _ _ _ _._
1~987~g
As the high-boiling point organic solvents according to
this invention each having a dielectric constant of 3.5 or
more, there are the following additional solvents such as
malonic acid diethyl, mayeline acid diethyl,
r-butyrolactone, benzoic acid methyl, benzilalcohol and
l-octanol.
These high-boiling point organic solvents according to
this invention can be used together with known low-boiling
point organic solvents such as acetic acid ether.
The pH of the non-rinsing stabilizing solution
according to this invention is preferably in the range of
3.0 - 9.5 and it is preferable to ad~ust the pH to the range
of 3.5 - 9. 0 for the prevention of precipitation as one of
the objects of this invention.
Further, as other chemical compounds which can be added
to the non-rinsing stabilizing solution, there are organic
acid salts (such as citric acid, acetic acid, succinic acid,
oxalic acid, benzoic acid, etc.), pH buffer agents (such as
phosphoric acid, borate, hydrochloric acid, phosphoric acid,
etc.) or surface active agents, anticeptics, metallic salts
such as Bi, Mg, Zn, Ni, AQ, Sn, Ti, Zr, etc. The amount of
addition of these compounds is optional provided that the pH
of the non-rinsing stabilizing solution of this invention be
maintained and they can be used in any combination among
them unless they give adverse effects on the stability of
1298~2~
- 45 ~
the stability of color photographic image preservation and
the prevention of precipitation.
In the process of stabilizing the photosensitive
material of this invention, the processing temperature
should preferably be in the range of 15C - SO~C and more
preferably, be in the range of 20C - 45C. It is
preferable that the processing time is as short as possible
in view of speedy processing but it is usually in the range
from 20 sec. to 10 minutes and the range between 1 - 5
minutes is the most prefera,ble. In the case of stabilizing
process by use of a plurality of stabilizing tanks, it is
preferable that the time for processing by the first-stage
tank be shorter than that by tne next-stage tank and so on,
and it is especially desirable that the processing time by
the first-stage tank is shorter by 20 - 50% than the
next-stage tank and so on.
In case the silver halide color photosensitive material
according to this invention contains at least one of cyan
couplers shown by the following general formula [VII] -
[IX], the effect of the invention is more favorably
displayed.
General formula lVII]
Qll
C Q hT~ Nll C1~2 2
n2l~n20
X ,.
., ` ,
lZ987Z9
- 46 -
wherein one of R20 and R21 designates a hydrogen atom
and the other designates a straight chain or branched alkyl
group having 2 - 12 carbon atoms, X designates a hydrogen
atom or a group capable of being split off upon coupling
reaction with an oxidized product of a color developing
agent and R22 designates a ballasting group.
General formula [VIII]
OH
d~N HY
n23CONII~
General formula IIX]
0~1
,~NIIC01123
YNll--~
wherein Y designates - COR24
/ 24 / 24
- CON \ , -S02R24, -Cl-N \
R25 S R
/R24
- SO2N -CoNHcoR24 or -CONHso2R24
\R25
lZ9t3'72~
- 47 -
(provided that R24 designates an alkyl group, alkenyl
group, cycloalkyl group, aryl or heterocyclic group
designates a hydrogen atom, alkyl, alkenyl, cycloalkyl
groups, aryl or heterocyclic group and R24 and R25 may
combine with each other to form a heterocycle of 5 - 6
members), R23 designates a ballast group and Z designates
a group capable of being split off upon reactions with an
oxidation product of a color developing agent.
The cyan couplers according to this invention can be
expressed by the above-mentioned general formulae [VII] -
lIX] which will now be described in further detail.
In this invention, the straight chain or branched alkyl
group having 2 - 12 carbon atoms which are expressed by
R20 and R21 of the general formula [VII] are, for
example, ethyl, propyl and butyl groups.
In the general formula [VII], the ballast group
expressed by R22 is an organic group having such a size
and shape as to give a coupler a sufficient voIume to
substantially prevent the coupler from scattering from the
layer to which it is applied, to another layer. Typical of
i~ is an alkyl or aryl group with total carbon atom number
of 8 - 32 of which one having 13 - 28 carbons is
preferable. These alkyl and aryl groups may have
substituent groups and as such, there are, for example,
alkyl group, aryl group, alcoxyl group, aryloxy
lZ9~3~29
- 48 -
group, carboxyl group, aryl group, ester group, hydroxy
group, cyano group, nitro group, carbamoil group, cyano
group, carboamide group, alkylthio group, arylthio group,
sulfonamide group, sulfamoil group and halogen and as
substituent groups for the alkyl group, there are those for
the aryl group mentioned above with the exception of the
aryl group.
Those that are preferable as belonging to the ballast
group are expressed by the following general formula.
-Cl - O - Ar
R26
where in R26 designates an alkyl group having 1 - 12
carbon atoms, Ar designates an aryl group such as phenyl
group which may have substituent groups. As substituent
groups, there are an alkyl group, hydroxy group, halogen
atom, alkylsulfonamide group but a branching alkyl group
such as a t-butyl alkyl group is the most preferable.
As is well known to a person with ordinary skill in the
art, the group capable of separation through coupling with
the oxide of a color developing agent defined by X in the
above-mentioned general formula [VII] determines the
equivalent of the coupler and controls the reactivity of
coupling. As typical examples, there are halogen
represented by chlorine and fluorine, aryloxy group,
... . ..
l~g~
- 49 -
sulfonamide, arylthio, heteroilthio, heteroiloxy,
sulfonyloxy and carbamoiloxy groups. More concrete examples
are those given in the Japanese Laid-open Patent Publication
Nos. 50-120334, 50-130414, 54-48237, 51-146828, 54-14736,
47-37425, 50-123341, 58-95345, Japanese Patent Publication
No. 48-36894, US Patent Nos. 3,476,563, 3,737,316 and
3,227,551.
Next, examples of compounds of cyancouplers expressed
by the general formula [VII] will be given hereunder though
this invention is not limited thereto. In these co~pounds,
R21, X, R22 and R20 are specified as shown.
~298729
-- so --
o
n J~ n ~ -
O I 31 " '~ ~ U ;~ ~ U
~ t~
u~ ~Y~; I i U
o
0~ O
Zi
~ h ~1 ~1 ~ ~r
.IJ t.~
,~ O .. ~ .
.
lZ987Z9
-- 51 --
~ U ~ U ~ ~ U ~
U ¦ U--U ~ --U
~:
~C
v~ _~ ~ h~ \/u
o
8 .
Z ,
~D 1` CO
Id ~ l l l l
,~ o t~ U
:~ ~ ~,
-,
~Z987;~9
o ~ ~ ~ I
~U T-U
~Ç
U~ o~
,
~ ~ ~ U
t, o
.~ ~;
. o
a) , , .,
~ C~
."
U~
~,
H
: _
lZ98729
-- s3 --
b~ b b~ b!
u e~
~ u J~ D o N
Ul -U
X
a bN b bN bN
a O
~ Z
~ .
H t ) ..
.. . .
lZ98~29
o I I . I !
1~: u ~ b~ N
~ .
~U
1~ ~ .
,~ U
_
O Z
V h I` oo a~ o
H O
lZ98'~Z9
~I U ~ U 'I
C ~ N
X
¦ U ~ O
l I
OP~ U ' ~ U ,U
~1 ~ ,
12987Z9
"
o u o I, I
, ~ ~
~ ~ m''
m~
X Y
U~ ~, t~
o~ o
~ Z
U~ ~
H U
.. !
,, ,, . . ... , , . . . ,.. , .. ,.. . , . _ _ ., . _ .. _ _ . ,, _,,, .. , ~ _ _ __. _ _. ._ _ ..... ~_ _, .. ... _ ... __. _
__ _ . _ . ... . . . . .. ..
. lZ987Z5~
- 57 -
The methods of synthesizing the chemical compounds
illustrated in this invention will now be described
hereunder but other compounds can be synthesized by the same
methods.
129872~
- 5~ -
Example of synthesization of Compound C-5
[(l)-a] Synthesization of 2 -nitro-4.6- dichloro-5-ethyl
phenol
33 g of 2-nitro-5-ethylphenol, 0.6 g of iodine and
1.5 g of ferric chloride were dissolved in 150 mQ of glacial
acetic acid and 75 mQ of sulfuryl chloride was dropped into
the solution for three hours at 40C. The precipitate
generating during the above process was refluxed into the
solution by heating after the sulfuryl chloride has been
dropped so as to make the precipitate dissolved in the
solution by reactions. It took about two hours for
refluxing the precipitate. Then the reacted solution was
poured into water to generate crystals and the crystals were
refined by recrystallization with methanol. The
confirmation of (l)-a was made by a nuclearmagnetic
resonance spectrograph and element analysis.
[(l)-a] Synthesization of 2-nitro-4, 6-dichloro-5-ethylphenol
21.2g of the compound of l(l)-a] was dissolved in
300 mQ of alcohol, a catalytic amount of Raney nickel was
added to the solution and hydrogen was passed through the
solution at normal temperature until no more hydrogen was
absorbed. After the reaction, the Raney nickel was removed
and retained by pressure reduction with alcohol. The
residual ~(l)-b] is acylated without being refined.
' ' ,
~ .
lZ98729
- 59 -
l(l)-c~ Synthesization of 2[2.4 -ji-tert-acylphenoxy)
acetoamide 1-4, 6-dichloro-5-ethylphenol
18.5 g of crude amide obtained by [(l)-b] was dissolved
in a mixture of 500 mQ of glacial acetic acid and 16.7 g of
acetic acid soda and an acetic acid solution prepared by
dissolving 28.0 g of 2.4 -di-tert-acylphenoxy-
acetic acid chloride in 50 mQ of acetic acid was dropped
into the first-mentioned solution at room temperature for
30 minutes and after agitating the solution for 30 minutes,
the reacted solution was poured into glacial water. After
that, the resultant precipitate was filtered and after
drying, it was recrystallized twice thereby obtaining a
desired product. The confirmation of the desired product
was performed by an element analysis and nuclear magnetic
resonance spectrograph.
2~ 25 3
C ¦ H Cl
Calculated value (%)65.00 ¦ 7.34 2.92 14.76
I
Measured value (%)64-91 ¦ 7-36 2.99 14.50
Next, the cyan couplers expressed by the general
formula ~VIII] or [IX] and used in this invention will be
described. In the general formulae [VIIIl and ~IX], Y
designates a group expressed by
lZ987Zg
- 60 -
/ R24 / 24
- CON~ , -SO2R24, - 1I N
R25 S R25
/ 24
2 \ , -CONHCO~24, or -CON~SO2R24
provided that R24 designates an alkyl group, preferably
one having 1 - 20 carbon atoms (such as methyl, ethyl,
t-butyl and dodecyl groups), alkenyl group preferably one
that has 2 - 20 carbon atoms such as an aryl group or
heptadecenyl group, etc.), cycloalkyl group, preferably of
5 - 7 member cycle (for example, cyclohexyl), aryl groups
(for example, phenyl, tryl and naphthyl groups), hetero-
cyclic group of 5 - 6 member cycles including 1 - 4
nitrogen, oxygen or sulphur atoms (such as furil, thienyl,
benzothiazoril groups, etc.). R25 designates a hydrogen
atom or a group expressed by R24, R24 and R25 may
combine with each other to form a heterocycle of 5 - 6
members. Further, R22 and R23 may be introduced with
desired substituent groups. For example, alkyl group of
1 - 10 carbon atoms (for example, methyl, i-propyl, i-butyl,
t-butyl and t-octyl groups), aryl groups such as phenyl and
naphthyl groups), halogen atoms (fluoride, chloride,
bromine), cyano, nitro, sulfonamide groups (for example,
methanesulfonamide, butansulfonamide, p-truensulfonamide,
lZ98~29
- 61 -
etc.), sulffamoil group (for example, methylsulfamoil,
phenylsulfamoil, etc.), sulfonyl group (for example,
methanesulfonyl, p-truensulfonyl, etc.), fluorosulfonyl
group, carbamoil group (for example, dimethyl carbamoil,
phenyl carbamoil, etc.), oxylcarbonyl group (for example,
pyridyl and pyrazolyl group) alcoxy group, aryloxy group and
acryloxy group.
In the general formulae [VIII] and [IX], R23
designates a ballast group required for giving an
anti-scattering property to the cyan coupler expressed by
the general formulae [VIII] and [IX] and the cyan pigment
formed by the cyan coupler. Preferably, an aryl group
having 4 - 30 carbon atoms, aryl group or heterocyclic
group. For example, straight chain or branching alkyl
groups ~such as t-butyl, n-octyl, t-octyl, n-dodecyl, etc.),
alkenyl group, cycloalkyl group and 5 -A 6 members
heterocyclic group.
In the general formulae [VIII] and [IX], Z designates a
group capable of separation at the time of coupling reaction
against hydrogen atom~ or oxide of a N-hydroaxyalkyl
substituent -p-phenylene diamine derivative developing
agent. For example, halogen atoms ~such as chlorine,
bromine, fluorine, etc.), substituted or non-substituted
alcoxyl group, aryloxy group, heterocyclic oxy group,
acyloxy group, carbamoiloxy group sulfonyloxy group,
~Z9~37Z9
- 62 -
alkylthio group, arylthio group heterocyclic thio group and
sulfonamide group and as more concrete examples, there are
US Patent No. 3,741,563, Japanese Laid-open Patent
Publication No. 47-37425, Japanese Patent Publication No.
48-36894, Japanese Laid-open Patent Publications Nos.
50-10135, 50-117422, 50-130441, 51-108841, 50-120343,
52-18315, 53-105226, 54-14736, 54-48237, 55-32071, 55-65957,
56-1938, 56-12643, 56-27147, 59-146050, 59-166956, 60-24547,
60-35731 and 60-37557.
In this invention, of the cyan couplers expressed by
the qeneral formula [VIII] or lIX], those expressed by the
follo~ing general formula [X], ~XI] or lXII] are more
preferable.
General formula LX]
OH
NHCONHR27
R23CONH ~j/
z
General formula [XI]
OH
~ NHCOR28
R23CONH
z
. . .
1298~g
_ 63 -
General formula [XII]
OH
~ NHCOR23
R2gCONH
z
In the general formula [X], R27 designates a
substituted or non-substituted aryl group (preferably,
phenyl group). As a substituent group, at least a
substituent group selected from S02R30, halogen atoms
(fluorine, chlorine and bromine, - CF3, - N02, - CN,
- COR30~ - CR30' S2R30'
/ R30 /R20
- CON \ , - S02~ _ OR30~ - oCR30'
\R
R31 31
/ R31 / R31 11 / OR30 -
- N~ , - N~ and - P
\ R30 S03R30 OR31
i8 included.
In this case, R30 designates an alkyl group,
preferably one having 1 - 20 carbon atoms ~such as methyl,
ethyl, tert-butyl and dodecyl groups), alkenyl, preferably
one having 2 - 20 carbon atoms (such as aryl, heptadecenyl
groups, etc.), cycloalkyl group, preferably 5 - 7 member
cyclic group (for example, cyclohexyl), aryl group (for
example, phenyl, tril, naphthyl groups, etc.). R31
. . .
.
.
~ . ...
,:
12987Z9
- 64 -
designates a hydrogen atom or a group expressed by R30.
The above-mentioned Rgo, R31, and R28, and ~29
of the general formulae [XI] and [XII] may be introduced
with desired further substituent groups. To be more
concrete, these substituent groups are those that can be
introduced into R24 or R25 in the general formulae
[VIII] and [IX] and halogen atoms (chlorine atoms, fluorine
atoms, etc.) are especially preferable.
The Z and R23 in the general formula [X], [XI] or
[XII] have the same meaning as the general formulae [VIII]
and [IX], respectively. Examples of ballast groups
expressed by R23 are those expressed by the following
general formula [XIII]~
General formula [XIII]
~ ( 33)
(R3~)K
wherein J designates an oxygen or sulfur atom or a
sulfonyl group, K designates an interger of O - 4, 1
designates O or Q, and when more than two Ks are present,
more than two Rs may be the same or different.
R34 designates a straight chain or branching alkylene
group having 1 - 2p carbon atoms or substituted aryl group
and R33 designates a monovalent group, preferably a
hydrogen atom, a halogen atom (such as chrome and bromine),
alkyl groop, preferably a straight chain or branching alkyl
,
~298729
- 65 -
group having 1 - 20 carbon atoms (such as methyl, t-butyl,
t-pentyl, t-octyl, dodecyl, pentadecyl, benzil and phenetil
groups), aryl group (such as phenyl, heterocyclic groups),
alcoxyl group, preferably a straight chain or branching
alcoxyl group having 1 - 20 carbon atoms (such as methoxy,
ethoxy, t-butyloxy, octyloxy, decyloxy and dodecyl oxy
groups), aryloxy group, (such as phenoxy group), hydrooxy
and acyloxy groups, preferably alkylcarbonyloxy group,
arylcarbonyl oxy group (such as acetoxy and benzoiloxy
groups), carboxy and arylcarbonyloxy group, preferably a
straight chain or branching alkylcarbonyl group, preferably
a phenoxycarbonyl group, alkylthio group, preferably an acyl
group having 1 - 20 carbon atoms, preferably a straight
chain or branching alkylcarbonyl group having 1 - 20 carbon
atoms, preferably a straight chain or branching alkylcarbo-
amide group, benzoncarboamide group, sulfonamide group,
preferably a straight chain or branching alkylsulfonamide
group or benzosulfonamide group, carbamoil group, preferably
a 6traight chain or branching alkylaminocarbonyl group or
phenylaminocarbonyl group, sulfamoil group, preferably a
straight chain or branching alkylaminosulfonyl or
phenylaminosulphonyl group.
Next, concrete examples of cyan couplers expressed by
the general formula IVIII] or [IXj will be shown but the
invention is not limited thereto.
. . .. .
,
~8'7Z9
- 66 -
lIllustrated Compounds]
C-29
OH
(t)C5Hll ~ NHCONH ~ CN
(t)C5Hll ~ O-CHCONH
C~Hg
C-30
OH
(t)C5HIl ~ NHCONH ~ CN
(t)C5Hll ~ O-CHCONH
\=/ I o ~
(n)c4H~ ~ OC~3
C-31
OH
(t)C~H" ~ NHCONH ~ CN
(t)C5Hl, ~ O-CHCONH ~
I
C6H13
(t)C~l7
1298~7;~9
c-32
OH
( n ) C,5H31 ~ NHCONH
~O--CEICONH~ a
I
C2H5 F
c-33
,~, NHCONH~
HO ~ O--CHCONH
(t)C ~Hg C1
C-34
OH
~ NHCONHCI5H3
HO ~O--CHCONHJ~
)=/ I ' C'
(t)C.~Hg C,2H25
lZ987;29
-- 68 --
c-35
(t) CsH~ 3, NEICONH ~ C
(t)CsHIl~O--CHCONH C
C2H5
c-36
OH
( t) CsHll ~ NHCONH ~ S 02C~Hg
(t)CsHIl~O--CHCONH
C2H5
C-37
OH
, ~ NHCONH ~ CN
Cl~l2s ~30--C~lCONH~ NO z
CH3
1298729
- 69 -
C-38
OH
~ N~lCONH ~3 CN
HO ~ O--CHC O N~J~j
C ~Hg OCH2COOC2H5
(t)C ~Hg
C-39
OH
(t)C ,~H9 ~ NHCONH~ 802C2H5
( t)C 4Hg ~ O--CHCONHJ~ CN
12 25
C-40
OH
,~NHCONH~C~
(n) C4H3~o2NH~3o--CHCON CN
CH3
lZ987Z9
-- 70 --
C-41
OEI
~, NHCONH~COQCH3
(CH3)3CCOO~O--CHCONHJ~
Cl2Hz5 OCH2CONHCH2CH20CH3
C-42
CF3
OH
( t) C5Hg ~ NHCONH ~
(t) C4H9 ~ O--CHCONHJ~ NO z
C,zH2s NHSO
C-43
OH
(t)C5H,l ~NHCONH~30zNHG~H9
(t)C5H~ 0--( CHz ) 3CONH
12987Z9
-- 71 --
c-44
,[~, NHCONH~Ca~2H5
(n)cl2H25N~c ~--CH2CONH C~ 3
c-45
CH3
OH
(t)C5Hll hl,NHCONH~
(t)CsH~ O--CHCONH~
\=/ I I CH 3
C4Hg C
C 46
OH
(t)C5HI, ~NHCONH ~OCH3
(t)C5H,~ O--CHCONI~
C,2H25 OCH2 COOH
~2~ 37Z9
-- 72 --
C-47
OH
~, NHCONH~
~O.-C~CONH
~ C 2H 5 C '
C~2s
C-48
C,2H~5 ,~NHCC)NH~
(t) C5H,l ~ O--CHCONH
(t)CsHI,
C-49
OH
Cl2H2s ~ NHCONH ~ S 02CH3
t)CSHI, ~ O--CHCONH~ ~ d
(t)C5EII,
~Z987Z9
-- 73 --
C-50
OH
,~ NHCoNH~3So2C~
(t)C 4 H 9 ~; 3 S 0 2 CHCONH I O C Z H s
C-51
OH
( t)C5HIl ,~,~ NHCONH ~ S 02C3H7
(t)C5Hl~ ~O--CHCONH~
C2Hs
C-52
OH
(t)C.~g I ~
~' CH 3 ,~NHCONH~S 02C6HI3
~t)C ~Ig~=~ O--C--CON
CH3
1Z9872~
-- 74 --
C-53
OH
~, NHCONH~ O C2H5
~ O--CHCONHJ~J
C,5H3, C2H5 C
C-54
,~NHCONH~P ~oCH33
Cl2E~2s ~C 2~ 3 CL
C-55
CL
,~NHCONH~ C
Cl2H25 ~30--CHCOMH~ CL
C 2H 5 OCON ( CH3)2
129872~
-- 75 --
c-56
CsHIl( t) ~ NHCONH ~ C
(t)(~~OCHCO CN
C4H9
c-57
OH
C5~1,( t) ~, NHCONH ~ ~3 02C2H5
(t)C5Hl~ ~OCHCONHJ~J C '
I
C2Hs
C-58
OH
CsHIl(t) ~NHCONH ~3F
(t)c5EI.l ~ OCHCONH~
C ,~Hg
lZ~87Z9
-- 76 --
c-59 OH C
C8Hl,(t) ,~ NHCONH ~9
(t)C~Hl7~0CHCONHJ~ C '
C6Hl3
c-60 C~
OH
C8HI7(t) ~,N~:IC ONH~C
(t) C8E~l7~ OCHCONH
C6Hl3
c 61
OH
C8HI7(t) ~, NHCONH ~F
( t) C8Hl7 ~ OCHCONHJ~J
C4Hg
~298729
- 77 -
c-62 C '
OH
C8HI7(t) ~, NHCONEI~ C '
(t)C8EII~OCHCONHJ~
C6Hl3 oCH2CH2S 02CH3
C-63 C t
OH
C8H~(t) hl--NHCON~C
(t)C~l74~ OCHCONH~
C 2 H 5 OCH2CH2S 02C OO~I
C-64
OH
C.C ~ NHCONH ~3 CN
(t)c5Hll~ocHcol`
~ ' ,1 " .
.' ' .
lZ98729
- 78 -
c-65
OH
~ NHCONH ~ ~oZc3H7
(t)C~I~ ~ OCHCONH
C6E113
C-66
OH
(t)c5H~ NHCONH~C '
(t)C~ll ~ O-CHCONH , CL
C-67
OH
~ NH~OzNHC~Hg
C~19~0zNH ~ O-CHCO~H
~ H CL
~' 12 25
1298729
-- 79 --
C-68
OH
,~NHCONHC o~902C~2~3
(t) C~H9~9--CHCONH
\=/ I F
~l2H2s
C-69
F F
OH
,~ N~C ONH~ O 2 ~ F
(n) Cl2H2sO~O--CHCON F F
C2Hs
C-70OH C2H5
,~ NHCoN~390~CF~
Cl6H330C
Il
'O
C-71
OH
~ N~:ICON O
¢~ O--CHCON~
~=/ C H C L
C~Hg~02rlH 12 2s
' ' ,
.
.- ~ . .
. .
," - ,, ~ . ..... .
, ~ .
1298729
- sn -
c-72
OE~
hl~NHCNH ~3C'F 3
C~Hg302NH~ CONH~
~ C~
c-73
OH
~,NHCO--CHCEl2 SO2C~2Hzs
(t)C,~EIgNHCNH~ aH3
S C~
C-74
(t)Cs
OH
HJ~NHCOCHO~(t)C5
C2H5S02~NHt'oN C4Hg
C~
,, . . , .. , . . .. . ... , . , . . _ .. _ . _ . .. , . . ... .. _ _ .. . , . _ . _ _ _ .. . , , , _ . , .
1298729
-- 81 --
C-75 OH
NHCO~CONHC12H25
C~ z NHC :)NH~ N--N
S~ 11
`N--N
c-76 ~3
OH
C2H5 ~ NHC()cH20 ~30Cl2H2s
NCONH~
CL
02H5
C-77
OH
,~ NHCoNH~3~ 2 ~3
(t)C~19~30--CHCON
OH3 OCH2 COOH
C-78
OH
Cl2H~s ~ NHCONH ~ CF 3
82--I`~,CONH~
IH~J ~
~ . .
. ~ . . .
. .
! ~ ~
.
~Z98729
-- 82 --
C-79
OH
,~ NHCONH~ ~
Cl6EI37CONH NO 2
c-80
OH
(t) CsHIl ,~, NHCONH ~3 S 0 2 CH 3
(t)C'sHII 4~o--CHCONH~
C.2 25
C-81
~,NHCONH~ ~30ZNH2
Ç3 O--OHCONHJ~JJ
OCOCH 3
C1H!I~O;,~I
- 83 - 1Z9~7~9
C-82
0~
CH3 ,[~NHCONH~02 OCH3
C,7H~O ~ O--CHCONH
CH3
c-83
0~
,[~3,NHCONH~ <CH3
~t~ C ~H~O--CH2C ONH
(t)C~Hg
C-84
OH
~ NHCONH ~ S O2 NHC2H 5
C~6H~3 OC~CONH~
C,~H2s
OCH2CH20CH3
lZ913729
-- 8~ --
C-85
OH
CH3--CH2--C~ C H~ C
11 .
CH3
C-86
CH3 C3H,3 ,~
C-87
OH
CH3 C~Hl7 h~NHC
CH3--aH2--C~OCHCNH~ o C'
3 C ~ C ~
~Z98729
-- 85 --
C-88
OH
CH 3 CloH2l ,~ NH~ ~3
CH3--CH2--C~OCHCNH ~ C~
~H3 C ~ CL
c-89
OH
CH 3 C`~2H2s ~ NHC ~3
CH 3--CH2--C ~ OCHC'NH~
CH3 CL CL
C- 9 O
OH
CH 3 C6HIl ~ NHC
CH3--( C~l2 ) 2--I ~ O¢HCNH~ o C L
C L C L
lZ9137;~:9
. -- 86 --
C-91
OH
l H 3 C8H~7 ,~ NHC'
CH3--( CH2) 2--C ~ OCHC o C L
3 C L CL
c-92
OH
CH3 C~H,7 ,~ NHCOOC3F7
CH 3 CH2 C ~ OCHCNH
CH3 CL
C-93
OH
(t)C5Hll ~, NHCO--C 3F7
(t) CsHIl ~ O--CHCONH~
C4Hg
C 94
F F
O~I ~
(t) C~ H~ ,~ NHCO ~ F
(t)C,H9~0--CHCONH I F F
C.,H9 F
~29~7~9
-- 87 --
c-95
,~ NHCO ~F
HO ~ O--CHCONH~W
(t3 C4Hg C'12H25
C-96
OH
(t)C5HII ~,, NHCOC ~ F 7
( t) C5H" ~ O--CHCONH~
I
C2Hs
C-97
OH
,~ NHCO (CF2)2 CHFC
Cl2~I2s 0 ~ O--CHCONH'W
C2Hs
C-98
OH
(t) C5HI, ,bl, NHCO ~30CF 2 CHFC '
( t) C5Hll ~ O--CHCONH OCF2CHFC '
C2H5
1298729
-- 88 --
C-99
OH
C4Hg ,~ NHCO (CF 2CF2 ) 2H
(t) C~ ~ O--CHCON
(t) C5H
C-l 00
OH
,~ NHCO ( CF2) ~H
CIZElz5 0 ~3 0--CHCONH
C ~Hg F
C-101
OH
C ~ H 9 5 2 NH ~ O--OH CONH~ NHC O
C'
C-102
CloH2~ ~ NHCO
O--CHCONH~ Cl2~25
C'
NHSO2CH3
129~3729
-- 89 --
C-103
OH
(t)csH~ , NHCO ~
(t)CsHIl ~ O--CHC ONH NH~ O 2 CE~ 3
C2H5
C-104
OH
,[~J NH9 0 2 CH 3
H3C (CH2)loCONH
C-105
OH
,~,NHCO(CH2) ~4CH3
HO ~} 9 2 NH'W
1298729
-- 90 --
C-106
,~ NHCO~D
~13 C ( CH2) ~2--C~I=CHCH 2 l~ON
GH 2 COOH
C-107
0
(~l2H25 ~ NHCO~
~30--CHcoNH~
C~
C4H9~3 O"NH
C-108
OH
~12H25 ~ NHCOC 3 F 7
¢~ O--CHCON~
)=/ ' C~
~ 2NH
(CH2)20czHs
lZ987;~:9
-- 91 --
C-109
[~3 H
~O--CHCONH
~3CHZ~~O2--NH
C-ll O
CL
OH
>C~CONHJ~ NHCO~
O6HI3 F
C-111
OH F F
(t)C5H~ HCo~ h
(t)C5H,l ~ O--CHOON~ F F
(i90)C3H7 C~
C-112
OH
C' ~6J~-NHCOC(CH3)3
C ~ ~$o--CHCONH
C~ C~O~21 CL
. ' ' .' .
,, , ~' .
, ,
lZ98'~;29
- 92
C-113
C 2E~S ,~ ~(t) C 4H 9
~OCH~ON
C~,
C~ n)
C-114
OH
C,~H~5 ~ NHCO ~tt)~ 4H9
OCHCONHJ~J
CL
C-115
OH
1 12HZ5 ~ NHCO ~(t) C4Hg
02N~OCHCOM
C_116
OH
C~H2S ~ NHCO~3(t)C~H9
OCHCONHJ~jJ
CL
C~
.
12~37;~:9
-- 93 --
C-117
OH
(` H
C~
C-118
OH
OCHCONH
C~
C-ll9
OH
Cl2H25 J~ NHCO ~3
O CHCONH
C~
C-12 O
OH
Cl2~I2S ~NHCo~
OCHCONH I CH 3
C '-
12987Z9
-- 94 --
C-121
0~
~ NHCO {~)
Cl2H2s ~ S ( CH ) 3CONH~
OCH2CONHCH2CH20C~13
C-122
0
(t)CsHII ,~NE~COC~2CH=C~
(t)c5Hl~.~O--( CH2)3
C-123
(t)C5Hll,~NHCOaH2~NHCO(:JH
(t)C5Hll ~ O--( CH2) 3CONH
C-124
OH
Cl2H~5 ~ NHCO
NC ~ OCHCONH~
1298~9
_ 9s _
C-125
/C~2~s ~ ~3
CN
C-126
OH
l2H25~r NHCO ~3
CL4~ OCHCONE:I
CL
CN
~-127
OH
CH 3 C~H25 ~ NHCO
H~[-- Ir )J
O--CHCON ~ CL
~ C~
CN
12~87;~:9
- 96 -
The cyan couplers preferably used in this invention can
be synthesized according to known methods and in the cases
of the compounds expressed by the general formula [VIII],
for example, they can be synthesized by the methods
described in , for example, US Patents Nos. 3,222,176,
3,446,622 and 3,996,253 and British Patent No. 1,011,940.
Further, in the cases of compounds expressed by the general
formula [IX], they are synthesized by the methods described
in, for example, by US Patent Nos. 2,772,162, 3,758,308,
3,880,661 and 4,124,396; British Patent Nos. 975,773,
8,011,693 and 8,011,694; Japanese Laid-open patent Nos.
47-21139, 50-112038, 55-163537, 56-29235, 55-99341,
56-116030, 52-67327, 56-55945, 56-80045 and 50-134644;
British Patent No. 1,011,940; US Patent Nos. 3,446,622 and
3~996~253; Japanese Laid-open Patent Publication Nos.
56-65134, 57-204543, 57-204544 and 57-204545; Japanese
Patent Application Nos. 56-131309, 56-131311, 56-131312,
56-131313, 56-131314, 56-130459 and 57-149791 and Japanese
Laid-open Patent Nos. 59-146050, 59-166956, 60-24547,
60-35731 and 60-37557.
The cyan couplers expressed by the general formula
[VII], [VIII] or [IX] can be used in combnation with the
others than those of this invention in the range not
contradicting the objects of this invention. Further, it is
possible to use one or more than two of the cyan couplers
lZg~29
- 97 -
expressed by the general formulae [VII], [VIII] and [IX].
When the cyan couplers of this invention expressed by
the general formulae [VII] - [IX] are to be contained in a
silver halide emulsion layer, they are in general used in
about 0.005 to 2 mol, preferably 0.01 to 1 mol per 1 mol of
a silver halide.
The silver halide halogen emulsions which can be used
in this invention, may include any of silver chloride,
silver bromide, silver iodide, silver chlorobromide, silver
chloriodide silver iodobromide or silver chloriodobromide.
The silver halide color photosensitive materials of the
invention may contain other various kinds of photographic
additives. For example, anti-foggants, stabilizing agents,
ultraviolet ray absorbents, anti-color-staining agents,
brightening agents, anti-discoloring agents, anti-static
agents, hardeners, surface active agents, plasticizers and
wetting agents such as those described in Research
Disclosure No. 17643. In the case of the silver halide
color photosensitive materials of this invention,
hydrophilic colloids may include synthesized hydrophilic
high polymers of a single or copolymer such as gelatin,
derivative gelatin, graft polymer of gelatin and other
polymers, protein such as albumin and casein, cellulose
derivatives such as hydroxyethylcellulose and carboxymethyl
cellulose, starch derivatives, polyvinyl alcohol, polyvinyl
lZ98729
- 98 -
imidazol and polyacrylamide.
As the supports for the silver halide color
photosensitive material according to this invention, there
are baryta paper, polyethylene-coated paper, polypropylene
synthesized paper, a transparent support attached with a
reflecting layer or using a reflecting body, for example,
glass plates, polyester films.such as polyethylene
terephthalate films, polyamide films, polycarbonate :
films, pclystyrene films, cell~llose acetate films,
cellulose nitrate films or other usual transparent
support. These supports are suitably selected
according to the purpose of using the photosensitive
material.
Silver halide emulsion layers and other photographic
component layer are coated in various coating methods such
as dipping, air doctor coating, curtain coating and hopper
coating and it is also possible to use the simultaneous
coating method which performs coating of two and more layers
simultaneously as described in U.S. Patent Nos. 2,761,791
and 2,941,898.
In this invention, it is possible to determine the
coating position of each emulsion layer at will. For
example, in the case of a paper photosensitive material for
full color print, it is preferable to arrange a
blue-sensitive silver halide emulsion layer, green-sensitive
lZ98729
99
silver halide emulsion layer and red sensitive emulsion
layer in that order from the support side. Further, each of
these silver halide emulsion layers may comprises two
component layers and more.
In the case of the photosensitive material according to
this invention, it is optional to provide an intermediate
layer of a suitable thickness depending on purposes and also
to use as a componet layer, an anti-curling layer, a
protective layer, an anti-halation layer, etc. in suitable
combinations. For these component layers, it is possible to
use hydrophilic colloids available for the above-mentioned
emulsion layer as binding agents.
As photosensitive materials to which this invention is
applicable, there are color paper, reversal paper, color
negative films, color positive films, direct positive films
and diffusion transfer photosensitive material.
EXAMPLES
This invention will be described in detail according to
the preferred embodiments though the invention is not
limited thereto.
Example 1
An anti-halation layer and a gelatin layer were
provided on a triacetate film base and a red sensitive
silver halide emulsion layer, a green sensitive silver
lZ98729
- 100 -
halide emulsion layer, a filter layer containing yellow
colloidal silver and a blue sensitive silver halide emulsion
layer with the total amount of silver in the order of 62 mg
per 100 cm were coated on the film base. The above-
mentioned emulsion layers contain silver iodobromide
with about 4.8 ~o~ silver iodide. In this
case, ~-(4-nitrophenoxy)-~-pivalyl-5-[~-2,4-di-t-
aminophenoxy) butylamide] -2-chloroacetoanilide as a yellow
coupler was used in the blue sensitive silver halide
emulsion layer, 1-(2,4,6-trichlorophenyl)-3- [~-(2,4-di-
t-aminophenoxy) -acetamide] benzamide -3-pyrazolone and
1-(2,4,6-trichlorophenyl) -3- [~-(2,4-di-t-amylphenoxy
-acetamide] benzamide -4-(4-methoxyphenylazo)-5-pyrazolone
as a magenta coupler was used in the green sensitive silver
halide emulsion layer and as a cyan coupler, the following
~-i) was used in the red sensitive silver halide emulsion
layer. In addition, usual additives such as a sensitizer, a
hardening agent and the like were added to each emulsion
layer provided that as a high-boiling point solvent, the
illustrated compound (A-25) (having a dielectric constant of
7.5) was used. The silver halide color photosensitive
material thus obtained was made a film sample (1) and the
like film sample (2) was prepared by use of fluidized
paraffin (having a dielectric constant of 2.2) instead of
129~g
- - 101 -
the high-boiling point solvent (A-25).
Cyan coupler (C-i)
OH
CoNHtOH2t4O - ~ C5Hll( )
5 11( )
This sample was subjected to stepwise exposure with
white light by using a KS-7 type sensitometer (a product of
Konishiroku Photo Industry Co., Ltd.) and was treated in the
following steps.
Processing steps (38C) Number of tanks Processing time
Color development 1 3 min. 15 sec.
Bleaching 1 4 min. 20 sec.
Fixation 1 3 min. 10 sec.
Non-rinsing stabilizing solution 2 1 min. 20 sec.
(Cascade)
Cleaning 1 30 sec.
The composition of the color developing solution used
was as follows:
Potassium carbonate ~8 g
Sodium hydrogen carbonate 2.5 g
Potassium sulfite 3.0 g
Sodium bromide 1.2 g
Potassium iodide 1.2 mg
Hydroxylamine sulfate 2.5 g
- 102 ~ 1 Z9 8t~Z ~
Sodium diethylenetriamine pentaacetate 2.0 g
4-amino-3-methyl-N-ethyl-N~
hydroxyethyl) aniline sulfate4.8 g
Potassium hydroxide 1.2 g
Water was added to obtain a total quantity
of 1 liter, and the pH thereof was adjusted to 10.06
by using potassium hydroxide or a 20% solution of
sulfuric acid.
The composition of the color developing
replenishing solution used was as follows:
Potassium carbonate 30 g
Sodium hydrogen carbonate 1.0 g
Potassium sulfite 4.3 g
Sodium bromide 0,9 g
Hydroxylamine sulfate 3.0 g
Sodium diethylenetriamine pentaacetate 2.5 g
4-amino-3-methyl-N-ethyl-N-(~-
hydroxyethyl) aniline sulfate5,5 g
Potassium hydroxide 1.4 g
Water was added to obtain a total quantity
of 1 liter, and the pH thereof was adjusted to 10.12
by using potassium hydroxide or a 20~ solution of
sulfuric acid.
The composition of the bleaching solution
and its replenishing solution was as follows:
lZ9~'~;29
- 103 -
Ammonium ethylnediaminetetra acetate iron
(III) complex 100 g
Ammonium bromide 140 g
Water was added to obtain a total quantity
of 1 liter, and the pH thereof was adjusted to 5.8 by
using glacial acetic acid and aqueous ammonia.
The composition of the non-rinsing fixing
solution and its replenishing solution was as
follows:
Ammonium thiosulfate 180 g
Sodium sulfite anhydrous 12 g
Potassium hydroxide 1 g
Sodium carbonate 8 g
Water was added to obtain a total quantity
of a 1 liter, and the pH thereof was adjusted to 7.0
by using concentra-ted aqueous ammonia or acetic acid.
The composition of the stabilizing
solution and its replenishing solution was as
follows:
2-methyl-4-isothiazoline-3-on 0.1 g
Ethylene glycol 1 g
Water was addg4ed to obtain a total
quantity of 1 liter.
The composition of the cleaning solution
and its replenishing solution was as follows:
!B
- 104 - 129~7~
Formalin (a 35~ aqueous solution) 7.0 ml
C9Hl9~ O(CH2CH2O)loH 1.5 ml
Water was added to obtain a total quantity
of 1 liter.
The surface active agents shown in the
following table 1 were properly added respectively to
the above-mentioned stabilizing solution and the
respective running tests were conducted while
adjusting the surface tension of each of them as
shown in Table 1. The amounts of replenishing
solution added were 600ml for color development and
stabilizing, 300ml for bleaching and 700ml for fixing
and cleaning per lm of the sample film respectively.
This running tests were discontinuously conducted
until the total amount of replenishment of the
non-rinsing stabilizing solution became three times
the volume of the non-rinsing stabilizing tank.
After the completion of the running tests, the
density of red color passing through the unexposed
section of each processed sample film was measured by
a photoelectric densitometer PDA-65 (manufactured by
Konishiroku Photo Industry Co., Ltd.).
lZ91~7~9
- 105 -
Further, each of the processed sample films was stored
for 15 days so that the film had 1.5 x 107 lux by use of a
xenon lamp at a temperature of 70C and a relative humidity
of 70% RH, red transmission density through
the maximum density portion was measured by the above-
mentioned densitometer and the discoloring rates (%) before
and after the storage of the films were obtained with the
results collectively shown in the Table 1.
129E~7;29
-- 106 --
~ .
O AW ~r O ~D '1 O~ t~J (~)
~ ~ _1 ~ 00 OD 00 a~
u~dP _~ r~ ~ .
~ C) .
A ~A l ~ ~ .
u~ o u1~ ~,~~r _~ _~ _I _I
O ~r~ ~ O O O O O O O
Q.~ .. . . . .
oo o o o o o
~ .
O A I
~ ~ ~ ~ û ~ û _ 7 ~ û ~ u u ~
n~ AW ~ W ~ .~ ~ .r~ ~
~ AWrCI W~ W~ .. -1 AW .rl AW '~1 AW ~ W _ AW
r1 '~1Al U ~a ~ ~ ~ ~ X ~ '~ ~ ~ X ~
'IN w ~ 111 ~111 ~ H H X 3 _ _ ~,
,4 .rl ~ 1O 1~ O ~ H U~H 11~ ~ 0 I ~D H l''t
E~l ,~ q -- . z ~D Z ~DH ~ H ~ H t`l ~ _ _
U) .
.
.
~r/O ~I .") _~t~l ~`1 ~1
A r-l-- -- --
9J ~ ~ ~`J ~ ~ - 8
~ ~ t~l ~ 1`~ -`1 ~ ~ Q- l`
~ ~_,ed-- ~3~ ~_ .
IUO~ u~ u~ u~u~
.
... ~ ................................... ..
A I O O O O C O O
l~j ~.1).1 ~ ~J ~ ~ .,
.,1 ~ ~ ~ ~ ~ ~ ~ ~
~ o ,, ~ ~ ~ ~ ~ ~ u~ ~ u~ ~ ~ u~ u~ wl r~ ~ . ~
wl z ~ ~ e .,, p ." ~ .,~ ~ ." ~
~ ~ ~ ~ ~,c ~ ~ ~:~
12915 7~9
- 107 -
From the table in the previous page, it will be
understood that in case the high-boiling point solvents of
this invention are used in the sample films and the surface
tension of each of the stabilizing solutions is within the
range determined in this invention, the unexposed sections
of each film are free of stains and to be more surprising, a
favorable discoloring prevention effect against light in a
high-temperature and high-humidity atmosphere is obtained.
However, these effects will not be obtained if the solvents
and the stabilizing solution are not used together.
Example 2
A sample ilm (3) was prepared by using the exemplified
compounds III-~xii) in the color negative photosensitive
material of the embodiment l with other conditions being
same as the sample film (l) of the example l.
As a result of a running test conducted in the same
manner as the test of the example l, it was found that the
surface tension of the stabilizing solution was in the order
of 37 dyne/cm at the time of termination of the test.
Then the sample film (3) was processed with the above
converging solution and the same experiment as that in the
example l was conducted with extremely favorable results.
That is, the cyan stain density of the unexposed section was
0.01 and the discoloring rate was 8.4%
lZ9~7~9
- 108 -
From the above, it will be understood that the effects
of this invention can also be obtained in such a manner that
the surface active agent of this invention is added to a
photosensitive material and liquated into the stabilizing
solution and the surface tension of the stabilizing solution
is controlled to the range defined in this invention.
Example 3
The exemplified compound III-(xii) was properly added
to the stabilizing solution used for the experiment 1 in the
example 1, the surface tensions of the solution were
controlled respectively according to the table 2 and the
same experiments as in the case of the example 1 were
conducted. The results are collectively shown in the table
2.
However, as it was not possible to keep the surface
tension of the stabilizing solution below 30 dynes/cm by
using only the compound of III-(xii), silicone was partially
used side by side.
lZ987Z9
- 109 -
D ~ _ ~ _ ~ N N N
0~ Co O Co ~ .~ O~ O~
t)
.'
.
~ Itl N _~ ~ ~1 _I N
C) ~ ~ O O O O O O O
~ V V
O ~ ~ ,0 e ~ ~ . _ ~ _ ~ _ ~ _ ~ _ ~
~ a)_ ~1~ ~1~ ,~ ~1~ ~1~r~
D- ~ ~ ~ a) ~1 Q) rl a~ rl ~ ~ ~ C~ rl
1~1 ~ ' 1 ~ X ~ X ~ X ~ X ~ X ~ X
~1 0 0 O In H O H O H H H H
P o~ U~ Z ~o ~ ~ H ~` -- -- --
~0 .'
,~C,~
,U.~ -~_
~.rll O ~U~ .
. ~l~,CU ~1` ~' ~ ~ .
C~
' _ _ _ _ _
~ oo C o o o C
~1 o~ 0oou~ ~J ~ul 0 ou) 0 C N U~ 0 C
.)~ 2 ~ .~ P .C C -~.C C ~ C ~ P 'I-S P
~ ~E~-~l E~-~l E~ ~ E~-~l E~ E~
_
129~37; :9
- 110 -
Further, in the case of the stabilizing solution shown
in Table 2, when the surface tension of the solution was
less than 20 dyne/cm, the surface of the sample film after
drying was stained.
From the table in the previous page, it will be
understood that when the surface tension of the stabilizing
solution is in the range of 20 - 60 dyne/cm, it is possible
with this invention to produce a favorable effect and when
it is in the range of 25 - 50 dyne/cm, a specifically
favorable effect is obtained.
Example 4
The silicone [FS Antifoam 025 (Dow Corning Corp.)] of
this invention as pure silicone was added in an amount of 20
mg per l-liter of the stabilizing solution in the example 2
and the same experiment was conducted to obtain a favorable
result with a discoloring rate of 7.3%. Further, when using
the FS antifoam BE (Dow Corning Corp.) instead of the FS
Antifoam 025, a favorable discoloring rate of 7.5% was
obtained.
In addition, when the silicone of this invention was
used together, the foaming action of the solution was
favorably improved at the time of a running test.
Example 5
The exemplified compounds (C-29) and (C-51) were used
instead of the cyan coupler (C-i) used in the sample film
12987~
- 111 -
(1) of the example 1 and the same experiment was conducted
with the results that the discoloring rate of cyan color
against light in a high-temperature and high-humidity
atmosphere was improved by 2 - 3% only in the examples of
this invention.
Example 6
The same experiment as in the example 1 was conducted
without using the anti-molding agent
(2-methyl-4-isothiazoline-3-on) used for the stabilizing
solution of the example 1 and it was found that, although
the effect of this invention were produced, the surface of
the sample film was somewhat stained and the color stain
generating condition was worsened by about 0.01.
