FIELD OF THE INVENTION
[0001] The invention relates to a solid developing composition for a silver halide photographic
light-sensitive material and a manufacturing method thereof, and particularly a solid
developing composition having improved storage stability for a silver halide photographic
light-sensitive material and a manufacturing method thereof.
BACKGROUND OF THE INVENTION
[0002] A developing composition for a silver halide photographic light-sensitive material
is usually supplied in the form of plural concentrated solutions (kit) to consumers.
Recently, in the color photographic processing industry, small-scaled developing stores,
so-called mini-labs, which process a photographic material using a small automatic
processor, rapidly increased and the amount of the processing kits used also increased.
A processing kit, in which plural concentrated solutions are packaged in plastic bottles
of 100 milliliter to 5 liter, is supplied to customers, but the processing kit still
requires much storage space. Further, the cost for transport is not low. The discarded
plastic bottles increase year by year, causing an environmental problem. The processing
kit for developer is usually supplied in plural separate parts. The consumers mix
the parts in a specific proportion to prepare developer replenisher, but errors frequently
occur during the mixing operations.
[0003] Powder photographic processing compositions are considered in order to overcome the
above problems. However, the powder compositions produce loose powder when dissolved
in water, and operators breathe in loose powder particles, resulting in health hazard.
Further, other photographic solutions may be contaminated with the components of the
loose powder and there occurs the possibility of other troubles in developing process.
[0004] In response to these problems Japanese Patent O.P.I Publication Nos. 2-109042/1990
and 2-109043/1990 disclose a technique of using a granular mixture of photographic
processing agents. Patent O.P.I Publication Nos. 5-119454/1993 and 5-113646/1993 disclose
a photographic processing system using a granular or tablet processing agent.
[0005] The above described techniques can prevent fine powder occurrence of the solid processing
agent, but there is a problem particularly in a tablet developing composition that
it is difficult to discharge tablets in a cartridge or to quantitatively supply tablets
in a supplying device on account of expansion of the tablets during storage. The problem
is noticeably displayed particularly when the tablets are transported by ship from
Japan to Southeast Asia, the Middle and Near East or Africa in 2 to 4 weeks, during
which the temperature difference between day and night is 15-20°C and the humidity
difference between day and night is 20-30%.
[0006] There is another problem that, when different granular processing agents are mixed
to obtain one granular processing composition, the granular processing composition
having a desired component content cannot be obtained. This causes a serious problem
that continuous photographic processing is impossible. In order to solve this problem,
Japanese Patent O.P.I. Publication No. 5-119454/1993 discloses a method of obtaining
a solid processing composition having a desired component content by using granular
compositions having an average particle size within a specific range. However, this
reference does not disclose a tablet developing composition and the method disclosed
therein could not sufficiently solve the above problems. Japanese Patent O.P.I. Publication
No. 5-142708/1993 discloses a method of mixing granular compositions having an average
particle size within a specific range and then tableting the mixture to obtain a solid
processing composition. This method prevents an inner reaction of a tablet color developing
composition during a long term storage, but is not sufficient to prevent expansion
of the tablet.
SUMMARY OF THE INVENTION
[0007] Accordingly, an object of the invention is to provide a tablet developing composition
having a desired component content ratio and less expansion during storage and a method
of manufacturing the same.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The above object of the invention can be attained by the following method.
1. A method of manufacturing a solid developing composition for a silver halide photographic
light-sensitive material, the method comprising the steps of :
mixing first granules comprising a developing agent and second granules comprising
an alkali agent,
wherein the content in each granule of granules having a particle size of 1000µm
or more (JIS) is not more than 10 weight % based on the total weight of each granule.
2. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of item 1, wherein the content in each granule
of granules having a particle size of 350 to 1000µm is not less than 40 weight %.
3. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of item 1 or 2, wherein the content in each
granule of granules having a particle size of 350 to 1000µm is 40 to 74 weight %.
4. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of item 1, 2 or 3, wherein the content in each
granule of granules having a particle size of 500 to 1000µm is not less than 40 weight
%.
5. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of items 1 through 4, wherein the mixing ratio
of the first granules comprising a developing agent and the second granules comprising
an alkali agent is 1:1 to 1:20.
6. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of items 1 through 5, wherein the developing
agent is a p-phenylenediamine color developing agent.
7. The method of manufacturing a solid developing composition for a silver halide
photographic light-sensitive material of items 1 through 6, wherein the alkali agent
is an alkali metal carbonate.
8. A tablet developing composition for a silver halide photographic light-sensitive
material, wherein the composition is obtained by compression-molding the above described
granules.
[0009] The invention will be explained below.
[0010] The present inventors have made an intensive study, and have solved the above problems
by controlling the size of granules containing a photographic component to a specific
particle size.
[0011] The solid processing composition of the invention refers to a processing composition
in the form of granules or tablets. When the solid processing composition of the invention
is in the form of granules, it is characterized in that the content of granules having
a particle size of 1000µm or more is not more than 10 weight % based on the total
weight of the granules. The particle size of the invention, unless otherwise specified,
refers to that according to JIS (JAPAN INDUSTRIAL STANDARD), and is measured by using
a JIS standard screen. For example, granules having a particle size of 1000µm or more
refer to granules remained on a 1000µm (16 mesh) screen after sieving by using the
screen. In the invention the content of granules having a particle size of 1000µm
or more is preferably not more than 8 weight %, and more preferably not more than
5 weight %.
[0012] In the granular composition of the invention the content of granules having a particle
size of 350 to 1000µm is preferably not less than 40 weight %, and more preferably
not less than 40 to 74 weight % in view of the effects of the invention and discoloration
during storage. It is also preferable in view of discoloration during storage that
the content of granules having a particle size of 500 to 1000µm is not less than 40
weight %.
[0013] The method of adjusting granules to the particle size within the invention includes
a well known method such as a method of crushing larger particles using a commercial
dresser or a method of sieving using a screen. There are hammer mill type, roll mill
type or screen mill type commercial dressers. In the screen mill type dresser, a screen
of not more than 1.2 mm is preferably used, and a screen of 0.8 to 1.2 mm is more
preferably used.
[0014] The granular processing composition of the invention can be obtained by using any
of the well-known processes such as the processes of a fluidized-layer granulation,
a stirring granulation, a rolling granulation, an extrusion granulation and a compression
granulation. The drying weight reduction of the solid composition in the invention
is preferably 0.5-5 weight %, and more preferably 0.8-2 weight % in view of the effects
of the invention. The drying weight reduction referred to herein is a weight variation
amount calculated from the weight reduced, which is measured under circumstances of
25°C and 40%RH after the composition is heated at 50°C to a constant weight which
is measured with a commercial electronic moisture meter. In order to obtain the weight
reduction within the above described range, a wet granulating method is preferable
which is carried out in the presence of a solvent. The solvent used in the wet granulating
method is preferably a polar solvent such as alcohol, acetone, acetonitrile or water
or a mixture thereof, and more preferably water. The addition amount of the solvent
is preferably 1 to 20 weight %, and more preferably 3 to 10 weight % based on the
total weight of material used. When the amount of the solvent is less than 1 weight
%, the granulation is not completed, and when the amount of the solvent exceeds 20
weight %, the granulation requires a longer time and granule properties are deteriorated
during the granulation.
[0015] The solid processing tablet in the invention may be in any form according to the
intended use, but is preferably in disk form in view of ease of producibility or processability.
The solid processing tablet is produced by well known compressors. The compressors
for producing the tablets include a hydraulic press machine, a single tableting machine,
a rotary tableting machine and a briqueting machine can be used.
[0016] The developing agent of the invention includes a color developing agent and a black-and-white
developing agent. The invention is noticeably effected using a p-phenylenediamine
color developing agent.
[0017] The p-phenylenediamine color developing agent represented by Formula (I) or (II)
preferably used in the invention will be shown below.
wherein R₁ and R₂ may be the same or different, and independently represent a substituted
or unsubstituted alkyl group. R₃ represents a hydrogen atom, a halogen atom, an unsubstituted
amino group, a hydroxyl group, an alkylamino group, an alkyl group, an alkoxy group,
an amido group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group
or a sulfamoylamino group.
wherein wherein R₄ through R₁₁ may be the same or different, and independently represent
a hydrogen atom, a halogen atom, an unsubstituted amine group, a nitro group, a hydroxyl
group, a cyano group, an alkyl group, an alkylamino group, an alkoxy group, an amido
group, a sulfonamide group, a carbamoyl group, an alkoxycarbonylamino group, a ureido
group, a sulfamoylamino group, a sulfonyl group, a carboxyl group or a sulfo group.
R₁₂ represents a hydrogen atom, a halogen atom, an unsubstituted amine group, a hydroxyl
group, an alkylamino group, an alkyl group, an alkoxy group, an amido group, a sulfonamide
group, an alkoxycarbonylamino group, a ureido group or a sulfamoylamino group.
[0018] Next, the invention will be explained in detail.
[0019] In Formula (I), the alkyl group represented by R₁, R₂ and R₃ includes a straight-chained
or branched alkyl group having preferably 1 to 6 carbon atoms, which may have a substituent.
The preferable substituent includes an alkenyl group, an alkinyl group, an aryl group,
a nitro group, a halogen atom, an unsubstituted amine group, a hydroxyl group, a cyano
group, an alkylamino group, an alkoxy group, an amido group, a sulfonamide group,
a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino
group, a sulfonyl group, a carboxyl group and a sulfo group.
[0020] The alkenyl group as the substituent includes a vinyl group and an allyl group, the
alkinyl group includes an ethenyl group, the aryl group includes a phenyl group, a
tolyl group and a naphthyl group, and the halogen atom includes a fluorine atom, a
chlorine atom and a bromine atom.
[0021] The alkylamino group includes an alkylamino group having 1 to 16 carbon atoms, and
preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group,
an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or
a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group. The alkoxy
group includes an alkoxy group having 1 to 16 carbon atoms, and preferably 1 to 6
carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group,
an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or
a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy,
ethoxy, 2-methoxyethoxy, 2-hydoxyethoxy, 2-hydoxybutoxy and 2-methanesulfonylethoxy
group. The amido group includes an amido group having 1 to 16 carbon atoms, and preferably
1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl
group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen
atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including
an acetoamido, 2-methoxypropionamido and pentanoylamido group.
[0022] The sulfonamido group includes a sulfonamido group having 1 to 16 carbon atoms, and
preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group,
an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or
a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a methanesulfonamido and benzenesulfonamido group. The carbamoyl group
includes a carbamoyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon
atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an
aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a
substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl,
N,N-dimethylcarbamoyl, N-ethylcarbamoyl and N-butylcarbamoyl group. The ureido group
includes a ureido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon
atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an
aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a
substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido,
methylureido and N,N-diethylureido group.
[0023] The sulfamoylamino group includes a sulfamoylamino group having 0 to 16 carbon atoms,
and preferably 0 to 6 carbon atoms, which may have a substituent such as an alkenyl
group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group
or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a sulfamoylamino, dimethylsulfamoylamino and dipropylsulfamoylamino
group. The sulfonyl group includes a sulfonyl group having 1 to 16 carbon atoms, and
preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group,
an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or
a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a methanesulfonyl and methanesulfonyl group.
[0024] Next, Formula (II) will be explained in detail.
[0025] In Formula (II), R₄ through R₁₁ may be the same or different, and independently represent
a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group,
an amino group, an alkylamino group, an alkoxy group, an amido group, a sulfonamide
group, a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino
group, a sulfonyl group, a carboxyl group or a sulfo group.
[0026] The halogen atom includes a fluorine atom, a chlorine atom and a bromine atom. The
alkyl group includes a straight-chained, branched or cyclic alkyl group having 1 to
16 carbon atoms, and preferably 1 to 6 carbon atoms, which may have a substituent
such as an alkenyl group, an alkinyl group, an aryl group, a hydroxyl group, a nitro
group, a cyano group or a halogen atom or a substituent formed with an oxygen, nitrogen,
sulfur or carbon atom including a methyl, ethyl, propyl, isopropyl, t-butyl, hydroxymethyl,
methanesulfonamidomethyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl,
3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetoamidoethyl,
2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl,
2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl,
2-carbamoyl-1-methylethyl and 4-nitrobutyl group.
[0027] The alkylamino group includes an alkylamino group having 1 to 16 carbon atoms, and
preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group,
an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or
a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a N,N-dimethylamino, N,N-diethylamino or N-butylamino group. The alkoxy
group includes an alkoxy group having 1 to 16 carbon atoms, and preferably 1 to 6
carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl group,
an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or
a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a methoxy,
ethoxy, 2-methoxyethoxy, 2-hydoxyethoxy, 2-hydoxybutoxy and 2-methanesulfonylethoxy
group. The amido group includes an amido group having 1 to 16 carbon atoms, and preferably
1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl
group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen
atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including
an acetoamido, 2-methoxypropionamido and pentanoylamido group.
[0028] The sulfonamido group includes a sulfonamido group having 1 to 16 carbon atoms, and
preferably 1 to 6 carbon atoms, which may have a substituent such as an alkenyl group,
an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group or
a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a methanesulfonamido and benzenesulfonamido group. The carbamoyl group
includes a carbamoyl group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon
atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an
aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a
substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a carbamoyl,
N,N-dimethylcarbamoyl, N-ethylcarbamoyl and N-butylcarbamoyl group. The alkoxycarbonylamino
group includes an alkoxycarbonylamino group having 1 to 16 carbon atoms, and preferably
1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl
group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen
atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including
a methoxycarbonylamino, ethoxycarbonylamino and butoxycarbonylamino group. The ureido
group includes a ureido group having 1 to 16 carbon atoms, and preferably 1 to 6 carbon
atoms, which may have a substituent such as an alkenyl group, an alkinyl group, an
aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen atom or a
substituent formed with an oxygen, nitrogen, sulfur or carbon atom including a ureido,
methylureido and N,N-diethylureido group.
[0029] The sulfamoylmino group includes a sulfamoylmino group having 0 to 16 carbon atoms,
and preferably 0 to 6 carbon atoms, which may have a substituent such as an alkenyl
group, an alkinyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group
or a halogen atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon
atom including a sulfamoylmino, dimethylsulfamoylmino and dipropypsulfamoylmino group.
The sulfonyl group includes a sulfonyl group having 1 to 16 carbon atoms, and preferably
1 to 6 carbon atoms, which may have a substituent such as an alkenyl group, an alkinyl
group, an aryl group, a hydroxyl group, a nitro group, a cyano group or a halogen
atom or a substituent formed with an oxygen, nitrogen, sulfur or carbon atom including
a methanesulfonyl and ethanesulfonyl group.
[0030] The above color developing agents are usually used in the form of hydrochloride,
sulfate or p-toluenesulfonic acid salt.
[0032] The example of the black-and-white developing agent includes phenidone, hydroquinone,
metol, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone
and hydroquinone monosulfonic acid.
[0033] The alkali agent of the invention is a compound giving pH 8 or more in its aqueous
solution. The preferable example includes sodium carbonate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium
phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium
tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfo-salicylate) and potassium 5-sulfo-2-hydroxybenzoate
(potassium 5-sulfo-salicylate). Sodium carbonate and sodium bicarbonate are especially
preferable.
[0034] The solid processing composition in the invention may optionally contain a chelating
agent, a development accelerating agent, a development inhibitor (halides), a fluorescent
brightening agent or a preservative as usually used in the developer.
[0035] The preservarive includes a sulfite (sodium sulfite or potassium sulfite), a bisulfite
(sodium bisulfite or potassium bisulfite), a metabisulfite (sodium metabisulfite orpotassium
metabisulfite) and a hydroxylamine derivative.
[0036] The solid developing composition preferably contains a compound represented by Formula
(H) or (B). The invention is more effected by the above compound. The solid developing
composition containing the above compound shows improved storage stability, strength,
stable photographic properties and prevention of fog. It is preferable that the solid
processing composition contain a hydroxyamine compound represented by Formula (H).
It is more preferable that the granular processing composition containing a developing
agent is obtained by mixing the developing agent with the hydroxyamine compound and
then granulating the mixture.
[0037] When granules containing a compound represented by the following Formula (H) or (B)
is prepared separate from granules containing a developing agent, the content in the
granules containing the compound of granules having a particle size of not less than
1000 µm is preferably not more than 10 weight %, and the content in the granules containing
the compound of granules having a particle size of 350 to 1000 µm is also preferably
40 to 74 weight %.
wherein R₂₁ and R₂₂ independently represent a hydrogen atom or a substituted or unsubstituted
alkyl group.
[0038] The compound of the invention represented by Formula (H) is preferably a compound
represented by Formula (H') in view of the invention.
wherein L represents a straight chained or branched, alkylene group having 1 to 10
carbon atoms, which may have a substituent, and preferably 1 to 5 carbon atoms. The
example includes a methylene, ethylene, trimethylene and propylene group, and the
substituent includes a carboxyl group, a sulfone group, a phosphone group, a phosphinic
acid residue, a hydroxy group and an ammonio group which may have an alkyl group having
1 to about 5 carbon atoms.
[0039] A represents a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid
residue, a hydroxy group, an amino group which may have an alkyl group having 1 to
5 carbon atoms, an ammonio group which may have an alkyl group having 1 to 5 carbon
atoms, a carbamoyl group which may have an alkyl group having 1 to 5 carbon atoms,
a sulfamoyl group which may have an alkyl group having 1 to about 5 carbon atoms and
a substituted or unsubstituted alkylsulfonyl group.
[0040] The example of A-L- represents a carboxymethyl, carboxyethyl, carboxypropyl, sulfoethyl,
sulfopropyl, sulfobutyl, phosphonomethyl, phosphonoethyl and hydroxyethyl group.
[0041] R₂₃ represents a straight chained or branched, alkyl group having 1 to 10 carbon
atoms, which may have a substituent. The substituent includes a carboxyl group, a
sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group and an
ammonio group which may have an alkyl group having 1 to 5 carbon atoms, provided that
R₂₃ and L may combine to form a ring.
[0042] The exemplified compound of the invention will be given below, but is not limited
thereto.
|
R₂₁ |
R₂₂ |
H-1 |
-H |
-H |
A-2 |
-H |
-CH₃ |
A-3 |
-CH₃ |
-CH₃ |
A-4 |
-H |
-C₂H₅ |
A-5 |
-CH₃ |
-C₂H₅ |
A-6 |
-C₂H₅ |
-C₂H₅ |
A-7 |
-C₃H₇ |
-C₃H₇ |
A-8 |
-C₃H₇ (i) |
-C₃H₇ (i) |
A-9 |
-C₄H₉ |
-C₄H₉ |
A-10 |
-C₄H₉ (i) |
-C₄H₉ (i) |
A-11 |
-C₄H₉ (t) |
-C₄H₉ (t) |
A-12 |
-CH₃ |
-CH₂CH₂COOH |
A-13 |
-CH₃ |
-CH₂CH₂SO₃H |
A-14 |
-CH₃ |
-CH₂COOH |
A-15 |
-CH₃ |
-CH₂CH₂PO₃H₂ |
A-16 |
-H |
-CH₂CH₂SO₃H |
A-17 |
-CH₂CH₂COOH |
-CH₂CH₂COOH |
A-18 |
-CH₂CH₂SO₃H |
-CH₂CH₂SO₃H |
A-19 |
-CH₂COOH |
-CH₂COOH |
A-20 |
-CH₂CH₂PO₃H₂ |
-CH₂CH₂PO₃H₂ |
A-21 |
-CH₂CH₂OH |
-CH₂CH₂OH |
A-22 |
-CH₃ |
-CH₂CH₂CONH₂ |
A-23 |
-CH₂CH₂CONH₂ |
-CH₂CH₂CONH₂ |
A-24 |
-CH₃ |
-CH₂CH₂OCH₃ |
A-25 |
-CH₂CH₂OCH₃ |
-CH₂CH₂OCH₃ |
A-26 |
-CH₃ |
-CH₂CH₂OH |
A-27 |
-CH₂CH(CH₃)COOH |
-CH₂CH(CH₃)COOH |
A-28 |
-CH₂CH₂CN |
-CH₂CH₂CN |
[0043] The compounds are usually used in free amine or in the form of hydrochloric acid,
sulfate, p-toluenesulfonic acid, oxalic acid, phosphoric acid or acetic acid salt.
[0045] In Formula (B), R₁₁, R₁₂ and R₁₃ independently represent a substituted or unsubstituted
alkyl, aryl or heterocyclic group; R₁₄ represents a hydroxy group, a hydroxyamino
group or a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy,
carbamoyl or amino group. The heterocyclic group includes a saturated or unsaturated
5- or 6-membered cyclic group; R₁₅ represents a divalent group selected from the group
consisting of -CO-, -SO₂- and -C(=NH)-; and n represents 0 or 1, provided that when
n is 0, R₁₄ represents an alkyl, aryl or heterocyclic group or R₁₃ and R₁₄ may combine
to form a heterocyclic ring.
[0046] The preferable example of compounds represented by Formula (B) includes (B-1) through
(B-33) on pages 40 to 43 of Japanese Patent O.P.I. Publication No. 4-86741/1992 and
(1) through (56) on pages 4 to 6 of Japanese Patent O.P.I. Publication No. 3-33846/1991.
[0047] The developing composition of the invention may contain an alkali halide such as
potassiun iodide or an organic anti-foggant, a nitrogen-containing heterocyclic compound
such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole,
indazole, hydroxyazaindolidine or adenine.
[0048] The developing composition of the invention preferably contain a triadinylstylbene
fluorescent brightening agent. The fluorescent brightening agent is preferably a compound
represented by the following Formula (E),
wherein X₂, X₃, Y₁ and Y₂ independently represent a hydroxy group, a halogen atom
such as chlorine or bromine, an alkyl group, an aryl group,
or -OR₂₅ in which R₂₁ and R₂₂ independently represent a hydrogen atom, an alkyl group
(which may have a substituent), or an aryl group (which may have a substituent), R₂₃
and R₂₄ independently represent an alkylene group (which may have a substituent),
and R₂₅ represents a hydrogen atom, an alkyl group (which may have a substituent)
or an aryl group (which may have a substituent); and M represents a cation. The groups
or substituents thereof in Formula (E) is the same as those described on pages 16
and 17 of Japanese Patent O.P.I. Publication No. 4-118649/1992. The examples of the
compounds are preferably compounds represented by [Chemical 8] through [Chemical 16]
of Japanese Patent O.P.I. Publication No. 5-119454/1993. These compounds can be synthesized
by the conventional method. Of these compounds the compounds especially preferably
used are E-4, E-24, E-34, E-35, E-36, E-37 and E-41.
[0049] The developing composition of the invention may contain an auxiliary developing agent
such as metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride or N,N,N',N''-tetramethyl-p-phenylenediamine
hydrochloride, or additives such as an anti-staining agent, an anti-sludging agent
and an interlayer accelerating agent.
[0050] The color or black-and-white developing composition of the invention preferably contains
a chelating agent (especially, exemplified compounds K-1 through K-22) represented
by the following Formula (K) which is described on described on pages 16 and 17 of
Japanese Patent O.P.I. Publication No. 4-118649/1992.
[0051] Of these compounds, K-2, K-9, K-12, K-13, K-17 and K-19 are preferable, and K-2 and
K-9 are especially preferable.
[0052] It is preferable in view of improved fluidity of a granule composition that the solid
developing composition of the invention contains at least one selected from compound
represented by the following Formula (D).
wherein R₁ represents an alkyl group; R₂ represents a hydrogen atom or an alkyl group
having 1 to 5 carbon atoms; L₁ represents an alkylene group having 1 to 5 carbon atoms;
and M represents a hydrogen atom, an alkali metal atom or NH₄.
[0053] In Formula (D), R₁ represents a straight-chained or branched, substituted or unsubstituted,
saturated or unsaturated aliphatic group having preferably 3 to 30 carbon atoms; R₂
represents a hydrogen atom or a straight-chained or branched, substituted or unsubstituted,
saturated or unsaturated aliphatic group having 1 to 5 carbon atoms, preferably a
hydrogen atom or a methyl, ethyl, propyl, butyl or amyl group and more preferably
a methyl group; L₁ represents a straight-chained or branched, substituted or unsubstituted,
alkylene or alkenylene group having 1 to 5 carbon atoms, preferably a methylene, ethylene,
propylene, butylene, carboxymethylmethylene, carboxymethylethylene or carboxyethylethylene
group and more preferably an ethylene group; the substituent includes a carboxymethyl,
carboxyethyl, carboxypropyl, carboxybutyl and carboxyamyl group; and M represents
a hydrogen atom, an alkali metal atom such as a sodium atom, a potassium atom or a
lithium atom or NH₄.
[0054] The typical examples of Formula (D) will be shown below, but the invention is not
limited thereto.
- D-1
- C₅H₁₁-CON(-CH₃)-CH₂CH₂-COONa
- D-2
- C₇H₁₅-CON(-CH₃)-CH₂CH₂-COOK
- D-3
- C₉H₁₉-CON(-CH₃)-CH₂CH₂-COONa
- D-4
- C₁₁H₂₃-CON(-CH₃)-CH₂CH₂-COONa
- D-5
- C₁₃H₂₇-CON(-CH₃)-CH₂CH₂-COONa
- D-6
- C₁₅H₃₁-CON(-CH₃)-CH₂CH₂-COOK
- D-7
- C₁₇H₃₅-CON(-CH₃)-CH₂CH₂-COOK
- D-8
- C₁₉H₃₉-CON(-CH₃)-CH₂CH₂-COONa
- D-9
- C₅H₁₁-CON(-CH₃)-CH₂-COONa
- D-10
- C₇H₁₅-CON(-CH₃)-CH₂-COONa
- D-11
- C₉H₁₉-CON(-CH₃)-CH₂-COONa
- D-12
- C₁₁H₂₃-CON(-CH₃)-CH₂-COONa
- D-13
- C₁₃H₂₇-CON(-CH₃)-CH₂-COOK
- D-14
- C₁₅H₃₁-CON(-CH₃)-CH₂-COOK
- D-15
- C₁₇H₃₅-CON(-CH₃)-CH₂-COONa
- D-16
- C₁₉H₃₉-CON(-CH₃)-CH₂-COONa
[0055] Of these compounds the preferable are compounds D-5 and D-12.
[0056] The content of the above compounds in the tablet composition is 0.1 to 5.0 wt%, and
preferably 0.3 to 3.0 wt% based on the total weight of the tablet composition.
[0057] The solid processing composition of the invention containing saccharides shows more
markedly the effects of the invention. The saccharides in the invention refer to monosaccharides,
polysaccharides in which monosaccharides bind through a glycoside bondage or derivatives
thereof.
[0058] Monosaccharides refer to as a polyhydroxy aldehyde, polyhydroxy ketone or their derivatives
such as reduced derivatives, oxidized derivatives, deoxy derivatives, amino derivatives
or thio derivatives. Most of them are represented by the general formula C
nH
2nO
n. The monosaccharides in the invention include derivatives derived from saccharide
skeleton represented by the above formula. The preferable are sugar alcohols having
a primary or secondary alcohol group to which an aldehyde or ketone group of saccharides
is reduced, and hexitol having six carbon atoms is especially preferable.
[0059] Polysaccharides include celluloses, starches or glycogens. The celluloses include
derivatives such as cellulose ethers in which all or a part of hydroxy group are etherified,
starches include maltose or dextrins that starches are hydrolyzed to various decomposition
compounds. Celluloses may be in an alkali salt form in view of solubility. Among polysaccharides,
celluloses or dextrins are preferably used, and dextrins are more preferably used.
[0060] Examples of monosaccharides in the invention will be shown below.
[0061] (Exemplified compounds)
- B-(1)
- glycelaldehyde
- B-(2)
- dihydroxyacetone (including a dimer)
- B-(3)
- D-erythrulose
- B-(4)
- L-erythrulose
- B-(5)
- D-threose
- B-(6)
- L-threose
- B-(7)
- D-ribose
- B-(8)
- L-ribose
- B-(9)
- D-arabinose
- B-(10)
- L-arabinose
- B-(11)
- D-xylose
- B-(12)
- L-xylose
- B-(13)
- D-lixose
- B-(14)
- L-lixose
- B-(15)
- D-xylulose
- B-(16)
- L-xylulose
- B-(17)
- D-ribulose
- B-(18)
- L-ribulose
- B-(19)
- 2-deoxy-D-ribose
- B-(20)
- D-allose
- B-(21)
- L-allose
- B-(22)
- D-altrose
- B-(23)
- L-altrose
- B-(24)
- D-glucose
- B-(25)
- L-glucose
- B-(26)
- D-mannose
- B-(27)
- L-mannose
- B-(28)
- D-gulose
- B-(29)
- L-gulose
- B-(30)
- D-idose
- B-(31)
- L-idose
- B-(32)
- D-galactose
- B-(33)
- L-galactose
- B-(34)
- D-talose
- B-(35)
- L-talose
- B-(36)
- D-quinobose
- B-(37)
- digitalose
- B-(38)
- Digitoxose
- B-(39)
- Cymalose
- B-(40)
- D-sorbose
- B-(41)
- L-sorbose
- B-(42)
- D-Tagatose
- B-(43)
- D-fucose
- B-(44)
- L-fucose
- B-(45)
- 2-deoxy-D-glucose
- B-(46)
- D-psicose
- B-(47)
- D-fructose
- B-(48)
- L-fructose
- B-(49)
- D-rhamnose
- B-(50)
- D-galactosamine
- B-(51)
- L-galactosamine
- B-(52)
- D-mannosamine
- B-(53)
- D-glycero-D-galactoheptose
- B-(54)
- D-glycero-D-mannoheptose
- B-(55)
- D-glycero-L-mannoheptose
- B-(56)
- D-glycero-D-guloheptose
- B-(57)
- D-glycero-D-idoheptose
- B-(58)
- D-glycero-L-glucoheptose
- B-(59)
- D-glycero-L-taloheptose
- B-(60)
- D-altroheptulose
- B-(61)
- D-mannoheptulose
- B-(62)
- D-altro-3-heptulose
- B-(63)
- D-glucuronic acid
- B-(64)
- L-glucuronic acid
- B-(65)
- N-acetyl-D-glucosamine
- B-(66)
- Glycerin
- B-(67)
- D-threitol
- B-(68)
- L-threitol
- B-(69)
- Erithorit
- B-(70)
- D-arabitol
- B-(71)
- L-arabitol
- B-(72)
- adnite
- B-(73)
- xylitol
- B-(74)
- D-sorbitol
- B-(75)
- L-sorbitol
- B-(76)
- D-mannitol
- B-(77)
- L-mannitol
- B-(78)
- D-iditol
- B-(79)
- L-iditol
- B-(80)
- D-talitol
- B-(81)
- L-talitol
- B-(82)
- dulcin
- B-(83)
- allodulcitol
- B-(84)
- D-erythritol
- B-(85)
- L-erythritol
[0062] Of these compounds, B-(66) through (85) are preferably used, and B-(74) through (85)
are more preferably used.
[0063] Examples of polysaccharides and their derivatives in the invention will be shown
below.
- D-(1)
- Maltose
- D-(2)
- Cellobiose
- D-(3)
- trehalose
- D-(4)
- gentiobiose
- D-(5)
- isomaltose
- D-(6)
- lactose
- D-(7)
- raffinose
- D-(8)
- gentianose
- D-(9)
- stachyose
- D-(10)
- xylan
- D-(11)
- araban
- D-(12)
- Glycogen
- D-(13)
- dextran
- D-(14)
- inulin
- D-(15)
- levan
- D-(16)
- galactan
- D-(17)
- agalose
- D-(18)
- amylose
- D-(19)
- sucrose
- D-(20)
- agarobiose
- D-(21)
- α-dextrin
- D-(22)
- β-dextrin
- D-(23)
- γ-dextrin
- D-(24)
- δ-dextrin
- D-(25)
- ε-dextrin
- D-(26)
- α-cyclodextrin
- D-(27)
- β-cyclodextrin
- D-(28)
- Phospherylase limit dextrim
- D-(29)
- Soluble starch
- D-(30)
- Thin-boling starch
- D-(31)
- White dextrin
- D-(32)
- Yellow dextrin
- D-(33)
- British gum
- D-(34)
- Pineflow (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(35)
- Pinedex100 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(36)
- Pinedex 1 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(37)
- Pinedex 2 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(38)
- Pinedex 3 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(39)
- Pinedex 4 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(40)
- Pinedex 6 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(41)
- Foodtex (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(42)
- Max (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(43)
- Glystar P (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(44)
- TK-16 (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(45)
- MPD (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(46)
- H-PDX (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(47)
- Stacodex (trade name, produced by Matsutani Kagaku Co., Ltd.)
- D-(48)
- Mabit (trade name, produced by Hayashibara Shoji Co., Ltd.)
- D-(49)
- Pullulan (trade name, produced by Hayashibara Shoji Co., Ltd.)
- D-(50)
- Methylcellulose
- D-(51)
- Dimethylcellulose
- D-(52)
- Trimethylcellulose
- D-(53)
- Ethylcellulose
- D-(54)
- Diethylcellulose
- D-(55)
- Triethylcellulose
- D-(56)
- Carboxymethylcellulose
- D-(57)
- Carboxyethylcellulose
- D-(58)
- Aminoethylcellulose
- D-(59)
- Hydroxymethylcellulose
- D-(60)
- Hydroxyethylcellulose
- D-(61)
- Hydroxypropylcellulose
- D-(62)
- Hydroxypropylmethylcellulose
- D-(63)
- Hydroxypropylmethylcelluloseacetatesuccinate
- D-(64)
- carboxymethylhydroxyethylcellulose
[0064] Of these compounds, D-(21) through (64) are preferably used, and compounds, D-(21)
through (49) are more preferably used.
[0065] The content of the saccharide in the solid color developing composition of the invention
is preferably 0.5 to 30 wt%, and more preferably 1.0 to 20 wt%.
EXAMPLES
[0066] The invention will be detailed in the following Examples, but is not limited thereto.
Example 1
[0067] A granule color developing composition and a tablet color developing composition
were prepared according to the following procedures.
Procedure (1)
[0068] In a hammer-mill available on the market 3700.0 g of anhydrous potassium carbonate,
600.0 g of sodium sulfite, 240.0g of pentasodium diethylenetriamine pentaacetate and
500.0g of sodium p-toluenesulfonate were pulverized to a particle size of not more
than 149µm. The fine powder was mixed with 800.0g of Pineflow (produced by Matsutani
Kagaku Co., Ltd.) and was granulated in a stirring granulator available on the market
at room temperature for 7 minutes while adding water thereto. Thereafter, the granules
were dried at 70°C using a fluid bed drier available on the market. The dried granules
were dressed with a dresser available on the market to have a particle size as shown
in Table 1. Thus, granule sample A was obtained.
Procedure (2)
[0069] In the same manner as in Procedure (1) were pulverized 630g of a color developing
agent CD-4 (4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate) and 240.0g of
bis(sulfoethyl)hydroxylamine disodium salt. The fine powder was mixed with 65g of
Pineflow and was granulated at room temperature. Thereafter, the granules were dried
at 40°C using a fluid bed drier available on the market. The dried granules were dressed
with a dresser available on the market to have a particle size as shown in Table 1.
Thus, granule sample C was obtained.
Procedure (3)
[0070] The above obtained granule samples in Procedures (1) and (2) were mixed in an amount
as shown in Table 2 at room temperature for 10 minutes through a cross rotary mixer
available on the market, and mixed with sodium N-miristoyl β-methylalanine (in an
amount of 0.5wt%) for 3 minutes. Thereafter, the resulting mixture granules were continuously
tableted making use of a rotary tableting machine to obtain tablets having a diameter
of 30 mm, a thickness of 10 mm and a weight of 11.0g. Thus, 600 tablet samples for
color developing were obtained from the granule samples.
Procedure (4)
[0071] The above granule samples obtained in Procedures (1) and (2) were mixed in an amount
as shown in Table 2 for 10 minutes through a cross rotary mixer available on the market.
Thus, granule samples for color developing were obtained.
Table 1
|
Particles plus 1000µm sieve (wt%) |
Particles minus 1000µm sieve and plus 500µm sieve (wt%) |
Particles minus 500µm sieve and plus 350µm sieve (wt%) |
Particles minus 350µm sieve and plus 149µm sieve (wt%) |
Particles minus 149µm sieve (wt%) |
A-1 |
20.6 |
31.7 |
16.9 |
22.3 |
8.4 |
A-2 |
31.4 |
37.6 |
16.2 |
12.8 |
2.0 |
A-3 |
0.0 |
34.1 |
37.5 |
22.8 |
5.6 |
A-4 |
0.5 |
45.8 |
22.2 |
22.6 |
8.9 |
C-1 |
73.5 |
22.1 |
3.3 |
0.7 |
0.3 |
C-2 |
12.6 |
19.3 |
23.2 |
39.4 |
5.6 |
C-3 |
2.2 |
53.4 |
21.0 |
19.8 |
3.7 |
C-4 |
1.0 |
24.4 |
37.1 |
33.9 |
3.5 |
[0072] The above obtained samples were evaluated according to the following experiments.
Experiment 1: Color developing agent content of the tablet samples
[0073] Sixty tablets of each tablet sample were dissolved in pure water. The content of
the color developing agent was measured through high speed liquid chromatography and
deviation D from the theoretical content was calculated.
[0074] Evaluation Criteria were as follows:
- ⓞ
- : -3% < D < +3%
- ○
- : -5% ≦ D ≦ -3% or +3% ≦ D ≦ +5%
- X
- : -30% < D ≦ -10% or +10% ≦ D < +30%
- XX
- : -50% ≦ D ≦ -30% or +30% ≦ D ≦ +50%
Experiment 2: Color developing agent content of the granule samples for color developing
[0075] In each 1000g of granule sample, 10g were taken from ten different portions of the
granule samples and the content of the color developing agent was measured in the
same manner as in Experiment 1 through high speed liquid chromatography. The evaluation
criteria were the same as in Experiment 1. The results of Experiments 1 and 2 are
shown in Table 2 and are identical to each other.
Experiment 3: Expansion degree of the tablet samples
[0076] Ten tablets from each tablet sample were placed in an aluminium vapor-deposited polyethylene
package, and stored at 40°C and 65%RH for one month. Thereafter, the expansion degree
of the tablets was measured and the change was calculated.
[0077] The results are shown in Table 2.
[0078] As is apparent from Table 2 above, the solid processing composition containing granules
having a particle size exceeding 1000µm in an amount of not less than 10 wt% shows
greater deviation in the content of a developing agent and greater expansion during
storage of tablet samples. On the other hand, the solid processing composition of
the invention containing granules having a particle size within the range of the invention
shows less deviation in the content of the developing agent and less expansion during
storage of tablet samples, giving excellent handling properties.
Example 2
[0079] A tablet color developing composition were prepared according to the following procedures.
Procedure (1)
[0080] In a hammer-mill available on the market 3700.0 g of anhydrous potassium carbonate,
600.0 g of sodium sulfite, 240.0g of pentasodium diethylenetriamine pentaacetate and
500.0g of sodium p-toluenesulfonate were pulverized to a particle size of not more
than 149µm. The fine powder was mixed with 800.0g of Pineflow and was granulated in
a stirring granulator available on the market at room temperature for 7 minutes while
adding water thereto. Thereafter, the granules were dried at 70°C using a fluid bed
drier available on the market. The dried granules were dressed with a dresser available
on the market to have a particle size as shown in Table 3. Thus, granule sample A
was obtained.
Procedure (2)
[0081] In the same manner as in Procedure (1) were pulverized 360.0g of hydroxylamine 1/2
sulfate, 30.0g of potassium bromide, 20.0g of disodium pyrocatechol-3,5-disulfonate
and mixed and granulated. Thereafter, the resulting granules were dressed with a dresser
to have a particle size as shown in Table 3. Thus, granule sample B was obtained.
[0082] In the same manner as in Procedure (1) were pulverized 630g of a color developing
agent CD-4 (4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate) and 240.0g of
bis(sulfoethyl)hydroxylamine disodium salt. The fine powder was mixed with 65g of
Pineflow and was granulated at room temperature. Thereafter, the granules were dried
at 40°C using a fluid bed drier. The dried granules were dressed with a dresser to
have a particle size as shown in Table 3. Thus, granule sample C was obtained.
Table 3
|
Particles plus 1000µm sieve (wt%) |
Particles minus 1000µm sieve and plus 500µm sieve (wt%) |
Particles minus 500µm sieve and plus 350µm sieve (wt%) |
Particles minus 350µm sieve and plus 149µm sieve (wt%) |
Particles minus 149µm sieve (wt%) |
A-1 |
11.4 |
32.7 |
35.4 |
18.3 |
2.2 |
A-2 |
9.5 |
36.5 |
38.2 |
10.4 |
5.4 |
B-1 |
6.1 |
22.0 |
18.2 |
37.7 |
16.0 |
C-1 |
10.9 |
28.4 |
26.4 |
24.3 |
10.0 |
C-2 |
8.8 |
29.3 |
35.8 |
19.4 |
6.7 |
Procedure (4)
[0083] All the above obtained granule samples in Procedures (1) through (3) were mixed at
room temperature for 10 minutes through a cross rotary mixer available on the market,
and mixed with sodium N-miristoyl β-methylalanine (in an amount of 0.5wt%) for 3 minutes.
Thereafter, the resulting mixture granules were continuously tableted making use of
a rotary tableting machine to obtain tablets having a diameter of 30 mm, a thickness
of 10 mm and a weight of 11.0g. Thus, 600 tablet samples for color developing were
obtained.
[0084] The above obtained samples were evaluated in the same manner as in Example 1. The
results are shown in Table 4.
Table 4
Granule Sample A |
Granule Sample B |
Granule Sample C |
Deviation of Developing Agent Content of Granule |
Expansion of Tablet Sample (%) |
|
A-1 |
B-1 |
C-1 |
X |
1.9 |
Comparative |
A-2 |
B-1 |
C-2 |
○ |
0.4 |
Invention |
Example 3
[0085] The procedures were carried out in the same manner as in Example 2, except that Exemplified
Compound C-1, C-15, C-17, C-18 or C-19 was used instead of the color developing agent
used in Example 2. The evaluation was out in the same manner as in Example 2. The
results were the same as Example 2.
Example 4
[0086] A tablet color developing composition were prepared according to the following procedures.
Procedure (A)
[0087] In a hammer-mill available on the market were pulverized 1500.0g of a color developing
agent CD-3 (4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline sulfate)
and 500g of bis(sulfoethyl)hydroxylamine sodium salt to a particle size of not more
than 149µm. The fine powder was mixed with 150.0g of D-mannitol and granulated at
room temperature for about 7 minutes while adding water in a stirring granulator available
on the market. Thereafter, the granules were dried at 40°C using a fluid bed drier.
The dried granules were dressed with a dresser to have a particle size as shown in
Table 5. Thus, granule sample A was obtained.
Procedure (B)
[0088] In the same manner as in Procedure (A) were pulverized disodium salt of Exemplified
Compound H-18, 400.0g of bis(sulfoethyl)hydroxylamine disodium salt, 1700.0g of sodium
p-toluenesulfonate and 300.0g of Tinopar SFP (produced by Ciba-Geigy Co., Ltd.) and
granulated while adding water. The resulting granules were dried at 50°C. The dried
granules were dressed with a dresser to have a particle size as shown in Table 5.
Thus, granule sample B was obtained.
Procedure (C)
[0089] In the same manner as in Procedure (A) were pulverized 3300.0 g of potassium carbonate,
37.0g of sodium sulfite, 330.0g of pentasodium diethylenetriamine pentaacetate, 130.0g
of sodium p-toluenesulfonate and 340.0g of lithium hydroxide monohydrate. The fine
powder was mixed with 800.0g of D-mannitol in a mixer available on the market. The
resulting mixture was granulated in the same manner as in Procedure (A). Thereafter,
the granules were dried at 60°C. The dried granules were dressed with a dresser to
have a particle size as shown in Table 5. Thus, granule sample C was obtained.
Table 5
|
Particles plus 1000µm sieve (wt%) |
Particles minus 1000µm sieve and plus 500µm sieve (wt%) |
Particles minus 500µm sieve and plus 350µm sieve (wt%) |
Particles minus 350µm sieve and plus 149µm sieve (wt%) |
Particles minus 149µm sieve (wt%) |
A-1 |
9.4 |
17.3 |
21.4 |
42.8 |
9.1 |
A-2 |
9.8 |
25.3 |
19.6 |
34.3 |
11.0 |
A-3 |
7.9 |
32.4 |
26.3 |
28.7 |
4.7 |
A-4 |
6.3 |
43.8 |
28.1 |
15.6 |
6.2 |
A-5 |
3.4 |
58.3 |
30.4 |
6.3 |
1.6 |
B-1 |
7.4 |
15.3 |
28.1 |
38.4 |
10.8 |
C-1 |
8.8 |
20.4 |
16.5 |
40.1 |
14.2 |
C-2 |
7.9 |
28.2 |
18.3 |
35.2 |
10.4 |
C-3 |
7.4 |
33.1 |
27.7 |
20.6 |
11.2 |
C-4 |
4.2 |
40.1 |
23.2 |
21.4 |
11.1 |
C-5 |
2.6 |
54.1 |
32.4 |
8.7 |
2.1 |
Procedure (D)
[0090] All the above obtained granule samples in Procedures (A) through (C) were mixed with
sodium N-miristoyl β-methylalanine (in an amount of 0.5wt%) for 3 minutes. Thereafter,
the resulting mixture granules were continuously tableted making use of a rotary tableting
machine to obtain tablets having a diameter of 30 mm, a thickness of 10 mm and a weight
of 10.5g. Thus, 900 tablet samples for color developing were obtained.
[0091] The above obtained granule and tablet samples were evaluated in the same manner as
in Example 1 and further evaluated according to the following. The results are shown
in Table 6.
Experiment 4
[0092] Ten tablets from each tablet sample were packaged in an aluminium vapor-deposited
polyethylene package and stored at 45°C and 40%RH for one month. Thereafter, the tablets
were observed for coloration.
- Δ
- : The entire surface of the tablet was colored brown.
- ○
- : The side surface of the tablet was colored.
- ⓞ
- : No coloration was observed.
[0093] As is apparent from table 6 above, the composition containing not less than 40wt%
of granules having a particle size of 350 to 1000µm shows improved results in deviation
of developing agent content and in expansion of tablets. The composition containing
not less than 40wt% of granules having a particle size of 500 to 1000µm further prevents
coloration during storage in addition to the above effects.
Example 5
[0094] A tablet black-and-white developing composition were prepared according to the following
procedures.
Procedure (A)
[0095] In a bandamu-mill available on the market were pulverized 1500.0g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazole
and 2300.0g of potassium hydroquinone monosulfate to a particle size of 10µm. The
fine powder was mixed with 100.0g of D-mannitol and granulated at room temperature
for about 7 minutes while adding water in a stirring granulator available on the market.
Thereafter, the granules were dried at 40°C using a fluid bed drier.
Procedure (B)
[0096] In the same manner as in Procedure (A) were pulverized 1000.0g of bis(sulfoethyl)hydroxylamine
disodium salt, 150.0g of sodium bromide and 0.2g of potassium iodide and mixed with
240.0g of Pineflow (Matsutani Kagaku Co., Ltd.). The mixture was granulated. The resulting
granules were dried at 50°C.
Procedure (C)
[0097] In the same manner as in Procedure (A) were pulverized 1400.0 g of potassium carbonate,
1100.0 g of potassium bicarbonate, 3700.0g of sodium sulfite, 330.0g of pentasodium
diethylenetriamine pentaacetate, 130.0g of amino(trimethylene sulfonic acid sodium
salt and 340.0g of lithium hydroxide monohydrate. The fine powder was mixed with 800.0g
of mannitol in a mixer available on the market. The resulting mixture was granulated
in the same manner as in Procedure (A). Thereafter, the granules were dried at 60°C.
Procedure (D)
[0098] All the above obtained granule samples in Procedures (A) through (C) were mixed with
sodium N-miristoyl β-methylalanine (in an amount of 0.5wt%) for 3 minutes. Thereafter,
the resulting mixture granules were continuously tableted making use of a rotary tableting
machine to obtain tablets having a diameter of 15 mm, a thickness of 5 mm and a weight
of 1.2g. Thus, 900 tablet samples for color developing replenisher were obtained.
[0099] The above obtained granule and tablet samples were evaluated in the same manner as
in Example 1. The results showed 10 % greater expansion than that of tablet samples
in Example 4, but the same deviation as that of Example 4 in the developing agent
content.