JP5593719B2 - Method for producing dioxazine violet derivative - Google Patents

Description

The present invention relates to a printing ink, paint, a process for preparing wide dioxazine violet usable derivatives such as the colored composition including plastics.

Dioxazine Violet (C.I. Pigment Violet 23) is a deep blue-purple violet pigment that has high coloring power, good light resistance and heat resistance, and is used in various coloring compositions. Yes. However, a pigment having a wide condensed ring as a skeleton like dioxazine violet generally tends to cause stacking due to its structure, and dispersion is not easy because aggregation is strong. As a result, when manufacturing dispersions such as printing inks using dioxazine violet, in terms of fluidity at the time of dispersion, dispersion stability over time, coloring power as ink, gloss of the coated surface when developed, etc. There's a problem.

  In order to solve these problems, various techniques have been developed so far to improve the dispersibility of dioxazine violet. Among them, the method using a pigment derivative synthesized by introducing various substituents into the dioxazine violet molecule as a dispersant is the most excellent in terms of improving dispersibility. So far, derivatives obtained by sulfonating dioxazine violet have been disclosed and put into practical use in Patent Documents 1 and 2 and the like. Patent Document 3 discloses a basic derivative in which an amine is bonded to dioxazine violet.

  However, although the pigment composition using such a pigment derivative is very good in terms of dispersibility and various properties resulting from it, it has a high elution property in water, various solvents, plastics, etc., which is a problem as a colored composition. There was a case. For example, gravure inks and flexographic inks have problems with retort resistance such as hot water bleed resistance of printed materials, and their use as packaging materials is limited. Ink-jet ink has a problem that the pigment derivative is dissolved in the ink and printing is blurred. The use of pigment derivatives in paints also has the disadvantage of increasing bleed and is not used in applications where bleed resistance is required. Even in plastics, there arises a problem of migration that causes a color transfer to a substance that contacts the plastic coloring material, and a plate-out problem that causes a color transfer to the apparatus during the manufacturing process of the plastic coloring material. Regarding offset ink, since the pigment derivative has a high affinity with water, the ink is easily emulsified by the fountain solution used at the time of printing, which causes printing troubles such as background stains.

JP-A-56-81371 Japanese Patent No. 3337234 Japanese Patent Laid-Open No. 56-118462

The present invention has been made in view of the above-mentioned present situation, and has excellent dispersibility when dispersing dioxazine violet, while being represented by the problem of bleeding of gravure ink, from an external substance to a coloring composition. It aims at providing the manufacturing method of the dioxazine violet derivative which does not have the problem of the elution to an aldehyde.

As a result of intensive studies on the structure of the dioxazine violet derivative and its production method, the present inventor has found a method for producing the dioxazine violet derivative that solves the above problems.

That is, the present invention has a weight ratio of the derivative (B) having two sulfo groups in the molecule and derivatives that one have a sulfo group in a molecule (A) is (A) :( B) = 100 : 0-50: 50 a is a method for producing a dioxazine violet derivatives, production of dioxazine violet derivative comprising the step of in a medium without sulfonic Kano by reacting dioxazine violet and sulfonating agent performing sulfonation Regarding the method .

The present invention also relates to a method for producing the dioxazine violet derivative, wherein the medium having no sulfonation ability is methanesulfonic acid and the sulfonating agent is sulfuric acid .

  By using the dioxazine violet derivative of the present invention, it is possible to produce a dispersion having good dispersibility, which has been difficult to achieve conventionally, and which does not cause a problem of elution of the derivative. Furthermore, this dispersion can be used for gravure inks and flexographic inks, whereby an ink having low bleeding, low bleeding and excellent retort resistance can be produced while realizing performances such as low viscosity, high coloring power and high gloss.

Ink-jet inks can realize inks with less blur and good image reproducibility while realizing performances such as low viscosity, high dispersion stability, high coloring power, and high gloss. In the paint, it is possible to produce a paint having no problem of bleeding out while having performances such as low viscosity, high coloring power and high gloss. With colored plastics, it is possible to produce plastics that have high coloring power and easy dispersion, and that are free from migration and plate-out problems. In offset ink, there is no problem in emulsification suitability, and an ink having high print suitability can be realized.

  Details of the present invention will be described below.

  As in the present invention, a dioxazine violet derivative having one or two sulfo groups in one molecule, which has a derivative (A) having one sulfo group in one molecule and two sulfo groups in one molecule A dioxazine violet derivative characterized in that the weight ratio of the derivative (B) is (A) :( B) = 100: 0 to 50:50 has not been studied until now. Derivatives having a sulfonic acid in the dioxazine violet skeleton are already known as long as the abundance ratio between the derivative (A) having one substituent and the derivative (B) having two substituents is not specified. ing. However, what is known as its production method is sulfonation of dioxazine violet with sulfuric acid, chlorosulfuric acid or the like. The present inventor also examined such a known production method, but in the production method that can be industrialized, the derivative (B) having two substituents is mainly used, and A: B has a larger A content than 50:50. A pigment derivative having the composition claimed in this patent cannot be produced.

  This is because dioxazine violet is significantly more reactive than other pigment skeletons such as copper phthalocyanine and quinacridone. When a similar pigment derivative is produced with copper phthalocyanine, quinacridone, or the like, the pigment is dissolved in 98% sulfuric acid or fuming sulfuric acid having a higher sulfuric acid concentration and reacted. Even under such intense reaction conditions, both pigments are not highly reactive, so that they react slowly over a period of several hours to obtain a pigment derivative having a desired number of substituents.

  On the other hand, in the case of dioxazine violet, when it is dissolved in 98% sulfuric acid, sulfonation proceeds simultaneously with dissolution, and almost all molecules react to the derivative B having two substituents within a few minutes. Therefore, in order to lower the reactivity, water is added to sulfuric acid to reduce the reactivity of sulfuric acid, and the reaction is carried out using sulfuric acid having a concentration of about 92% as in Comparative Example 1 below. In dilute sulfuric acid, dioxazine violet hardly dissolves, and the reaction proceeds in a solid-liquid reaction mode. In such a system, the dissolution of dioxazine violet becomes the rate-limiting step of the reaction, and the reaction from the raw material dioxazine violet to the derivative A having one substituent is slow. However, once the sulfonated derivative A having one substituent is obtained, it is already in a dissolved state, so that it is immediately sulfonated to become a derivative B having two substituents. Therefore, in such a reaction system, the derivative B having two substituents is the main component.

  For the production of a pigment derivative such that the A: B content is higher than 50:50 as in the derivative of the present invention, dioxazine violet and a sulfonating agent are reacted in a medium having no sulfonation ability. There is a need for a method of producing a derivative having a step of converting into a derivative. In this reaction system, sulfonation can be performed under mild conditions without lowering the solubility of dioxazine violet or the dispersibility in a solvent. Such reaction conditions cannot be realized in a reaction system using sulfuric acid as a reaction solvent, which has been studied so far. Production of a pigment derivative having the composition claimed in this patent such that A: B has a higher content of A than 50:50, which could not be achieved industrially until now by this reaction method. Can do.

  The derivative of the present invention contains a derivative (A) having only one sulfo group in one molecule of dioxazine violet. Derivatives (B) having two sulfo groups and other substances may be contained, but when the weight ratio of A: B is 50:50 or more and the weight ratio of B is high, elution from various dispersions Therefore, it is necessary that the ratio of A: B is in the range of 50:50 to 100: 0. Further, if the ratio of B is decreased, the dissolution resistance can be improved without deteriorating the dispersion characteristics, so that the ratio of A: B is in the range of 67:33 to 100: 0, and further 80: It is still more desirable to be in the range of 20-100: 0. The weight ratio of A and B can be measured by liquid phase chromatography.

  Although the ratio of A and B in one dioxazine violet derivative is not particularly specified, the total amount of A and B in the derivative is 5% by weight in order to exhibit the effect of improving the dispersion characteristics as a pigment derivative. % Or more, and desirably 20% or more.

  The counter ion of the sulfo group of the derivative is a hydrogen ion, an ammonium ion, an ammonium ion in which at least one is substituted with an alkyl group, or a 1-3 valent metal ion. Among them, sodium, magnesium, aluminum, potassium, calcium, manganese, iron, cobalt, nickel, copper, zinc and the like are desirable as metal ions.

  The form of the derivative is not limited in the present invention, but some processing such as powder, a press cake containing water, or a mixture with resin may be performed. It may also be mixed with other dioxazine violet pigments as a pigment. In this case, the mixing ratio is not particularly defined, but in order to exert the effect of improving the dispersion characteristics as a pigment derivative, the ratio of the present derivative is required to be 0.1% or more, preferably 1% or more. .

  The derivative of the present invention may be used as a pigment dispersant by mixing and dispersing with a pigment and a resin, and if necessary, a solvent, other additives and the like. The mixing ratio in the pigment dispersion is desirably in the range of the derivative of the present invention: pigment: resin = 0.2 to 40 wt%: 1 to 90 wt%: 5 to 90 wt%. Although all known pigments can be used as the type of pigment, among them, pigments having a wide condensed ring as a skeleton, specifically, dioxazine violet, phthalocyanine, quinacridone, etc. are preferable, and dioxazine violet is most preferable. . As the resin, all known resins can be used. Further, the pigment dispersion of the present invention may be a mixture of the above three components or a dispersion using a disperser or the like.

  The derivatives of the present invention can be used in various dispersions such as printing inks, coating compositions, and plastic coloring compositions. Here, the printing ink represents all printing inks such as offset ink, gravure ink, flexo ink, and ink for inkjet.

  The offset ink mainly includes sheet-fed ink, offset rotary ink, newspaper ink, UV ink and the like depending on the application and drying method, but the present invention is not limited to these.

  The offset ink can be produced by mixing and dispersing the pigment derivative of the present invention, a pigment, and an offset ink vehicle. Vehicles for offset ink include, for example, rosin-modified phenolic resins, petroleum resins, alkyd resins, or resins such as these dry oil-modified resins, and vegetable oils such as linseed oil, tung oil, soybean oil, and n-paraffin as necessary. , Isoparaffin, aromatech, naphthene, α-olefin and the like, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight), resin: vegetable oil: solvent = 10-50 The range of wt%: 0-30 wt%: 20-60 wt% is preferred. In the offset ink, known additives such as an ink solvent, a dryer, a leveling improver, a thickener, and a pigment dispersant can be appropriately blended as necessary.

  The gravure ink or flexographic ink can be produced by mixing and dispersing the pigment derivative of the present invention and a pigment, a gravure ink vehicle or a flexographic ink method vehicle. The vehicle is composed of a resin and a solvent, and the mixing ratio thereof is in the range of resin: solvent = 5-50 wt%: 50-95 wt%, based on the total weight of the vehicle components (100 wt%). preferable.

  Examples of the resin include gum rosin, wood rosin, tall oil rosin, calcified rosin, lime rosin, rosin ester, maleic acid resin, gilsonite, dammar, shellac, polyamide resin, vinyl resin, nitrocellulose, cyclized rubber, chlorinated rubber, ethyl cellulose , Cellulose acetate, ethylene-vinyl acetate copolymer resin, chlorinated polypropylene resin, urethane resin, polyester resin, styrene resin, styrene acrylic resin, alkyd resin, and the like. Examples of the solvent include hydrocarbon solvents such as n-hexane, toluene and chlorobenzole, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol and glycerin, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, Examples thereof include ester solvents such as ethyl lactate and ethyl acetoacetate, ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and ethyl ether, and water.

  For gravure ink or flexographic ink, if necessary, for example, barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate, and other extender pigments. As additives, known additives such as plasticizers, ultraviolet light inhibitors, antioxidants, antistatic agents, and pigment dispersants can be appropriately blended.

  The inkjet ink can be produced by mixing and dispersing the pigment derivative of the present invention, a pigment, and an inkjet ink vehicle. A vehicle for inkjet ink is composed of a resin, an activator, and a solvent, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight), resin: solvent = 1-10% by weight: 90. A range of ˜99% by weight is preferred. Examples of the resin include resins that are soluble in water such as acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluororesin, and water-dispersible emulsions or colloidal dispersion resins. These resins are added with neutralizing agents such as ammonia, amines and inorganic alkalis as required. Examples of the solvent include water, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, and substituted pyrrolidone. Also, alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of accelerating the drying property of the ink-jet ink. Also, alcohols such as glycerin can be used to suppress drying at the head. Furthermore, an antiseptic, a penetrating agent, a chelating agent, and an anionic, nonionic, cationic, zwitterionic activator, and pigment dispersant can be added to the inkjet ink in order to improve the dispersion stability of the pigment.

  The paint can be produced by mixing and dispersing the pigment derivative of the present invention, a pigment, and a paint vehicle. The paint vehicle is composed of a resin and a solvent, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight), resin: solvent = 5-45% by weight: 55-95% by weight. The range of is preferable.

  Examples of the resin include nitrocellulose, alkyd resin, aminoalkyd resin, acrylic resin, aminoacrylic resin, urethane resin, polyvinyl acetal resin, epoxy resin, polyester resin, vinyl chloride resin, vinylidene fluoride resin, vinyl fluoride resin, Examples include polyethersulfone resins and silicone resins. Solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ethers / alcohols, ethers / esters organic solvents, water, etc. Can be mentioned.

  Other organic pigments such as barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate and the like are within the range not inhibiting the effect of the present invention. In addition to extender pigments, auxiliary agents such as curing agents, curing accelerators, flame retardants, anti-settling agents, anti-sagging agents, film-forming aids, preservatives, silane coupling agents for improving coating adhesion, anti-mold Agents, antifoaming agents, viscosity modifiers, leveling agents, UV absorbers, infrared absorbers, antifreeze agents, plasticizers, pH adjusters, antibacterial agents, light stabilizers, matting agents, antioxidants, pigment dispersants, Known additives such as pigment derivatives can be appropriately blended.

  The plastic composition can be produced by mixing and dispersing the pigment derivative of the present invention, a pigment, and a resin for plastic. Plastic resins include polypropylene, polyethylene, ethylene / propylene copolymer, α-olefin and acrylic acid or maleic acid copolymer, ethylene / vinyl acetate copolymer, ethylene and acrylic acid or maleic anhydride copolymer. Polyolefin resins such as polymers, vinyl resins such as polyvinyl chloride and polyvinyl acetate, acetal resins such as formal resins and butyral resins, acrylic resins such as polyacrylonitrile and methacrylic resins, polystyrene, acrylonitrile / butadiene / styrene copolymers And the like, polyester resins such as polyethylene terephthalate and polycarbonate, nylons such as 6-nylon, unsaturated polyester resins, epoxy resins, urea resins, melamine resins, and cellulose resins.

  The plastic includes other organic pigments, inorganic pigments, waxes or derivatives thereof, heavy metal deactivators, alkali metal, alkaline earth metal, or zinc metal soap, hydrotalcite, as long as the effects of the present invention are not impaired. Nonionic surfactants, cationic surfactants, anionic surfactants, antistatic agents composed of amphoteric surfactants, flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylene bisalkylamides And various additives for known polymers such as antioxidants, ultraviolet absorbers, processing aids, fillers, pigment dispersants, pigment derivatives and the like. In order to satisfy the required quality and coloring workability, the pigment is dispersed in advance with these components to obtain a powdery dry color, granular bead color, liquid paste color, etc., and then mixed with the resin. May be. Moreover, what is called a masterbatch which is comprised from a pigment, a plastics, and other said additive and contains a pigment in high concentration may be manufactured, and resin may be colored using a masterbatch. Further, the plastic dispersion of the present invention may be used as a toner.

  Next, the typical manufacturing method of the dioxazine violet derivative of this invention is demonstrated.

  A typical method for producing the dioxazine violet derivative of the present invention includes a method of sulfonation by reacting dioxazine violet and a sulfonating agent in a medium having no sulfonation ability. The medium without sulfonation ability is a medium in which sulfonation does not proceed when dioxazine violet is dissolved or dispersed in the medium. Specifically, phosphoric acid compounds such as nitric acid, phosphoric acid and polyphosphoric acid, compounds other than sulfuric acid having a sulfone group such as methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid, acetic acid, benzoic acid and the like. Examples thereof include compounds having a carboxyl group, acids such as silicic acids and boric acid, and other organic solvents, but the present invention is not limited to these specific examples. Of these, compounds having a sulfone group other than sulfuric acid such as polyphosphoric acid and methanesulfonic acid are preferred, and methanesulfonic acid is most preferred. A plurality of these compounds may be used as a reaction solvent. The amount of the medium having no sulfonation ability used for the reaction is preferably 2 to 100 times by weight, more preferably 3 to 10 times by weight with respect to dioxazine violet.

  As the sulfonating agent, sulfuric acid, fuming sulfuric acid, pyrosulfuric acid, chlorosulfuric acid, and sulfur trioxide are the most desirable industrially. However, a reaction in which transsulfonation is performed using alkylbenzenesulfonic acid as a sulfonating agent may be used. . The amount of the sulfonating agent to be used is not clearly defined in this patent because it greatly varies depending on the type of sulfonating agent, the type of acid used as the reaction solvent, the purity of the acid, the temperature and stirring state of the reaction, and the reaction time. About 0.1 to 100 mol is desirable for 1 mol of dioxazine violet. The sulfonating agent may be added before adding dioxazine violet to the medium, or may be added after adding dioxazine violet to the medium. As a method of addition, it may be added all at once, or may be gradually dropped over about 10 minutes to 5 hours. From the viewpoint of controlling the reaction, it is desirable to gradually add dropwise after dissolving dioxazine violet.

  The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 0 ° C to 60 ° C. The reaction at a low temperature is desirable because the ratio of the derivative A having one substituent to the derivative B having two substituents can be increased.

  After sulfonation by the above method, the dioxazine violet derivative of the present invention can be produced by purification or, if necessary, salt formation with a desired cation as a counter ion of the sulfo group. The present invention is not particularly limited to purification and salt formation methods.

  The simplest purification method includes a method in which the reaction slurry is mixed with water or the like to precipitate a dioxazine violet derivative, and then the acid is removed by washing with filtered water. Mixing with water or the like includes a method of gradually adding the reaction slurry into water or a method of instantaneously mixing with water using an aspirator, and it is desirable to use an aspirator from the standpoint of mixing efficiency. Further, before mixing with water or the like, the reaction slurry may be mixed with an appropriate amount of water, sulfuric acid, or an acid having no sulfonation ability, and appropriately diluted. While washing with water may be performed with normal water, it may be performed with water containing an acid or a salt.

  Regarding the salt formation method, the purified dioxazine violet derivative is dispersed in water to form a slurry, and 0.5 to 10 equivalents of ions are added to the number of moles of sulfonic acid to form a salt, followed by filtration, A method of washing with water is common. The amount of ions may be 0.5 to 10 equivalents, but 1.0 to 3 equivalents is more desirable. In addition, in the case of ions having an ionic valence n which is not monovalent, the equivalents of the above ions are each divided by n. In salt formation, it is desirable to add an alkali component to make it basic once, and then add ions, but ions may be directly added to an acidic or neutral slurry. The salt formation can be performed at 0 ° C. to 100 ° C., but 40 ° C. to 90 ° C. is desirable from the viewpoint of salt formation speed and ease of process.

  The finally obtained wet cake of dioxazine violet derivative is usually dried and pulverized and used as a powdered dioxazine violet derivative. There is no particular limitation on the drying and pulverization method at that time, and examples thereof include freeze-drying and spray-drying. Further, the dioxazine violet derivative may be used as a wet cake. In addition, the derivative obtained by the reaction and other pigment composition may be mixed after completion of all the steps or in the middle of any step such as purification, salt formation, drying and pulverization.

  Furthermore, the dioxazine violet derivative of the present invention may be added and pigmented as necessary. The dioxazine violet derivative of the present invention may be mixed with a polycyclic pigment such as a dioxazine violet pigment to form a pigment. Any known pigmentation method can be used, and examples thereof include a solvent method, a solvent milling method, a solvent salt milling method, an acid paste method, and a dry milling method.

  Further, the dioxazine violet derivative of the present invention provides crystal growth inhibition, crystal stability provision, aggregation prevention, easy dispersibility provision when using a pigment composition as a colorant, crystal stability provision, aggregation prevention, coloring power improvement, etc. For these purposes, rosin derivatives such as rosin, metal rosin and rosin ester, resins, activators, other pigment derivatives and the like may be mixed with the derivative during or after any step.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

Example 1
To a mixed solution of 70 parts of methanesulfonic acid and 4 parts of 22% fuming sulfuric acid, 10 parts of dioxazine violet was added and reacted at 55 ° C. for 5 hours. After the reaction, the reaction slurry was mixed with 1000 parts of water, stirred for 2 hours, and then filtered. The obtained paste was dispersed in 1000 parts of water and stirred at pH 9 for 2 hours. Hydrochloric acid was added to adjust the pH to 1, followed by filtration. The paste was further washed with 500 parts of 1% hydrochloric acid and 500 parts of 0.2% hydrochloric acid. The obtained paste was dried and pulverized to obtain 11 parts of dioxazine violet derivative 1.

Example 2
To 10 parts of the dioxazine violet derivative 1 obtained by the method of Example 1, 1000 parts of N, N′dimethylformamide was added, stirred at 120 ° C. for 4 hours, cooled to room temperature, filtered, and then N, N 'Washed with dimethylformamide. The obtained filtrate was added with 1000 parts of N, N′dimethylformamide, stirred at 120 ° C. for 4 hours, cooled to room temperature, filtered, and washed with N, N′dimethylformamide and water. The paste was dried and pulverized to obtain 6 parts of dioxazine violet derivative 2.

Example 3
To 5 parts of the dioxazine violet derivative 2 obtained by the method of Example 2, 1000 parts of N, N′dimethylformamide was added, stirred at 120 ° C. for 4 hours, cooled to room temperature, filtered, and subsequently subjected to N, N 'Washed with dimethylformamide. The obtained paste was dried and pulverized to obtain 4 parts of dioxazine violet derivative 3.

Example 4
To a mixed solution of 50 parts of methanesulfonic acid and 6 parts of 22% fuming sulfuric acid, 10 parts of dioxazine violet was added and reacted at 40 ° C. for 8 hours. After the reaction, the reaction slurry was mixed with 1000 parts of water, stirred for 2 hours, and then filtered. The obtained paste was dispersed in 1000 parts of water and stirred at pH 9 for 2 hours. Hydrochloric acid was added to adjust the pH to 1, followed by filtration. The paste was further washed with 500 parts of 1% hydrochloric acid and 500 parts of 0.2% hydrochloric acid. The obtained paste was dried and pulverized to obtain 11 parts of dioxazine violet derivative 4.

Example 5
To a mixed solution of 100 parts of polyphosphoric acid and 1.6 parts of 98% sulfuric acid, 10 parts of dioxazine violet was added and reacted at 55 ° C. for 1 hour. After the reaction, the reaction slurry was mixed with 1000 parts of water, stirred for 2 hours, and then filtered. The obtained paste was dispersed in 1000 parts of water and stirred at pH 9 for 2 hours. Hydrochloric acid was added to adjust the pH to 1, followed by filtration. The paste was further washed with 500 parts of 1% hydrochloric acid and 500 parts of 0.2% hydrochloric acid. The obtained paste was dried and pulverized to obtain 11 parts of dioxazine violet derivative 5.

Example 6
The reaction, purification, and washing with hydrochloric acid were performed under the same conditions as in Example 4, and 11 parts of the obtained hydrous paste was taken as non-moisture and dispersed in 1000 parts of water. The pH was adjusted to 9 with sodium hydroxide, 3.1 parts of dodecylamine was added, and the precipitate was filtered, washed with water, dried and ground to obtain 14 parts of dioxazine violet derivative 6.

Example 7
The reaction, purification, and washing with hydrochloric acid were performed under the same conditions as in Example 4, and 11 parts of the obtained hydrous paste was taken as non-moisture and dispersed in 1000 parts of water. The pH was adjusted to 9 with sodium hydroxide, 3 parts of aluminum sulfate was added, the precipitate was filtered, washed with water and dried to obtain 11 parts of dioxazine violet derivative 7.

Comparative Example 1
To 100 parts of 92% sulfuric acid, 10 parts of dioxazine violet was added and reacted at 35 ° C. for 4 hours. After the reaction, the reaction slurry was mixed with 1000 parts of water, stirred for 2 hours, and then filtered. The obtained paste was dispersed in 1000 parts of water and stirred at pH 9 for 2 hours. Hydrochloric acid was added to adjust the pH to 1, followed by filtration. The paste was further washed with 500 parts of 1% hydrochloric acid and 500 parts of 0.2% hydrochloric acid. The obtained paste was dried and pulverized to obtain 11 parts of dioxazine violet derivative 8.

Examples 8-14, Comparative Example 2
500 parts of N, N′dimethylformamide was added to 0.01 part of each of dioxazine violet derivatives 1 to 8, and ultrasonic waves were applied for 10 minutes, followed by heating and stirring at 120 ° C. for 1 hour. The pigment slurry was filtered as it was with a disk filter (DISMICR HP020AN manufactured by Advantech Toyo Corporation) without cooling. The resulting filtrate was analyzed on a Waters liquid chromatograph mass spectrometer platform LCZ using a Waters reverse phase HPLC column SYMMETRY® as the column. Derivative (A) having one substituent having a parent signal with an m / z of 667 on the anion side, Derivative having two substituents having a parent signal with an m / z of 747 on the anion side Identified as (B). The area ratio of absorbance at 610 nm of the UV spectroscopic detector was defined as the weight ratio of the derivative (A) having one substituent and the derivative (B) having two substituents. The measurement results are shown in Table 1.

Table 1

Preparation of pigment composition 3 parts of the above dioxazine violet derivatives 1-8 are added to 97 parts of dioxazine violet pigment ("LIONOGEN VIOLEET FG-6240" manufactured by Toyo Ink Co., Ltd.) and mixed well to add dioxazine violet. Pigment compositions 1 to 8 were prepared. Further, 5 parts of the above dioxazine violet derivative 1-8 are added to 95 parts of dioxazine violet pigment ("LIONOGEN VIOLEET FG-6240" manufactured by Toyo Ink Manufacturing Co., Ltd.) and mixed well to obtain dioxazine violet pigment composition 9 ~ 16 were created.

Reference Examples 15 to 21, Comparative Examples 3 and 4
To 6 parts of dioxazine violet pigment compositions 1 to 8 and LIONOGEN VIOLET FG-6240, 35 parts of polyurethane varnish, 49 parts of solvent (mixture of MEK and propyl acetate), 10 parts of other additives and 150 parts of 3 mm alumina beads The mixture was mixed and dispersed for 60 minutes with a paint conditioner to prepare a gravure ink. The viscosity of the prepared ink was measured with a B-type viscometer (60 rpm). The gloss value (60 °) of a printed material obtained by spreading the ink prepared on a film with a bar coater was measured. Moreover, this printed matter was adhered to the printed matter of white ink with the printing surface superimposed, immersed in water, and boiled at 100 ° C. for 60 minutes. The shade of the color transferred onto the printed product of white ink was judged visually to evaluate the bleeding resistance. ○ indicates a level where there is almost no bleed, Δ indicates a level where slight bleed is confirmed, and x indicates a level where bleed is problematic. The results are shown in Table 2. However, “Example” in Table 2 represents “Reference Example”.

  When a derivative having a ratio of A to B higher than 50:50, a derivative having a higher A ratio than 67:33, or a derivative having a higher A ratio than 80:20 was used, bleeding occurred. Low pigment content. Various properties such as viscosity and gloss were also very good.

Table 2

Reference Examples 22 to 28, Comparative Examples 5 and 6
Dioxazine violet pigment compositions 1-8 and 9 parts of LIONOGEN VIOLET FG-6240, 11 parts of nitrocellulose varnish, 75 parts of solvent (mixture of methanol, IPA, toluene, ethyl acetate), 5 parts of other additives and A gravure ink was prepared by mixing 200 parts of 3 mm steel beads and dispersing for 60 minutes with a paint conditioner. The viscosity of the prepared ink was measured with a B-type viscometer (60 rpm). The gloss value (60 °) of a printed material obtained by spreading the ink prepared on a film with a bar coater was measured. Moreover, this printed matter was adhered to the printed matter of white ink with the printing surface superimposed, immersed in water, and boiled at 100 ° C. for 60 minutes. The shade of the color transferred onto the printed product of white ink was judged visually to evaluate the bleeding resistance. The results are shown in Table 3. However, “Example” in Table 3 represents “Reference Example”.

  When a derivative having a ratio of A to B higher than 50:50, a derivative having a higher A ratio than 67:33, or a derivative having a higher A ratio than 80:20 was used, bleeding occurred. Low pigment content. Various properties such as viscosity and gloss were also very good.

Table 3

Reference Examples 29 to 35, Comparative Examples 7 and 8
Flexox ink was prepared by mixing 60 parts of aqueous flexo varnish, 31 parts of water and 200 parts of 3 mm steel beads with 9 parts of dioxazine violet pigment compositions 1-8 and LIONOGEN VIOLET FG-6240, and dispersing for 120 minutes with a paint conditioner. It was created. The viscosity of the prepared ink was measured with a B-type viscometer (60 rpm). The gloss value (60 °) of a printed material obtained by spreading the ink prepared on a film with a bar coater was measured. Moreover, this printed matter was adhered to the printed matter of white ink with the printing surface superimposed, immersed in water, and boiled at 100 ° C. for 60 minutes. The shade of the color transferred onto the printed product of white ink was judged visually to evaluate the bleeding resistance. The results are shown in Table 4. However, “Example” in Table 4 represents “Reference Example”.

  When a derivative having a ratio of A to B higher than 50:50, a derivative having a higher A ratio than 67:33, or a derivative having a higher A ratio than 80:20 was used, bleeding occurred. Low pigment content. Various properties such as gloss were also good.

Table 4

Reference Examples 36-42, Comparative Examples 9, 10
Nitrocellulose varnish 12 parts, ethanol 66 parts, other additives 2 parts and 3 mm steel beads 200 parts are mixed with dioxazine violet pigment compositions 1-8 and LIONOGEN VIOLET FG-6240 20 parts, and a paint conditioner is used for 60 minutes. A flexographic ink was prepared by dispersing. The viscosity of the prepared ink was measured with a B-type viscometer (60 rpm). The gloss value (60 °) of a printed material obtained by spreading the ink prepared on a film with a bar coater was measured. Moreover, this printed matter was adhered to the printed matter of white ink with the printing surface superimposed, immersed in water, and boiled at 100 ° C. for 60 minutes. The shade of the color transferred onto the printed product of white ink was judged visually to evaluate the bleeding resistance. The results are shown in Table 5. In Table 5, “Example” represents “Reference Example”.

  When a derivative having a ratio of A to B higher than 50:50, a derivative having a higher A ratio than 67:33, or a derivative having a higher A ratio than 80:20 was used, bleeding occurred. Low pigment content. Various properties such as gloss were also very good.

Table 5

Reference Examples 43 to 49, Comparative Examples 11 and 12
Dioxazine violet pigment compositions 9-16 and 6 parts of LIONOGEN VIOLET FG-6240, 19 parts of xylene, 56 parts of phthalkid 133-60 (manufactured by Hitachi Chemical), 28 parts of melan 20 (manufactured by Hitachi Chemical), 1 mmΦ of zirconia beads 300 g was added and dispersed with a scandex for 90 minutes to prepare a paint.

The viscosity of the prepared ink was measured with a B-type viscometer (60 rpm). The obtained paints were spread on art paper with an applicator and baked at 140 ° C. for 1 hour. On top of that, a white paint was uniformly developed and allowed to stand at 230 ° C. for 4 hours. The shade of the color that exudes into the white paint was visually confirmed to evaluate the bleed resistance. The case where the bleed was clearly confirmed was rated as x, the case where there was some bleed as Δ, and the case where no bleed was confirmed as ◯. The results are shown in Table 6. However, “Example” in Table 6 represents “Reference Example”.

  If a derivative having a ratio of A to B greater than 50:50, an A ratio greater than 67:33, or a derivative having a greater A ratio than 67:33, or a derivative having an A ratio greater than 80:20, bleeding may occur. There were few and various characteristics, such as a viscosity, were also favorable.

Table 6

Examples 50 to 56, Comparative Examples 13 and 14
To 0.8 parts of dioxazine violet pigment compositions 1 to 8 and LIONOGEN VIOLET FG-6240, 3.2 parts of rosin-modified phenolic resin varnish was added and dispersed with a Hoovermarler to prepare a dark ink. This dark ink was measured at room temperature using a stationary fluidity tester (manufactured by Toyoe Seiko Co., Ltd.). The number is the distance that the ink has flowed in 10 minutes, and the larger the value, the better the fluidity. Further, the emulsification ability was measured using LITOTRONIC III manufactured by NOVOMATICS, and the weight of water that could be taken in by a constant weight of ink was defined as the maximum emulsification amount. If the maximum emulsification amount is too high, it will be excessively mixed with water on the printing press, causing problems such as scumming or dod gain during printing, which is an undesirable physical property. The results are shown in Table 7 below. However, “Example” in Table 7 represents “Reference Example”.

  When a derivative having a ratio of A to B higher than 50:50 and a ratio of A higher than 67:33 was used, a derivative having a higher ratio of A than 80:20 was further bleeded. Low pigment content. Various properties such as fluidity were also good.

Table 7

  As described above, the dioxazine violet derivative of the present invention is a colored composition represented by the problem of bleeding of gravure ink while having good dispersibility as compared with the dioxazine violet derivative that has been put to practical use so far. The problem of elution from water to external substances has been dramatically improved. Therefore, the dioxazine violet derivative of the present invention can be used for various applications such as various printing inks, paints, plastics, and the like that require elution resistance from the colored composition to an external substance.

Claims (2)

The weight ratio of the derivative (A) having one sulfo group in one molecule and the derivative (B) having two sulfo groups in one molecule is (A) :( B) = 100: 0 to 50:50. A method for producing a dioxazine violet derivative, comprising a step of reacting dioxazine violet and a sulfonating agent in a medium having no sulfonation ability to effect sulfonation. The method for producing a dioxazine violet derivative according to claim 1, wherein the medium having no sulfonation ability is methanesulfonic acid and the sulfonating agent is sulfuric acid .