U.S. patent application number 09/827098 was filed with the patent office on 2001-11-15 for method of producing disazo pigment.
This patent application is currently assigned to TOYO INK Mfg. Co., Ltd.. Invention is credited to Kitamura, Kenji, Maki, Hitoshi, Noguchi, Hideto, Shirao, Masami.
Application Number | 20010041793 09/827098 |
Document ID | / |
Family ID | 26589748 |
Filed Date | 2001-11-15 |
United States Patent
Application |
20010041793 |
Kind Code |
A1 |
Maki, Hitoshi ; et
al. |
November 15, 2001 |
Method of producing disazo pigment
Abstract
Disclosed is a method of producing a disazo pigment, in which a
coupling reaction is carried out while feeding, into an acidic
aqueous solution, a tetrazo aqueous solution containing a tetrazo
component of benzidines and a coupler aqueous solution containing a
coupling component, wherein the coupling component is a mixture
comprising a main component represented by the formula (1):
CH.sub.3COCH.sub.2CONH--X, wherein X represents a phenyl group
optionally having one or the same or different plural substituents
selected from the group consisting of a methyl group, methoxy group
and chlorine atom; a first additional component represented by the
formula (2): CH.sub.3COCH.sub.2CONH--Y, wherein Y represents a
phenyl group having a substituent selected from the group
consisting of --CONR.sub.2 group, --SO.sub.2NR.sub.2 group and
--NHCOR group, and the phenyl group may further have a substituent
selected from the group consisting of a methyl group, methoxy
group, chlorine atom, --CONR.sub.2 group, --SO.sub.2NR.sub.2 group
and --NHCOR group, and wherein Rs may be the same or different
mutually, and represent a hydrogen atom, C1 to C4 alkyl group (the
alkyl groups may be mutually connected to form a ring) or C1 to C4
alkylene NR'.sub.2, further wherein R's represent a hydrogen atom
or C1 to C4 alkyl groups which may be mutually different (the alkyl
groups may be mutually connected to form a ring); and, a second
additional component represented by the formula (3):
CH.sub.3COCH.sub.2CONH--Z, wherein Z represents a phenyl group
substituted by any one of a carboxyl group or alkali metal salts
thereof, hydroxyl group or sulfonic acid group or alkali metal
salts thereof, and said phenyl group may further has a substituent
selected from the group consisting of a methyl group, methoxy
group, chlorine atom, carboxyl group or alkali metal salts thereof,
hydroxyl group or sulfonic acid group or alkali metal salts
thereof. According to the method, disazo pigments can be obtained
which manifest excellent transparency and flowability of the inks
produced therefrom, and excellent flushing property and flushing
drain coloration resistance in the pigment production process, or
excellent dispersibility when ink is formed under dry
condition.
Inventors: |
Maki, Hitoshi; (Chuo-ku,
JP) ; Noguchi, Hideto; (Chuo-ku, JP) ;
Kitamura, Kenji; (Chuo-ku, JP) ; Shirao, Masami;
(Chuo-ku, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
TOYO INK Mfg. Co., Ltd.
3-13, Kyobashi 2-chome, Tokyo
Chuo-ku
JP
104-0031
|
Family ID: |
26589748 |
Appl. No.: |
09/827098 |
Filed: |
April 6, 2001 |
Current U.S.
Class: |
534/718 |
Current CPC
Class: |
C09B 41/006 20130101;
C09B 67/0055 20130101 |
Class at
Publication: |
534/718 |
International
Class: |
C09B 029/32 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 10, 2000 |
JP |
2000-107463 |
Feb 16, 2001 |
JP |
2001-039375 |
Claims
What is claimed is:
1. A method of producing a disazo pigment, in which a coupling
reaction is carried out while feeding, into an acidic aqueous
solution, (a) a tetrazo aqueous solution containing a tetrazo
component of benzidines and (b) a coupler aqueous solution
containing a coupling component, wherein the coupling component is
a mixture comprising the following components: a main component
represented by the formula (1): CH.sub.3COCH.sub.2CONH--X (1)
wherein x represents a phenyl group optionally having one or the
same or different plural substituents selected from the group
consisting of a methyl group, methoxy group and chlorine atom; a
first additional component represented by the formula (2):
CH.sub.3COCH.sub.2CONH--Y (2) wherein Y represents a phenyl group
having a substituent selected from the group consisting of
--CONR.sub.2 group, --SO.sub.2NR.sub.2 group and --NHCOR group, and
the phenyl group may further have a substituent selected from the
group consisting of a methyl group, methoxy group, chlorine atom,
--CONR.sub.2 group, --SO.sub.2NR.sub.2 group and --NHCOR group, and
wherein Rs may be the same or different mutually, and represent a
hydrogen atom, C1 to C4 alkyl group (the alkyl groups may be
mutually connected to form a ring) or C1 to C4 alkylene NR'.sub.2,
further wherein R's represent a hydrogen atom or C1 to C4 alkyl
groups which may be mutually different (the alkyl groups may be
mutually connected to form a ring); and, a second additional
component represented by the formula (3): CH.sub.3COCH.sub.2CONH--Z
(3) wherein Z represents a phenyl group substituted by any one of a
carboxyl group or alkali metal salts thereof, hydroxyl group or
sulfonic acid group or alkali metal salts thereof, and said phenyl
group may further has a substituent selected from the group
consisting of a methyl group, methoxy group, chlorine atom,
carboxyl group or alkali metal salts thereof, hydroxyl group or
sulfonic acid group or alkali metal salts thereof.
2. The method according to claim 1, wherein the molar ratio of the
total amount of the first and the second additional components to
the amount of the main component is within the range from 99:1 to
70:30.
3. The method according to claim 1, wherein the molar ratio of the
first additional component to the second additional component is
within the range from 1:9 to 9:1.
4. The method according to claim 1, wherein the coupler aqueous
solution and the tetrazo aqueous solution are fed into the acidic
aqueous solution in a manner such that the ratio of the molar
feeding rate of the coupling component to the molar feeding rate of
the tetrazo component is within the range from 200:80 to
200:99.
5. The method according to claim 1, further comprising adding a
water-soluble inorganic salt to an aqueous disazo pigment slurry
obtained from said coupling reaction.
6. The method according to claim 1, further comprising surface
treating a disazo pigment material obtained from said coupling
reaction with rosins or a vehicle for printing ink.
7. A disazo pigment obtained by the method of claim 1.
8. A printing ink composition comprising a vehicle for printing ink
and a disazo pigment obtained by the method of claim 1.
9. The method according to claim 1, wherein said coupling reaction
is carried out in a manner such that said coupling component is not
substantially deposited within the acidic aqueous solution and said
tetrazo component substantially immediately reacts with said
coupling component.
10. The method according to claim 1, wherein said coupler aqueous
solution and said tetrazo aqueous solution are concurrently fed
into said acidic aqueous solution from separately set respective
feeders.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method of producing a
disazo pigment, a disazo pigment obtained by the method, and a
printing ink obtained therefrom. More particularly, the present
invention relates to a method of producing a disazo pigment that
can produce printing ink excellent in transparency and flowability,
and excellent in flushing property and flushing drain coloration
resistance when ink formation is subsequently conducted under
non-dry condition, or can produce printing ink excellent in
dispersibility when ink formation is subsequently conducted under
dry condition, a disazo pigment produced by the method, and
printing ink thereof.
[0003] 2. Description of the Prior Art
[0004] Among printing industries, there have been, in recent years,
very strong demands for high-speed printing to increase
productivity. At present, a printing machine which is able to print
around 4 meters per second is prevailing, and the demands for high
speed printing are still more and more increasing. Accordingly, as
a coloring material, high color strength and flowability are
required for printing ink. Further, with the recent progress in
graphical printing techniques, printing inks having high
transparency are also asked in view of multi-color printing
technique. Thus, in the recent enhanced and mass-productive
printing industry, need of printing ink excellent even in
flowability and transparency in addition to basic properties such
as dispersibility is extremely high, and it is really one of key
technologies to decide further development in the near future of
printing industries.
[0005] In contrast with such a recent circumstance of printing
industries, offset inks in general process publication have
conventionally been obtained by a method in which an aqueous wet
cake of a pigment is phase-converted by flushing with a vehicle for
ink or a solvent to make ink, or a method in which a pigment
obtained by drying an aqueous wet cake is dispersed by strong
shearing force in a vehicle for ink.
[0006] However, in the former method, stable quality can not be
easily obtained because of large influences on quality such as
opacification and decrease in strength and the like due to the
property lacking in stability of an aqueous wet cake itself of a
pigment and to heat applied for a long period of time by poor
flushing property. Further, there is a problem of coloration by
mixing of a small amount of a disazo pigment component into a drain
discharged in flushing.
[0007] Consequently, the latter method that can be conducted via a
process less influential adversely on such qualities has so far
been conducted, primarily. However, ink prepared from a dried
material of an aqueous wet cake turns out to be remarkably inferior
as a final ink product, in transparency, flowability and color
strength as compared with ink prepared from an aqueous wet cake not
dried. In the case of disazo pigments, such inferior qualities of
ink prepared from a dried substance in comparison with those from a
non-dried one are due to the remarkably affected crystal growth of
pigment particles, exclusively, which is promoted by the heat
applied during the drying process.
[0008] In the production of disazo pigments, methods based on
simultaneous coupling of two components have conventionally been
known. For example, Japanese Patent Application Published (JP-B)
No. 55-10630 discloses a method of mixed coupling of
acetoacetanilide and a second coupling component having a polar
group substituted on its phenyl group. Japanese Patent Application
Laid-Open (JP-A) No. 1-110578 discloses a method of coupling a
mixture of two or more compounds selected from acetoacetanilide,
acetoaceto-o-anisidide, acetoaceto-o-toluidide,
acetoaceto-o-chloroanilide, acetoaceto-2,4-xylidide and
acetoaceto-2,5-dimethoxy-4-chloroanilide. However, in any of these
methods, qualities of ink made from a dried substance of a produced
disazo pigment are remarkably inferior in view of transparency,
flowability and color strength to those of ink made from a wet
cake.
[0009] Continuous investigations have been made also on improvement
of qualities of ink made from a wet cake. For example, Japanese
Patent Application Published (JP-B) No. 45-11026 discloses a method
of mixing a disazo pigment with a sulfonic acid compound thereof.
Japanese Patent Application Published (JP-B) No. 55-49087 discloses
a method using a mixture, as a coupling component, of a polar
coupling component having a carboxyl group and/or sulfonic acid
group and a non-polar coupling component. Japanese Patent
Application Laid-Open (JP-A) Nos. 63-72762 and 63-178169 both
disclose an asymmetric disazo compound comprising a polar coupling
component and a non-polar coupling component.
[0010] Further, recently, Japanese Patent Official Gazette No.
2682749 discloses a method of producing a disazo pigment using, as
a coupling component, a mixture of 2 to 40 mol % of acetoacetic
acid-m-xylidide, 97.9 to 60 mol % of acetoacetic acid-o-toluidide
and 0.1 to 10 mol % of 2-acetoacetaminobenzoic acid. However, it
has been known that these coupling components show solubility in
water, consequently, flushing is extremely delayed, resulting in
growth of crystals owing to heat history of a long period of time,
change of hue, and opacification.
[0011] Japanese Patent Official Gazette No. 2943996 (filed as an
International Patent Application PCT/JP97/00547, Publication
No.WO97/31067) discloses a method of coupling a non-polar coupling
component and a tetrazo component of benzidines. However, in this
method, which uses a single coupling component, basic problems
present at a microscopic level such as crystal growth are not
solved, and there is no other evaluation than the evaluation that
the resulting ink's performance is not sufficient yet.
[0012] Additionally, there is also known a method in which the
surface of a pigment composition is coated with rosins and a
vehicle for printing ink to impart various resistances and
suitability to the pigment composition. However, this method does
not improve basic abilities of the pigment composition before
coating, and the coating material does not have so high effect as
to compensate low abilities of the pigment composition itself. For
example, Japanese Patent Application Laid-Open (JP-A) No. 1-146962
discloses a method of surface-treating an organic pigment using a
dispersing aid composed of a resin, rosin, aluminum resinate,
aluminum rosinate or a mixture thereof. However, the amount of this
dispersing aid used is as extremely high as 50 to 100 mol % based
on the organic pigment, namely, dilution is effected by the
dispersing aid and increase in dispersing ability is not admitted
from the standpoint of a usual pigment composition, though the
dispersing aid contributes to improvement in color developing
property from the standpoint of ability per coloring matter
equivalent.
SUMMARY OF THE INVENTION
[0013] The present inventors have continued intensive study
heretofore, and resultantly found that the above-mentioned problems
can be simultaneously solved by using as coupling components, in
addition to a main component, specific two coupling components
together, namely, by allowing these two components to be admixed
with the main component at a molecular level and simultaneously to
be in contact with a tetrazo component in a coupling reaction, and
by progressing the reaction, as described in detail below.
[0014] Thus, the present invention is a method of producing a
disazo pigment, in which a coupling reaction is carried out while
feeding, into an acidic aqueous solution, a tetrazo aqueous
solution containing a tetrazo component of benzidines and a coupler
aqueous solution containing a coupling component, wherein the
coupling component is a mixture comprising a main component
represented by the formula (1):
CH.sub.3COCH.sub.2CONH--X (1)
[0015] wherein X represents a phenyl group optionally having one or
the same or different plural substituents selected from the group
consisting of a methyl group, methoxy group and chlorine atom;
[0016] a first additional component represented by the formula
(2):
CH.sub.3COCH.sub.2CONH--Y (2)
[0017] wherein Y represents a phenyl group having a substituent
selected from the group consisting of --CONR.sub.2 group,
--SO.sub.2NR.sub.2 group and --NHCOR group, and the phenyl group
may further have a substituent selected from the group consisting
of a methyl group, methoxy group, chlorine atom, --CONR.sub.2
group, --SO.sub.2NR.sub.2 group and --NHCOR group, and wherein Rs
may be the same or different mutually, and represent a hydrogen
atom, C1 to C4 alkyl group (the alkyl groups may be mutually
connected to form a ring) or C1 to C4 alkylene NR'.sub.2, further
wherein R's represent a hydrogen atom or C1 to C4 alkyl groups
which may be mutually different (the alkyl groups may be mutually
connected to form a ring); and,
[0018] a second additional component represented by the formula
(3):
CH.sub.3COCH.sub.2CONH--Z (3)
[0019] wherein Z represents a phenyl group substituted by any one
of a carboxyl group or alkali metal salts thereof, hydroxyl group
or sulfonic acid group or alkali metal salts thereof, and said
phenyl group may further has a substituent selected from the group
consisting of a methyl group, methoxy group, chlorine atom,
carboxyl group or alkali metal salts thereof, hydroxyl group or
sulfonic acid group or alkali metal salts thereof.
[0020] In the pigment synthesis method of the present invention, a
plurality of disazo pigment molecules can be simultaneously
produced such as a disazo compound containing a non-polar coupler
of the general formula (2) and a polar coupling component of the
general formula (3), a symmetric disazo compound containing only a
non-polar coupling component of the general formula (1), and the
like. Not only a disazo compound comprising a polar coupling
component of the general formula (3), but also a disazo compound
comprising a polar coupling component of the general formula (1)
and a polar coupling component of the general formula (2), and a
disazo compound comprising a polar coupling component of the
general formula (2) and a polar coupling component of the general
formula (3), can also be present. These plural types of disazo
compound molecules are adsorbed on and/or incorporated in, each
other, in the crystallization process of the disazo pigment.
[0021] By the method of the present invention, each pigment
particle comes to be constituted of various types of pigment
molecule, each type being originated from a different combination
of two out of three coupling components used. Although further
deliberate investigation will be necessary in the future, it is
supposed based on the present understanding of the inventors that
due to some appropriate balance between polar parts and non-polar
parts of pigment particles obtained, (1) the crystal growth as
above mentioned is suppressed moderately during the drying process
and also in heating during the flushing process, and
simultaneously, (2) phenomena intrinsic in a mixed colorant system,
which are liable to occur when a plurality of pigments are
compounded merely as a mixture and lead to a reduction in qualities
of the pigment such as color separation, can also be avoided.
[0022] The method of the present invention is preferably carried
out in a manner such that the coupling component is not
substantially deposited in the reaction system and the tetrazo
component immediately reacts with the coupling component after fed.
As one method for this, desirable is a constitution of reaction
system in which a coupler aqueous solution and a tetrazo aqueous
solution are injected into the above-mentioned acidic aqueous
solution concurrently, from separately set respective feeders such
as injecting tubes.
[0023] A coupling reaction can generally proceed in a weak acid
aqueous solution at a low temperature, but solubility of a coupling
component is considerably low in a weak acid solution. Therefore,
in the conventional acid deposition method in which a tetrazo
component is injected in a weak acid solution where a coupling
component has been precipitated in advance, most part of the
coupling component are present as aggregates in the reaction
solution. The coupling reaction proceeds as a liquid/solid reaction
between each of coupler particles (aggregates) and the tetrazo
component dissolved in the solution, accordingly. Therefore, with
the progress of coupling reaction, proceeding of dissolution of the
solid coupler into the reaction solution may become insufficient,
the amount of coupling component dissolved in the aqueous solution
decreases, and as a result, coupling reaction proceeds near or on
the surface of the coupler particles. In such a case that is likely
to occur in the situation aforementioned, pigment materials
generated from the reaction may cover the not-yet-dissolved and
thus non-reacted coupler particle surface and therefore the
dissolution of the coupler or the coupling reaction itself is
prohibited afterward.
[0024] Within the typically conducted reaction technique,
therefore, drawbacks such as decrease in yield and adverse effect
of non-reacted coupler residue on pigment properties are likely not
to be avoided as described in Japanese Patent Official Gazette
No.2943996. Additionally, some orientation phenomena of each of the
coupling component molecule in the aqueous reaction solution as
well as orientation and/or heterogeneous distribution of each
component molecule in the aggregates are expected to occur, if
based on the typical solid-liquid reaction above-mentioned, due to
the difference in polarity between the three different types of
coupling component. It is supposed that such orientations and
heterogeneous distributions lead to the unfavorable situation that
each different pigment molecule supposed to be derived freely from
each combination of different or same coupling components (1), (2)
and (3) cannot be formed freely as mentioned above.
[0025] Supply of polarity and non-polarity, and randomization or
equalized opportunity of their distribution into the pigment
molecules and crystals will be both achieved by making the coupling
component a three-component system, and by adopting the preferable
concurrent injection process as aforementioned, respectively, and
thus the effect of three-component coupling of the present
invention can be fully displayed.
[0026] By comparing each example with the corresponding comparative
example (a) wherein the coupling component was of the 3-components
system and the reaction process was by the typical acid deposition
method, and with another corresponding comparative example (b)
wherein the coupling component was only a main component and the
reaction process was a process according to the preferable
concurrent injection, the superiority of such a specific
constitution of the present invention will be clearly
appreciated.
[0027] In the method of the present invention, the molar ratio of
the total amount of the first and the second additional components
to the amount of the main component is preferably within the range
from 99:1 to 70:30. The molar ratio of the first additional
component to the second additional component is preferably within
the range from 1:9 to 9:1. The coupler aqueous solution and the
tetrazo aqueous solution are preferably fed into the acidic aqueous
solution in a manner such that the ratio of the molar feeding rate
of the coupling component to the molar feeding rate of the tetrazo
component is within the range from 200:80 to 200:99.
[0028] The method of the present invention may further comprise
adding a water-soluble inorganic salt to an aqueous disazo pigment
slurry obtained from the coupling reaction. Also, the method may
further comprise surface treating a disazo pigment material
obtained from said coupling reaction with rosins or a vehicle for
printing ink.
[0029] The present invention also includes, within the scope, a
disazo pigment obtained by the method, and a printing ink
composition that comprises a vehicle for printing ink and a disazo
pigment obtained by the method.
[0030] A disazo pigment produced by the method of the present
invention manifests, as described in detail below by way of
examples, remarkably excellent properties such as flowability and
transparency of the ink produced, flushing property in production,
flushing drain coloring resistance, and dispersibility.
DETAILED DESCRIPTION OF THE INVENTION
[0031] A coupling component of the general formula (1) in the
present invention may be a general coupling component that can be
coupled with a tetrazo component comprising benzidines to form a
yellow compound and is not specifically limited. Examples thereof
include acetoacetanilide, acetoaceto-o-toluidide,
acetoaceto-p-toluidide, acetoaceto-o-xylidide,
acetoaceto-m-xylidide, acetoaceto-p-xylidide,
acetoaceto-o-xylidide, acetoaceto-o-methoxyanilide,
acetoaceto-m-methoxyanilide, acetoaceto-p-methoxyanilide,
acetoaceto-2,4-dimethoxyanilide, acetoaceto-2,5-dimethoxyanilide,
acetoaceto-2,3-dimethoxy-4-chloroanilide- ,
acetoaceto-2,3-dimethoxy-5-chloroanilide,
acetoaceto-2,4-dimethoxy-5-chl- oroanilide,
acetoaceto-2,5-dimethoxy-3-chloroanilide,
acetoaceto-2,5-dimethoxy-4-chloroanilide,
acetoaceto-o-chloroanilide, acetoaceto-p-chloroanilide.
[0032] In the present invention, --CONR.sub.2 group that is a
substituent on a phenyl group in a coupling component represented
by the general formula (2) is the one that comes into the category
generally called carbonamide groups or alkylcarbamoyl groups.
Herein, Rs may be the same or different mutually, and each
represents a hydrogen atom, C1 to C4 alkyl group or C1 to C4
alkylene NR'.sub.2. R' represents a hydrogen atom or a C1 to C4
alkyl group, two of which may be different mutually. Each of Rs and
R's may take a structure in which two alkyl groups, both bonding to
the same nitrogen atom, are connected each other so as to form a
ring.
[0033] --SO.sub.2NR.sub.2 group which is a substituent on a phenyl
group in a coupling component represented by the general formula
(2) is the one that comes into the category generally called
sulfonamide groups or alkylsulfamoyl groups. Herein, R has the same
meaning as described above. --NHCOR group which is a substituent on
a phenyl group in a coupling component represented by the general
formula (2) is the one that comes into the category generally
called alkanoylamino groups. Herein, R has the same meaning as
described above.
[0034] More specifically, examples of a non-polar coupling
component of the general formula (2) include
acetoaceto-o-carbamoylanilide, acetoaceto-p-carbamoylanilide,
acetoaceto-m-methylaminocarboxyanilide,
acetoaceto-p-ethylaminocarboxyanilide,
acetoaceto-p-dimethylaminocarboxya- nilide,
acetoaceto-m-diethylaminocarboxyanilide, acetoaceto-m-dibutylamino-
carboxyanilide,
acetoaceto-m-dimethylaminomethylaminocarboxyanilide,
acetoaceto-p-dimethylaminoethylaminocarboxyanilide,
acetoaceto-p-dimethylaminopropylaminocarboxyanilide,
acetoaceto-p-diethylaminopropylaminocarboxyanilide,
acetoaceto-m-dipropylaminomethylaminocarboxyanilide,
acetoaceto-p-sulfamoylanilide,
acetoaceto-p-methylaminosulfonylanilide,
acetoaceto-p-propylaminosulfonylanilide,
acetoaceto-p-diethylaminosulfony- lanilide,
acetoaceto-p-dimethylaminomethylaminosulfonylanilide,
acetoaceto-p-dimethylaminopropylaminosulfonylanilide,
acetoaceto-2-methyl-5-carbamoylanilide,
acetoaceto-p-methylcarbamoylanili- de,
acetoaceto-2,5-dimethyl-4-carbamoylanilide,
acetoaceto-2-methoxy-4-car- bamoylanilide,
acetoaceto-2,5-dimethoxy-4-carbamoylanilide,
acetoaceto-2-chloro-4-carbamoylanilide,
acetoaceto-p-acetamideanilide,
acetoaceto-2-chloro-4-acetamideanilide,
acetoaceto-2-methoxy-4-acetamidea- nilide.
[0035] In the coupling component of general formula (3), the phenyl
group is substituted by at least one of a carboxyl group or alkali
metal salts thereof, a hydroxyl group, a sulfonic group or alkaline
metal salts thereof, to give a polar acetanilide type compound, in
contrast to the terminal phenyl group in the coupling component
represented by general formula (1). The phenyl group may further
have one, or the same or different substituents selected from the
group consisting of a methyl group, methoxy group, chlorine atom,
carboxyl group or alkali metal salts thereof, hydroxyl group, and
sulfonic group or alkali metal salts thereof. More specifically,
examples of the coupling compound of general formula (3) include
4-acetoacetylaminobenzenesulfonic acid,
4-acetoacetylamino-2-methylbenzenesulfonic acid,
2-acetoacetylamino-3-chl- oro-4-methylbenzenesulfonic acid,
4-acetoacetylamino-3-methoxy-2-methylben- zenesulfonic acid,
2-acetoacetylamino-5-methoxy-4-methylbenzenesulfonic acid,
2-acetoacetylamino-3,5-dichlorobenzenesulfonic acid,
2-acetoacetylaminobenzoic acid, 2-acetoacetylamino-4-chlorobenzoic
acid, 2-acetoacetylaminoterephthalic acid,
3-acetoacetylamino-6-hydroxybenzoic acid,
3-acetoacetylamino-6-methoxybenzoic acid, 2-acetoacetylaminophenol,
and alkali metal salts thereof.
[0036] The aqueous solution of a coupling component used in the
present invention contains a compound of general formula (1) and a
compound of general formula (2) which are non-polar coupling
components, and a compound of general formula (3) which is a polar
coupling component. This aqueous solution of coupling components is
preferably an alkali solution, which can dissolve all coupling
components. As the alkali, for example, inorganic bases such as
sodium hydroxide, potassium hydroxide and the like are listed.
[0037] The tetrazo aqueous solution according to the present
invention contains a tetrazo compound obtained by tetrazotizing
benzidines by known methods. As benzidines, for example,
derivatives of benzidine such as 3,3'-dichlorobenzidine,
2,2',5,5'-tetrachlorobenzidine, and 3,3'-dimethoxybenzidine and the
like are listed. The tetrazo aqueous solution containing a tetrazo
component of benzidines is preferably an acidic aqueous solution,
and particularly, an aqueous solution acidified with hydrochloric
acid is preferably used. A combination is preferable in which the
above-mentioned aqueous solution of coupling components is an
alkali solution and the aqueous solution of a tetrazo component is
an acidic solution.
[0038] In the present invention, it is preferable that the molar
ratio of the total amount of a coupling component of the general
formula (2) and a coupling component of the general formula (3) to
the amount of a coupling component of the general formula (1) is
within the range between 99:1 and 70:30. Further, it is preferable
that the molar ratio of a coupling component of the general formula
(2) to a coupling component of the general formula (3) is within
the range between 1:9 and 9:1. If the amount of a coupling
component of the general formula (3) is less than the
above-mentioned value, transparency and clearness decease, while if
the above-mentioned value, flushing suitability decreases.
[0039] In the present invention, an acidic aqueous solution into
which a coupler aqueous solution and a tetrazo aqueous solution are
to be injected is previously charged in a vessel for reaction. The
vessel may be, typically, a batch type stirring vessel. As the
batch type stirring vessel, any of known vessels may be used. It is
also, typically, necessary that the vessel is constituted of a
water vessel for keeping liquid mediums which are required to be
added to the water vessel for each liquid medium requiring
stirring, and a stirring machine having a stirring blade to stir
the liquid medium. An acidic solution in the batch type stirring
vessel may advantageously be one which can maintain the coupling
reaction system in the pH range from 3 to 6.9, preferably in the pH
range from 3.5 to 6.3. For this purpose, known acid aqueous
solutions used in conventional coupling methods, for example,
aqueous solutions of acetic acid, formic acid and the like can be
used.
[0040] Maintaining pH in the above-mentioned range is preferable
for minimizing sub-reactions such as decomposition and
concentration of a tetrazo component, and the like, and maintaining
pH in the above-mentioned range from the initiation of the reaction
to completion of the reaction is more preferable. For this, it is
preferable to allow a pH buffer to be present in an acidic aqueous
solution in the batch type stirring vessel, though an acid or
alkali may also be added intermittently or continuously during the
reaction. From the standpoint of easiness of operation, it is
preferable to use an aqueous solution system having pH buffering
property, for example, buffering aqueous solutions such as "acetic
acid-sodium acetate" system, "formic acid-sodium formate" system
and the like which are often used in conventional coupling
reactions because then variation of pH is little and maintenance of
pH becomes easier.
[0041] In the present invention, injection of a coupler aqueous
solution and a tetrazo aqueous solution containing a tetrazo
component of benzidines into an acidic aqueous solution in a batch
type stirring vessel can be conducted, for example, simultaneously
through separate injecting tubes into the acidic aqueous
solution.
[0042] For uniform adsorption of disazo compounds containing all
coupling components used in the present invention on primary
particles of a disazo pigment, or inclusion of such a disazo
compound in a crystal structure, it will be advantageous that the
compound is injected concurrently into the acidic aqueous solution
so that any of the coupling components is not deposited in the
reaction system and an unreacted tetrazo component immediately
reacts as described above. More specifically, for example, in
injecting a coupler aqueous solution and a tetrazo aqueous solution
into an acidic aqueous solution, injection time ranges of these
aqueous solutions is so controlled that they are at least partially
overlapped. For instance, injection time ranges of both aqueous
solutions may be partially overlapped, or the whole ranges of them
may be overlapped, namely, same each other. If necessary, some time
may exist, during which only one solution, either a coupler
solution or tetrazo solution, is injected.
[0043] If a coupler aqueous solution and a tetrazo aqueous solution
are in direct contact, the coupling components will be deposited to
give solid. As a consequence, the produced amount of disazo
compounds that have, if sufficiently synthesized, the effects to
improve transparency and flowability of the ink produced, flushing
suitability, drain coloring resistance and dispersibility during
the synthesis process, will decrease. In such a case, therefore,
these properties are likely not to be improved as expected in the
present invention.
[0044] To avoid this, it is preferable that in a vessel equipped
with a batch type stirring machine filled with an acidic aqueous
solution, injecting tube outlets are provided on positions distant
each other, and injection is conducted (herein referred to as
simultaneous injection, or concurrent injection or feeding),
stirring is effected sufficiently, and a tetrazo component and
coupling components are reacted assuredly in an acidic aqueous
solution. Further, it may also be permissible that an acidic
aqueous solution is extracted from a stirring vessel and allowed to
circulate through outside portions, and the tetrazo aqueous
solution and coupler aqueous solution are injected into this
circulating line, or one of them is injected into the circulating
line and other is injected into the stirring vessel.
[0045] In the present invention, the ratio of the molar injecting
rate of all coupling components to the molar injecting rate of a
tetrazo component is not particularly restricted, and usually, it
is preferable that they are continuously injected so that the ratio
is within the range from 200:80 to 200:99, preferably from 200:90
to 200:99 to cause a coupling reaction. By this, after injecting
into an acidic aqueous solution, the whole portion of a tetrazo
component is immediately reacted with coupling components, and no
unreacted tetrazo component remain in the reaction system. As a
result, sub-reactions due to decomposition and concentration of a
tetrazo component are prevented, and color hue staining is
prevented.
[0046] The ratio of molar injecting rates is not required to be
maintained at a constant value through the whole period of the
reaction, and may also be changed with the progress of injection in
the above-mentioned range of the molar injecting rate ratio.
Further, initiation of injection of a coupler aqueous solution may
also be effected before the injection of a tetrazo aqueous
solution. Further, it may also be permissible that surface treating
agents such as nonionic surfactants, anionic surfactants and rosin
solutions are injected and surface treatment of the produced
pigment particles can be effected simultaneously. As such
activating agents, Emulgen 120 (trade name, manufactured by Kao
Corp.), Aromox DMC-W (trade name, manufactured by Lion Corp.) and
the like are exemplified. Though an effect is obtained even if the
amount of surfactants to be added is small, an effect is larger
when the amount is larger to a certain extent. When surfactants are
used, the amount thereof is determined in view of also cost,
quality of a product and properties of printing ink used, in
addition to reaction rate required, and generally, surfactants can
be used in an amount from 0.2 to 10.0% by weight based on a pigment
produced as an effective component.
[0047] As described above, if a tetrazo component and coupling
components are simultaneously injected at the above-mentioned molar
rate ratio, no tetrazo component is present at all in the reaction
system at the completion of injection, coupling components which
can cause reaction are remain in a small amount. Then, it is
possible that a coupler aqueous solution containing all coupling
components in admixture, and a tetrazo aqueous solution containing
a teterazo component of benzidines are injected continuously into
an acidic aqueous solution, then, the tetrazo aqueous solution is
only injected additionally. For example, it is also possible that
after the completion of simultaneous injection, a tetrazo aqueous
solution is only injected additionally, allowed to react completely
with coupling components, to further enhance the coupling reaction
rate.
[0048] In the present invention, it is preferable to select
appropriate conditions for injecting a coupler aqueous solution
containing all coupling components in admixture into an acidic
aqueous solution so that when the coupler aqueous solution is mixed
with the acidic aqueous solution, particularly a non-polar coupling
component of the general formula (2) and a polar coupling component
of the general formula (3) dissolved are not deposited. This is
varied depending on a lot of factors such as kinds of a non-polar
coupling component and a polar coupling component to be reacted,
the concentration of a coupler aqueous solution, injecting speed,
pH and amount of an acidic aqueous solution, and is determined in
view of the coupling rate of a coupler aqueous solution with a
tetrazo aqueous solution, the scattering rate and solubility in an
acidic aqueous solution, and the like. Further, the optimum
injection amount of a coupler can also be determined
experimentally.
[0049] In the present invention, it is preferable to pour a coupler
aqueous solution having the total concentration of all coupling
components from 0.1 to 1.0 mol/liter and a tetrazo aqueous solution
having a concentration from 0.05 to 0.8 mol/liter into an acidic
aqueous solution from the standpoint of operation, economy and
small load. The amount of injecting per unit time of a coupler
aqueous solution and a tetrazo aqueous solution into an acidic
aqueous solution is not particularly restricted, and is determined
in the range wherein a coupling component is not deposited in an
acidic aqueous solution.
[0050] The range in which all coupling components are not deposited
varies depending on various conditions such as the kind, pH, amount
and stirred condition of an acidic aqueous solution, position of an
outlet of a injecting tube, and the like, and the injecting amount
is determined from general opinions in view of time required for
production, production process, and the like. Namely, when the
injecting amount of a coupler aqueous solution into an acidic
aqueous solution is smaller, all coupling components are not
deposited easily, however, the concentration in the reaction system
decreases, leading to longer time for production of a pigment
product. The ratio of the injection amount of a coupler aqueous
solution to the injection amount of a tetrazo aqueous solution into
an acidic aqueous solution per unit time is preferably within the
range from 100:1 to 1000:50.
[0051] In the present invention, reaction conditions such as
temperature and pH in coupling and method of controlling this are
selected from conventional known conditions in coupling and
controlling methods, and there is no specific restriction. pH and
temperature may be changed with time or injecting amount, or may be
maintained constant throughout the reaction.
[0052] When the present invention is effected in preferable
embodiments, since an acidic tetrazo aqueous solution and an
alkaline coupler aqueous solution are injected simultaneously, a
coupling reaction can be conducted while maintaining the initial pH
until the end by controlling pH and flow rate of the solutions so
that acids and alkalis in these aqueous solutions are neutralized.
The method of producing a pigment of the present invention is
particularly effective for obtaining C.I. Pigment Yellow 12, 13,
14, 17 and 83 surface-treated with a pigment derivative.
[0053] The pigment of the present invention preferably contains
98.0 to 70.0% of a disazo compound containing per one molecule two
coupling components of the general formula (1) and 2.0 to 30.0% of
a disazo compound containing per one molecule one or two coupling
components of the general formula (2) and/or coupling components of
the general formula (3), depending on the compounding ratio of
coupling components previously controlled. A disazo pigment in thus
obtained acidic aqueous solution can be removed out from the
reaction system by continuous solid-liquid separation, or be
removed out from the reaction system by batch-wise solid-liquid
separation after completion of the reaction.
[0054] For improving pigment properties of a disazo pigment in the
present invention, a water-soluble inorganic salt selected from
aluminum sulfate, aluminum chloride and calcium chloride may be
added to aqueous slurry of a disazo pigment, or surface treatment
of a pigment may be performed with rosins or vehicles for printing
ink. As the rosins for surface treatment, there are listed a sodium
hydroxide solution and potassium hydroxide solution and the like of
rosins usually used for rosin-treatment of pigment such as gum
rosin, wood rosin, tall oil rosin, disproportionated rosin,
polymerized rosin, hydrogenated rosin, maleated rosin, and the
like. As the vehicle for printing ink for surface treatment, a
rosin-modified phenol resin which has high acidic value and becomes
an alkali aqueous solution is preferable, and an alkyd resin,
petroleum resin and the like may also be used together with the
rosin-modified phenol resin. The amount of the rosin or vehicle for
printing ink added is from 2 to 150% by weight, preferably from 3
to 80% by weight based on a disazo pigment produced by coupling in
terms of solid content.
[0055] A disazo pigment composition obtained by the production
method of the present invention can be kneaded with a vehicle for
printing ink and used in printing ink excellent in transparency and
flowability. A vehicle for offset ink is composed, for example, of
a resin such as a rosin-modified phenol resin, petroleum resin,
alkyd resin or dry oil-modified resin thereof, and if necessary, a
vegetable oil such as linseed oil, tung oil, soybean oil or the
like, and a solvent such as n-paraffin, isoparaffin, aromatic,
naphthene, ?-olefin and the like. A mixing ratio of resin,
vegetable oil, and solvent is preferably, in this order,
20-50:0-30:10-60 by weight. A vehicle for offset ink containing the
disazo pigment compounded of the present invention can be made into
printing ink by appropriate compounding of known additives such as
an ink solvent, drier, leveling improver, thickening agent and the
like, if necessary.
[0056] A vehicle for gravure ink is composed, for example, of a
resin mixture such as gum rosin, wood rosin, tall oil rosin,
calcificated rosin, lime rosin, rosin ester, maleic acid resin,
gilsonite, dammar, shellac, polyamide resin, vinyl resin,
nitrocellulose, cyclorubber, chlorinated rubber, ethylcellulose,
cellulose acetate, ethylene-vinyl acetate copolymer resin, urethane
resin, polyester resin, alkyd resin and the like, and a solvent
such as n-hexane, toluene, methanol, ethanol, acetone, ethyl
acetate, ethyl lactate, ethylene glycol monoethyl ether, ethylene
glycol monomethyl ether, ethylene glycol monobutyl ether, isopropyl
alcohol, chlorobenzol, ethyl ether, methyl ethyl ketone, ethyl
acetoacetate, and the like. A compounding ratio of a resin mixture
to a solvent is preferably 10-50:30-80, by weight. A vehicle for
gravure ink containing the disazo pigment compounded of the present
invention can be made into printing ink by appropriate compounding
of known additives such as a plasticizer, ultraviolet ray
inhibitor, antioxidant, antistatic agent and the like as
auxiliaries, in addition to extenders such as barium sulfate,
barium carbonate, calcium carbonate, gypsum, alumina white clay,
silica, silica white, talc, calcium silicate, precipitated
magnesium carbonate and the like, if necessary.
EXAMPLES
[0057] The examples describe the present invention further
specifically below, but do not limit the scope of the present
invention. "Parts" and "%" in the examples mean "parts by weight"
and "% by weight" unless otherwise stated.
[0058] Each of comparative examples (a) such as 1a, 2a, and so on
is the case wherein the coupling component was the same as that of
the corresponding example, and by means of the acid deposition
process. Each of comparative examples (b) such as 1b, 2b, and so on
is the case wherein the coupling component was of only a main
component, and by means of concurrent injection procedure. Each of
comparative examples (c) such as 1c, 2c, and so on is the case
wherein the coupling component including, as an additional
component, only a component expressed in formula (3), was used, and
by means of concurrent injection procedure. Finally, Each of
comparative examples (d) is the case wherein the coupling component
including, as an additional component, only a component expressed
in formula (2), was used, and by means of concurrent injection
procedure.
[0059] In Example 4, a heat treatment was done after a rosin
treatment whereas in other examples a heating treatment was done
before the rosin treatment to extend pigment particles. According
to the reversed procedure, further modification of crystal growth
characteristics, transparency of the ink produced, etc. are
expected as well as flowability being varied, by enhancing the
surface treatment effect through making an agent like rosin
permeate into the pigment particles.
Example 1
[0060] 3,3'-dichlorobenzidine hydrochloride was tetrazotized
according to an ordinary method using 3-fold mol of hydrochloric
acid and 2-fold mol of sodium nitrite to prepare a 0.125 mol/l
tetrazo aqueous solution of 10.degree. C. 325.7 parts of
acetoacetanilide, 6.6 parts of 2-acetoacetylaminobenzoic acid, 9.5
parts of 2-hydroxy-5-acetoacetylbenzo- ic acid and 19.8 parts of
acetoaceto-p-carbamoylanilide were dissolved in an aqueous solution
containing 120 parts of sodium hydroxide to prepare a 0.259 mol/l
coupler aqueous solution of 25.degree. C.
[0061] As a buffer solution, 5000 parts of an acidic aqueous
solution of 24.degree. C. having a pH of 4.7 composed of 300 parts
of 80% acetic acid, 80 parts of sodium hydroxide and water was
prepared, and this was charged into a reactor equipped with a
stirring machine. Two injecting tubes having outlets at positions
remote each other in this pH buffer solution were set on this
reactor, and the tetrazo aqueous solution and the coupler solution
were injected into the pH buffer solution through the injecting
tubes, respectively. Injections of these solutions were initiated
simultaneously, and injected for 40 minutes at the same volume flow
rate (193 ml/min.) using constant flow pumps, and the injections
were completed at the same time. During the injection, a tetrazo
was not detected from a reaction solution collected from the liquid
surface. Yield of the coupling reaction on a coupler basis at this
completion of injection was 96.5%.
[0062] Then, only the tetrazo aqueous solution was additionally
injected until a trace amount of the tetrazo was recognized in the
reaction system, and as a result, yield of the coupling reaction on
a coupler basis was 98.6%. Detection of tetrazo was conducted by
color development reaction using .beta.-naphthol. Yield rate of
coupling reaction was determined from the amount of unreacted
coupler obtained by the analysis of liquid chromatography.
[0063] The slurry obtained from the above-mentioned process was
heated up to 60.degree. C., then, to this was added an aqueous
sodium hydroxide solution to control the pH to 10.5, and tall
oil-based rosin soap was added in an amount of 31 parts in terms of
solid, then, pH was controlled to 6.5 with an aqueous hydrochloric
acid solution. Further, 70 parts of 8% aqueous aluminum sulfate
solution were added, then, the solution was filtrated and purified
to obtain a wet pigment composition (Sample 1) containing a disazo
pigment.
Comparative Example 1a
[0064] A tetrazo aqueous solution was prepared in the same manner
as in Example 1. 0.259 mol/l coupler aqueous solution of 25.degree.
C. was prepared in the same manner as in Example 1 except that the
amount of sodium hydroxide used was changed to 144 parts.
[0065] As a buffer solution, 5000 parts of an acetic acid solution
composed of 300 parts of 80% acetic acid and water were prepared,
and this was charged into a reactor equipped with a stirring
machine. The coupler aqueous solution was injected at a flow rate
of 193 ml/min. for 40 minutes into this acetic acid solution, to
deposit the coupler. An injecting tube having an outlet in this
coupler slurry was set on the reactor, and the tetrazo aqueous
solution was injected at a flow rate of 184 ml/min. through this
injecting tube. This injection was conducted until a trace amount
of a tetrazo was detected at the reaction liquid surface. Yield of
the coupling reaction was 92.1%.
[0066] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 1a) containing a disazo pigment.
Comparative Example 1b
[0067] Preparations of a tetrazo aqueous solution and a buffer
solution and its injection into a reactor were conducted in the
same manner as in Example 1 except that 354 parts of
acetoacetanilide was dissolved in an aqueous solution containing
120 parts of sodium hydroxide to prepare a 0.259 mol/l coupler
aqueous solution of 25.degree. C.
[0068] During the injection, tetrazo was not detected in the
reaction solution collected from the liquid surface. Yield of the
coupling reaction on a coupler basis at this completion of
injection was 96.5%. Then, only the tetrazo aqueous solution was
additionally injected until a trace amount of a tetrazo was
recognized in the reaction system, and as a result, yield of the
coupling reaction on a coupler basis was 98.6%.
[0069] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 1b) containing a disazo pigment. This pigment
corresponds to a pigment described in Japanese Patent Official
Gazette No. 2943996.
Comparative Example 1c
[0070] Preparations of a tetrazo aqueous solution and a buffer
solution and its injection into a reactor were conducted in the
same manner as in Example 1 except that 325.7 parts of
acetoacetanilide and 35.4 parts of 3-acetoacetylaminobenzoic acid
were dissolved in an aqueous solution containing 120 parts of
sodium hydroxide to prepare a 0.259 mol/l coupler aqueous solution
of 25.degree. C.
[0071] During the injection, tetrazo was not detected in a reaction
solution collected from the liquid surface. Yield of the coupling
reaction on a coupler basis at this completion of injection was
96.5%. Then, only the tetrazo aqueous solution was additionally
injected until a trace amount of a tetrazo was recognized in the
reaction system, and as a result, yield of the coupling reaction on
a coupler basis was 98.6%.
[0072] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 1c) containing a disazo pigment. This pigment
corresponds to the disazo pigment composition described in Japanese
Patent Application Laid-Open (JP-A) No. 2000-7931.
Comparative Example 1d
[0073] Preparations of a tetrazo aqueous solution and a buffer
solution and its injection into a reactor were conducted in the
same manners as in Example 1 except that 325.7 parts of
acetoacetanilide and 35.2 parts of acetoaceto-p-carbamoylanilide
were dissolved in an aqueous solution containing 120 parts of
sodium hydroxide to prepare a 0.259 mol/l coupler aqueous solution
of 25.degree. C.
[0074] During the injection, tetrazo was not detected from the
reaction solution collected from the liquid surface. Yield of the
coupling reaction on a coupler basis at this completion of
injection was 96.5%. Then, only the tetrazo aqueous solution was
additionally injected until a trace amount of a tetrazo was
recognized in the reaction system. As a result, Yield of the
coupling reaction on a coupler basis was 98.6%.
[0075] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 1d) containing a disazo pigment.
Ink Making 1
[0076] The wet pigment compositions obtained in Example 1 and
Comparative Examples 1a-1d were used to make inks and
evaluated.
[0077] Into a flusher was added 230 parts of vanish for
planographic ink (manufactured by Toyo Ink Mfg. Co., Ltd., varnish
containing rosin-modified phenol resin) heated to 70.degree. C. To
this was added the wet pigment composition obtained in an amount of
80 parts in terms of pigment solid content, and flushing was
conducted for 20 minutes while kneading. Free water was removed,
then, the flusher was heated up to 100.degree. C. while dehydrating
under decompression, to remove water. After recognizing removal of
water, 250 parts of vanish for planographic ink (manufactured by
Toyo Ink Mfg. Co., Ltd., varnish containing rosin-modified phenol
resin) and 30 parts of a solvent for ink were added gradually to
prepare ink.
[0078] Time required for separation of water was measured in
producing the above-mentioned ink, and coloration degree of
discharged water, transparency and flowability of inks prepared
were measured. The results are shown in Table 1.
[0079] Coloration Degree of Flushing Drain
[0080] A drain separated in flushing in a flusher was removed into
a colorless 100 ml glass bottle, and coloration degree was compared
visually based on gray scale. Turbid condition providing
insufficient light transmittance was represented by 1, and utterly
colorless condition was represented by 5. In this way, the results
were evaluated by 5 grade evaluation criterion.
[0081] Transparency of Ink
[0082] On white color developing paper on which a black band
pattern had been printed using black ink, each ink prepared was
developed, and the color developing condition on the black band
pattern was visually observed. When ink was developed on the black
band and the black band was not seen at all, the condition was
judged as opaque and represented by transparency level 1. When
development of the test ink on the black band was not recognized
easily, the condition was judged as transparent, and represented by
level 10. In this way, the results were evaluated by 10 grade
evaluation criterion.
[0083] Flowability of Ink
[0084] Each ink prepared of a constant volume was weighed on a
spread meter, and one minute after, the distance from the center
point to the flow end of the flowed ink was measured. When the
measured value was larger, flowability was judged as higher. Table
1 shows each relative value represented by percentage when the
measured value of the wet pigment composition of the example was
100%.
1TABLE 1 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 1 100 10 5'50" 5 Sample 1-a 60 5 5'30" 5 Sample
1-b 50 3 4'30" 5 Sample 1-c 100 6 14'50" 1 Sample 1-d 90 5 5'20"
5
Example 2
[0085] Preparations of a tetrazo aqueous solution and a buffer
solution and its injection into a reactor were conducted in the
same manners as in Example 1 except that 300.9 parts of
acetoacetanilide, 30.9 parts of 3-acetoacetylaminobenzoic acid,
23.7 parts of 2-hydroxy-5-acetoacetylbenz- oic acid and 13.2 parts
of acetoaceto-p-carbamoylanilide were dissolved in an aqueous
solution containing 120 parts of sodium hydroxide to prepare a
0.259 mol/l coupler aqueous solution of 25.degree. C.
[0086] Yield of the coupling reaction at the completion of
injection was 96.5%. Then, the tetrazo aqueous solution was
additionally injected until a trace amount of a tetrazo was
recognized in the reaction system, and as a result, yield of the
coupling reaction this time on a coupler basis was 98.5%.
[0087] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 2) containing a disazo pigment.
Comparative Example 2a
[0088] Preparations of a tetrazo aqueous solution and a buffer
solution were conducted and a coupling reaction was allowed to
progress in a reactor in the same manners as in Comparative Example
1a except that 300.9 parts of acetoacetanilide, 30.9 parts of
3-acetoacetylaminobenzoic acid, 23.7 parts of
2-hydroxy-5-acetoacetylbenzoic acid and 13.2 parts of
acetoaceto-p-carbamoylanilide were used to prepare a coupler
aqueous solution, to obtain a wet pigment composition (Sample 2a)
containing a disazo pigment.
Comparative Example 2b
[0089] The wet pigment composition obtained in Comparative Example
1b is called here, for convenience, a wet pigment composition
(Sample 2b) of Comparative Example 2b.
Comparative Example 2c
[0090] Preparations of a tetrazo aqueous solution and a buffer
solution were conducted and a coupling reaction was allowed to
progress in a reactor in the same manners as in Comparative Example
1c except that 300.9 parts of acetoacetanilide, 71.1 parts of
2-hydroxy-5-acetoacetylben- zoic acid were used to prepare a
coupler aqueous solution, to obtain a wet pigment composition
(Sample 2c) containing a disazo pigment.
Comparative Example 2d
[0091] Preparations of a tetrazo aqueous solution and a buffer
solution were conducted and a coupling reaction was allowed to
progress in a reactor in the same manners as in Comparative Example
1d except that 300.9 parts of acetoacetanilide and 66.0 parts of
acetoaceto-p-carbamoyla- nilide were used to prepare a coupler
aqueous solution, to obtain a wet pigment composition (Sample 2d)
containing a disazo pigment.
Ink Making 2
[0092] The wet pigment compositions obtained in Example 2 and
Comparative Examples 2a-2d were used to make inks and evaluated in
the same manners as in Ink making 1. The results are shown in Table
2.
2TABLE 2 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 2 100 10 6'30" 3 Sample 2-a 70 6 5'50" 3 Sample
2-b 45 3 4'30" 5 Sample 2-c 100 7 17'10" 1 Sample 2-d 90 5 4'50"
5
Example 3
[0093] Preparations of a tetrazo aqueous solution and a buffer
solution and its injection into a reactor were conducted in the
same manners as in Example 1 except that 325.7 parts of
acetoacetanilide, 22.3 parts of sodium
4-acetoacetylaminobenzenesulfonate, and 24.4 parts of
acetoaceto-p-dimethylaminopropylcarbamoylanilide were dissolved in
an aqueous solution containing 120 parts of sodium hydroxide to
prepare a 0.259 mol/l coupler aqueous solution of 25.degree. C.
[0094] Yield of the coupling reaction at the completion of
injection was 96.5%. Then, the tetrazo aqueous solution was
additionally injected until a trace amount of a tetrazo was
recognized in the reaction system, and as a result, yield of the
coupling reaction on a coupler basis was 98.5%.
[0095] The slurry obtained by the above-mentioned process was
subjected to heating, rosin treatment, filtration and purification
in the same manners as in Example 1 to obtain a wet pigment
composition (Sample 3) containing a disazo pigment.
Comparative Example 3a
[0096] A wet pigment composition (Sample 3a) containing a disazo
pigment was obtained in the same manners as in Comparative Example
1a except that 325.7 parts of acetoacetanilide, 22.3 parts of
sodium 4-acetoacetylaminobenzenesulfonate, and 24.4 parts of
acetoaceto-p-dimethylaminopropylcarbamoylanilide were used to
prepare a coupler aqueous solution.
Comparative Example 3b
[0097] The wet pigment composition obtained in Comparative Example
1b is called here, for convenience, a wet pigment composition
(Sample 3b) of Comparative Example 3b.
Comparative Example 3c
[0098] A wet pigment composition (Sample 3c) containing a disazo
pigment was obtained in the same manners as in Comparative Example
1c except that 325.7 parts of acetoacetanilide and 44.6 parts of
sodium 4-acetoacetylaminobenzenesulfonate were used to prepare a
coupler aqueous solution.
Comparative Example 3d
[0099] A wet pigment composition (Sample 3d) containing a disazo
pigment was obtained in the same manners as in Comparative Example
id except that 325.7 parts of acetoacetanilide and 48.8 parts of
acetoaceto-p-dimethylam- inopropylcarbamoylanilide were used to
prepare a coupler aqueous solution.
Ink Making 3
[0100] The wet pigment compositions obtained in Example 3 and
Comparative Examples 3a-3d were used to make inks and evaluated in
the same manners as in Ink Making 1. The results are shown in Table
3.
3TABLE 3 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 3 100 9 6'30" 4 Sample 3-a 60 6 6'10" 4 Sample
3-b 40 3 4'30" 5 Sample 3-c 90 7 15'40" 1 Sample 3-d 80 5 5'50"
3
Example 4
[0101] A wet pigment composition (Sample 4) containing a disazo
pigment was obtained in the same manners as in Example 1 except
that after the coupling reaction, an aqueous sodium hydroxide
solution was added to the resulted slurry to control pH to 10.5,
and tall oil-based rosin soap was added in an amount of 31.0 parts
in terms of solid content, then, 70 parts of a 8% aqueous aluminum
sulfate solution was added, and pH was controlled to 6.5 with an
aqueous hydrochloric acid solution, then, the mixture was heated up
to 60.degree. C.
Comparative Example 4a
[0102] A coupling reaction was conducted in the same manner as in
Comparative Example la, then, rosin treatment and heating treatment
were conducted in the procedure described in Example 4, to obtain a
wet pigment composition (Sample 4a) containing a disazo
pigment.
Comparative Example 4b
[0103] A coupling reaction was conducted in the same manner as in
Comparative Example 1b, then, rosin treatment and heating treatment
were conducted in the procedure described in Example 4, to obtain a
wet pigment composition (Sample 4b) containing a disazo
pigment.
Comparative Example 4c
[0104] A coupling reaction was conducted in the same manner as in
Comparative Example 1c, then, rosin treatment and heating treatment
were conducted in the procedure described in Example 4, to obtain a
wet pigment composition (Sample 4c) containing a disazo
pigment.
Comparative Example 4d
[0105] A coupling reaction was conducted in the same manner as in
Comparative Example 1d, then, rosin treatment and heating treatment
were conducted in the procedure described in Example 4, to obtain a
wet pigment composition (Sample 4d) containing a disazo
pigment.
Ink Making 4
[0106] The wet pigment compositions obtained in Example 4 and
Comparative Examples 4a-4d were used to make inks and evaluated in
the same manners as in Ink making 1. The results are shown in Table
4.
4TABLE 4 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 4 100 9 7'00" 4 Sample 4-a 60 6 6'10" 4 Sample
4-b 50 3 5'00" 5 Sample 4-c 90 6 12'40" 1 Sample 4-d 80 5 5'50"
3
Example 5
[0107] A coupling reaction was allowed to progress in the same
manner as in Example 1 except that 366.7 parts of
acetoaceto-o-toluidide, 9.5 parts of
5-acetoacetylamino-2-hydroxybenzoic acid and 10.0 parts of
acetoaceto-2-methoxy-4-carbamoylanilide were dissolved in an
aqueous solution containing 120 parts of sodium hydroxide to
prepare a 0.259 mol/l of coupler aqueous solution of 25.degree.
C.
[0108] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 5) containing a disazo
pigment.
Comparative Example 5a
[0109] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1a except that 366.7 parts of
acetoaceto-o-toluidide, 9.5 parts of
5-acetoacetylamino-2-hydroxybenzoic acid and 10.0 parts of
acetoaceto-2-methoxy-4-carbamoylanilide were used to prepare a
coupler aqueous solution.
[0110] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 5a) containing a disazo
pigment.
Comparative Example 5b
[0111] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1b except that 382 parts of
acetoaceto-o-toluidide was used instead of 354 parts of
acetoacetanilide.
[0112] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 5b) containing a disazo
pigment.
Comparative Example 5c
[0113] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1c except that 366.7 parts of
acetoaceto-o-toluidide and 19.0 parts of
5-acetoacetylamino-2-hydroxybenz- oic acid were used to prepare a
coupler aqueous solution.
[0114] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 5c) containing a disazo
pigment.
Comparative Example 5d
[0115] A coupling reaction was allowed to progress in the same
manner as in Comparative Example id except that 366.7 parts of
acetoaceto-o-toluidide and 20.0 parts of
acetoaceto-2-methoxy-4-carbamoyl- anilide were used to prepare a
coupler aqueous solution.
[0116] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 5d) containing a disazo
pigment.
Ink Making 5
[0117] The wet pigment compositions obtained in Example 5 and
Comparative Examples 5a-5d were used to make inks and evaluated in
the same manners as in Ink making 1. The results are shown in Table
5.
5TABLE 5 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 5 100 9 7'00" 5 Sample 5-a 60 6 6'10" 4 Sample
5-b 40 3 4'30" 5 Sample 5-c 90 7 15'40" 1 Sample 5-d 80 5 5'50"
4
Example 6
[0118] A coupling reaction was allowed to progress in the same
manner as in Example 1 except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloro- anilide, 11.1 parts of
o-acetoacetylaminobenzoic acid and 12.7 parts of
acetoaceto-2-chloro-4-carbamoylanilide were dissolved in an aqueous
solution containing 120 parts of sodium hydroxide to prepare a
0.259 mol/l of coupler aqueous solution of 25.degree. C.
[0119] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 6) containing a disazo
pigment.
Comparative Example 6a
[0120] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1a except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide, 11.1 parts of
o-acetoacetylaminobenzoic acid and 12.7 parts of
acetoaceto-2-chloro-4-ca- rbamoylanilide were used to prepare a
coupler aqueous solution.
[0121] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 6a) containing a disazo
pigment.
Comparative Example 6b
[0122] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1b except that 543 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide was used instead of 354
parts of acetoacetanilide.
[0123] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 6b) containing a disazo
pigment.
Comparative Example 6c
[0124] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 1c except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide and 22.2 parts of
o-acetoacetylaminobenzoic acid were used to prepare a coupler
aqueous solution.
[0125] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 6c) containing a disazo
pigment.
Comparative Example 6d
[0126] A coupling reaction was allowed to progress in the same
manner as in Comparative Example id except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide and 25.5 parts of
acetoaceto-2-chloro-4-carbamoylanilide were used to prepare a
coupler aqueous solution.
[0127] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition (Sample 6d) containing a disazo
pigment.
Ink Making 6
[0128] The wet pigment compositions obtained in Example 6 and
Comparative Examples 6a-6d were used to make inks and evaluated in
the same manners as in Ink making 1. The results are shown in Table
6.
6TABLE 6 Dehydration Drain Sample No. Flowability Transparency time
coloration Sample 6 100 9 7'00" 5 Sample 6-a 60 6 6'10" 5 Sample
6-b 50 3 5'00" 5 Sample 6-c 90 6 12'40" 1 Sample 6-d 80 5 5'50"
4
Example 7
[0129] The wet pigment composition (Sample 1) obtained in Example 1
was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 7) containing a disazo
pigment.
Comparative Example 7a
[0130] The wet pigment composition (Sample 1a) obtained in
Comparative Example 1a was dried and ground at 90.degree. C. for 12
hours to obtain a powder pigment composition (Sample 7a) containing
a disazo pigment.
Comparative Example 7b
[0131] The wet pigment composition (Sample 1b) obtained in
Comparative Example 1b was dried and ground at 90.degree. C. for 12
hours to obtain a powder pigment composition (Sample 7b) containing
a disazo pigment. This pigment corresponds to a pigment described
in Japanese Patent No. 2943996.
Comparative Example 7c
[0132] The wet pigment composition (Sample 1c) obtained in
Comparative Example 1c was dried and ground at 90.degree. C. for 12
hours to obtain a powder pigment composition (Sample 7c) containing
a disazo pigment. This pigment corresponds to a pigment described
in Japanese Patent Application Laid-Open (JP-A) No. 2000-7931.
Comparative Example 7d
[0133] The wet pigment composition (Sample 1d) obtained in
Comparative Example 1d was dried and ground at 90.degree. C. for 12
hours to obtain a powder pigment composition (Sample 7d) containing
a disazo pigment.
Ink Making 7
[0134] The wet pigment compositions obtained in Example 7 and
Comparative Examples 7a-7d were used to make inks.
[0135] Into a stainless vessel was added 300 parts of vanish for
planographic ink (manufactured by Toyo Ink Mfg. Co., Ltd., varnish
containing rosin-modified phenol resin) heated to 60.degree. C. and
100 parts of a powder pigment composition obtained, and a mill base
was prepared from them using a high shearing mixer. This mill base
was kneaded using triple roll. On the triple roll, 150 parts of
vanish for planographic ink (manufactured by Toyo Ink Mfg. Co.,
Ltd., rosin-modified phenol resin) and 10 parts of a solvent for
ink containing no aromatic were added to the base ink to prepare
ink.
[0136] Transparency, dispersibility and flowability of the ink
prepared by the above-mentioned method were measured. The results
are shown in Table 7.
[0137] Dispersibility of Ink
[0138] The prepared ink was color-developed in a grind gauge, and
positions on which three or more streaks appeared caused by a
fraction of a pigment material that was not dispersed are
represented in terms of 10 grade criterion starting from 0 in which
2.5 micron is represented by 1 unit.
7 TABLE 7 Sample No. Flowability Transparency Dispersibility Sample
7 100 9 1 Sample 7-a 60 6 4 Sample 7-b 50 3 7 Sample 7-c 120 6 3
Sample 7-d 80 5 5
Example 8
[0139] The wet pigment composition (Sample 5) obtained in Example 5
was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 8) containing a disazo
pigment.
Comparative Example 8a
[0140] The wet pigment composition (Sample 5a) obtained in Example
5a was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 8a) containing a disazo
pigment.
Comparative Example 8b
[0141] The wet pigment composition (Sample 5b) obtained in Example
5b was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 8b) containing a disazo
pigment.
Comparative Example 8c
[0142] The wet pigment composition (Sample 5c) obtained in Example
5c was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 8c) containing a disazo
pigment.
Comparative Example 8d
[0143] The wet pigment composition (Sample 5d) obtained in Example
5d was dried and ground at 90.degree. C. for 12 hours to obtain a
powder pigment composition (Sample 8d) containing a disazo
pigment.
Ink Making 8
[0144] The wet pigment compositions obtained in Example 8 and
Comparative Examples 8a-8d were used to make inks and evaluated.
The results are shown in Table 8.
8TABLE 8 Sample No. Flowability Transparency Dispersibility Sample
8 100 9 1 Sample 8-a 60 6 5 Sample 8-b 50 3 7 Sample 8-c 120 6 3
Sample 8-d 80 5 4
Example 9
[0145] A coupling reaction was allowed to progress in the same
manner as in Example 7 except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloro- anilide, 11.1 parts of
2-acetoacetylaminobenzoic acid and 12.7 parts of
acetoaceto-2-chloro-4-carbamoylanilide were dissolved in an aqueous
solution containing 120 parts of sodium hydroxide to prepare a
0.259 mol/l of coupler aqueous solution of 25.degree. C., which was
used in this example.
[0146] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition which was further dried and ground
at 90.degree. C. for 12 hours to obtain a powder pigment (Sample 9)
containing a disazo pigment.
Comparative Example 9a
[0147] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 7a except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide, 11.1 parts of
2-acetoacetylaminobenzoic acid and 12.7 parts of
acetoaceto-2-chloro-4-ca- rbamoylanilide were used to prepare a
coupler aqueous solution.
[0148] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition which was further dried and ground
at 90.degree. C. for 12 hours to obtain a powder pigment (Sample
9a) containing a disazo pigment.
Comparative Example 9b
[0149] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 7b except that 543 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide were used instead of 354
parts of acetoacetanilide to prepare a coupler aqueous
solution.
[0150] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition which was further dried and ground
at 90.degree. C. for 12 hours to obtain a powder pigment (Sample
9b) containing a disazo pigment.
Comparative Example 9c
[0151] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 7c except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide and 22.2 parts of
2-acetoacetylaminobenzoic acid were used to prepare a coupler
aqueous solution.
[0152] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition which was further dried and ground
at 90.degree. C. for 12 hours to obtain a powder pigment (Sample
9c) containing a disazo pigment.
Comparative Example 9d
[0153] A coupling reaction was allowed to progress in the same
manner as in Comparative Example 7d except that 515.9 parts of
acetoaceto-2,5-dimethoxy-4-chloroanilide and 25.5 parts of
acetoaceto-2-chloro-4-carbamoylanilide were used to prepare a
coupler aqueous solution.
[0154] The pigment slurry obtained was heated up to 80.degree. C.,
then, subjected to rosin treatment, filtration and purification to
obtain a wet pigment composition which was further dried and ground
at 90.degree. C. for 12 hours to obtain a powder pigment (Sample
9d) containing a disazo pigment.
Ink Making 9
[0155] The wet pigment compositions obtained in Example 9 and
Comparative Examples 9a-9d were used to make inks.
[0156] 20 parts of a powder pigment, 60 parts of a vehicle for
gravure ink containing nitrocellulose, 80 parts of a mixed solvent
(toluene:ethyl acetate:isopropyl alcohol=60:20:10) and 150 parts of
alumina beads were placed in a vessel and dispersed for 60 minutes
by a paint conditioner, then, 80 parts of a vehicle for gravure ink
containing a polyamide resin was added to this to prepare ink.
[0157] Transparency and flowability of the ink were measured. The
results are shown in Table 9.
[0158] Flowability of Ink
[0159] Flowability of the ink was measured by a Brookfield type
viscometer (B type viscometer). When a measured value is lower, the
flowability is better. Measured values are shown by percentage when
a measured value of the ink prepared from a powder pigment
composition of the example was represented by 100.
[0160] Transparency of Ink
[0161] Ink was color-developed on an acetate-based film using a bar
coater. Black paper is laminated on the rear surface of the film,
and appearance of the black paper was observed. When the black
paper was not seen at all from the front side of the developed
film, it was judged as opaque and visual judge was 1. When the
black paper could be seen clearly, it was judged as transparent and
visual judge was 10. The results are shown in terms of 10 grade
criterion by such a visual judge.
9 TABLE 9 Sample No. Flowability Transparency Sample 9 100 9 Sample
9-a 155 6 Sample 9-b 350 3 Sample 9-c 110 8 Sample 9-d 120 7
* * * * *