JP5801976B1 - Method for producing pigment composition - Google Patents

Abstract

[PROBLEMS] To significantly improve the fluidity of pigment-containing inks and paints, to prevent pigment particles from agglomerating, and to exhibit excellent gloss and sharpness while preventing the generation of foreign matters. Provided is a method for producing a pigment composition capable of producing a colored article. SOLUTION: C. I. This is a method for producing a pigment composition containing CI Pigment Red 177. The step of desulfonating the compound represented by the general formula (1) in a reaction solution containing 80 to 90% sulfuric acid and 100 parts by mass of the compound represented by the general formula (1) is 0. And a step of adding 5 to 30 parts by mass of a basic pigment dispersant to the reaction solution and a step of introducing the reaction solution into water. [Selection figure] None

Description

The present invention relates to the production how the pigment composition.

  In general, it is difficult to mix and disperse pigments (particles) in a stable state in vehicles such as paints, gravure inks and offset inks, and this causes the following problems. For example, fine pigment particles once dispersed in a vehicle tend to agglomerate in the vehicle. The vehicle in which the pigment particles are aggregated has a problem that the viscosity thereof increases. Also, inks and paints using a vehicle in which pigment particles are dispersed tend to cause various problems such as a reduction in coloring power and a decrease in the gloss of the coating film.

  By the way, a color filter (hereinafter abbreviated as “CF”) used for manufacturing a liquid crystal color display, an imaging device, and the like is manufactured by using the pigment dispersion liquid, for example, by the following method. First, a CF pigment dispersion (CF pigment colorant) in which three pigments of red (R), green (G), and blue (B) are dispersed in a photosensitive resin solution is prepared. . Then, these CF pigment colorants are applied to a CF substrate by a spin coating method to form a colored film. Next, after exposing the colored film formed through the photomask and developing it to pattern the colored film and forming desired pixels on the substrate, CF can be obtained.

  As pigments for producing CF, green pigments, red pigments, blue pigments and the like as described below are used. Examples of the green pigment include C.I. I. Commonly used are phthalocyanine greens such as pigment green (hereinafter abbreviated as “PG”) 36, PG7, and PG58. Examples of red pigments include C.I. I. Commonly used are diketopyrrolopyrrole red such as Pigment Red (hereinafter abbreviated as “PR”) 254; anthraquinone red such as PR177; azo red such as PR242. Examples of the blue pigment include C.I. I. Phthalocyanine blue such as pigment blue (hereinafter abbreviated as “PB”) 15: 6 is common.

  Since there is a difference between the hue of these pigments and the color characteristics required for the liquid crystal display, pigments for complementary colors are used in combination. For example, for green and red pigments, C.I. I. Yellow pigments such as Pigment Yellow (hereinafter abbreviated as “PY”) 138, PY139, and PY150 are used in small amounts as complementary pigments. For blue pigments, C.I. I. A small amount of a violet pigment such as Pigment Violet (hereinafter abbreviated as “PV”) 23 is used as a complementary color pigment.

  It is difficult to disperse the above-mentioned pigment in a dispersion medium (photosensitive resin liquid or the like) using an ordinary disperser, and only a pigment dispersion having a poor pigment dispersion state may be obtained. A color filter pixel formed using a CF pigment colorant in which the pigment is not well dispersed has insufficient light transmittance, and light transmittance as a color filter pixel is insufficient. That is, the CF pigment colorant obtained by dispersing the pigment using a normal disperser is insufficient as a colorant for forming CF pixels.

  On the other hand, an acrylic polymer having a high acid value is mainly used as a resin for a photoresist, which is a pigment dispersion medium, so that a colored film after exposure can be easily developed with an alkaline aqueous solution. However, a pigment colorant (photoresist) containing a pigment as described above and an acrylic polymer having a high acid value has a problem that the pigment tends to aggregate and the viscosity tends to increase. Moreover, since the aggregation of the pigment proceeds with time and the viscosity increases, there is a problem that the storage stability is low. If CF is produced using a pigment colorant that has a high viscosity or agglomerates of pigments and exhibits a thixotropic viscosity, the central portion of the colored film before exposure rises. For this reason, there arises a problem that unevenness of hue or density difference occurs between the pixel located in the central portion of the substrate and the pixel located in the peripheral portion. This problem becomes more prominent when attempting to produce a CF with a larger screen.

  Therefore, the CF pigment colorant is required to have a good pigment dispersion state and a low viscosity as compared with general ordinary dry paints and baked paints while containing a pigment at a high concentration. . In general, the pigment colorant for CF has good storage stability because the pigment does not aggregate even when the pigment concentration is 5 to 20% by mass, and the viscosity is about 5 to 20 mPa · s. Is required.

  In order to satisfy the above requirements, conventionally, a method of adding a pigment derivative as a pigment dispersant, a method of treating a pigment with a pigment derivative, and the like have been proposed. Specifically, when an anthraquinone red such as PR177 is used as a pigment, it has been proposed to use a substituted derivative of anthraquinone as a pigment dispersant (see Patent Documents 1 and 2).

  Further, in order to produce CF with high brightness and excellent contrast, the CF pigment needs to be finer particles. In order to obtain a finer particulate pigment, for example, there is a method of grinding PR177 using a kneader such as a kneader in the presence of a specific pigment derivative (pigment dispersant), a water-soluble inorganic salt, and a solvent. It has been proposed (see Patent Document 3). In addition, a method has been proposed in which PR177 and a pigment derivative having a specific structure are dissolved in sulfuric acid, mixed with water and precipitated, and the acidic component is removed to refine PR177 (see Patent Documents 4 and 5). .

Japanese Patent No. 3625143 JP 60-88185 A JP-A-9-272812 International Publication No. 2009/025325 JP2013-253199A

  In recent years, there is a desire to further improve the performance of CF. Specifically, it is necessary to further improve the transparency of the colored pixels, increase the contrast of the transmitted light of the colored pixels, or increase the pigment concentration of the colored pixels. However, it is difficult to obtain a pigment colorant capable of producing CF that satisfies the above-described performance by the conventional techniques proposed in Patent Documents 1 and 2. Furthermore, since the foreign material may generate | occur | produce in the coating-film (colored film), the pigment colorant obtained by the prior art is requested | required for improvement.

  In addition, since the methods proposed in Patent Documents 3 to 5 are all methods for refining PR177, which is a pigment, it is necessary to separately provide a refining step. For this reason, it has been desired to further simplify and rationalize the process for preparing the pigment composition containing PR177.

The present invention has been made in view of the problems of the prior art as described above, and the problem is that the fluidity of pigment-containing inks and paints can be remarkably improved, it is possible to prevent particle agglomeration of the pigment, and, while preventing the occurrence of foreign matters, it is to provide a manufacturing how excellent gloss and possible pigment composition produce colored articles that exhibit sharpness. Another object of the present invention is over time thickening suppression by aggregation of the pigment, a method of manufacturing a storage stability better pigment composition, and to provide a manufacturing how the pigment composition having excellent storage stability There is.

That is, according to the present invention, the following pigment composition is provided.
[1] C.I. I. A method for producing a pigment composition containing CI Pigment Red 177, the step of desulfonating a compound represented by the following general formula (1) in a reaction solution containing 80 to 90% sulfuric acid; A step of adding 0.5 to 30 parts by mass of a basic pigment dispersant to the reaction solution with respect to 100 parts by mass of the compound represented by the general formula (1), and a step of adding the reaction solution to water. , have a, wherein the basic pigment dispersant, a manufacturing method of a pigment composition comprising at least one of compounds represented by compounds represented by the following general formula by the following general formula (2) (3).

（前記一般式（１）中、Ｍは、それぞれ独立に、水素原子、ナトリウム、カリウム、カルシウム、バリウム、又はストロンチウムを表す）

（前記一般式（２）中、Ｘは、水素原子又はアシルアミノ基を表し、Ｙは、５位に水素原子又はアシルアミノ基を有するアントラキノニルアミノ基、フェニルアミノ基、又はフェノキシ基を表し、Ｒ１〜Ｒ４は、それぞれ独立に、置換若しくは未置換のアルキル基又はシクロアルキル基を表し、Ｒ１とＲ２及びＲ３とＲ４は、それぞれ独立に、隣接する窒素原子とともに、窒素原子、酸素原子、又は硫黄原子を含んでもよい環を形成してもよく、ｎ又はｍは、それぞれ独立に、２〜３０の数を表す。前記一般式（３）中、Ｒ５及びＲ６は、それぞれ独立に、下記一般式（４）で表される置換基、下記一般式（５）で表される置換基、又は下記式（６）で表される置換基を表す）

（前記一般式（４）中、Ｒ７及びＲ８は、それぞれ独立に、水素原子、置換若しくは未置換のアルキル基、又はシクロアルキル基を表し、Ｒ７とＲ８は、隣接する窒素原子とともに複素環を形成してもよく、前記複素環は、隣接する窒素原子以外の窒素原子、酸素原子、又は硫黄原子を含んでもよく、ｏは、２〜３０の数を表す。前記一般式（５）中、Ｒ９は、メチル基、イソプロピル基、（４−メトキシフェニル）エチル基、又はピリジル基を表す）

(In the general formula (1), each M independently represents a hydrogen atom, sodium, potassium, calcium, barium, or strontium)

(In the general formula (2), X represents a hydrogen atom or an acylamino group, Y represents an anthraquinonylamino group having a hydrogen atom or an acylamino group at the 5-position, a phenylamino group, or a phenoxy group; ~ R4 each independently represents a substituted or unsubstituted alkyl group or cycloalkyl group, and R1 and R2 and R3 and R4 each independently represent a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom. And n or m each independently represents a number of 2 to 30. In the general formula (3), R5 and R6 are each independently the following general formula ( 4) represents a substituent represented by the following general formula (5), or a substituent represented by the following formula (6))

(In the general formula (4), R7 and R8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a cycloalkyl group, and R7 and R8 form a heterocyclic ring together with the adjacent nitrogen atom. The heterocyclic ring may contain a nitrogen atom other than the adjacent nitrogen atom, an oxygen atom, or a sulfur atom, and o represents a number of 2 to 30. In the general formula (5), R9 Represents a methyl group, an isopropyl group, a (4-methoxyphenyl) ethyl group, or a pyridyl group)

[2] In the above [1], the compound represented by the general formula (1) is desulfonated at 120 to 200 ° C. for 3 to 8 hours, and the reaction solution is poured into water at a temperature of 60 ° C. or lower. The manufacturing method of the pigment composition of description .

  According to the method for producing a pigment composition of the present invention, the fluidity of a pigment-containing ink or paint can be remarkably improved, pigment particles can be prevented from agglomerating, and foreign matter can be prevented from being generated. Meanwhile, a pigment composition capable of producing a colored article exhibiting excellent gloss and sharpness can be produced. For this reason, the pigment composition produced by the method for producing a pigment composition of the present invention is used as a colorant for printing inks such as offset ink and gravure ink, various paints, and plastics, It is useful as a colorant for photographic dry or wet toner, ink jet recording ink, thermal transfer recording ink, image display, image recording, CF resist, writing instrument ink, and the like. In addition, when the pigment composition produced by the method for producing a pigment composition of the present invention is used, the fluidity of various paints and the like is remarkably improved, the pigment particles are prevented from agglomerating, and the generation of foreign matter is prevented. A composition can be provided.

<Method for producing pigment composition>
Hereinafter, the details of the present invention will be described with reference to preferred embodiments. The production method of the present invention comprises C.I. I. A method for producing a pigment composition containing CI Pigment Red 177, a step of desulfonating a compound represented by the following general formula (1) in a reaction solution containing 80 to 90% sulfuric acid; It has the process of adding 0.5-30 mass parts of basic pigment dispersant to a reaction liquid with respect to 100 mass parts of compounds represented by (1), and the process of throwing a reaction liquid into water.

（前記一般式（１）中、Ｍは、それぞれ独立に、水素原子、ナトリウム、カリウム、カルシウム、バリウム、又はストロンチウムを表す）

(In the general formula (1), each M independently represents a hydrogen atom, sodium, potassium, calcium, barium, or strontium)

  The compound represented by the general formula (1) can be produced by the method described in JP-B-38-25842. Specifically, as shown in the following formula, 1-amino-4-bromoanthraquinone-2-sulfonic acid sodium salt (7) is added in an aqueous solvent in the presence of 1 to 3 equivalents of metallic copper, and the pH is 2 to 5. Is heated to 50 to 100 ° C. in an aqueous sulfuric acid solution to obtain a dyeing solution. Then, the compound represented by General formula (1) can be manufactured by the yield of about 92% by salting out the obtained dye liquid according to a conventional method, filtering and drying.

As shown in the following formula, PR177, which is a pigment having a red hue, desulfonates the compound represented by the general formula (1) in a reaction liquid (for example, sulfuric acid aqueous solution) containing 80 to 90% sulfuric acid. It can be produced by reacting. In addition, it is preferable that the temperature of said desulfonation reaction shall be 120-200 degreeC. The time for the desulfonation reaction is preferably 3 to 8 hours.

  The manufacturing method of the pigment composition of this invention has the process of adding a basic pigment dispersant to the reaction liquid after desulfonation reaction. As the basic pigment dispersant, it is preferable to use a dispersant containing at least one of a compound represented by the following general formula (2) and a compound represented by the following general formula (3). As the basic pigment dispersant, only one of the compound represented by the following general formula (2) and the compound represented by the following general formula (3) may be used, or it may be represented by the following general formula (2). Both a compound represented by formula (3) and a compound represented by the following general formula (3) may be used.

（前記一般式（２）中、Ｘは、水素原子又はアシルアミノ基を表し、Ｙは、５位に水素原子又はアシルアミノ基を有するアントラキノニルアミノ基、フェニルアミノ基、又はフェノキシ基を表し、Ｒ１〜Ｒ４は、それぞれ独立に、置換若しくは未置換のアルキル基又はシクロアルキル基を表し、Ｒ１とＲ２及びＲ３とＲ４は、それぞれ独立に、隣接する窒素原子とともに、窒素原子、酸素原子、又は硫黄原子を含んでもよい環を形成してもよく、ｎ又はｍは、それぞれ独立に、２〜３０の数を表す。前記一般式（３）中、Ｒ５及びＲ６は、それぞれ独立に、下記一般式（４）で表される置換基、下記一般式（５）で表される置換基、又は下記式（６）で表される置換基を表す）

(In the general formula (2), X represents a hydrogen atom or an acylamino group, Y represents an anthraquinonylamino group having a hydrogen atom or an acylamino group at the 5-position, a phenylamino group, or a phenoxy group; ~ R4 each independently represents a substituted or unsubstituted alkyl group or cycloalkyl group, and R1 and R2 and R3 and R4 each independently represent a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom. And n or m each independently represents a number of 2 to 30. In the general formula (3), R5 and R6 are each independently the following general formula ( 4) represents a substituent represented by the following general formula (5), or a substituent represented by the following formula (6))

（前記一般式（４）中、Ｒ７及びＲ８は、それぞれ独立に、水素原子、置換若しくは未置換のアルキル基、又はシクロアルキル基を表し、Ｒ７とＲ８は、隣接する窒素原子とともに複素環を形成してもよく、前記複素環は、隣接する窒素原子以外の窒素原子、酸素原子、又は硫黄原子を含んでもよく、ｏは、２〜３０の数を表す。前記一般式（５）中、Ｒ９は、メチル基、イソプロピル基、（４−メトキシフェニル）エチル基、又はピリジル基を表す）

(In the general formula (4), R7 and R8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a cycloalkyl group, and R7 and R8 form a heterocyclic ring together with the adjacent nitrogen atom. The heterocyclic ring may contain a nitrogen atom other than the adjacent nitrogen atom, an oxygen atom, or a sulfur atom, and o represents a number of 2 to 30. In the general formula (5), R9 Represents a methyl group, an isopropyl group, a (4-methoxyphenyl) ethyl group, or a pyridyl group)

  The compound represented by the general formula (2) (basic pigment dispersant) can be produced according to the method described in Japanese Patent No. 3625143. The compound represented by the general formula (3) (basic pigment dispersant) can be produced according to the method described in “Production Example 4” of Japanese Patent Publication No. 60-88185.

  Any of the above basic pigment dispersants exhibits an excellent action as a pigment dispersant even in a small amount. In addition, since pigment compositions and colored compositions prepared using these basic pigment dispersants are difficult to thicken or gel during storage, foreign matter is generated in the coating film (film) formed using them. Hard to do. Specific examples (specific examples 1 to 7) of the compounds represented by the general formulas (2) and (3) are shown below.

  The compound (basic pigment dispersant) represented by the general formula (2) can be synthesized, for example, as follows. 1-aminoanthraquinone, aniline, and cyanuric chloride are reacted at 130 ° C. to 160 ° C. for 2 to 6 hours in an inert solvent such as o-dichlorobenzene. Further, 1 mol of “polyamine having a substituent having one secondary amino group and two basic nitrogen atoms and not having a primary amino group” was added, and the mixture was added at 150 to 170 ° C. By reacting for ˜4 hours, the compound represented by the general formula (2) can be obtained.

  Used when synthesizing the compound represented by the general formula (2) “has a substituent having one secondary amino group and two basic nitrogen atoms, and does not have a primary amino group Specific examples of “polyamine” include N, N, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N ″, N ″ -tetraethyldiethylenetriamine, N, N, N ″, N ″ -tetra (n-propyl ) Diethylenetriamine, N, N, N ″, N ″ -tetra (i-propyl) diethylenetriamine, N, N, N ″, N ″ -tetra (n-butyl) diethylenetriamine, N, N, N ″, N ″ -tetra (I-butyl) diethylenetriamine, N, N, N ″, N ″ -tetra (t-butyl) diethylenetriamine, 3,3′-iminobis (N, N-dimethylpropylamine), 3,3′-iminobi (N, N-diethylpropylamine), 3,3′-iminobis (N, N-di (n-propyl) propylamine), 3,3′-iminobis (N, N-di (n-butyl) propylamine ), 3,3′-iminobis (N, N-di (i-butyl) propylamine), 3,3′-iminobis (N, N-di (t-butyl) propylamine), 3,3′-iminobis (N, N-dimethylpropylamine), 2,9-dimethyl-2,5,9-triazadecane, 2,10-dimethyl-2,10-triazadecane, 2,12-dimethyl-2,6,12-triaza Tridecane, 2,12-dimethyl-2,5,12-triazatridecane, 2,16-dimethyl-2,9,16-triazaheptadecane, 3-ethyl-10-methyl-3,6,10 -Triazaundecane 5,13- di (n- butyl) 5,9,13 triazacyclononane heptadecane, di - (2-picolyl) amine, di - (3-picolyl) amine, and the like.

  The compound (basic pigment dispersant) represented by the general formula (3) can be synthesized, for example, as follows. First, PR177 and cyanuric chloride are reacted at 100 to 110 ° C. in an inert solvent such as dimethylacetamide. Next, a compound represented by the general formula (3) can be obtained by reacting an N, N-dialkylaminoalkylamine compound such as N, N-diethylaminopropylamine at 130 to 140 ° C. In addition to N, N-dialkylaminoalkylamine compounds, for example, N-aminoalkyl-N-cyclohexylamine compounds such as N- (3-aminopropyl) cyclohexylamine, and piperazine compounds such as 1-methylpiperazine are used. It can also be used.

  Specific examples of N, N-dialkylaminoalkylamine compounds include N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-dibutylaminoethylamine, N, N-dimethylaminopropylamine, N, N -Diethylaminopropylamine, N, N-dibutylaminopropylamine, N, N-dimethylaminobutylamine, N, N-diethylaminobutylamine, N, N-dibutylaminobutylamine and the like. Of these N, N-dialkylaminoalkylamine compounds, N, N-diethylaminopropylamine and the like are preferable.

  Specific examples of the N-aminoalkyl-N-cyclohexylamine compound include N- (1-aminoethyl) -N-cyclohexylamine, N- (1-aminopropyl) -N-cyclohexylamine, and N- (1-amino). Butyl) -N-cyclohexylamine, N- (2-aminopropyl) -N-cyclohexylamine, N- (2-aminobutyl) -N-cyclohexylamine, N- (3-aminopropyl) cyclohexylamine, N- ( And 3-aminobutyl) cyclohexylamine. Of these N-aminoalkyl-N-cyclohexylamines, N- (3-aminopropyl) cyclohexylamine and the like are preferable.

  Specific examples of the piperazine compound include 1-methylpiperazine, 1-ethylpiperazine, 1- (2-pyridyl) piperazine, 1-amino-4-methylpiperazine and the like. Of the piperazine compounds, 1-methylpiperazine and the like are preferable.

The compound represented by the general formula (2) and the compound represented by the general formula (3) can be expected to have the following effects in addition to the effect as a pigment dispersant. For example, when a basic pigment dispersant is added to the reaction solution after the desulfonation reaction and then the reaction solution is poured into water, pigment particles are precipitated. The compounds (pigment dispersants) represented by the general formulas (2) and (3) have an effect as a crystal growth inhibitor that prevents coarsening of the pigment particles that precipitate. The temperature of the reaction liquid when adding the basic pigment dispersant is preferably 60 ° C. or less. The pigment (PR177) produced by the desulfonation reaction is dissolved in an aqueous sulfuric acid solution (reaction solution). And if the reaction liquid which added the basic pigment dispersant is thrown in water, pigment particles will precipitate. The basic pigment dispersant can be present not only on the surface of the pigment particles but also inside the pigment particles. For this reason, depending on the addition amount of the basic pigment dispersant, the performance as a pigment dispersant may not be sufficiently exhibited. Therefore, a method of adding (processing) a basic pigment dispersant later is also effective. Specifically, there are usage methods such as (1) to (4) shown below, and the pigment can be dispersed well by any method.
(1) A pigment and a pigment dispersant are mixed in advance by a known method, and the obtained pigment composition is added to a vehicle or the like to disperse the pigment in the vehicle.
(2) A pigment and a pigment dispersant are separately added at a predetermined ratio to a vehicle or the like, and the pigment is dispersed in the vehicle.
(3) The pigment and the pigment dispersant are separately dispersed in a vehicle or the like, and then the obtained dispersions are mixed at a predetermined ratio to disperse the pigment in the vehicle.
(4) A pigment dispersant is added at a predetermined ratio to a dispersion obtained by dispersing the pigment in a vehicle or the like, and the pigment is dispersed in the vehicle.

  In the manufacturing method of the pigment composition of this invention, 0.5-30 mass parts with respect to 100 mass parts of compounds represented by General formula (1) to the reaction liquid after desulfonation reaction, Preferably it is 2-2. Add 30 parts by weight of basic pigment dispersant. Moreover, as a basic pigment dispersing agent, when using the compound represented by General formula (2) and the compound represented by General formula (3) in combination, both compounding ratio (mass reference | standard) is General formula (2). ): Compound represented by formula (3) = preferably 5:95 to 95: 5, and more preferably 25:75 to 75:25.

  In the case where the compound represented by the general formula (2) and the compound represented by the general formula (3) are used in combination, it is preferable to appropriately adjust the blending ratio of the two. For example, when the compounding ratio of the compound represented by the general formula (2) is lowered, the viscosity tends to decrease and the stability tends to improve. On the other hand, when the compounding ratio of the compound represented by the general formula (3) is lowered, the viscosity tends to increase. That is, by using together the compound represented by the general formula (2) and the compound represented by the general formula (3) at an appropriate blending ratio, the viscosity of the resulting pigment composition and coloring composition is lowered, Storage stability can be improved.

  When the amount of the basic pigment dispersant added to the reaction solution after the desulfonation reaction is less than 0.5 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1), the basic pigment dispersion The effect of the agent becomes insufficient. On the other hand, when the amount of the basic pigment dispersant to be added exceeds 30 parts by mass, the effect of dispersing the pigment reaches its peak and disadvantageous in terms of productivity. Furthermore, the physical properties of paint and ink vehicles prepared using a pigment composition containing an excessive amount of the basic pigment dispersant are reduced, and the hue of the pigment changes greatly depending on the color of the basic pigment dispersant itself. Sometimes.

  The pigment composition obtained by the production method of the present invention may contain a pigment other than PR177 (other pigments) for the purpose of toning and the like. Specific examples of other pigments include soluble / insoluble azo pigments, high molecular weight azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, methine / azomethine pigments, perylene pigments, perinone pigments, isolone pigments, Indolinone pigments, isoindoline pigments, metal complex pigments and the like can be mentioned.

<Coloring composition>
The coloring composition of this invention contains the pigment composition manufactured by the manufacturing method of the above-mentioned this invention, and film forming material. The colored composition of the present invention can be obtained, for example, by mixing a refined pigment composition and a film forming material such as a resin (polymer or copolymer), oligomer, or monomer. The coloring composition of the present invention can be used in a wide range of fields as a colorant for image display, image recording, printing ink, writing ink, plastic, pigment printing, paint and the like. In particular, it is suitable as an image display material in which the transparency of colored pixels is a problem, particularly as a pigment colorant for a color filter (CF). Of course, the colored composition of the present invention is also useful as a material for an image recording agent such as an ink for ink jet recording, an electrodeposition recording liquid, and a developer for electrophotography. These materials for image recording agents are used in image recording methods such as an ink jet recording method, an electrodeposition recording method, and an electrophotographic method. If the colored composition of the present invention is used, a material for an image recording agent capable of providing a high-quality image can be prepared by any image recording method, not limited to the above-described examples.

  Hereinafter, further details of the coloring composition of the present invention will be described by taking as an example a pigment dispersion for a color filter (a pigment coloring agent for CF) which is a pigment coloring agent for image display. In order to prepare the CF pigment colorant, first, the above pigment composition is added to a liquid containing a film-forming material and premixed. Next, if a dispersion treatment is performed, a pigment colorant for CF can be obtained. More specifically, a pigment colorant for CF can be obtained by adding and mixing the fine pigment composition of the present invention obtained by the production method of the present invention to a liquid containing a film-forming material. it can. In addition, the pigment composition of the present invention is added to and mixed with a liquid containing a film-forming material or a cationic polymer dispersant, and then ground using a horizontal wet medium disperser (bead mill) such as a dyno mill. Even when pulverized and dispersed, a pigment colorant for CF can be obtained.

  As a liquid containing a film-forming material used for preparing a CF pigment colorant, a solution of a film-forming polymer contained in a conventionally known CF pigment colorant can be used. Examples of the liquid medium used for the liquid containing the film forming material include an organic solvent, water, and a mixed liquid of an organic solvent and water. In addition, conventionally well-known additives, such as a dispersion | distribution adjuvant, a smoothing agent, an adhesive agent, can be added to the pigment pigment for CF as needed.

  The amount of the pigment composition contained in the colored composition (pigment colorant) of the present invention varies depending on the application, but is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the film-forming material, More preferably, it is 50-250 mass parts. Further, as the liquid containing the film forming material, a liquid containing a photosensitive film forming material or a liquid containing a non-photosensitive film forming material can be used. Specific examples of the liquid containing the photosensitive film-forming material include a liquid containing a photosensitive film-forming material used for ultraviolet curable ink, electron beam curable ink, and the like. Specific examples of the liquid containing a non-photosensitive film-forming material include, for example, varnishes used for printing inks such as letterpress inks, lithographic inks, gravure inks and screen inks; varnishes used for room temperature drying or baking paints Varnish used for electrodeposition coating; varnish used for thermal transfer ribbon, and the like.

  The CF pigment colorant is required to have a good pigment dispersion state and a low viscosity as compared with general ordinary dry paints and baking paints while containing a pigment in a high concentration. For this reason, generally, even if the pigment concentration is 5 to 20% by mass, the pigment does not aggregate, the viscosity is about 5 to 20 mPa · s, and the storage stability is required to be good. The More preferably, it is 5 to 15 mPa · s, and it is required that the viscosity increase rate after being allowed to stand at 25 ° C. for 1 month (after being left) is within 10%. This is because if the viscosity increases, it becomes impossible to form a film with a certain film thickness.

  Specific examples of photosensitive film-forming materials that can be used for CF pigment colorants include photosensitive cyclized rubber resins, photosensitive phenolic resins, photosensitive polyacrylate resins, photosensitive polyamide resins, and photosensitive polyimides. Examples thereof include photosensitive resins such as polyester resins, unsaturated polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins. In addition, you may add various monomers as a reactive diluent to the liquid containing these photosensitive resins.

  If a photopolymerization initiator such as benzoin ether or benzophenone is added to the pigment colorant containing the photosensitive resin as listed above as the film forming material and kneaded by a conventionally known method, a photocurable photosensitive resin is obtained. Pigment dispersion. Moreover, if a thermal polymerization initiator is used instead of the photopolymerization initiator, a thermosetting pigment dispersion can be obtained.

  Specific examples of non-photosensitive film-forming materials that can be used for CF pigment colorants include styrene- (meth) acrylic acid ester-based (co) polymers, soluble polyamide-based resins, soluble polyimide-based resins, and soluble polyamideimide-based materials. Resin, soluble polyesterimide resin, water-soluble salt of styrene-maleic acid ester copolymer, water-soluble salt of (meth) acrylic acid ester- (meth) acrylic acid copolymer, water-soluble aminopolyester resin, etc. And the water-soluble salts thereof.

  Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.

(Preparation of basic pigment dispersants 1-7)
<Production Example 1>
To 600 parts of o-dichlorobenzene, 62 parts of 1-aminoanthraquinone and 25 parts of cyanuric chloride were added and stirred at 130 ° C. for 5 hours. After cooling, 50 parts of N, N, N ″, N ″ -tetraethyldiethylenetriamine was further added and stirred at 170 ° C. for 3 hours. After filtration, washing with methanol, and drying, 81 parts of basic pigment dispersant 1 of Example 1 was obtained. A compound having a molecular weight of 736 was detected by mass spectrometry using Matrix Assisted Laser Desorption / Ionization (Matrix Assisted Laser Desorption / Ionization) (hereinafter abbreviated as “MALDI”), and it was confirmed that the basic pigment dispersant 1 had the desired structure. did.

<Production Example 2>
In the same manner as in Production Example 1, 1-aminoanthraquinone and 3,3′-iminobis (N, N-dimethylpropylamine) were sequentially condensed with cyanuric chloride to obtain 78 parts of basic pigment dispersant 2 of Specific Example 2. Got. A compound having a molecular weight of 708 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 2 had the target structure.

<Production Example 3>
44 parts of PR177 and 37 parts of cyanuric chloride were added to 800 parts of dimethylacetamide, and the mixture was stirred at 100 to 110 ° C. for 5 hours. After cooling, 125 parts of N- (3-aminopropyl) cyclohexylamine was further added and reacted at 130-140 ° C. for 3 hours. After cooling, the mixture was filtered and washed with methanol and water. By drying, 110 parts of basic pigment dispersant 3 of specific example 3 was obtained. A compound having a molecular weight of 1219 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 3 had the target structure.

<Production Example 4>
In the same manner as in Production Example 3, PR177 and N, N-diethylaminopropylamine were sequentially reacted with cyanuric chloride to obtain 106 parts of Basic Pigment Dispersant 4 of Specific Example 4. A compound having a molecular weight of 1115 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 4 had the target structure.

<Production Example 5>
In the same manner as in Production Example 3, PR177 and 1-methylpiperazine were sequentially reacted with cyanuric chloride to obtain 98 parts of Basic Pigment Dispersant 5 of Specific Example 5. A compound having a molecular weight of 994 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 5 had the target structure.

<Production Example 6>
In the same manner as in Production Example 3, PR177 and N, N-diethylethylenediamine were sequentially reacted with cyanuric chloride to obtain 103 parts of Basic Pigment Dispersant 6 of Specific Example 6. A compound having a molecular weight of 1087 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 6 had the target structure.

<Production Example 7>
In the same manner as in Production Example 3, PR177 and 1-amino-4-methylpiperazine were sequentially reacted with cyanuric chloride to obtain 97 parts of a basic pigment dispersant 7 of Specific Example 7. A compound having a molecular weight of 1054 was detected by mass spectrometry using MALDI, and it was confirmed that the basic pigment dispersant 7 had the target structure.

(Preparation of pigment composition)
<Production Example 8>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 1 obtained in Production Example 1 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.4 parts of pigment composition 1.

<Production Example 9>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 2 obtained in Production Example 2 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.3 parts of pigment composition 2.

<Production Example 10>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 3 obtained in Production Example 3 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and dried to obtain 17.3 parts of pigment composition 3.

<Production Example 11>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 4 obtained in Production Example 4 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.4 parts of pigment composition 4.

<Production Example 12>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 5 obtained in Production Example 5 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.2 parts of pigment composition 5.

<Production Example 13>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 6 obtained in Production Example 6 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.4 parts of pigment composition 6.

<Production Example 14>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 4.2 parts of the basic pigment dispersant 7 obtained in Production Example 7 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.3 parts of pigment composition 7.

<Production Example 15>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 2.1 parts of the basic pigment dispersant 2 obtained in Production Example 2 and 2.1 parts of the basic dispersant 4 obtained in Production Example 4 were added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.3 parts of pigment composition 8.

<Production Example 16>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 1.4 parts of the basic pigment dispersant 2 obtained in Production Example 2 and 2.8 parts of the basic dispersant 4 obtained in Production Example 4 were added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.3 parts of pigment composition 9.

<Production Example 17>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 2.8 parts of the basic pigment dispersant 2 obtained in Production Example 2 and 1.4 parts of the basic dispersant 4 obtained in Production Example 4 were added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 17.3 parts of pigment composition 10.

<Comparative Production Example 1>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 0.1 part of the basic pigment dispersant 4 obtained in Production Example 4 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 13.6 parts of pigment composition 11.

<Comparative Production Example 2>
21 parts of the compound represented by the general formula (1) was added to 155 parts of 80% sulfuric acid and stirred at 140 ° C. for 5 hours. After cooling to 60 ° C., 7.35 parts of the basic pigment dispersant 4 obtained in Production Example 4 was added. After cooling to 40 ° C., it was poured into 1500 mL of water. The precipitate was filtered, washed with water until neutral, and then dried to obtain 19.5 parts of pigment composition 12.

[Preparation of pigment dispersion (pigment colorant for color filter (CF))]
< Reference Example 1>
An acrylic resin varnish having an average molecular weight of 12,000 and a solid content of 40% obtained by copolymerizing methacrylic acid / benzyl acrylate / styrene / hydroxyl acrylate in a molar ratio of 25/50/15/10 was used. A pigment dispersion was prepared according to the following method. After mixing and premixing 50 parts of the above acrylic resin varnish, 20 parts of the pigment composition 1 and 20 parts of propylene glycol-1-monomethyl ether-2-acetate (hereinafter abbreviated as “PGMAc”) as a solvent. Then, dispersion treatment was performed using a horizontal bead mill to obtain the CF pigment colorant of Reference Example 1.

< Reference Examples 2 to 10>
CF pigment colorants for Reference Examples 2 to 10 were obtained in the same manner as Reference Example 1 except that Pigment Compositions 2 to 10 were used instead of Pigment Composition 1.

<Comparative Example 1>
A CF colorant for Comparative Example 1 was obtained in the same manner as in Reference Example 1 except that Pigment Composition 11 was used in place of Pigment Composition 1.

<Comparative Example 2>
A CF colorant for Comparative Example 2 was obtained in the same manner as in Reference Example 1 except that Pigment Composition 12 was used instead of Pigment Composition 1.

  Table 1 shows the main composition of the obtained CF pigment colorant.

[Evaluation]
Regarding the CF pigment colorants of Reference Examples 1 to 10 and Comparative Examples 1 and 2, (1) fluidity, (2) gloss of the color development surface, (3) presence or absence of foreign matter in the coating film, and (4) contrast Evaluated. Each evaluation method is shown below. The evaluation results are shown in Table 2.

(1) Fluidity (viscosity, storage stability)
Using an E-type viscometer, the viscosity (mPa · s) immediately after preparation of each CF pigment colorant (initial stage) and after standing for 1 month at 25 ° C. (after standing) was measured. The measurement conditions were temperature: room temperature (25 ° C.) and rotor rotation speed: 6 rpm. Further, the rate of change in viscosity ((viscosity after standing / initial viscosity) × 100 (%)) was calculated from the initial viscosity and the viscosity after standing, and the storage stability was evaluated according to the following criteria.
○: 110% or less △: More than 110% and less than 140% ×: More than 140%

(2) Gross color coater (winding thickness 0.45 mm) of the color development surface was used to develop the CF pigment colorant on the polypropylene film to form the color development surface. The gloss of the developed color surface was observed visually and using a gloss meter, and “gloss of the color developed surface” was evaluated according to the following criteria. In addition, when observing using a gloss meter, it can be determined that the higher the color development surface gloss, the better.
◎: Very good ○: Good ×: Bad

(3) Presence / absence of foreign matter in coating film Using a spinner, a CF pigment colorant was applied to a glass substrate, dried at 90 ° C for 2 minutes, and then heated at 270 ° C for 30 minutes to form a coating film. The surface (application surface) of the coating film formed using a microscope was observed at 200 times to confirm the presence or absence of foreign matter, and “existence of foreign matter in the coating” was evaluated according to the following criteria.
◎: No foreign matter ○: Slight foreign matter ×: Foreign matter

(4) Contrast A CF pigment colorant was applied to a glass substrate using a spinner, dried at 90 ° C. for 2 minutes, and then heated at 230 ° C. for 30 minutes to form a coating film. With respect to the three coating films formed by changing the spinner speed, the brightness and dark brightness were measured with a contrast meter (manufactured by Eye System Co., Ltd.) to obtain the contrast (bright brightness / dark brightness). Further, the chromaticity x of the coating film was measured with a spectrophotometer (trade name “U-2000A”, manufactured by Hitachi, Ltd.). Chromaticity x and contrast were plotted on a graph, an approximate straight line was drawn, and the contrast at chromaticity x = 0.650 was read. Using the contrast value of the coating film formed with the CF pigment colorant of Comparative Example 2 as 100%, the relative ratio (%) of the contrast of the coating film formed with other CF pigment colorants was calculated, and is shown below. Contrast was evaluated according to criteria.
○: 110% or more Δ: 90% or more and less than 110% ×: less than 90%

As shown in Table 1, it is clear that the pigment compositions 1 to 10 obtained in Production Examples 8 to 17 are those in which the aggregation of the pigment and the increase in viscosity over time are suppressed. In addition, if the CF pigment colorant for Reference Examples 1 to 10 prepared using the pigment compositions 1 to 10 is used, a coating film that has good gloss on the color developing surface and does not generate foreign matters with high contrast. Can be formed.

  Further, the pigment compositions 1 to 10 were used as printing inks such as offset inks; various paints such as nitrocellulose lacquers and melamine alkyd paints; and colorants of synthetic resins such as vinyl chloride resins, and their applicability was examined. . As a result, in any case, it was confirmed that the pigment did not aggregate and showed good dispersibility. In addition, recently, pigment compositions 1 to 10 are used for the preparation of dry or wet toner for electrophotography, ink for ink jet recording, ink for thermal transfer recording, ink for writing instruments and the like that are particularly required to have high dispersibility. And examined its applicability. As a result, it was confirmed that excellent dispersibility was exhibited in any case.

  The pigment composition produced by the production method of the present invention includes printing ink (offset ink, gravure ink, etc.), various paints, plastics, pigment printing agents, electrophotographic dry or wet toner, ink jet recording ink, thermal transfer recording It is useful as a composition to be blended in ink, color filter resist, writing instrument ink, and the like.

Claims (2)

C. I. A method for producing a pigment composition containing CI Pigment Red 177, comprising:
A step of desulfonating a compound represented by the following general formula (1) in a reaction solution containing 80 to 90% sulfuric acid;
Adding 0.5 to 30 parts by mass of a basic pigment dispersant to the reaction liquid with respect to 100 parts by mass of the compound represented by the general formula (1);
Have a, a step of introducing the reaction solution into water,
The manufacturing method of the pigment composition in which the said basic pigment dispersant contains at least any one of the compound represented by the following general formula (2), and the following general formula (3) .

(In the general formula (1), each M independently represents a hydrogen atom, sodium, potassium, calcium, barium, or strontium)

(In the general formula (2), X represents a hydrogen atom or an acylamino group, Y represents an anthraquinonylamino group having a hydrogen atom or an acylamino group at the 5-position, a phenylamino group, or a phenoxy group; ~ R4 each independently represents a substituted or unsubstituted alkyl group or cycloalkyl group, and R1 and R2 and R3 and R4 each independently represent a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom. And n or m each independently represents a number of 2 to 30. In the general formula (3), R5 and R6 are each independently the following general formula ( 4) represents a substituent represented by the following general formula (5), or a substituent represented by the following formula (6))

(In the general formula (4), R7 and R8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a cycloalkyl group, and R7 and R8 form a heterocyclic ring together with the adjacent nitrogen atom. The heterocyclic ring may contain a nitrogen atom other than the adjacent nitrogen atom, an oxygen atom, or a sulfur atom, and o represents a number of 2 to 30. In the general formula (5), R9 Represents a methyl group, an isopropyl group, a (4-methoxyphenyl) ethyl group, or a pyridyl group) The compound represented by the general formula (1) is desulfonated at 120 to 200 ° C. for 3 to 8 hours,
The method for producing a pigment composition according to claim 1, wherein the reaction solution is poured into water at a temperature of 60 ° C or lower.