JP4759966B2 - Method for producing monoazo lake pigment composition - Google Patents

Description

  In the present invention, a dispersibility in a medium to be colored is good and a highly glossy colored product can be obtained. I. The present invention relates to a monoazo lake pigment composition containing Pigment Red 48: 3 as a main component and a method for producing the same.

  The red monoazo lake pigment called Permanent Red 2B or Watching Red consists of a substance represented by the following general formula.

  As the monoazo lake pigment, a pigment having a different hue depending on the type of the metal atom (Me) to be laked is marketed. Specifically, C.I. I. Pigment Red 48: 3 is a monoazo lake pigment having a lake metal atom of strontium (Sr) in the above general formula. I. Pigment Red 48: 2 is a monoazo lake pigment having a lake metal atom of calcium (Ca) in the above general formula. And since these all have good solvent resistance, they are used for the production of printing inks such as plastic molded products, flexographic printing inks and gravure printing inks, for example.

  C. I. Pigment red 48: 2 and C.I. I. Pigment Red 48: 3, and C.I. I. Monoazo lake pigment compositions based on CI Pigment Red 48: 2 are already well known as disclosed in Patent Documents 1 and 2. These patent documents disclose that aqueous printing inks can be prepared from monoazo lake pigments.

In Patent Document 1, a mixture of a diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and calcium chloride and 2-hydroxy-3-naphthoic acid are coupled, and strontium inorganic C. obtained by rake formation with salt. I. Pigment red 48: 2 and C.I. I. Pigment Red 48: 3, and C.I. I. A monoazo lake pigment composition based on CI Pigment Red 48: 2 and an aqueous printing ink containing it are described.
Patent Document 2 discloses a strontium azo lake pigment and a surfactant prepared separately from an alkaline earth metal lake pigment other than strontium of an azo dye having two or more carboxylic acid groups or sulfonic acid groups. A monoazo lake pigment composition containing 1 to 20% by weight of a slightly soluble strontium salt or a strontium salt of a resin, and an aqueous printing ink containing the same.

  However, although these patent documents disclose that viscosity stability and the like are improved when an aqueous printing ink is prepared from a monoazo lake pigment, C.I. I. The present invention relates to an improved technique based on the assumption that Pigment Red 48: 2 is a main component.

  On the other hand, C.I. I. Improvement techniques based on the assumption that only Pigment Red 48: 3 is used as a main component are also known as Patent Documents 3 to 5. These are all mixed cups using other raw materials other than 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2-hydroxy-3-naphthoic acid as raw materials for the diazo component or coupler component This is due to the ring method.

Patent Document 3 discloses a mixed coupler containing a diazo component composed of a diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 2-hydroxy-3-naphthoic acid and its amide derivatives. C. obtained by coupling with components and raked with a strontium inorganic salt. I. A monoazo lake pigment composition based on CI Pigment Red 48: 3 is described.
In Patent Document 4, a diazo component composed of a diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and a coupler component containing 2-hydroxy-3-naphthoic acid were coupled. A mixed azo dye containing an azo dye, a diazo component composed of a diazonium salt of alternic acid and a coupler component containing 2-hydroxy-3-naphthoic acid is raked with a strontium inorganic salt. C. obtained. I. A monoazo lake pigment composition based on CI Pigment Red 48: 3 is described.
Patent Document 5 discloses a diazo component composed of a diazonium salt of a mixed aromatic amine containing 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and an imidazolone ring-containing aromatic amine, and 2-hydroxy C. obtained by coupling with a coupler component containing -3-naphthoic acid and raked with a strontium inorganic salt. I. A monoazo lake pigment composition based on CI Pigment Red 48: 3 is described.

  However, all of the improved techniques of Patent Documents 3 to 5 are obtained by combining a special raw material as a diazo component or a coupler component with C.I. I. Since it is a monoazo lake pigment composition containing CI Pigment Red 48: 3 as a main component, it is not only difficult to produce stably, but also unsuitable for mass production, and it complicates compliance with chemical safety regulations. There was a drawback of becoming.

Therefore, it can be produced stably and in large quantities, can easily comply with chemical safety regulations, has good dispersibility in the medium to be colored, and can obtain a highly glossy colored product. I. A monoazo lake pigment composition containing CI Pigment Red 48: 3 as a main component is desired.
JP-A-53-96032 JP-A-63-51463 JP 62-54763 A JP 2001-49140 A JP 2004-143198 A

  The present invention can be stably produced without using special raw materials, uses only existing chemical substances whose safety has been confirmed, has good dispersibility in the medium to be colored, and has high gloss. A colored product is obtained. I. An object is to provide a monoazo lake pigment composition containing CI Pigment Red 48: 3 as a main component.

  The inventors have described C.I. I. As a result of intensive studies to obtain a highly glossy colored product having good dispersibility in a medium to be colored in a system mainly containing CI Pigment Red 48: 3, C.I. I. Pigment Red 48: 3 as a main component. I. Pigment Red 48: 2 is used together to solve the above-mentioned problems, and they are not manufactured and mixed separately, but both are formed by using a strontium inorganic salt and a calcium inorganic salt together to form a lake. It has been found that the above-mentioned problems can be more easily solved by simultaneously producing pigments, and the present invention has been completed.

That is, the present invention is a method in which a diazonium salt of 1 -amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2-hydroxy-3-naphthoic acid are coupled and then laked with a divalent metal inorganic salt. In the method for producing a monoazo lake pigment composition that is raked with a divalent metal inorganic salt simultaneously with coupling, a strontium inorganic salt and a calcium inorganic salt are used as the divalent metal inorganic salt. Mole ratio) = 62.7 to 86.0 / 37.3 to 14.0 . I. Pigment Red 48: 3 as a main component and C.I. I. Pigment red 48: 3 and C.I. I. Pigment Red 48: 2 at the same time to generate to provide a method of manufacturing a monoazo laked pigment composition wherein Rukoto.

The monoazo lake pigment composition of the present invention comprises C.I. I. Pigment Red 48: 3 as a main component. I. Since it contains CI Pigment Red 48: 2, there is a particularly remarkable effect that a dispersibility in a medium to be colored is good and a highly glossy colored product is obtained.
Further, the production method of the monoazo lake pigment composition of the present invention is a monoazo lake pigment composition that has a better dispersibility in a medium to be colored and can obtain a colored product with higher gloss without using a special raw material. Can be produced using only existing chemical substances.
In any of the inventions, there is also an effect that it is easier to comply with the chemical safety regulations.

The monoazo lake pigment composition of the present invention has C.I. I. CI pigment red 48: 3 65-87% and C.I. I. 35 to 13% of CI Pigment Red 48: 2. Here, C.I. I. As described above, CI Pigment Red 48: 3 and 48: 2 are substances in which Me ²⁺ is strontium and Me ²⁺ is calcium, respectively, in the general formula.

  The monoazo lake pigment composition of the present invention comprises C.I. I. C.I. in terms of mass so as not to impair the original properties such as hue of CI Pigment Red 48: 3. I. Pigment red 48: 3 and C.I. I. When the total of Pigment Red 48: 2 is 100%, the former 65 to 87% and the latter 35 to 13% are contained.

  The monoazo lake pigment composition of the present invention comprises C.I. I. Pigment red 48: 3 and C.I. I. Pigment Red 48: 2 may be used, but if necessary, C.I. I. Other red monoazo lake pigments other than CI Pigment Red 48 series, rosins, surface treatment agents, and the like may be included. Of course, C.I. I. Pigment red 48: 3 and C.I. I. Either or both of CI Pigment Red 48: 2 can be coated with other red monoazo lake pigments, rosins, and surface treatment agents.

  C. I. Examples of other red organic pigments other than CI Pigment Red 48 series include C.I. I. Pigment red 49: 2, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 3, C.I. I. And CI Pigment Red 64: 1. These may be contained alone or in combination of two or more in the monoazo lake pigment composition of the present invention.

  C. in terms of mass. I. Pigment red 48: 3 and C.I. I. Per 100 parts of CI Pigment Red 48: 2, and C.I. I. Pigment red 63: 1 and / or C.I. I. Pigment Red 63: 3 in total 0.3 to 15 parts, especially C.I. I. Pigment red 63: 1 and C.I. I. When the pigment red 63: 3 is contained in an amount of 0.3 to 15 parts, particularly 5 to 10 parts, the hue range obtained is C.I. I. Pigment red 48: 3 and C.I. I. Compared to the case of using only CI Pigment Red 48: 2, it is preferable because it can be spread and shifted to bluish red.

  By the way, C.I. I. Pigment Red 63: 3 is a substance in which the rake metal atom (Me) is strontium in the following general formula; I. Pigment Red 63: 1 is made of a substance in which the rake metal atom (Me) is calcium in the above general formula.

  Examples of rosins include all known and commonly used rosins. For example, rosin mainly composed of abietic acid, disproportionated rosin, partially hydrogenated rosin, fully hydrogenated rosin, maleic acid modified rosin, fumaric acid modified Examples thereof include rosin, polymerized rosin, and water-insoluble salts thereof. Rosin is a C.I. I. Pigment red 48: 3 and C.I. I. 0.5 to 30 parts, preferably 0.5 to 20 parts can be included per 100 parts of the total mass of CI Pigment Red 48: 2.

  Examples of the surface treating agent include hydrophilic synthetic resins such as styrene-maleic acid copolymer, styrene- (meth) acrylic acid copolymer, cellulose, carboxymethyl cellulose, and polyvinyl alcohol, polyethylene glycol monoalkyl ether, and alkylbenzene sulfonic acid. Surfactants such as salts, polyoxyalkylene alkyl ether phosphates, saccharide alkylene oxide adducts, wetting agents such as polyethylene glycol, polypropylene glycol, polyhydric alcohol alkylene oxide adducts, and polyvalents such as trimellitic acid and pyromellitic acid Carboxylic acid is mentioned. These may be contained alone or in combination of two or more in the monoazo lake pigment composition of the present invention.

  The surface treatment agent is C.I. I. Pigment red 48: 3 and C.I. I. 0.5 to 30 parts, preferably 0.5 to 10 parts, can be included per 100 parts of the total mass converted to CI Pigment Red 48: 2.

  The monoazo lake pigment composition of the present invention comprises C.I. I. Pigment red 48: 3 and C.I. I. CI Pigment Red 48: 2 may be prepared separately and then mixed to prepare a mixture of diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2- In the method for producing a monoazo lake pigment composition, hydroxy-3-naphthoic acid is coupled and then laked with a divalent metal inorganic salt, or simultaneously laked with a divalent metal inorganic salt. As a metal inorganic salt, it is possible to produce using a strontium inorganic salt and a calcium inorganic salt in a molar ratio of 62.7 to 86.0 / 37.3 to 14.0. I. Pigment red 48: 3 and C.I. I. It is preferable in that it can be more uniformly mixed with Pigment Red 48: 2 at the molecular level.

  This manufacturing method is a conventional C.I. I. In the production method of CI Pigment Red 48: 3, an azo dye is produced according to a conventional method, and a part of the strontium inorganic salt that is an equivalent of an acid group contained in the azo dye and is a divalent metal inorganic salt used for rake formation. Substituting with a calcium inorganic salt.

  As for 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2-hydroxy-3-naphthoic acid, it is preferable to use a highly pure product as much as possible.

  The diazo component may be only the diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, but within 15 mol% of the total diazo component, Isomers and derivatives of aromatic amines such as 1-amino-4-methylbenzene-3-sulfonic acid and diazonium salts of other aromatic amines such as tobias acid (2-aminonaphthalenesulfonic acid) I can do it.

  When adjusting the hue, 0.003 to 0.15 mol of diazonium salt of tobias acid is used in combination with 1 mol of diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid in terms of mass. It is preferable.

  The coupler component may be only 2-hydroxy-3-naphthoic acid, but if it is within 15 mol% of the coupler component, this coupler component may contain phenols other than 2-hydroxy-3-naphthoic acid or naphthol. For example, 2-hydroxynaphthalene and the like.

  As the diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, an aqueous solution or a water suspension prepared according to a conventional method can be used. By reacting 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, hydrochloric acid and nitrite at a low temperature, an aqueous solution or suspension of a diazo component containing the corresponding diazonium salt is obtained. As 2-hydroxy-3-naphthoic acid, an aqueous solution prepared according to a conventional method can be used. An aqueous solution of a coupler component can be obtained by dispersing 2-hydroxy-3-naphthoic acid in warm water and dissolving it as alkaline.

  An aqueous suspension of an azo dye is prepared by coupling the diazo component thus obtained and a coupler component according to a conventional method. At this time, the coupler component may be added to the diazo component, the diazo component may be added to the coupler component, or the coupler component and the diazo component may be added to water.

  The reaction conditions for obtaining the azo dye by coupling are not particularly limited, but can usually be carried out at a temperature of 0 to 30 ° C. for 30 minutes to 3 hours.

  The reaction conditions for obtaining the monoazo lake pigment by lake formation are not particularly limited, but an azo dye, a strontium inorganic salt and a calcium inorganic salt are mixed, and usually at a temperature of 40 to 90 ° C. for 15 minutes to It can be done in 2 hours.

  In addition, in the manufacturing method of the monoazo lake pigment composition of this invention, after making it couple | bond, you may rake or may rake simultaneously with coupling.

  In the present invention, a strontium inorganic salt and a calcium inorganic salt are used in combination as a divalent metal salt used for lake formation, and these strontium inorganic salt and calcium inorganic salt are converted into strontium inorganic salt / calcium inorganic salt (molar ratio) = 62. .7 to 86.0 / 37.3 to 14.0. Examples of the strontium inorganic salt include strontium chloride and strontium nitrate, and examples of the calcium inorganic salt include calcium chloride and calcium carbonate.

  Depending on the rake reaction rate, strontium inorganic can be obtained from an azo dye obtained from 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2-hydroxy-3-naphthoic acid. C. is a corresponding monoazo lake pigment at a ratio approximately corresponding to the molar ratio of the salt to calcium inorganic salt. I. Pigment red 48: 3 and C.I. I. A monoazo lake pigment composition containing CI Pigment Red 48: 2 is obtained.

  When 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and tobias acid are used in combination as the diazo component and coupling and rake formation as described above are performed, C.I. I. Pigment red 48: 3, C.I. I. Pigment Red 48: 2 as well as C.I. I. Pigment red 63: 1 and C.I. I. Pigment Red 63: 3 can also be produced, so that they are more uniformly mixed at the molecular level, and a monoazo lake pigment composition having a hue adjusted can be easily obtained.

  In the production method of the monoazo lake pigment composition, the surface treatment agent as described above is added to the aqueous solution of the coupler component, the aqueous solution of the azo dye or the aqueous suspension, and the monoazo lake pigment aqueous suspension as necessary. You can go.

  C. I. Pigment red 48: 3 and C.I. I. The monoazo lake pigment aqueous suspension containing CI Pigment Red 48: 2 as an essential component is adjusted for pH as necessary, and further heated at a temperature higher than the lake temperature and lower than 150 ° C. for a predetermined time according to a conventional method. Aging may be performed. Aging can be carried out under normal pressure or under pressure. By aging, the particle diameter and distribution of pigment particles can be adjusted. By aging at a lake temperature of 150 ° C. or less and a pH of 9 to 12, the raw material in the agglomerated pigment particles and the product free carboxyl groups and sulfonic acid groups can be more reliably neutralized to form a salt form. In particular, the storage stability of a water-based ink or a water-based paint using a combination of a film-forming resin containing a carboxyl group and a basic compound, which will be described later, is preferable.

  The monoazo lake pigment aqueous suspension after aging can be made into a wet monoazo lake pigment composition such as a wet cake or wet slurry by filtering or washing with water. Purification can also be performed by repeating filtration and washing with water. In washing with water, hot water may be used, or an alkaline dilute aqueous solution may be used if necessary. The free carboxyl groups and sulfonic acid groups contained inside and outside the pigment particles are surely neutralized to form a salt form to further improve the dispersion stability of the pigment particles in aqueous inks and aqueous paints described later. Then, it is preferable.

  By drying the monoazo lake pigment composition in a wet state, a dry monoazo lake pigment composition such as powder or granule can be obtained. The dried monoazo lake pigment composition in the form of a lamp can also be unraveled by crushing. Further, the monoazo lake pigment composition in a dry state can be narrowed in particle size distribution by classification.

  The monoazo lake pigment composition of the present invention is used for various known and commonly used applications, for example, printing inks such as lithographic printing inks, gravure printing inks, flexographic printing inks, paints, colored plastic molded articles, etc., for electrostatic image development. It can be applied to high-tech applications such as toners, color filters, and water-based inks for ink jet recording.

  The monoazo lake pigment composition of the present invention comprises C.I. I. Pigment Red 48: 3 as a main component. I. Pigment Red 48: 2 is contained in a small amount. I. Pigment Red 48: 3 alone or C.I. I. Pigment Red 48: 2 as a main component. I. Compared to containing a small amount of CI Pigment Red 48: 3, it is suitable for the preparation of ink or paint regardless of oiliness or aqueousness.

  Of these, water-based inks and water-based paints can be suitably prepared from the monoazo lake pigment composition of the present invention and the water-based vehicle. This aqueous vehicle mainly contains a film-forming resin for fixing and fixing a pigment on a substrate when the solvent is volatilized, and water as a solvent. In addition, aqueous | water-based means the liquid medium in which a liquid medium contains only water or 60% or more of water by mass conversion.

  Examples of film-forming resins for preparing aqueous gravure printing inks include polyamide resins, styrene resins, maleic acid resins, acrylic resins, nitrocellulose, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resins, polyurethane resins. And water-soluble or water-dispersible resins such as polyester resins, or a mixture of two or more of these.

  When a film-forming resin containing a carboxyl group and a basic compound are used in combination, an aqueous vehicle in which the film-forming resin is stably dissolved or dispersed in water can be prepared. Examples of the basic compound include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as diethylamine, triethylamine and diethanolamine. A suitable aqueous vehicle for preparing an aqueous gravure printing ink contains a basic compound and a styrene- (meth) acrylate- (meth) acrylate copolymer as a film-forming resin.

  The aqueous gravure printing ink can be prepared by mixing the monoazo lake pigment composition of the present invention and the aqueous vehicle, and further with other hydrophilic organic solvent, extender pigment, auxiliary agent and the like.

  Examples of the hydrophilic organic solvent include ethanol, methanol, isopropanol (IPA), acetone, ethyl acetate, ethyl lactate, cellosolve, diacetone alcohol and the like. Examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, talc, calcium silicate, and precipitated magnesium carbonate. Examples of other auxiliary agents include waxes, surfactants, antifoaming agents, plasticizers, ultraviolet inhibitors, antioxidants, antistatic agents and the like.

The water-based paint can be prepared in the same manner as the water-based ink.
Examples of the film-forming resin for preparing the water-based paint include alkyd resins, silicone resins, fluororesins and the like in addition to the above-described resins. In order to increase the coating strength, a curing agent can be used in combination with the film-forming resin. Examples of such a curing agent include melamine resin, urea resin, polyisocyanate, and the like. Moreover, as a thickener used as an adjuvant, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, etc. are mentioned, for example.

  Water-based gravure printing ink and water-based paint are necessary in terms of mass, for example, using 10 to 50 parts of a film-forming resin, 30 to 80 parts of a liquid medium containing water, and 1 to 25 parts of the monoazo lake pigment composition of the present invention. Depending on the case, it can be prepared so that the total amount becomes 100 parts including auxiliary agents and low viscosity suitable for printing and coating.

  The red water-based gravure printing ink thus obtained can be used in combination with known and commonly used yellow or indigo water-based gravure printing inks to print intermediate or full-color images by subtractive color mixing.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part and% in an example are a mass reference | standard.

279 parts (1.26 mol) of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 21 parts (0.09 mol) of tobias acid are put into 1500 parts of water and stirred. Further, 226 parts of 35% hydrochloric acid is added and stirred. Add 1000 parts of ice and cool. Add 335 parts of 30% sodium nitrite and diazotize to make a diazotized solution. Separately, 299 parts (1.59 mol) of 3-hydroxy-2-naphthoic acid as a coupler solution is charged and stirred in 2000 parts of water, and 814 parts of 20% sodium hydroxide is added and dissolved at 50 ° C. Add 4000 parts of ice and cool to 0 ° C.
The diazotization solution is added to this coupler solution, and pH 11 to 12 and temperature 3 to 7 ° C. are confirmed and adjusted within 10 minutes. Check the end of the coupling, and after 30 minutes, adjust the temperature to 2-8 ° C and then adjust the pH to 9.
As soon as the temperature rises and the hue of the dye changes from yellow to blue (at the same time, the crystal shape changes from acicular to granular), 139 parts (0.438 mol) of 35% calcium chloride and strontium chloride 355 parts (1.331 mol) of a hydrate solution was added and raked. I. A pigment composition suspension containing CI Pigment Red 48: 3, 48: 2, 63: 1, and 63: 3 was obtained. The obtained suspension of the pigment composition was adjusted to pH 11, and then heat-aged at a rake temperature or higher and 150 ° C. or lower, filtered and washed to separate the pigment composition wet cake. The wet cake of the isolated pigment composition was dried at 110 ° C., and the dried lamp was pulverized with a juicer to obtain a red pigment composition powder.
This pigment composition is C.I. I. Pigment Red 48: 3/48: 2/63: 1/63: 3 = 71.5 / 21.8 / 1.4 / 5.3 (% by mass). This pigment composition can be produced stably and in large quantities with existing raw materials, is composed of only known substances, and is easy to comply with chemical safety regulations.

Similarly to Example 1, the diazotization liquid and the coupler solution were separately prepared.
Coupling is carried out in the same manner as in Example 1. For rake formation, a solution in which 92 parts (0.290 mol) of 35% calcium chloride and 398 parts (1.493 mol) of strontium chloride hexahydrate are dissolved is added. Except for the above, the same procedure as in Example 1 was carried out. I. A pigment composition suspension containing CI Pigment Red 48: 3, 48: 2, 63: 1, and 63: 3 was obtained. Thereafter, the same operation as in Example 1 was carried out to obtain a red pigment composition powder.
This pigment composition is C.I. I. Pigment Red 48: 3/48: 2/63: 1/63: 3 = 79.3 / 14.0 / 1.0 / 5.7 (mass%). This pigment composition can be produced stably and in large quantities with existing raw materials, is composed of only known substances, and is easy to comply with chemical safety regulations.

A diazotization solution is prepared in the same manner as in Example 1, except that 279 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 21 parts of tobias acid are substituted with 1-amino-4- A diazotization liquid was prepared in the same manner as in Example 1 except that only 300 parts (1.354 mol) of methyl-5-chlorobenzene-2-sulfonic acid was used. Separately, a coupler solution was prepared in the same manner as in Example 1 above.
Coupling and rake formation were carried out in the same manner as in Example 1, and C.I. I. A pigment composition suspension containing CI Pigment Red 48: 3 and 48: 2 was obtained. Thereafter, the same operation as in Example 1 was performed to obtain a red pigment composition powder.
This pigment composition is C.I. I. Pigment Red 48: 3/48: 2 = 76.8 / 23.2 (mass%). This pigment composition is an existing raw material and is composed only of known substances, and it is easy to comply with chemical safety regulations.

Comparative Example 1
In the same manner as in Example 1 except that a solution of 481 parts (1.804 mol) of strontium chloride hexahydrate was used instead of a solution of 139 parts of 35% calcium chloride and 355 parts of strontium chloride, C . I. A pigment composition suspension containing CI Pigment Red 48: 3 and 63: 3 was obtained. Thereafter, the same operation as in Example 1 was performed to obtain a red pigment composition powder.
This pigment composition is C.I. I. Pigment Red 48: 3/63: 3 = 93.3 / 6.7 (mass%).

Comparative Example 2
Instead of a solution of 139 parts of 35% calcium chloride and 355 parts of strontium chloride, a solution of 427 parts (1.345 mol) of 35% calcium chloride and 113 parts (0.424 mol) of strontium chloride hexahydrate is used. Except for C.I. I. A pigment composition suspension containing CI Pigment Red 48: 3, 48: 2, 63: 1, and 63: 3 was obtained. Thereafter, the same operation as in Example 1 was performed. I. A red pigment composition powder containing CI Pigment Red 48: 3, 48: 2, 63: 1 and 63: 3 was obtained.
This pigment composition is C.I. I. Pigment Red 48: 3/48: 2/63: 1/63: 3 = 12.9 / 37.1 / 37.1 / 12.9 (mass%).

Comparative Example 3
Instead of 279 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 21 parts of tobias acid, 300 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid (1. A diazotized solution was prepared in the same manner as in Example 1 except that only 354 mol) was used. Further, instead of a solution of 139 parts of 35% calcium chloride and 355 parts of strontium chloride, a solution of 427 parts (1.345 mol) of 35% calcium chloride and 113 parts (0.424 mol) of strontium chloride hexahydrate. Except that C. was used in the same manner as in Example 1 above. I. A suspension containing Pigment Red 48: 3 and 48: 2 was obtained. Thereafter, the same operation as in Example 1 was performed to obtain red pigment powder A.
This pigment powder A is C.I. I. Pigment Red 48: 3/48: 2 = 26.0 / 74.0 (mass%).
Example except that 305 parts (1.368 mol) of tobias acid was used instead of 279 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 21 parts of 2-aminonaphthalenesulfonic acid In the same manner as in No. 1, a diazotization solution was prepared. Further, instead of a solution of 139 parts of 35% calcium chloride and 355 parts of strontium chloride, a solution of 427 parts (1.345 mol) of 35% calcium chloride and 113 parts (0.424 mol) of strontium chloride hexahydrate. Was used. Otherwise, in the same manner as in Example 1 above, C.I. I. A suspension containing Pigment Red 63: 1 and 63: 3 was obtained. Thereafter, the same operation as in Example 1 was performed to obtain a deep red pigment powder B.
This pigment powder B is C.I. I. Pigment Red 63: 1/63: 3 = 74.0 / 26.0 (mass%).
C. 90 parts of the red pigment powder A thus obtained and 10 parts of the deep red pigment powder B were thoroughly mixed until uniform. I. Pigment red 48: 3, 48: 2, 63: 1 and 63: 3 were obtained.
This pigment composition is C.I. I. Pigment Red 48: 3/48: 2/63: 1/63: 3 = 66.8 / 23.4 / 2.6 / 7.4 (mass%).

Preparation method of water-based gravure printing ink 16 parts of each powder pigment composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and meat varnish [Johncrill (registered trademark) 61J / distilled water manufactured by Johnson Polymer Co., Ltd.] / IPA = 30/30/5 (mass ratio) mixed product] 38 parts and 160 parts of 3 mm glass beads are weighed in a 250 ml polybin, and dispersed for 60 minutes with a paint conditioner manufactured by Toyo Seiki Co., Ltd. 84 parts of John Crill (registered trademark) 74J manufactured by Johnson Polymer Co., Ltd. was added and dispersed for 5 minutes to obtain an aqueous gravure printing ink (hereinafter referred to as primary color ink).
On the other hand, in a 100 ml polybin, 20 parts of Daiflex Astia (registered trademark) D250 [white ink manufactured by Dainippon Ink & Chemicals, Inc.] and 4 parts of the above primary color ink are weighed and mixed with the above paint conditioner for 30 minutes. Hereinafter, this is referred to as light color ink.).

Evaluation method (gloss, transparency, tinting strength)
On art paper with black background, No. With a 6 bar coater, the primary color ink is developed, and after natural drying, the Gretag density meter SPL50 manufactured by Gretag, the spectrophotometer Microflash 200d manufactured by Datacolor, and the gloss meter (60 ° gloss) manufactured by BYK-Chemie Japan are used. Measure the color development surface. Similarly, light-colored ink was also developed and the coloring power was measured with a spectrophotometer. The results are shown in Table 1.
In addition, about the coloring power, the coloring power of each ink when the coloring power of the printed image in the ink prepared from the pigment composition of the comparative example 1 was made into 100% was displayed.

  The meanings of symbols in Table 1 are as follows. ◎: Excellent ○: Good ×: Impossible

The aqueous gravure printing ink of Example 1 prepared by using the pigment composition of the present invention has gloss, transparency and coloring power as compared with those of Comparative Examples 1 to 3 corresponding to the prior art. It is clear that both are markedly superior.
The aqueous gravure printing ink of Example 3 prepared using the pigment composition of the present invention has slightly lower transparency and coloring power than that of Example 1, but is yellowish, slightly opaque and highly glossy. It is clear that

Claims (4)

A diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid and 2-hydroxy-3-naphthoic acid are coupled and then laked or coupled with a divalent metal inorganic salt. At the same time, in the method for producing a monoazo lake pigment composition that is raked with a divalent metal inorganic salt, the strontium inorganic salt and the calcium inorganic salt are strontium inorganic salt / calcium inorganic salt (molar ratio) = 62 as the divalent metal inorganic salt. .7 to 86.0 / 37.3 to 14.0 in combination to form a rake. I. Pigment Red 48: 3 as a main component and C.I. I. Pigment red 48: 3 and C.I. I. A method for producing a monoazo lake pigment composition, wherein Pigment Red 48: 2 is produced simultaneously. The monoazo lake pigment composition according to claim 1, wherein 0.003 to 0.15 mole of diazonium salt of tobias acid is used in combination with 1 mole of diazonium salt of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid. Method. The method for producing a monoazo lake pigment composition according to claim 1 or 2, wherein the aging is performed at a rake temperature of 150 ° C or lower and a pH of 9 to 12 after the rake. The method for producing a monoazo lake pigment composition according to any one of claims 1 to 3, for preparing a water-based ink or a water-based paint.