BACKGROUND OF THE INVENTION
[0001] The present invention relates to a method for preparing a hydrophobic substance for
use in photography, and more particularly relates to a method for preparing a hydrophobic
substance characterized in that: all kinds of hydrophobic substance can be precipitated
when oil-in-water type dispersion is formed only by water-insoluble low boiling point
organic solvent substantially without using high boiling point organic solvent; and
a hydrophobic substance of a predetermined particle size can be easily obtained.
[0002] When a photosensitive material is prepared, a dispersion of a predetermined particle
size is obtained in such a manner that: after a hydrophobic substance such as a color-image
forming compound (a coupler), compound for use in diffusion transfer material, anti-color
fogging agent, anti-color fading agent, anti-color mixing agent, UV absorbent and
whitening agent, has been dissolved in a high boiling point organic solvent such as
alkylphthalate, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides
and fatty acid esters, the solution is dispersed in water. In this case, it is very
important to control the particle size of the dispersed substance. Especially when
a coupler is used to finally prepare a photosensitive material, the particle size
has influence on photographic characteristics.
[0003] In the field of photosensitive material, the following proposals have been made as
a method to obtain oil-in-water type dispersion in which high boiling point organic
solvent is dispersed.
(1) In the official gazette of Japanese Patent Publication No. 15005/1984, an embodiment
has been disclosed in which a high pressure dispersing apparatus is used and the solution
is dispersed by both shearing and colliding force.
(2) In the official gazette of Japanese Patent Application Open to Public Inspection
No. 293537/1986, an embodiment has been disclosed in which the solution is dispersed
by a high speed mixer.
The following methods has been disclosed as a method by which a hydrophobic substance
is precipitated in the form of fine particles.
(3) In British Patent No. 1,193,349 and European Patent Application Open to Public
Inspection No. 374, 837, a method has been disclosed in which a hydrophobic substance
is precipitated and stable colloid is obtained, wherein the phenomenon is utilized
in which the dissolution degree of a hydrophobic substance differs according to pH.
(4) In British Patent, a method has been disclosed in which: after coupler has been
dissolved in a low boiling point organic solvent, it is coated; and in the coating
process, the aforementioned low boiling point organic solvent is evaporated so that
the solvent can be removed.
[0004] However, in the case of the aforementioned oil-in-water type dispersion method in
which a high boiling point organic solvent is utilized, the high boiling point organic
solvent remains in a coating film, so that the thickness of the film is increased.
Accordingly, sharpness is deteriorated, and further color bleeding is caused by the
high boiling point organic solvent.
[0005] Furthermore, the methods disclosed by British Patent No. 1,193,349 and European Patent
Application Open to Public Inspection No. 374, 837 are disadvantageous in that: the
methods can be applied only to coupler in which the solubility is changed by pH. Furthermore,
the methods can not be applied to the coupler having an ester group capable of being
hydrolyzed upon the change of pH value. Precipitation caused by the change of pH can
be quickly stabilized by a binder or surface active agent, so that a fine particle
size can be obtained. However, it is difficult to control the particle size.
[0006] On the other hand, in order to simultaneously remove unnecessary organic solvent
and salt generated by neutralization, it is necessary to adopt the noodle washing
method and ultrafiltration method. However, a long period of time and a large amount
of water are required, and further, polluted waste liquid must be processed, so that
consideration must be given to the environmental problems.
[0007] The method of British Patent 1,099,414 is disadvantageous in that: oil-in-water type
dispersion comes into contact with a solvent over a long period of time; and accordingly,
the oil-in-water type dispersdoid coagulates, so that coarse particles are generated.
SUMMARY OF THE INVENTION
[0008] The first object of the present invention is to solve the aforementioned problem
by forming a oil-in-water type dispersion without substantially using a high boiling
point organic solvent.
[0009] The second object of the present invention is to provide a method for preparing a
hydrophobic substance for photographic use by which fine particles of a hydrophobic
substance can be obtained, irrespective of the kind of the hydrophobic substance,
whereby the particle size can be easily controlled.
[0010] The aforementioned problems can be solved by adopting a method for dispersing a hydrophobic
substance for photographic use in water characterized in that: the first solution
in which the aforementioned hydrophobic substance is substantially dissolved only
in a water-insoluble low boiling point organic solvent, and the second solution in
which only a surfactant, or both a surfactant and a binder are dissolved in water,
are dispersed in each other so as to form a oil-in-water type of dispersion; and when
the dispersion is stirred under reduced pressure, the aforementioned water insoluble
low boiling point organic solvent contained in the aforementioned oil-in-water type
dispersion, is removed so as to form finally dispersed precipitates of a hydrophobic
substance.
[0011] When the aforementioned dispersing operation is performed, a high speed stirring
type of dispersing apparatus may be utilized so that the dispersion is stirred under
the condition that the dispersing circumferential speed is not less than 10 m/sec.
[0012] It is preferable to start the stirring operation under reduced pressure within 5
minutes after the oil-in-water type of dispersion has been formed.
[0013] In the process of removing the aforementioned water-insoluble low boiling point organic
solvent, it is preferable to continue the removing operation until the content of
the water-insoluble low boiling point organic solvent becomes not more than 1 wt%.
[0014] According to the present invention, the coating thickness can be prevented from becoming
thick, sharpness can be improved, and the occurrence of bleeding of color can be prevented
without using a high boiling point organic solvent.
[0015] Further, according to the present invention, fine particles of a hydrophobic substance
can be obtained and the particle size can be easily controlled irrespective of the
kinds of hydrophobic substances.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
Fig. 1 is a schematic drawing showing an example of the manufacturing apparatus of
the present invention; and
Fig. 2 is a correlation diagram between the standing time and the average particle
size of the obtained hydrophobic substance.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The present invention will be described in detail as follows.
[0018] The summary of the invention will be explained referring to Fig. 1 showing a manufacturing
apparatus in which a coupler is utilized as a hydrophobic substance.
[0019] That is, in the first dissolution tank 1, the first solution is obtained by dissolving
a hydrophobic coupler in a water insoluble low boiling point organic solvent. On the
other hand, in the second dissolution tank 2, the second solution is obtained by dissolving
both a surface active agent and a binder in water. The obtained first and second solution
are emulsionized and dispersed in a dispersion tank 3 provided with a high speed stirring
type dispersing apparatus 3A so that an oil-in-water type of dispersion is made. After
that, the dissolution tank 3 is evacuated by a vacuum pump 4, and at the same time
the high speed stirring type dispersing apparatus 3A is operated so that the water
insoluble low boiling point organic solvent is evaporated. The solvent vapor is condensed
by cooling with a refrigerant 6 in a heat exchanger 5 so that the water insoluble
low boiling point organic solvent is removed in the form of liquid, which is recovered
into a recovery tank 7, and at the same time a coupler is precipitated from the recovered
liquid in the dissolution tank 3. Then, a stabilized solid-liquid dispersion in which
a solid is dispersed in a liquid medium, can be obtained by the action of a surfactant
and a binder.
[0020] In the aforementioned example, the first dissolution tank 1 and the second dissolution
tank 2 may be provided with a heating jacket 8 and a heater in order to facilitate
dissolution, dispersion, and stabilization so that the temperature of the solution
can be controlled. A dissolver type, oar type, propeller type, and homo-mixer type
of high speed stirring dispersing apparatus can be adopted. It is preferable to maintain
the temperature in the dispersion tank 3 at 15 - 60°C.
[0021] On the other hand, the first and the second solution may not be put into the dispersion
tank 3 separately, but may be mixed with each other and put into the tank 3. Usually,
after the first and the second solution have been put into the dispersion tank 3,
the operation of the high speed stirring type of dispersing apparatus is started.
However, in the case of continuous dispersion, the dispersing operation can be performed
while the first and the second solution are being supplied during the operation of
the high speed stirring type of dispersing apparatus 3A.
[0022] The operation conducted during dispersion has great influence on the dispersing property.
The particle size of the dispersion mainly depends on the rotation speed of the dispersing
apparatus, the stirring time, and the amount of the activator. The dispersing circumferential
speed is preferably not less than 10 m/sec and not more than 100 m/sec.
[0023] It is preferable to stir under reduced pressure immediately after the oil-in-water
dispersion has been made in the process of dispersion. Depending on the standing time
from the completion of dispersion to the start of stirring operation, the particle
size to be obtained grows as shown in Fig. 2. Consequently, it is desirable to restrict
the standing time within 5 minutes. Fig. 2 shows an example in which the solution
temperature is maintained at 45°C during the process of standing.
[0024] The stirring time relates to the particle size to be obtained. However, it is preferable
to maintain the stirring time in 3 - 60 minutes. When an evacuating operation is performed
in order to remove the water-insoluble low boiling point organic solvent, the pressure
is gently reduced to 100 Torr, and preferably the evacuating operation may be conducted
according to the method disclosed in the Japanese Patent Application open to Public
Inspection No. 102303/1990. Further, the temperature of the solution in the case of
removal of the water impermeable low boiling point organic solvent is preferably 40
- 80°C, and more preferably 50 - 70°C. The removal of the water-insoluble low boiling
point organic solvent is preferably conducted until its content becomes not more than
1 wt%.
[0025] The amount of the surface active agnet to be added relates to the kinds of binder
and coupler of the water-insoluble low boiling point organic solvent. However, the
amount of the surface active agent is preferably in the range from the critical micelle
concentration to 50 times of the critical micelle concentration. When these factors
are controlled, the liquid particle size can be controlled to be 0.01 - 3 µm in the
present invention. The circumferential dispersing speed in the process of dispersion
and the stirring circumferential speed in the process of removal of the water-insoluble
low boiling point organic solvent, may be different from each other.
[0026] A solution in which only the surface active agent is dissolved in water may be utilized
as the second solution without using the hydrophilic binder. When the hydrophilic
binder is used, the content may be 3 - 30 wt% in the solution put in the dispersing
tank 3.
[0027] In the present invention, the boiling point of the water-insoluble low boiling point
organic solvent is not more than 100°C, and more preferably not more than 85°C. The
specific examples are ethyl acetate, methyl acetate, m-hexane, m-pentane, benzene,
cyclohexane, cyclopentane, chloroform, and dichloromethane.
[0028] In the present invention, the objective hydrophobic substance is substantially dissolved
only in the water-insoluble low boiling point organic solvent. In this case, it is
preferable that a high boiling point organic solvent is not contained at all.
[0029] When a high boiling point organic solvent such as dimethyl form-amide (DMF) is used
as an auxiliary solvent, a small amount of the solvent, for example, not more than
5 wt% can be added so that the sharpness is not deteriorated and bleeding of dye is
prevented.
[0030] A coupler which is a hydrophobic substance applied the various photographic materials
of the present invention, is a color image forming compound which forms a dye upon
reaction with an oxidized product of color developing agent, for example aromatic
amine (the first class amine). In general, a non-diffusible coupler having a hydrophobic
group referred to as a ballast group, is preferably used, and either 4 equivalent
or 2 equivalent coupler may be used. The aforementioned coupler includes a colored
coupler provided with color correction effect, and a DIR coupler which releases a
developing inhibitor while developing is conducted. A widely known closed ketomethylene
coupler can be utilized as a yellow coupler. Benzoyl acetoamide compounds and pivaloyl
acetoamide compounds are advantageously used.
[0031] Pyrazolone compounds, indazolone compounds, and cyanoacetyl compounds can be used
as a magenta coupler, wherein pyrazolone compounds are advantageous.
[0032] Phenol compounds and naphthol compounds can be used as a cyan coloring coupler.
[0033] A coupler disclosed in the official gazette of Japanese Patent Application Open to
Public Inspection No. 42121/1977 can be used as a colored coupler.
[0034] A coupler disclosed in the Japanese Patent Application Open to Public Inspection
No. 69624/1977 can be used as a DIR coupler. Except for the aforementioned DIR coupler,
a compound which releases a developing inhibitor during a developing process may be
contained in the photographic material, and for example, a compound disclosed in the
official gazette of Japanese Patent Application Open to Public Inspection No. 9116/1978
can be used.
[0035] The following non-ionic surface active agents are used for the present invention:
a saponin (steroid) derivative; an alkyleneoxide derivative (for example, polyethylene
glycol, condensation of polyethylene glycol/polypropylene glycol, polyethylene glycol
alkyl or alkylaryl ether, polyethylene glycol ester, polyethylene glycol sorbitan
ester, polyalkylene glycol alkylamine or amide, and polyethylene oxide additive product
of silicon); a glycidol derivative (for example, alkenyl succinic acid polyglyceride,
and alkylphenol polyglyceride); fatty acid ester of polyhydric alcohol; alkyl ester
of sugar; and urethane or ether.
[0036] The anion surface active agents containing the following acidic groups such as a
carboxyl group, a sulfo group, a sulfate ester group, and a phosphoric ester group
are used for the present invention: saponin of triterpenoide, alkylcarboxylic acid
slat, alkylsulfonic acid salt, alkylbenzene sulfonic acid salt, alkylnaphthalene sulfonic
acid salt, alkylsulfate ester, alkyl phosphoric ester, N-acyl-N-alkyltaurine, sulfosuccinic
acid ester, sulfoalkylpolyoxyethylene alkylphenyl ether, and polyoxy ethylene alkyl
phosphoric ester.
[0037] The following amphoteric surface active agents are used for the present invention:
amino acid; aminoalkyl sulfonic acid; aminoalkyl sulphuric acid or phosphoric ester;
alkylbetaine; amineimide; and amineoxide.
[0038] The following cationic surface active agents can be used for the present invention:
heterocyclic quarternary ammonium salt such as alkylamine salt, aromatic or aliphatic
quarternary ammonium salt, pyridinium, and idazolium; and aliphatic or heterocyclic
phosphonium or sulfonium salt.
[0039] Especially, an anionic surface active agent such as dodecyl benzene sulfonic acid,
dodecyl sodium sulfate, and "Aerosol A102" (made by Cyananid Co.) is preferably used.
[0040] Protein such as gelatin, a gelatin derivative, a graft polymer of gelatin and other
high polymers, albumin, and casein is used for the aforementioned water soluble binder.
[0041] A cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, and
cellulose sulfate ester, and a sugar derivative such as sodium alginate and a starch
derivative are also used for the aforementioned water soluble binder.
[0042] Synthetic hydrophilic high molecular substance such as polyvinyl alcohol, polyvinyl
alcohol acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid,
polyacrylic amide, polyvinyl imidazol, and polyvinyl pyrazole, or synthetic hydrophilic
high molecular substance of a copolymer of the compounds described above, are used
for the aforementioned water soluble binder.
[0043] Usually, it is desirable to use gelatin for the binder.
[0044] A dye developer diffusible dye releasing coupler (DDR coupler) and diffusible dye
releasing reducer (DRR compound) are used for the aforementioned compound for diffusion
transfer use.
[0045] For example, a hydroquinone derivative, aminophenol derivative, gallic acid derivative
and ascorbic acid derivative are used as the aforementioned anti-stain agent.
[0046] For example, a hydroxybenzene derivative, dihydroxynaphthalene derivative, aminonaphthol
derivative, sufonicamide phenol derivative, and sulfonic amide naphthol derivative
are used for the aforementioned anti-fading agent.
[0047] For example, a benzotritriazole compound substituted by an aryl group, 4-thiazolidone
compound, benzophenone compound, cinnamic acid ester compound, butadiene compound,
and benzoxazole compound can be used for the aforementioned ultraviolet ray absorbent.
Further, an ultraviolet ray absorbing coupler and ultraviolet ray absorbing polymer
may be used.
[0048] For example, a compound of stilbenzene, triazine, oxazole or cumalin is used for
the aforementioned whitening agent.
[0049] Next, an example will be shown to clarify the effect of the present invention.
[0050] The following coupler and surface active agent were used in the example of the present
invention.
〈Coupler (1)〉
[0051]
〈Coupler (2)〉
[0052]
〈Surface active agent (1)〉
[0053] Dodecyl benzene sodium sulfonate
〈Surface active agent (2)〉
[0054] Dodecyl benzene sodium sulfate
〈Surface active agent (3)〉
[0055] (Aerosol A102)
[0056] The following were used for spectral sensitizers (S-1), (S-2), a coating aid (Su-1),
and a thickening agent (V-1).
EXAMPLE 1
[0057] The first solution of the following composition was dissolved for one hour at 60°C.
Coupler (1) |
5 kg |
Ethyl acetate |
10 ℓ |
DMF |
300 mℓ |
[0058] On the other hand, the second solution of the following composition was dissolved
for one hour at 60°C.
[0059] Subsequently, the first and the second solution were mixed, and dispersed by a dispersing
apparatus provided with a disperser having a diameter of 10 cm, at a circumferential
dispersing speed of 20 m/sec for 10 and 20 minutes, and at a circumferential dispersing
speed of 30 m/sec for 10 minutes. Then, the solution was evacuated and stirred until
the residual concentration of ethylacetate became not more than 0.3 wt% so as to remove
ethylacetate, and subsequently, the solution was diluted with water to make 100 ℓ.
[0060] The dispersed particle size of thus obtained solid-liquid dispersion in which a solid
was dispersed in a liquid medium was measured by means of the photon correlation method,
and the results shown in Table 1 were obtained. A photosensitive material was made
by the method described later, and its photographic characteristics were investigated
to obtain the results shown in Table 1.
[0061] In this case, the sharpness was measured by means of the modulation transfer function
method. The detailed results are described on pages 430 - 437 of "Photographic Chemistry"
(which was written by Akira Sasai and published by Shashin Kogyo Shuppansha). In this
measurement, the photosensitive material was exposed to white light through an MTF
chart and developed, and its sharpness was represented by MTF values at 40 cycle/mm.
TABLE 1
Cirmcumferential Dispers-ing Speed |
Inventive Example |
Blank |
Comparative Example |
|
20 m/sec |
30 m/sec |
25 m/sec |
- |
Dispers-ing Time |
10 min |
20 min |
10 min |
15 min |
- |
Particle Size |
485 nm |
125 nm |
90 nm |
160 nm |
50 nm |
Dmax |
109% |
120% |
108% |
100% |
103% |
MTF |
0.66 |
0.68 |
0.70 |
0.58 |
0.68 |
[0062] The aforementioned comparative example in Table 1 is described in Example 1 disclosed
in the European Patent Application Open to Public Inspection No. 374837. "Blank" in
Table 1 shows the values in the case where a high boiling point organic solvent was
used. The condition of Blank is conventional as described in the official gajette
of Japanese Patent Publication No. 56010/1986.
[0063] According to Table 1, the particle size could be controlled by the circumferential
dispersing speed and stirring time. In the comparative example, the particle size
could not be controlled, and the coloring density was only 103%.
[EXAMPLE 2]
[0064] The first solution of the following composition was obtained being stirred for one
hour at 60°C.
Coupler (2) |
5 kg |
Ethylacetate |
10 ℓ |
[0065] The composition of the second solution was as follows, wherein the dissolving conditions
were the same.
Water |
50 ℓ |
Surface active agent (3) |
2 ℓ (Concentration 33%) |
[0066] A dispersing operation was conducted in the same manner as that of Example 1 to remove
ethylacetate. The particle size of dispersion and coloring density are shown in Table
2. It was ensured that the particle size could be controlled in the case of coupler
(2).
TABLE 2
|
20 m/sec 20 min |
50 m/sec 20 min |
Blank |
Particle size |
254 nm |
105 nm |
200 nm |
Dmax |
115% |
104% |
100% |
MTF |
0.68 |
0.70 |
0.57 |
[Spectral sensitization and coating recipe]
[0067]
- Silver iodobromide emulsion
- 0.9 g
- Spectral sensitizer (S-1)
- 0.0001 (mol/silver 1 mol)
- Spectral sensitizer (S-2)
- 0.0004 (mol/silver 1 mol)
- Coupler dispersing solution
- 0.5 (mol/silver 1 mol)
- Gelatin
- 1.0 g
- Coating aid (Su-1)
- 1.2 mℓ/200 mℓ of the above solution
- Thickening agent (V-1) 4% solution
- Controlled to be 32 cp
- Silver iodobromide emulsion:
- Silver iodobromide emulsion, containing the average grain size of 0.7 µm, was prepared
by the double jet method, and the average iodo content of which was 7.5 mol%, was
chemically sensitized to be the most appropriate sensitivity with sodium thiosulfate
and chloroauric acid.
[0068] The coated sample was exposed to white light through a step wedge for sensitometory,
and processed under the following conditions.
〈PROCESS〉
[0069]
TABLE 3
Process |
Processing Time |
Processing Temperature |
Replenishing Amount |
Color Development |
3 min 15 sec |
38±0.3°C |
780 ml |
Bleach |
45 sec |
38±2.0°C |
150 ml |
Fixing |
1 min 30 sec |
38±2.0°C |
830 ml |
Stabilization |
60 sec |
38±5.0°C |
830 ml |
Drying |
1 min |
55±5.0°C |
- |
[0070] In the above table, the amount of replenishment is expressed by the unit of mℓ/m²
of photosensitive material.
〈Color Developing Solution〉
[0071]
[0072] Water is added to make 1 ℓ, and pH is adjusted to 10.06 using potassium hydroxide
or 20% sulphuric acid.
〈Color Developer Replenishing Solution〉
[0073]
[0074] Water is added to make 1 ℓ, and pH is adjusted to 10.18 using potassium hydroxide
or 20% sulphuric acid. 〈Bleach〉
Water |
700 ml |
1. 3 diaminopropane-tetraacetic acid ammonium slat |
125 g |
Ethylene diamine tetraacitic acid |
2 g |
Sodium nitrate |
40 g |
Ammonium bromide |
150 g |
Glacial acetic acid |
40 g |
[0075] Water is added to make 1 ℓ, and pH is adjusted to 4.4 using aqueous ammonia solution
or glacial acetic acid.
〈Bleach Replenishing Solution〉
[0076]
Water |
700 ml |
1. 3 diaminopropane--tetraacetic acid ammonium slat |
175 g |
Ethylene diamine tetraacitic acid |
2 g |
Thorium nitrate |
50 g |
Ammonium bromide |
200 g |
Glacial acetic acid |
50 g |
[0077] Water is added to make 1ℓ, and pH is adjusted to 4.0 using aqueous ammonia solution
or glacial acetic acid.
〈Fixing Solution〉
[0078]
Water |
800 ml |
Thiocyanic acid ammonium |
120 g |
Thioammonium sulfate |
150 g |
Sodium sulfite |
15 g |
Ethylene diamine tetraacetic acid |
2 g |
[0079] Water is added to make 1ℓ, and pH is adjusted to 6.2 using aqueous ammonia solution
or glacial acetic acid.
〈Fixer Replenishing Solution〉
[0080]
Water |
800 ml |
Thiocyanic acid ammonium |
150 g |
Thioammonium sulfate |
180 g |
Sodium sulfite |
20 g |
Ethylene diamine tetraacetic acid |
2 g |
〈Stabilizing Solution and Replenisher〉
[0081]
Water |
900 ml |
The following compound A |
2.0 g |
Dimethylolurea |
0.5 g |
Hexamethylenetetramine |
0.2 g |
1, 2-benzisothiazoline-3-one |
0.1 g |
Siloxane |
0.1 g |
Aqueous ammonia solution |
0.5 ml |
[0082] Water is added to make 1 ℓ, and pH is adjusted to 8.5 using aqueous ammonia solution
or 50% sulphuric acid.
[0083] As described above, according to the present invention, a hydrophobic substance of
fine particles can be obtained irrespective of the kind of the substance, as well
as the deterioration of sharpness and dye bleeding caused when a high boiling point
organic solvent remains in a coated film can be prevented.