JP2003253150A - Fine quinacridone solid solution pigment and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine quinacridone-based solid solution pigment which is finer and has a larger specific surface area than conventional quinacridone-based solid solution pigments and which has more excellent coloring power when mixed with a coloring medium. Further, by simultaneously cyclizing and hydrolyzing each intermediate of unsubstituted quinacridone and a quinacridone having a halogen atom in an aromatic ring in the presence of a specific compound, a fine solid solution is produced, and the pigment is produced under conventional pigmentation conditions. The resulting production method is provided. SOLUTION: The BET specific surface area by the nitrogen adsorption method is 50.
A fine quinacridone-based solid solution pigment comprising a solid solution of unsubstituted quinacridone and quinacridone having a halogen atom in an aromatic ring, which has a solid solution pigment of １５０150 m ² / g. 2,5-dianilinoterephthalic acid and 2,5-having a halogen atom on an aromatic ring
A method for producing a fine quinacridone-based solid solution pigment which cyclizes and hydrolyzes dianilinoterephthalic acid in the presence of an organic compound having a sulfonic acid group or a metal salt of sulfonic acid as a functional group, and then forms a pigment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fine quinacridone solid solution pigment and a method for producing the same.

[0002]

2. Description of the Related Art Pigments mainly composed of a solid solution of unsubstituted quinacridone and 4,11-dichloroquinacridone include
As described in U.S. Pat. No. 4,099,980, C.I.
I. Pigment Red 207 is known.
While other known quinacridone pigments such as unsubstituted quinacridone pigment and dimethylquinacridone pigment exhibit a red to magenta hue, the solid solution pigment is characterized by exhibiting a yellowish red color.

In addition, C.I. I. Pigment Red 2
07 contains quinacridone containing a chlorine atom as a substituent, and has high chemical durability such as solvent resistance.

C. I. Pigment Red
The manufacturing method of 207 is described in JP-A-60-35055.
Japanese Patent Publication No. 3607336, JP-A-9
The method disclosed in Japanese Patent Publication No. 176507 is known. These production methods are carried out by once producing a crude quinacridone compound or a crude quinacridone solid solution, and then subjecting it to a pigmentation (sometimes called finishing treatment) such as a known acid pasting method, a solvent salt milling method or a solvent method. It is a quinacridone-based solid solution pigment.

In addition, C.I. I. Pigment Red
Although not related to 207, a quinacridone-based solid solution pigment mainly composed of a solid solution of an unsubstituted quinacridone and a 2,9-disubstituted quinacridone, and an unsubstituted quinacridone and 3,
As a method for producing a quinacridone-based solid solution pigment mainly composed of a solid solution with a 10-di-substituted quinacridone, JP-A-200-200
No. 0-281930 is known, in which quinacridone is pigmented by a step of simultaneously cyclizing and hydrolyzing them in a reaction system using intermediates corresponding to unsubstituted quinacridone and di-substituted quinacridone, respectively. In order to obtain a solid solution pigment, and to improve the color characteristics,
It is also described that a pigment dispersant and a surfactant can be added at any time during the production of the solid solution pigment.

[0006]

However, each of the quinacridone-based solid solution pigments obtained by the above-mentioned conventional production methods has a drawback that the specific surface area is small and the properties such as coloring power are insufficient. It was In addition, JP 2000
In the production method described in JP-A-281930, it is described that the reaction is carried out by adding a surfactant, a pigment dispersant or the like at an arbitrary stage, but at which stage it is preferable to include them. There is no suggestion of whether to obtain. In addition, in the publication, in the examples, as a result, the solid solution pigment was obtained in the absence of a surfactant, a pigment dispersant, etc., so that there was a drawback that only a solid solution pigment having a small specific surface area could be obtained. . That is, the publication does not clarify the relationship between the addition time of the surfactant or the pigment dispersant and the specific surface area of the obtained solid solution pigment.

[0007]

Therefore, the inventors of the present invention have made earnest studies in view of the above circumstances, and in order to obtain a solid solution pigment having a larger specific surface area, an unsubstituted quinacridone and a halogen atom are contained in an aromatic ring. Intermediates corresponding to each of the quinacridones (ie 2,5-dianilinoterephthalic acid,
In the method for producing a solid solution pigment in which 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring is used and they are simultaneously cyclized and hydrolyzed, the presence of a specific compound at the time of cyclization makes the pigment more It has been found that a fine solid solution pigment having a larger specific surface area can be obtained even when finely formed and subsequent pigmentation is performed under the conventional conditions, and the present invention has been completed.

That is, the present invention provides a fine quinacridone-based solid solution pigment composed of a solid solution of an unsubstituted quinacridone and a quinacridone having a halogen atom in an aromatic ring, which has a BET specific surface area of 50 to 150 m ² / g as measured by a nitrogen adsorption method. After cyclization of 5,5-dianilinoterephthalic acid and 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring in the presence of an organic compound containing a sulfonic acid group or a sulfonic acid metal salt as a functional group, hydrolysis Provided is a method for producing a fine quinacridone-based solid solution pigment that is made into a pigment.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The fine quinacridone-based solid solution pigment of the present invention has a larger specific surface area than a conventional quinacridone-based solid solution pigment comprising a solid solution of an unsubstituted quinacridone and a quinacridone having a halogen atom in an aromatic ring.

The fine quinacridone-based solid solution pigment of the present invention contains unsubstituted quinacridone and quinacridone having a halogen atom in the aromatic ring. Examples of the quinacridone having a halogen atom in the aromatic ring include dichloroquinacridone such as 2,9-dichloroquinacridone, 3,10-dichloroquinacridone, and 4,11-dichloroquinacridone. Unsubstituted quinacridone and 4,11
A quinacridone-based solid solution pigment containing dichloroquinacridone, C.I. I. Pigment Red 207.

C. I. Pigment Red 2
07 is a Bragg angle (2θ ± 0.2 according to a powder X-ray diffraction pattern by CuKα characteristic X-ray (wavelength 0.1541 nm).
) = 26.7 °, 13.3 ° and 6.4 °, which are solid solutions having major peaks.

The quinacridone-based solid solution pigment of the present invention is finer than the above-mentioned conventional pigments and can be dispersed in a medium to be colored such as a resin with a weaker force than conventional pigments. This degree of fineness can be expressed by the specific surface area. The specific surface area of this quinacridone-based solid solution pigment can be measured according to BET specific surface area JIS Z 8830-1990 (method for measuring specific surface area of powder by gas adsorption) in a nitrogen adsorption method. According to this measuring method, the fine quinacridone-based solid solution pigment is 50 to 150 m ² / g, preferably 90 in particular.
Is about 120 m ² / g.

The fine quinacridone-based solid solution pigment of the present invention comprises, for example, the first step of cyclizing and hydrolyzing 2,5-dianilinoterephthalic acid and 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring. The quinacridone-based solid solution obtained in one step can be produced by improving the production method comprising the second step of forming a pigment. The most significant feature of the production method of the present invention is that an organic compound containing a sulfonic acid group or a metal salt of sulfonic acid as a functional group is present during this cyclization.

The first step is, for example, 2,5-dianilinoterephthalic acid and 2,5 having a halogen atom in the aromatic ring.
-Dianilinoterephthalic acid is cyclized and hydrolyzed in polyphosphoric acid in the presence of an organic compound containing a sulfonic acid group or a sulfonic acid metal salt as a functional group.

The polyphosphoric acid used in the present invention may be prepared by a known and conventional method. For example, it can be prepared by adding phosphoric anhydride to 85% phosphoric acid and stirring. The amount of this polyphosphoric acid used is 100 in total for each intermediate in terms of mass.
300 to 650 parts per part is preferable because the viscosity in the system is relatively easy to control and the yield of the solid solution pigment per unit reaction container relative to the charged amount of the intermediate is excellent.

Examples of 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring used in the present invention include 2,5-di (2-chloroanilino) terephthalic acid and 2,5-di (2-chloroanilino) terephthalic acid.
5-di (3-chloroanilino) terephthalic acid, 2,5-
2,5-dianilinoterephthalic acid having a chlorine atom in an aromatic ring such as di (4-chloroanilino) terephthalic acid can be preferably used. The ratio of each intermediate to be charged into the reaction vessel is
Although not particularly limited, the molar ratio (2,5-dianilinoterephthalic acid: 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring) = 30: 70 to 7
It can be selected from the range of 0:30.

Examples of the organic compound containing a sulfonic acid group or a sulfonic acid metal salt as a functional group (hereinafter referred to as a sulfonic acid compound) used in the present invention include quinacridone sulfonic acid, sodium quinacridone sulfonate, aluminum quinacridone sulfonate, Metal salts of quinacridone sulfonic acid derivatives such as calcium quinacridone sulfonate or quinacridone sulfonic acid derivatives, sodium dialkylsulfosuccinate, aluminum dialkylsulfosuccinate, calcium dialkylsulfosuccinate,
Examples thereof include sulfonic acid type surfactants such as sodium alkyl sulfonate and sodium alkylbenzene sulfonate, and metal salts thereof. Among them, when an organic compound containing an alkyl group and a sulfonic acid group or a sulfonic acid metal salt as a functional group is used, the quinacridone-based solid solution pigment finally obtained can be made finer even after the same pigmentation step. It is preferable in terms.

The amount of the sulfonic acid compound used is
In terms of mass, the total amount of 2,5-dianilinoterephthalic acid and 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring is generally 1 to 15 parts, especially 2 to 100 parts per 100 parts.
It is preferable to make it 8 parts.

For the cyclization, 110 to 14 are prepared by charging a reaction vessel with polyphosphoric acid, each of the intermediates and sulfonic acid compounds.
It can be performed by stirring at 0 ° C. for 1 to 5 hours. In the present invention, as a result of the presence of the sulfonic acid-based compound in the system, the contents in the stirring system, which had been difficult to stir per se in the past with high viscosity, from the start to the end of the cyclization are far better than before. It can maintain a very low viscosity. The end point of this reaction can be determined, for example, by sampling the contents in the reaction system over time with an appropriate time width and confirming that the peak of the infrared absorption spectrum peculiar to the intermediate has disappeared. A cyclization mixture is thus obtained.

In the subsequent hydrolysis, for example, the cyclized mixture obtained by the above-mentioned operation is used in an amount of 3 to 15 in terms of mass.
It can be carried out by mixing with a double equivalent of a large excess of water or a liquid medium such as an inorganic acid. As this inorganic acid, for example, phosphoric acid or sulfuric acid can be used. For this mix,
It is preferable to add the cyclization mixture while stirring a liquid medium such as water or an inorganic acid. If necessary, heating may be performed at this time so that the temperature becomes higher than that during cyclization. This hydrolysis can be performed by stirring at 10 to 180 ° C. for 0.25 to 3 hours. When the cyclized mixture exceeding 100 ° C. is added to a large excess of water or the like at room temperature or lower, the product particles are crystallized and precipitated from the highly viscous cyclized mixture. At this time, the temperature difference between the cyclized mixture and the liquid medium is large,
A lower temperature of the liquid medium, such as 0 ° C., is preferable because a hydrolysis mixture containing finer particles is obtained.

[0021] As a reaction vessel used for cyclization, dehydration (hydrolysis of polyphosphoric acid) of the intermediate or for pigmentation described later, as long as the charged intermediate or product is not released to the outside of the system, Anything can be used. In addition, a sealable reaction container such as an autoclave is preferably used for pigmentation described below.

The mixture thus obtained through cyclization and dehydration is removed from liquid components such as acid and water contained in unreacted raw materials and the like to obtain a crude quinacridone solid solution, which is then subjected to pigmentation in the second step. . This removal can be performed by cooling the hydrolyzed mixture and then filtering it, or by filtering it while it is hot.

The residue of the crude quinacridone solid solution from which the liquid component has been removed may be used as it is in the second step.
It is preferable to use after washing. This washing is performed with water, hot water, a base, etc., in an amount equal to or more than twice the mass of the residue, for 1 to 5 times.
It is preferable to perform it once. It is also possible to add this residue to a large excess of hot water, stir it, and filter it. When an acid is used for the cyclization or hydrolysis, it is preferable to use a base in combination with water or hot water for washing.

The residue of the crude quinacridone solid solution thus washed is pigmented in the second step as it is as a wet cake or after being dried. To obtain a solid solution pigment with less aggregation and a large specific surface area, it is preferable to use a wet cake in the second step.

A conventionally known solvent salt milling method or solvent method can be employed for this pigmentation. The former method uses 3 to 2 of the crude pigment solid content in terms of mass.
0 times equivalent amount of water-soluble inorganic salt and 0.5-10 of crude pigment
This is a method of kneading a crude pigment at 60 to 120 ° C. in the presence of a water-soluble organic solvent in an amount twice as much. As the water-soluble inorganic salt,
Examples include sodium chloride and sodium sulfate,
Examples of the water-soluble organic solvent include diethylene glycol and triethylene glycol. The kneading time at this time is usually 0.5 to 8 hours.

On the other hand, the latter method is a method in which the crude pigment is mixed in a large excess of 3 to 15 times the mass of the crude pigment solid content at 80 to 150 ° C. and the crude pigment is stirred. Examples of the organic solvent here include xylene, isobutanol, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMS).
O), dimethylimidazolidinone (DMI) and the like. The stirring time at this time is usually 0.5 to 15 hours. The end point of stirring can be determined, for example, by sampling the contents in the system with an appropriate time width over time to obtain the required crystal particle size. In controlling the crystal, water may be used in combination with the organic solvent, or a base may be used in combination.

In contrast to the conventional conditions, in the present invention, it is preferable to employ the solvent method which can achieve pigmentation with lower energy than the solvent salt milling method.

The pigmented mixture thus obtained by the solvent salt milling method is washed with, for example, water or hot water and dried, and the pigmented mixture obtained by the solvent method is filtered, for example, after washing with water or water. A fine quinacridone-based solid solution pigment can be obtained by washing with hot water and drying.

The fine quinacridone-based solid solution pigment obtained by the production method of the present invention is known from the standpoint of easy dispersibility and transparency based on its fineness, for example, known inks such as printing inks,
It can be used for coloring paints, molded products, electrostatic charge developing toners, liquid crystal color filters and the like.

The toner for electrostatic charge development includes, for example, 100 parts by weight of a binder resin and a fine quinacridone solid solution pigment of 0.1 part by weight.
1 to 20 parts as an essential component, if necessary, wax and a charge control agent are further added and melt-kneaded to obtain an average particle diameter of 5
It can be manufactured by pulverizing to a size of up to 20 microns and classifying only a predetermined particle size range. As the binder resin at this time, a known resin capable of achieving fluidity as a toner, such as styrene-acrylic resin, epoxy resin,
A polyester resin or the like can be used. As the wax, for example, low molecular weight polyolefin, carnauba, fatty acid ester, etc. can be used, and as the charge control agent, for example, quaternary ammonium salt, pyridinium salt, chromium complex salt, metal-containing dye, boron compound, etc. can be used.

The electrostatic charge developing toner thus obtained is
It can be used as a non-magnetic one-component developer by itself or as a two-component developer mixed with a carrier. Since the fine quinacridone-based solid solution pigment obtained by the production method of the present invention can obtain a printed image having more excellent transparency than ever before, in forming a full-color image by additive color mixing of YMC, it is more vivid and more vivid. A printed image can be obtained.

[0032]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. Hereinafter,% and parts are based on mass unless otherwise specified.

Example 1 In a reaction vessel equipped with a stirrer, 85
% Phosphoric acid (80 parts) was added, and 140 parts of phosphoric anhydride was added under stirring and vigorously stirred for 20 minutes to obtain polyphosphoric acid. 25 [Anionic surfactant manufactured by Kao Corporation. Sodium dodecylbenzene sulfonate] 11 parts were added. Next, 2,5-di (2-chloroanilino) terephthalic acid 22 parts, 2,5-dianilinoterephthalic acid 33
Parts were added to a reaction vessel and reacted at 125 ° C. for 3 hours to obtain a reaction mixture. Water at 15 ° C in a container with another stirring device 1
650 parts are added, the reaction mixture is added under vigorous stirring, stirring is continued for 30 minutes, suction filtration is carried out, and a wet cake of crude quinacridone solid solution pigment 2
30 parts were obtained.

230 parts of this wet cake and 880 parts of water were placed in another container equipped with a stirrer, and 25 parts of a 48% aqueous sodium hydroxide solution was added thereto to adjust the pH to about 13,
After stirring at 80 ° C. for 1.5 hours, suction filtration was performed. Further, hot water was added and washing was repeated until the filtrate obtained by suction filtration became neutral.

In a pressurizable reaction vessel equipped with a stirrer, 160 parts of the washed crude quinacridone solid solution pigment wet cake (30 g in terms of solid content, excluding water), water 1
60 parts (including water in wet cake) and DMF4
After 20 parts were charged, a 48% aqueous sodium hydroxide solution was added thereto to adjust the pH to about 10, and then the contents were charged into an autoclave container having an internal volume of 1 L and stirred at 127 ° C. and a pressure of 0.15 MPa for 8 hours. Then, the pressure was returned to normal pressure, and the mixture was allowed to cool to room temperature and suction filtered. Further, hot water was added and washing was repeated until the filtrate obtained by suction filtration became neutral, and the obtained quinacridone-based solid solution pigment wet cake was dried with a hot-air dryer set at 98 ° C, and the lump was manually thawed. did. The yield was 96%.

From the analysis of the crystal pattern by the powder X-ray diffraction pattern by the CuKα characteristic X-ray, it was found that the crystal mixture of the unsubstituted quinacridone and 4,11-dichloroquinacridone was obtained, not the substituted quinacridone and 4,11. -Based on a solid solution with dichloroquinacridone, C.I. I. P
IGMENT RED 207. The BET specific surface area of the obtained fine quinacridone-based solid solution pigment measured by a nitrogen adsorption method was measured with Microsoap 4232II (manufactured by Microdata Corporation), and the specific surface area was 113 m ^2.
/ G.

[Comparative Example 1] Neoperex No. The same operation as in Example 1 was carried out except that 25 was not used to obtain a quinacridone solid solution pigment. The yield was 95% and the specific surface area was 42 m ² / g.

[Comparative Example 2] Neoperex No. A quinacridone-based solid solution pigment was obtained by the completely same operation as in Example 1 except that the same amount of 25 was added at the stage of pigmentation by the solvent method. Yield 95%, specific surface area 44
m was ² / g.

[Comparative Example 3] In order to obtain a fine quinacridone-based solid solution pigment, the pigment prepared in Comparative Example 1 was used for pigmentation based on the solvent salt milling method. Seven times the amount of sodium chloride was added to the pigment, and solvent salt milling was performed at 90 ° C. for 8 hours to obtain a quinacridone-based solid solution pigment. The energy consumption was much higher than that of Example 1. Specific surface area of 72 m ² / g
Therefore, the value of the specific surface area as in Example 1 could not be obtained.

Table 1 shows the measurement results of the specific surface areas of the quinacridone solid solution pigments of Example 1 and Comparative Examples 1 to 3.

[0041]

[Table 1] Table 1

As is clear from the measurement results of Table 1, the quinacridone solid solution pigment of the present invention obtained in Example 1
It was found that the specific surface area was remarkably large as compared with the pigments of Comparative Examples 1 to 3, and the pigment particles were very fine.

The quinacridone-based solid solution pigments of Example 1 and Comparative Examples 1 to 3 are all X-ray diffractometer LINT.
Bragg angle (2θ ± 0.2 °) = 26.7 °, 13.3 according to powder X-ray diffraction diagram by CuKα characteristic X-ray (wavelength 0.1541 nm) at 1100 [manufactured by Rigaku Corporation].
It was a solid solution having major peaks at ° and 6.4 °.

(Test Example) << Baking Paint Test with Melamine Alkyd Resin >> 4.0 g of each quinacridone solid solution pigment obtained in Example 1 and Comparative Examples 1 to 3 and Amylak No. 1026 clear (manufactured by Kansai Paint Co., Ltd.) 16.0 g and baking thinner No. 3 [Kansai Paint Co., Ltd.] 10.0 g and 3
80 g of mmφ glass beads was put in a polyethylene bottle having a capacity of 100 ml, and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour. 50.0 g of 1026 clear was added, and the mixture was further dispersed for 10 minutes with a paint conditioner to obtain primary color paints.

3.0 g of each of the obtained primary color paints and Amilac No. Put 1531 White [Kansai Paint Co., Ltd.] 10.0 g in a polyethylene cup,
A planetary stirrer KK-102 (manufactured by Kurashiki Spinning Co., Ltd.) and the like were uniformly mixed to obtain a light color paint.

The obtained light-colored paints were placed side by side on art paper, coated and spread with a 6-mil (152 μm) film applicator, and allowed to stand for about 1 hour.
It was put in a dryer adjusted to 0 ° C. and baked and dried for about 20 minutes.

<Evaluation Criteria> Coloring Power: A coating film of art paper applied and developed by the above-mentioned test method was subjected to datacolor international S.
PECTRA FLASH 500 spectrophotometer [US da
manufactured by Tacolor International Co., Ltd.], using the Y value (L * a * b * colorimetric system) as a coloring power as an index, and using the pigment of Comparative Example 1 as a standard (100%), Example 1 and Comparative Examples 2 and 2,
The tinting strength of the pigment of 3 was measured.

[0048]

[Table 2] Table 2

As is clear from the measurement results of Table 2, the quinacridone solid solution pigment of the present invention obtained in Example 1
The coloring strength was higher than that of the pigments of Comparative Examples 1 to 3 respectively. It has been found that the quinacridone-based solid solution pigment of the present invention is a pigment having very fine pigment particles and excellent coloring power because it is easily dispersed.

[0050]

The fine quinacridone-based solid solution pigment of the present invention has a remarkably large specific surface area as compared with the conventional quinacridone-based solid solution pigment, and therefore has a particularly remarkable effect of having a superior coloring power when mixed with a medium to be colored. Play. In the method for producing a fine quinacridone-based solid solution pigment of the present invention, an intermediate corresponding to each of unsubstituted quinacridone and quinacridone containing a halogen atom in an aromatic ring is used, and they are simultaneously treated in the presence of a specific sulfonic acid compound. Since it cyclizes and hydrolyzes, the corresponding solid solution can be formed in a finer form, and even if the subsequent pigmentation by the solvent method is performed under the conventional conditions, a finer solid solution pigment with a larger specific surface area can be obtained. Has a particularly remarkable effect of being able to be.

Claims (5)

[Claims] 1. A BET specific surface area by a nitrogen adsorption method of 5
A fine quinacridone-based solid solution pigment comprising a solid solution of unsubstituted quinacridone and quinacridone having a halogen atom in an aromatic ring, which is 0 to 150 m ² / g. 2. The solid solution is a solid solution of an unsubstituted quinacridone and 4,11-dichloroquinacridone, and a Bragg angle (2θ ± 0.2) according to a powder X-ray diffraction pattern by CuKα characteristic X-ray (wavelength 0.1541 nm). 2 °) = 2
The solid solution pigment according to claim 1, which is a solid solution having major peaks at 6.7 °, 13.3 ° and 6.4 °. 3. In the presence of an organic compound containing 2,5-dianilinoterephthalic acid and 2,5-dianilinoterephthalic acid having a halogen atom in an aromatic ring as a functional group containing a sulfonic acid group or a sulfonic acid metal salt. A method for producing a fine quinacridone-based solid solution pigment, which comprises cyclizing with, hydrolyzing, and forming a pigment. 4. The production method according to claim 3, wherein the organic compound containing a sulfonic acid group or a sulfonic acid metal salt as a functional group further has an alkyl group. 5. The use amount (mass conversion) of an organic compound containing a sulfonic acid group or a sulfonic acid metal salt as a functional group,
A total of 10 of 2,5-dianilinoterephthalic acid and 2,5-dianilinoterephthalic acid having a halogen atom in the aromatic ring
The production method according to claim 3, wherein the amount is 1 to 15 parts per 0 part.