JPH11293139A - Red pigment wet cake composition, and lithographic ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red pigment wet cake composition comprising only a non-aggregating crystal type pigment, combinedly having improved dispersibility, excellent colorability and excellent transparency, and having a low water content, especially a red pigment wet cake composition smaller in load in waste water treatment and in a short in time for waste water treatment in a flush process in the preparation of a lithographic ink. SOLUTION: This red pigment wet cake composition comprises C.I. pigment red 57:1 whose surface may be treated with one of various kinds of surface- treating agents and which has a characteristic crystal structure having relatively strong diffraction strength at 2 θ (diffraction angle degrees) of 4.54±0.05 deg., 11.05±0.05 deg., 20.74±0.05 deg., and 25.44±0.05 deg., and has a water content of <=55 wt.% in the wet cake. The lithographic ink contains the wet cake composition and a vehicle for the ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic red ink, which exhibits improved dispersibility, tinting strength, and transparency, and a flash step when producing a base ink for lithographic ink. The present invention relates to an environment-friendly red pigment wet cake composition that reduces the utility and eliminates the need for wastewater treatment, and to a lithographic ink containing the composition.

[0002]

2. Description of the Related Art I. Pigment Red 57: 1
(Standard name: Brilliant Carmine 6B) is well known as a pigment.

Conventionally, C.I. I. Pigment Red 5
Since a 7: 1 red azo lake pigment wet cake has a water content of 70 to 80% by weight, a process of removing water by decantation (temporary dewatering process) is required in a flash process at the time of base ink production performed by an ink maker. This is a problem as a bottleneck in base ink productivity. Also, the wastewater generated by this decantation has a high COD and is colored red, so that wastewater treatment is required, which has been a major factor in increasing the cost of ink manufacturers.

In order to reduce the temporary dewatering step of the flash step, C.I. I. Pigment Red 57: 1 red azo lake pigment wet cake was partially dried using a Nauta mixer to produce a press cake having a water content of 55% by weight or less. However, when used in a lithographic ink, it exhibited poor performance in terms of dispersibility and coloring power.

This calcium azo lake pigment, when dried, has a 2θ (diffraction angle) of 4.86 in the X-ray diffraction diagram.
± 0.05, 18.36 ± 0.05, 18.74 ± 0.
05, 26.08 ± 0.05 and 27.38 ± 0.0
5 contained a characteristic crystal structure having a relatively high diffraction intensity (hereinafter referred to as β-type crystal).

[0006] As described above, it has been found that a wet cake of a calcium azo lake pigment whose water content has been reduced by partial drying becomes only β-type crystals or a mixture of other types with the β-type crystals. When used in the above, poor performance was exhibited in dispersibility, coloring power and transparency.

[0007] A method for producing a wet cake pigment having a low moisture content by partially drying is already known. For example, in JP-A-54-123140,
A wet cake having a water content of less than 35% by weight is shown, and JP-A-57-53568 discloses a wet cake having a water content of 20 to 50% by weight.
Although a 35% by weight wet cake is shown, all of these methods are partially dried, and thus C.I. I. Pigment Red 57: 1
It has been found that the calcium azo lake pigment composed of comprises a cohesive β-type crystal.

It is already known that β-type crystals are heat-stable, and β-type crystals are formed when heat is applied to more unstable crystals other than β-type crystals.

[0009]

However, C.I. which is composed of heat-labile crystals and has a moisture content of 55% by weight or less in the wet cake. I. Pigment Red 57: 1
Red pigment wet cake compositions are not previously known.

[0010] The present invention, when used to prepare a lithographic red ink, exhibits improved dispersibility, tinting strength and transparency, as well as a leap in the flashing process when producing a lithographic ink base ink. The present invention relates to an environment-friendly red pigment wet cake composition which can be shortened in time, reduces utility and does not require wastewater treatment.

In particular, in the flushing process when an ink maker manufactures a base ink, the problem of eliminating the temporary dewatering process, which is a bottleneck in productivity and is a source of wastewater with a large load, is eliminated. Is to solve.

[0012]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above-mentioned situation, and found that C.I. I. Pigment Red 57: 1, among several crystal forms other than β-form,
In the X-ray diffraction diagram, 2θ (diffraction angle °) 4.54 ±
0.05, 11.05 ± 0.05, 20.74 ± 0.0
5, and a characteristic crystal structure having a relatively strong diffraction intensity at 25.44 ± 0.05 (hereinafter referred to as α-type crystal).
Having C.I. I. Pigment Red 57: 1 is less likely to agglomerate than the same pigment of β-type crystal and has excellent dispersibility, and if the pigment surface is brought into contact with a surface treatment agent, when a heat load is applied later, Also found that the transition to β-type crystals became more difficult.

That is, in order to exhibit improved dispersibility, coloring power and transparency when used in a lithographic ink,
C. I. Pigment Red 57: 1 calcium azo lake pigment wet cake is composed of α-type crystals, and it has been found that it is necessary that pigments of cohesive β-type crystals are not mixed.

In order to eliminate the temporary dehydration step in preparing the lithographic ink, C.I. I. Pigment Red 57: 1 calcium azo lake pigment wet cake water content of 55% by weight or less.

In the case where the pigment particle surface is hydrophobic (non-polar) such as a phthalocyanine pigment, a wet cake having a water content of about 55 to 50% by weight has been relatively easily manufactured. A soluble monoazo pigment such as the azo lake pigment is difficult to remove water from the wet cake because the pigment particle surface is hydrophilic, and only
The wet cake composition in which the cohesive β-form crystals are mixed and the water content is 55% or less is obtained only by the partial drying.

An object of the present invention is to provide a wet cake having a calcium azo lake pigment of CI Pigment Red 57: 1, which has an α-type crystal, and has a moisture content of 55% or less. The problem is solved for the first time by using the “composition”.

That is, the present invention provides the following inventions.

(1) In the X-ray diffraction diagram, 2θ (diffraction angle °) 4.54 ± 0.05, 11.05 ± 0.05,
B. a wet cake having a characteristic crystal structure having relatively strong diffraction intensities of 20.74 ± 0.05 and 25.44 ± 0.05, comprising not more than 55% by weight of water in the wet cake; I. Pigment Red 57: 1 red pigment wet cake composition.

(2) C.I. I. Pigment Red 5
7: 1 was surface-treated with at least one surface treatment agent selected from the group consisting of rosin, low molecular surfactant, modified alkyd resin, and modified phenol resin. I. Pigment Red 57: 1.

(3) C.I. I. Pigment Red 5
7: 1 is at least one selected from the group consisting of strontium, aluminum, magnesium and zirconium
C. surface-treated with various metal salts I. Pigment Red 57: 1.

(4) A calcium lake obtained from a cobase consisting of an aromatic aminosulfonic acid which may have a substituent other than 2-amino-5-methylbenzenesulfonic acid and a coupler consisting of 2-hydroxynaphthoic acid. Azo pigment (X), calcium lake azo pigment (Y) obtained from a base composed of 2-amino-5-methylbenzenesulfonic acid and a cocoupler composed of a compound other than 2-hydroxynaphthoic acid, 2-amino-5-methyl Selected from the group consisting of calcium lake azo pigments (Z) obtained from a cobase consisting of an aromatic aminosulfonic acid optionally having a substituent other than benzenesulfonic acid and a cocoupler consisting of a compound other than 2-hydroxynaphthoic acid. Described in (1) above, further comprising a small amount of a calcium lake azo pigment to be used. Composition.

(5) C.I. I. Pigment Red 5
7: 1 was surface-treated with at least one surface treatment agent selected from the group consisting of light oils and fats and oils. I. Pigment Red 57: 1.

(6) The composition according to the above (1), wherein the wet cake has a water content of 20% by weight or more and 50% by weight or less.

(7) C.I. I. Pigment Red 5
7: 1, an azo dye comprising a reaction product of 2-amino-5-methylbenzenesulfonic acid cyazonium salt and 2-hydroxynaphthoic acid is subjected to calcium lake formation in the presence of rosin to form an aqueous suspension. C. obtained under acidic conditions. I. Pigment Red 57: 1.

(8) C.I. I. Pigment Red 5
After adding a mixed solvent of a hydrophobic solvent and an oxidized aliphatic hydrocarbon solvent to an aqueous dispersion of 7: 1, removing part or all of the solvent, and filtering the dispersion, α-type crystals, And,
C. having a moisture content of 55% by weight or less; I. Pigment Red 57: 1 A method for producing a red pigment wet cake composition.

(9) C.I. I. Pigment Red 5
7: 1 is a surface treating agent, and C.I. I. Pigment Red 57: 1.

(10) The method according to the above (9), wherein the surface treatment agent is at least one surface treatment agent selected from the group consisting of rosin, low molecular surfactant, modified alkyd resin and modified phenol resin.

(11) The method according to the above (9), wherein the surface treating agent is at least one metal salt selected from the group consisting of strontium, aluminum, magnesium and zirconium.

(12) The method according to the above (9), wherein the surface treatment agent is at least one type of surface treatment agent selected from the group consisting of light oils and fats and oils.

(13) Non-surface treatment C.I. I. Pigment Red 57: 1, with the surface treatment agent being used in an amount of 5.0 to 35.0 parts by weight per 100 parts by weight of CI Pigment Red 57: 1. I. Pigment Red 57: 1, the production method according to the above (9), (10), (11) or (12).

(14) A method for producing an anhydrous concentrated coloring vehicle for ink, comprising mixing the composition of the above (1) with a vehicle for ink, performing a flushing treatment, and then immediately heating and dehydrating.

(15) An aqueous concentrated coloring vehicle for ink, in which the composition of the above (1) and a vehicle for ink are mixed and flushed, and then heated and dewatered immediately without separation of temporary wastewater. Production method.

(16) The composition of the above (1) and a vehicle for ink are mixed and subjected to a flushing treatment, followed by immediate heating and dehydration to produce an anhydrous vehicle for ink having a high pigment concentration, and then a vehicle for ink. The method of manufacturing ink to dilute it.

(17) The above (1), (2), (3),
A lithographic ink comprising the wet cake composition according to (4), (5) or (6) and an ink vehicle.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The composition of the present invention has an X-ray diffraction pattern
2θ (diffraction angle °) 4.54 ± 0.05, 11.05 ±
0.05, 20.74 ± 0.05, and 25.44 ±
C. a wet cake having a characteristic crystal structure having a relatively high diffraction intensity of 0.05, and having a moisture content of 55% by weight or less; I. Pigment Red 57: 1 is a red pigment wet cake composition.

In the present invention, C.I. I. Pigment Red 57: 1 is an α-type crystal. Then, it may be that the surface is not surface-treated with a surface-treating agent or may be surface-treated, but when used for preparing an ink, the surface-treated C.I. I. Pigment Red 57: 1 is preferred.

In the composition of the present invention, the water content in the wet cake may be 55% by weight or less, but the water content in the wet cake is preferably 20 to 50% by weight in that the flushing time can be further shortened. Are preferred. When the water content is within this preferred range, the time required for flushing in the flushing step at the time of ink preparation can be greatly reduced. For flushing,
Details will be described later.

Surface-treated C.I. I. Pigment Red 57: 1 As a surface treatment agent for obtaining an α-type crystal,
The following are exemplified. (I) at least one surface treatment agent selected from the group consisting of rosin, low molecular surfactants, modified alkyd resins, and modified phenolic resins.

(Ii) At least one selected from the group consisting of strontium, aluminum, magnesium and zirconium for the purpose of improving the water resistance and dispersibility of the pigment.
Seed metal salts.

(Iii) At least one surface treating agent selected from the group consisting of higher alcohols and polymeric surfactants for the purpose of improving the fluidity of flash bases and planographic inks.

(Iv) At least one surface treating agent selected from the group consisting of light oils and fats and oils, which is a component of the lithographic ink, for the purpose of making the particle surface of the pigment lipophilic. With this surface treatment agent, it is possible to further reduce the water content of the wet cake composition.

The above-mentioned rosin includes known rosins,
Examples include wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, maleated rosin, and the like. As the low molecular surfactant, there is known one having a molecular weight of 1000 or less, and examples thereof include an anionic surfactant, a cationic surfactant, and a nonionic surfactant. As the modified alkyd resin, for example, linseed oil, tung oil, alkyd resin containing an unsaturated double bond based on a non-drying oil such as soybean oil in the molecule, or a dry oil-based alkyd resin and the non-drying oil Mixtures are mentioned. Examples of the modified phenol resin include rosin-modified phenol resin.

Examples of the strontium salt, aluminum salt, magnesium salt and zirconium salt include strontium chloride, strontium bromide, strontium hydroxide, strontium carbonate, aluminum hydroxide, aluminum chloride, aluminum nitrate, magnesium chloride,
Examples include magnesium hydroxide, magnesium nitrate, magnesium phosphate, zirconium chloride, zirconium phosphate and the like.

As higher alcohols, those having 10 carbon atoms
The above are mentioned, for example, lauryl alcohol, tridecanol, cetyl alcohol, isootadecanol and the like. As the polymer surfactant, there is a known and commonly used polymer having a molecular weight of more than 1000, for example,
12-hydroxystearate with a molecular weight of 100
Solsperse 3000 (ZENEC) equivalent to 0 to 3000
A), a block copolymer of polyoxyethylene polyoxypropylene, Pluronic L-101 having a molecular weight of 3000 (manufactured by Asahi Denka Kogyo Co., Ltd.), molecular weight of 1,000
Zero or more water-soluble cellulose ethers, Metrolose S
H-60 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

As the light oil, a light oil having a boiling point of 230 to 350 ° C. which may contain an aromatic component, for example, having a boiling point range of 26
AF-7 (manufactured by Nippon Oil Co., Ltd.), a dearomatic solvent having a temperature of 0 to 281 ° C., and a mixture of α-olefins having a boiling point range of 270 to 310 ° C., dialen 168 (manufactured by Mitsubishi Chemical Corporation), and 90% or more IP Solvent 2835 (produced by Idemitsu Petrochemical Co., Ltd.) containing a paraffin component and having a boiling range of 271 to 338 ° C. No. 5 solvent having a boiling point range of 276 to 313 ° C. containing 20 to 30% of an aromatic component (Nippon Oil Co., Ltd.) And Naphthesol H (manufactured by Nippon Oil Co., Ltd.) containing 70% or more of a naphthene component and having a boiling range of 246 to 276 ° C. Examples of oils and fats include linseed oil, soybean oil, tung oil, safflower oil, castor oil and the like.

Examples of such a surface treatment include a method in which an azo dye is converted into a calcium lake in the presence of a surface treatment agent, and a method in which an unsurface-treated lake azo pigment is surface-treated with a surface treatment agent. Surface treatment can also be performed by using two or more different surface treatment agents in combination. Azo dyes first
And then subjecting the surface-treated lake azo pigment to a surface treatment with a second surface treating agent to obtain a multi-surface treated lake azo pigment.

C. not subjected to surface treatment I. Pigment Red 57: 1 The surface treatment amount of (i) to (iv) to the calcium azo lake pigment composed of an α-type crystal may be appropriately adjusted according to the type of the surface treatment agent used. For example, 5.0 to 3 per part by weight
Preferably, the amount is 5.0 parts by weight.

The surface treatment with or without the surface treatment agent may be C.I. I. Pigment Red 57:
The composition of the present invention comprising the α-type crystal of the present invention may be used in combination with, for example, a known and commonly used cobase (component) or cocoupler (component). I. Pigment Red 57: 1 A calcium lake azo pigment having another chemical structure other than the α-type crystal and β-type crystal may be included in the composition of the present invention in a small amount.

Such a C.I. I. Pigment Red 5
Examples of the calcium lake azo pigment having another chemical structure other than the 7: 1 α-type crystal and β-type crystal include the following.

(X) A calcium lake obtained from a cobase consisting of an aromatic aminosulfonic acid which may have a substituent other than 2-amino-5-methylbenzenesulfonic acid and a coupler consisting of 2-hydroxynaphthoic acid. Azo pigment.

(Y) A calcium lake azo pigment obtained from a base comprising 2-amino-5-methylbenzenesulfonic acid and a cocoupler comprising a compound other than 2-hydroxynaphthoic acid.

(Z) A copolymer obtained from a cobase comprising an aromatic aminosulfonic acid which may have a substituent other than 2-amino-5-methylbenzenesulfonic acid and a cocoupler comprising a compound other than 2-hydroxynaphthoic acid. Calcium lake azo pigments selected from the group consisting of calcium lake azo pigments (Z).

These can be used for controlling the hue and the crystal particle diameter.

Such a C.I. I. Pigment Red 5
The content of the calcium lake azo pigment having a different chemical structure in the composition other than the 7: 1 α-type crystal and the β-type crystal in the composition is not particularly limited as long as it is a small amount. 1.0 to 20.
It is preferably in the range of 0 parts by weight.

C. not surface-treated with a surface treating agent
I. Pigment Red 57: 1 can be manufactured by a known and commonly used manufacturing method. Specifically, first, 2-amino-5-methylbenzenesulfonic acid, which is a base (component), is reacted with hydrochloric acid and nitrite, and the corresponding diaminonium 2-amino-5-methylbenzenesulfonic acid is reacted. Get the salt. Next, under basic conditions, this is reacted with 2-hydroxynaphthoic acid as a coupler (component) to obtain an azo dye (coupling reaction).

Next, the azo dye is reacted with a known and commonly used calcium salt to obtain a calcium azo lake pigment (lake reaction).

The thus obtained calcium azo lake pigment is C.I. I. Pigment Red 57: 1, a typical example of which is represented by the following general formula 1.

Formula 1

[0060]

Embedded image

The surface treatment may be performed simultaneously with the formation of the calcium lake azo pigment by including the required amount of the surface treatment agent between the coupling reaction and the lake formation reaction. Alternatively, a co-coupler (component) may be used in combination with the coupler (component) during the coupling reaction, or a co-base (component) may be used in combination with the base (component). I. Pigment Red 57: 1 α
A calcium lake azo pigment having a different chemical structure than the type crystal and β type crystal may be included in the composition in a small amount. Of course, these methods can be employed in combination.

In a process for producing a calcium lake azo pigment, an example of a method of obtaining a suspension of the pigment in water in the presence of a surface treating agent in any reaction step before lake formation is as follows. There are various methods.

C. I. Pigment Red 57: 1 α
Calcium azo lake pigment composed of a type crystal is generally treated with rosin, but further, dialkyl sulfosuccinate is magnesium, strontium,
A method in which a metal salt is precipitated with a non-alkali metal such as aluminum on the surface of the pigment (Japanese Patent Publication No. 47-45410).
JP-A-54-7287), kneading a middle or higher fatty acid such as stearic acid or lauric acid or a metal salt thereof together with a pigment to prepare an easily disintegrable granular pigment.
Also, by adding a primary or secondary amine having an alicyclic group in a pigment dispersion and heating and stirring at 50 to 100 ° C., to produce a pigment that is easily dispersed in an organic liquid medium or an aqueous medium. Pigment processing method (JP-A-46-3234)
No. 3), by adding a long-chain aliphatic amine in an amount equivalent to 8 to 25% by weight in the form of a free amine to a water-moist pigment, improved in organic solvents, varnishes and other pigment carriers. Method for imparting dispersibility (Japanese Patent Publication No. 48-18
No. 21), a method of adding a nonionic surfactant such as cholesterine, lanosterin, agnosterin, lanopalmitic acid to a dye / pigment to impart a high degree of dispersibility in a vehicle (Japanese Patent Publication No. 53-3408). A method of treating such an activator, or a modified rosin,
A method of manufacturing a pigment which is partially softened and adsorbed by adding a resin such as alkyd and an inorganic salt such as sodium chloride and sodium carbonate, and then salt-milling the resin to disperse it extremely well in an organic material (Japanese Patent Publication No. Sho 46) -6719), a method of producing a cellulose-containing preparation by adding ethyl cellulose to a pigment moistened in water and milling the mixture under an organic solvent (Japanese Patent Publication No. 47-19513).
A method in which a thermoplastic resin that can be solubilized in water-moistened pigment is treated in the presence of a basic substance such as sodium hydroxide to produce an easily dispersible non-dust pigment (Japanese Patent Publication No. 57-57).
It is also possible to perform a resin treatment as disclosed in Japanese Patent No. 49664).

The amount of the surface treatment agent used in the method of obtaining a suspension in water of the pigment in the presence of the surface treatment agent in any reaction step before lake formation is usually determined by the amount of each component constituting the pigment. 5.0 to 35.0 per 100 parts by weight of total weight
It is in the range of parts by weight. More specifically, azo dye 100
It is in the range of 6.0 to 40.0 parts by weight per part by weight.

For lithographic inks, C.I. I. Pigment Red 57: 1 α-type crystal, at least C.I. I. Pigment Red 5
A 7: 1 α-form crystal is preferred. This is obtained, for example, by performing calcium lake in the presence of rosin on an azo dye obtained after the coupling reaction and comprising a reaction product of 2-amino-5-methylbenzenesulfonic acid diazonium salt and 2-hydroxynaphthoic acid. I can do it.

In a method for obtaining an aqueous dispersion of the pigment in the presence of rosin as a surface treatment agent before the lake reaction of the corresponding azo dye obtained after the coupling reaction, a calcium salt is added. Preferably, the system is acidified by performing a calcium lake.

The cobase (component) comprising an aromatic aminosulfonic acid which may have a substituent other than the above 2-amino-5-methylbenzenesulfonic acid includes, for example, 1-amino-4-chloro- 5-methylbenzene-2-
Sulfonic acid, 1-aminonaphthalene-2-sulfonic acid,
6-amino-4-chloro-m-toluenesulfonic acid, 4
-Amino-2-chloro-p-toluenesulfonic acid, 4-
Amino-o-toluenesulfonic acid, tobias acid and the like. Examples of co-couplers (components) composed of compounds other than 2-hydroxynaphthoic acid include 2-hydroxynaphthoic acid amide, β-naphthol, and naphthol A.
S, acetoacetanilide and the like. They are,
It can be used to control hue and crystal particle size.

The present inventors have developed C.I.
I. Pigment Red 57: 1 The calcium azo lake pigment wet cake was intensively studied to reduce the water content to 55% by weight or less without a drying step. An example of an effective method found as a result is given below, but is not limited thereto.

That is, C.I. I. After adding a hydrophobic solvent and an oxygenated aliphatic hydrocarbon solvent to an aqueous dispersion of Pigment Red 57: 1, it is effective to remove a part or all of the solvent and filter the dispersion. . C. I. Pigment Red 57: 1 has a strongly hydrophilic surface, so even if the pigment content is immediately filtered from the aqueous dispersion without adding these solvents, a wet cake composition having a water content of 55% by weight or less is obtained. Cannot be obtained, and only a wet cake having a higher moisture content can be obtained. By performing the above operation, the α-type crystal was obtained and the water content was 55% by weight.
The following C.I. I. Pigment Red 57: 1 was found to be easily obtained.
More specifically, for example, the following method is used.

The azo dye is laked with a calcium salt in water to give C.I. I. Pigment Red 57: 1
After synthesizing an aqueous dispersion of the calcium azo lake pigment of the above, after adding a hydrophobic solvent and an oxygenated aliphatic hydrocarbon solvent having an affinity for water to the aqueous dispersion of the pigment (pigment slurry), Usually, stirring and heating are performed, and the pigment is flushed into the solvent at one end.

Examples of the hydrophobic solvent used herein include aromatic solvents such as toluene, xylene, styrene, and dimethylstyrene; paraffin solvents such as hexane and heptane; olefin solvents such as 1-tetradecene and 1-octadecene; Examples include naphthenic solvents such as ethylcyclohexane and bicyclohexane, and terpene solvents such as α-pinene, limonene and dipentene.

Examples of the oxygenated aliphatic hydrocarbon solvent include alcohols, ketones, ethers and esters. Alcohols include methanol, ethanol, isopropanol, n-propanol, n-
Butanol, isobutyl alcohol, cyclohexyl alcohol, n-pentanol, tert-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, hexyl glycol, pentaerythritol, 2-
Butene-1,4-diol, N, N-dimethylethanolamine, etc., ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl hexanone, ethers: diethyl ether, methyl vinyl ether, isobutyl vinyl ether isopropyl ether, methyl phenyl ether Etc., and esters such as methyl acetate,
Examples include ethyl acetate and isoamyl acetate.

The hydrophobic solvent and the oxygenated aliphatic hydrocarbon solvent can be used in the form of a mixed solvent obtained by mixing them in advance.

C. I. Pigment Red 57: 1 aqueous dispersion, the total amount of the hydrophobic solvent and the oxygenated aliphatic hydrocarbon solvent is not particularly limited, but the latter solvent is used in an amount of 15.0 to 150.000 per 100 parts by weight of the former pigment. It is preferably 0 parts by weight. The weight ratio (weight ratio) between the hydrophobic solvent and the oxygenated aliphatic hydrocarbon solvent is usually 1/4 to
10/1.

A method of obtaining a multi-surface-treated lake azo pigment by subjecting the azo dye to calcium lake formation in the presence of a first surface-treating agent and then surface-treating the surface-treated lake azo pigment with a second surface-treating agent. As one, a rosin surface-treated calcium lake azo pigment, for example, a surface-treated lake azo pigment obtained by calcium-lacking an azo dye in the presence of rosin, is further surface-treated with a specific oxygenated aliphatic hydrocarbon solvent to form a multi-surface. There is also a method of obtaining a treated lake azo pigment.

In this case, for example, in performing the surface treatment of the lake azo pigment, a higher alcohol such as tridecanol exemplified as a surface treatment agent is selected and used as the specific oxygenated aliphatic hydrocarbon solvent. can do.

When the rosin-treated calcium lake azo pigment is stirred and heated with a hydrophobic solvent and an oxygenated aliphatic hydrocarbon solvent composed of a lower alcohol such as isobutanol having a very small surface treatment effect. Is a single surface treatment of rosin alone, but if a hydrophobic solvent is used and the same amount or a smaller amount of tridecanol (that is, the amount used as a surface treatment agent) is used instead of the lower alcohol, rosin And a higher alcohol can be obtained.

Similarly, when a lower alcohol is used and the same amount or a smaller amount (ie, the amount used as a surface treatment agent) of light oil is used instead of the hydrophobic solvent such as xylene, rosin and light oil are used. And a double surface treated lake azo pigment.

Of course, in these methods, only one surface treatment is performed,
It can also be used when performing surface treatment with higher alcohol or light oil.

A part or all of the solvent is removed from the thus obtained aqueous dispersion of the pigment containing the solvent.

Next, a part or all of the solvent is recovered by steam distillation to obtain a water-rich aqueous dispersion (aqueous slurry) of the pigment again. After filtering this aqueous dispersion and filtering off the pigment component, usually, inorganic salts and impurities are washed. When the water is sufficiently squeezed while not being dried, an azo lake pigment wet cake composition having a water content of 55% by weight or less is obtained. When immediately filtering off the pigment content from the aqueous dispersion without adding these solvents, the wet cake composition having a water content of 55% by weight or less is similarly used, even if the water content is carefully squeezed so as not to dry. No product can be obtained, and only a wet cake with a higher moisture content can be obtained.

In the present invention, when the above-mentioned heating and stirring are carried out using a hydrophobic solvent and an oxygenated aliphatic hydrocarbon solvent having no or little effect on the pigment surface treatment, any of these solvents can be used. It is preferable to collect all.

As a method for removing the solvent, azeotropic distillation regardless of steam distillation, or a method by filtration and washing may also be used. In any case, it is preferable to select conditions so that the crystal form does not change to the β form. Although various methods can be considered as a technical method for reducing the water content to 55% by weight or less, in the present invention, a conventional method is employed in which the pigment surface is directly heated to a high temperature to partially dry the pigment surface. Instead of using the method of reducing the water content, even if heating that can induce the transition to the β-form is performed, the heating is performed via a medium such as a liquid medium to directly induce the transition to the β-form. By not heating, maintain the α-type, and dehydrate,
As a result, it has been found that it is preferable to form an array of crystals in which the pigment is rapidly dispersed in the vehicle. According to the preferred method for producing the composition of the present invention, the composition of the present invention does not substantially undergo a heat history such that a crystal form other than the β form is transformed into the β form in the step of obtaining the composition. X-ray analysis of the wet cake of the calcium azo lake pigment obtained by this method showed that the crystal conversion to β-type crystals was suppressed and α-type crystals were confirmed.

A lithographic ink can be prepared using the wet cake composition of the present invention. This lithographic ink is
It comprises the wet cake composition of the present invention and a vehicle for ink.

As the vehicle for the ink, any known and commonly used vehicles can be used, and examples thereof include modified alkyd resins, modified phenol resins, and petroleum resins. Also, a mixture of a saturated alkyd resin and a drying oil or a mixture of rosin and a phenol resin can be used. In preparing the ink, a solvent such as n-paraffin, isoparaffin, aromatic, naphthene, or α-olefin is usually used in combination. Vegetable oils such as linseed oil, tung oil, soybean oil and the like can be further used as needed.

These are usually used in vehicles for inks 20 to
It is prepared so as to be 50% by weight, 10 to 60% by weight of the above-mentioned solvent such as paraffin, and 0 to 30% by weight of vegetable oil.

From the composition of the present invention, an ink can be prepared, for example, as follows. First, the ink is mixed with an ink vehicle, flushed, and then immediately heated and dehydrated, so that it contains no water and has a higher pigment concentration than the final ink. (Anhydrous vehicle).

In the composition of the present invention, the colored primary waste water having a high COD is not generated after the flanking treatment.
For example, the conventional secondary dewatering step, that is, the heat dehydration, can be performed without performing the operation of separating the primary drainage such as decantation, which has been conventionally performed.

In the case where a conventional wet cake composition comprising an α-type crystal pigment is obtained without contacting the hydrophobic solvent and the oxygenated aliphatic hydrocarbon solvent as described above,
It is more difficult to reduce the water content than when contacting them. The α-type crystal is subjected to a water separation operation such as decantation and a secondary dehydration step, regardless of the presence or absence of the contact treatment with the hydrophobic solvent and the oxygenated aliphatic hydrocarbon solvent.徐 々 に gradually transitions to β-type crystal. In the case of a wet cake composition having a water content of more than 55% by weight, although a decanting operation is required, the dispersibility and the dispersibility of the lithographic ink obtained by flushing using a β-type crystal pigment having strong aggregation are improved. It is more excellent in coloring power and transparency.

In the present invention, even if the heating that can induce the transition to the β-form is performed, the direct heating that induces the transition to the β-form is performed through a medium such as a liquid medium. By maintaining the α-form and dehydrating so that the water content is 55% by weight or less, a composition having a crystal arrangement in which the pigment is rapidly dispersed in the vehicle is provided. is there.

Accordingly, the dispersibility of the β-type crystal in the vehicle for ink and the like is much better than the dispersibility in the same vehicle as obtained by heating and partially drying the pigment surface. . Only after the step of mixing with the ink vehicle and heating and dehydrating (secondary dehydrating step), the α-type crystal form becomes β
It can only transfer to the mold. In the case where the α-form was stably dispersed in the ink vehicle, when the crystal form was changed to β-form in the vehicle in this heating and dehydration step due to heat history, the dispersibility was initially excellent. It is possible to maintain stable dispersion stability.

The ink-free vehicle having a high pigment concentration is then diluted with an ink vehicle to produce an ink having a required hue at a predetermined pigment concentration.

In any step of preparing the ink, known and commonly used additives such as a curing accelerator and a leveling agent can be used in combination.

In the present invention, when the above-mentioned calcium azo lake pigment wet cake was used for flashing according to a conventional method, the primary dehydration step was omitted, and a flash base could be produced. Is
Excellent dispersibility, coloring power and transparency were exhibited. Details of these will be described in Examples.

[0095]

The present invention will be described below in detail with reference to examples. Hereinafter, unless otherwise specified, "parts" are parts by weight,
"%" Is% by weight.

Example 1 After dispersing 20.0 parts of 2-amino-5-methylbenzenesulfonic acid in 200 parts of water, 22.0 parts of 20% hydrochloric acid was added.
While maintaining the temperature at 0 ° C., 25.1 parts of a 30% aqueous sodium nitrite solution was added dropwise to obtain a diazo liquid. Next, 20.6 parts of 2-hydroxynaphthoic acid was dispersed in 242 parts of water at 60 ° C.
11.5 parts of a 1% aqueous solution of caustic soda was added to obtain a coupler solution. The coupler solution was cooled to 0 ° C., and the above diazo solution was added dropwise with stirring, and the mixture was stirred at 0 ° C. for 60 minutes to terminate the coupling reaction. Then, 40 parts of a 10% rosin soda aqueous solution was added, and the mixture was stirred for 60 minutes. To obtain a suspension.

A solution obtained by dissolving 18.6 parts of calcium chloride in 70 parts of water was added to the suspension, and the mixture was stirred for 60 minutes to complete the lake formation reaction. After the lake formation reaction is completed,
The mixture was stirred while heating for 1 minute to obtain a suspension of calcium lake azo pigment (CI Pigment Red 57: 1) in water.

Xylene (hydrophobic solvent) 25
And a mixed solvent consisting of 50 parts of isobutanol (lower alcohol) and stirring at 80 ° C. for 2 hours. Next, the solvent was distilled off and collected in 40 minutes by steam distillation, and the aqueous suspension was formed again. This suspension was filtered, washed, and dehydrated while being careful not to dry it, to obtain 98 parts of a wet cake of a calcium lake azo pigment having a water content of 49%. As a result of measuring the X-ray diffraction of this cake, 2θ = 4.
Α-type crystals having relatively strong diffraction intensities at 56, 11.08, 20.76 and 25.46.

After 150 parts of the lithographic ink vehicle was placed in a 1 L test flasher and kept at 60 ° C., 196 parts (100 parts of pigment) of this wet cake was added and flushed. Since there was no primary drainage and there was no need for decantation (the primary dehydration step was omitted), decompression heating dehydration (referred to as a secondary dehydration step) was started immediately. After the completion of the dehydration under reduced pressure, a lithographic base ink was prepared by a dilution operation using 125 parts of a vehicle and 10 parts of light oil.

Comparative Example 1 (General flash method) A wet cake (water content: 71.5%) was obtained according to a synthesis method according to Example 1 without solvent treatment. As a result of measuring the X-ray diffraction of this cake, 2θ = 4.54, 11.06, 2
Α having relatively strong diffraction intensity at 0.74, 25.44
It was a type crystal.

350.9 parts of this cake and vehicle 150
Flashing was performed at 60 ° C. using a part. as a result,
Primary wastewater 1 which was flushed in 25 minutes and stained red
50 parts (COD 2000 ppm) resulted. This primary wastewater is removed by decantation (primary dehydration step),
Next, vacuum dehydration (secondary dehydration step) was performed for 1 hour to completely flush. A base ink was prepared by the same dilution operation as in Example 1.

Comparative Example 2 The wet cake synthesized in Comparative Example 1 was semi-dried to a water content of 50% and measured by X-ray diffraction. As a result, 2θ = 4.57.
4.86, 11.06, 18.37, 18.74, 2
At 0.74, 25.46, 26.10, and 27.37, α-type and β-type having relatively strong diffraction intensity were mixed.
When a flush according to Example 1 was performed using this cake, no primary drainage occurred. Immediately thereafter, dehydration by heating under reduced pressure was performed immediately, and a base ink was prepared by the same dilution operation as in Example 1.

Example 2 The suspension in water at 80 ° C. before the solvent treatment in Example 1 was added to
A solution prepared by dissolving 1.0 part of strontium chloride in 50 parts of water was added to obtain a strontium-treated solution.
For a minute. Next, the treatment liquid after stirring was adjusted with a 10% aqueous hydrochloric acid solution to adjust the pH to 9.8.

In addition, 4.8 aluminum chloride hexahydrate was added.
A part of the solution was dissolved in 20 parts of water to obtain an aluminum salt-treated solution, and the pH was adjusted to 5.8 with a 5% aqueous sodium hydroxide solution, followed by stirring for 30 minutes.

Further, a mixed solvent treatment was carried out according to Example 1.
Steam distillation, followed by filtration, washing and dehydration were performed to obtain 90 parts of a cake having a water content of 43%. As a result of measuring the X-ray diffraction, 2θ = 4.56, 11.02, 20.71, 2
It was an α-type crystal having a diffraction intensity of 5.40.

The same flushing as in Example 1 was carried out using 175 parts of this cake (100 parts of pigment). as a result,
The flush was completed instantaneously and there was no primary drainage (the primary dehydration step was omitted). Subsequently, similarly to the first embodiment,
After the secondary dehydration step, the base ink was diluted.

Example 3 The procedure of Example 1 was followed except that 2.5 parts of AF-7 (light oil manufactured by Nippon Oil Co., Ltd.) was added immediately after the completion of the lake-forming reaction. The water content of 80.7 parts of the obtained cake was 38.1.
%, And as a result of measuring X-ray diffraction, 2θ = 4.54;
It was an α-type crystal having diffraction intensities of 11.03, 20.72 and 25.46.

Also, as a result of flashing,
The operation was completed instantaneously, and no primary drainage occurred at that time. Subsequently, dilution after secondary dehydration was performed in the same manner as in Example 1.

Example 4 Immediately after the completion of the lake formation reaction, Surfynol 61 (Ai
r Productsand Chemicals, I
nc. Example 1 except that 2.5 parts of a nonionic low molecular weight surfactant having a molecular weight of about 100) and 2.5 parts of heptane and methyl isobutyl ketone were used in place of xylene and isobutanol, respectively. According to. The water content of 76.9 parts of the obtained cake was 35%, and as a result of measuring X-ray diffraction, 2θ = 4.56 and 11.
Α-type crystals having diffraction intensities of 05, 20.74 and 25.48.

Also, as a result of flashing,
The operation was completed instantaneously, and no primary drainage occurred at that time. Subsequently, dilution after the secondary dehydration step was performed in the same manner as in Example 1.

Example 5 After completion of the lake-forming reaction, 2.25 parts of Hariphenol 511 (Rosin-modified phenolic resin manufactured by Harima Kasei Co., Ltd.), 1.1 parts of linseed oil and 1.65 parts of No. 5 solvent were heated and dissolved. All procedures were as in Example 1, except that 5 parts of vehicle were added. The moisture content of 76.5 parts of the obtained cake was 29%, and as a result of measuring X-ray diffraction, 2θ = 4.
Α-type crystals having diffraction intensities of 53, 11.08, 20.77, and 25.43.

As a result of flashing, the first embodiment
The operation was completed instantaneously, and no primary drainage occurred at that time. Subsequently, dilution after the secondary dehydration step was performed in the same manner as in Example 1.

Examples 6, 7, 8, 9, 10, 11, 12 All of the same procedures as in Example 1 were carried out except that a small amount of cobase (component) and cocoupler (component) were further treated to make calcium chloride 18.7 parts. A wet cake was prepared according to the same procedure and the same flash as in Example 1 was performed.

As a result, 6, 7, 8, 9, 10, 11,
In all 12, there was no primary drainage.

Table 1 below summarizes the throughput of the cobase (component) and the cocoupler (component), the water content of the obtained cake, and the results of X-ray diffraction measurement.

However, in Table 1, regarding the cobase (component) used, 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid is referred to as (A), hereinafter referred to as 1-aminonaphthalene-2-sulfonic acid. (B), 6-amino-4-chloro-m-toluenesulfonic acid (C), 4-amino-2-
Chlor-p-toluenesulfonic acid (D), 4-amino-
It was described as o-toluenesulfonic acid (E). Similarly, in Table 1, β-naphthol was defined as (a), naphthol AS (b) and acetoacetanilide (c) with respect to the cocoupler (component).

[0117]

[Table 1]

[0118]

[Table 2]

In each of the wet cake compositions of the calcium lake azo pigments obtained in the examples, C.I. I. Pigment Red 57: 1 component consisted of only α-form.

Test Example 1 66 parts of the prepared base ink, 34 parts of the vehicle in Example 5 and a total of 34 parts of No. 5 solvent were kneaded with three rolls to obtain a lithographic dark ink having a tack of 8.0. .

(Dispersibility) The dispersibility of each dark ink was evaluated using a grind gauge. In contrast to Comparative Examples 1 and 2, Examples 1 to 12 had excellent dispersion. ：: good △: slightly good ×: poor

(Transparency) The transparency of each dark color ink was visually determined. Except for Comparative Example 2, the results were almost the same.
：: good ×: poor

(Tinting Power) A light-colored ink was prepared by mixing 0.1 part of each base ink and 2.0 parts (titanium oxide) of a white ink. Gretag Limited
As a result, it was as good as Comparative Example 2 except that it was inferior. The evaluation results are summarized in Table 2 below.
：: good ×: poor

[0124]

[Table 3]

[0125]

Since the composition of the present invention contains only α-type crystals and has a water content of 55% by weight or less, the flash step for producing a base ink for lithographic ink is drastically shortened, and utility of the composition is reduced. An environmentally friendly product that not only reduces wastewater but also reduces wastewater load has been realized. The lithographic ink obtained by using this base ink exhibited excellent dispersibility, coloring power and transparency.

Claims (7)

[Claims] 1. In an X-ray diffraction diagram, 2θ (diffraction angle °) 4.54 ± 0.05, 11.05 ± 0.05, 2
Having a characteristic crystal structure with relatively strong diffraction intensity at 0.74 ± 0.05, and 25.44 ± 0.05,
The wet cake has a moisture content of 55% by weight or less,
C. I. Pigment Red 57: 1 red pigment wet cake composition. 2. C. I. Pigment Red 57: 1
But rosin, low molecular surfactant, denatured alkyd resin,
C. surface-treated with at least one surface treating agent selected from the group consisting of modified phenolic resins. I. Pigment Red 57: 1. 3. C. I. Pigment Red 57: 1
Is surface-treated with at least one metal salt selected from the group consisting of strontium, aluminum, magnesium and zirconium. I. Pigment Red 5
The composition of claim 1, wherein the composition is 7: 1. 4. A calcium lake azo obtained from a cobase consisting of an aromatic aminosulfonic acid which may have a substituent other than 2-amino-5-methylbenzenesulfonic acid and a coupler consisting of 2-hydroxynaphthoic acid. Pigment (X), calcium lake azo pigment (Y) obtained from a base composed of 2-amino-5-methylbenzenesulfonic acid and a cocoupler composed of a compound other than 2-hydroxynaphthoic acid, 2-amino-5-methylbenzene It is selected from the group consisting of a calcium lake azo pigment (Z) obtained from a cobase consisting of an aromatic aminosulfonic acid which may have a substituent other than sulfonic acid and a cocoupler consisting of a compound other than 2-hydroxynaphthoic acid. The composition of claim 1 further comprising a small amount of a calcium lake azo pigment. 5. The method according to claim 5, I. Pigment Red 57: 1
Is surface-treated with at least one surface treatment agent selected from the group consisting of light oils and fats and oils. I. Pigment Red 57: 1. 6. The composition according to claim 1, wherein the water content in the wet cake is from 20% by weight to 50% by weight. 7. A lithographic ink comprising the wet cake composition according to claim 1, and a vehicle for an ink.