JP5557563B2 - Color material dispersion and method for producing the same - Google Patents

Description

The present invention relates to a dispersion containing pigment fine particles comprising a dichlorodiketopyrrolopyrrole pigment and a method for producing the same.

Several production methods have been proposed in consideration of the crystal form of the dichlorodiketopyrrolopyrrole pigment as a fine particle.
Patent Document 1 discloses that diketopyrrolopyrrole pigment obtained by the acid paste method is subjected to salt milling in an organic solvent in the presence of a pigment derivative, thereby suppressing crystal growth and obtaining a small primary particle size. . However, the acid paste method is not preferable for safety because concentrated sulfuric acid is used. In addition, salt milling requires the use of a specially finely processed inorganic salt, which is costly.

In Patent Document 2, a crude dichlorodiketopyrrole pigment in which α-type crystal modification and β-type crystal modification are mixed is once dried and then in the presence of a grinding agent (water-soluble inorganic salt such as sodium chloride) and a wetting agent. Discloses a method of wet milling. As a result, a fine and sized α-type crystal modified dichlorodiketopyrrole pigment is obtained, and it is stated that it is possible to transfer the crystal transformation to α-type in the process of further refinement or granulation. Yes. In other words, a diketopyrrolopyrrole pigment obtained by direct synthesis without using the acid paste method can be used to obtain a fine and sized α-type crystal modified dichlorodiketopyrrole pigment.
However, the crude dichlorodiketopyrrole pigment containing the α-type crystal modification and β-type crystal modification used in this method tends to have a larger particle size than that of the β-type crystal modification alone. In the first place, the manufacturing procedure disclosed here has a production limitation that requires a wet pulverization step for miniaturization. Furthermore, the inorganic salt used as a milling agent in this wet pulverization step causes a cost increase. A method that is more efficient and advantageous in terms of cost is desired.

In Patent Document 3, by using an α-type diketopyrrolopyrrole pigment in which the ratio of the X-ray diffraction peak intensity between predetermined plane indices falls within a predetermined range as a color filter, the viewing angle dependency and contrast of a liquid crystal display or the like are increased. It is stated that the ratio improves. In order to obtain the diketopyrrolopyrrole pigment having the X-ray diffraction peak pattern as described above, specifically, the diketo is obtained by reacting the raw material (substrate) at a high temperature (preferably 70 ° C. to 80 ° C.) in the presence of a strong base. An alkali metal salt of a pyrrolopyrrole pigment is formed and then slowly added to a stirred protonated medium so as to avoid a temperature rise to obtain a crude diketopyrrolopyrrole crystal, which is then crystallized. A method is mentioned.
However, in this method, since the pigment solution is hot, the solubility of the pigment in the vicinity of the precipitated particles is increased and particle growth is likely to occur. In order to slowly add the pigment solution, the particles generated at the initial stage of the addition are aged and added later. There is a limit to the miniaturization of pigment particles for reasons such as easy growth due to lamination of pigment solutes. It is conceivable that a particle growth inhibitor such as a pigment derivative coexists at the time of particle precipitation for the purpose of suppressing the growth of pigment particles, but there is a concern about decomposition or side reaction of the particle growth inhibitor under high temperature and strong base conditions during synthesis. Is not realistic. Furthermore, since the pigment solution is slowly added, there is a problem that productivity is low. In addition, the pigment fine particles obtained here are assumed to be completely α-type transformed, that is, the α-type crystallinity of about 1, and the diketopyrrolo in which α-type crystals and β-type crystals are mixed. No mention is made of performance improvements such as contrast ratio with pyrrole pigments.

JP 2001-264528 A JP 2008-24873 A Japanese Patent No. 4144655

An object of the present invention is to provide a dispersion of pigment fine particles composed of a dichlorodiketopyrrolopyrrole pigment that achieves high contrast when used as a color filter and can keep the viscosity of a dispersion as a raw material low. . The present invention further provides a colorant dispersion of pigment fine particles composed of a dichlorodiketopyrrolopyrrole pigment that can be suitably used for a color filter, efficiently and cost-effectively under mild conditions without requiring an extra step. It is an object of the present invention to provide a production method that can be prepared with less burden and can suitably cope with mass production.

In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the crystal transformation of the dichlorodiketopyrrole pigment is not completely made into the α-type crystal transformation, but is limited to a specific α-type crystallinity range. Further, by setting the crystallite size of the dichlorodiketopyrrole pigment determined by X-ray diffraction measurement within a specific range, pigment fine particles composed of a dichlorodiketopyrrolopyrrole pigment that can be suitably used for a color filter are obtained. It was found that it can be obtained. Furthermore, as a method for producing a coloring material comprising a dichlorodiketopyrrole pigment having an α-type crystallinity and crystallite size in this specific range, fine particles of a dichlorodiketopyrrolopyrrole pigment prepared by a reprecipitation method are grown. It has been found that it can be produced efficiently and with reduced cost burden by contacting the organic solvent with an organic solvent in the presence of an inhibitor to convert the crystal transformation into α-form. The present invention has been made based on the above findings, that is, the above-described problems have been solved by the following means.

（式中、Ｘ^１及びＸ^２は、各々独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、または置換もしくは無置換の芳香族基を表す。Ｒ^３及びＲ^４は、各々独立に、水素原子、または置換もしくは無置換のアルキル基を表す。ただし、Ｒ^３及びＲ^４の少なくとも一方は置換もしくは無置換のアルキル基である。）
（６）下記［ｉ］及び［ｉｉ］の工程を経て製造されることを特徴とする、（１）〜（５）のいずれか１項に記載のジクロロジケトピロロピロール顔料を含む顔料微粒子を含有する色材分散物の製造方法。
［［ｉ］良溶媒に溶解させたジクロロジケトピロロピロール顔料を含む顔料溶液を前記顔料に対して難溶であり前記良溶媒に相溶する貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる工程。］
［［ｉｉ］前記［ｉ］の工程で得られたジクロロジケトピロロピロール顔料の微粒子を、前記粒子成長抑制剤の存在下に下記結晶型調整有機溶媒と接触させて、ジクロロジケトピロロピロール顔料のα型結晶化度を高める工程。］
［結晶型調整有機溶媒：エーテル系溶媒、スルホキシド系溶媒、エステル系溶媒、アミド系溶媒、芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒、ニトリル系溶媒、ハロゲン系溶媒、アルコール系溶媒、ケトン系溶媒、イオン性液体、二硫化炭素溶媒、またはこれらの混合物］
（７）前記ジクロロジケトピロロピロール顔料を含む顔料溶液が、ジクロロジケトピロロピロール顔料を塩基存在下で有機溶媒に溶解して得られたものであることを特徴とする（６）に記載の色材分散物の製造方法。
（８）前記［ｉ］の工程を前記粒子成長抑制剤の存在下で行うことを特徴とする（６）又は（７）に記載の色材分散物の製造方法。
（９）前記顔料微粒子の平均粒径を１００ｎｍ以下とすることを特徴とする（６）〜（８）のいずれか１項に記載の色材分散物の製造方法。
（１０）前記粒子成長抑制剤が下記一般式（２）で表されることを特徴とする（６）〜（９）のいずれか１項に記載の色材分散物の製造方法。

（式中、Ｘ^１及びＸ^２は、各々独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、または置換もしくは無置換の芳香族基を表す。Ｒ^３及びＲ^４は、各々独立に、水素原子、または置換もしくは無置換のアルキル基を表す。ただし、Ｒ^１及びＲ^２の少なくとも一方は置換もしくは無置換のアルキル基である。）
（１１）前記［ｉ］の工程で生成させたジクロロジケトピロール顔料の微粒子が、β型結晶変態の混在状態またはβ型結晶変態であることを特徴とする（６）〜（１０）のいずれか１項に記載の色材分散物の製造方法。
（１２）前記［ｉｉ］の工程を摩砕剤の非存在下で行うことを特徴とする（６）〜（１１）のいずれか１項に記載の色材分散物の製造方法。
（１３）前記［ｉｉ］の工程を、前記［ｉ］の工程で生成したジクロロジケトピロロピロール顔料微粒子を乾燥することなく行うことを特徴とする（６）〜（１２）のいずれか１項に記載の色材分散物の製造方法。
（１４）前記［ｉｉ］の工程を、−１０℃〜１００℃で行う（６）〜（１３）のいずれか１項に記載の色材分散物の製造方法。
(1) A colorant dispersion containing a particle growth inhibitor represented by the following general formula (1) and pigment fine particles containing a dichlorodiketopyrrolopyrrole pigment , defined by the following (1) to (3) wherein the α-type crystallinity of the pigment particles and 0.65 to 0.90 being, (- 151) and 6.0~13.0nm the crystallite size of the crystal plane direction (111) crystal plane direction crystals A colorant dispersion having a child size in a range of 5.0 to 23.0 nm.
P- [X- (Y) k] n ... General formula (1)
(In the formula, P represents a diketopyrrolopyrrole pigment compound residue or a quinacridone pigment compound residue. X represents a single bond or a divalent linking group. Y represents —NR ₂ R ₃ , a sulfo group, or a carboxyl group. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group, which may have a substituent, or R ₂ and R ₃ formed integrally. (K represents an integer of 1 or 2. n represents an integer of 1 to 4.)
(1) Powder X-ray diffraction measurement using CuKα rays is performed on the dichlorodiketopyrrole pigment. The measurement is performed in accordance with Japanese Industrial Standard JIS K03131 (general rules for X-ray diffraction analysis) in the range of Bragg angle (2θ) from 23 ° to 30 °.
(2) From the X-ray diffraction pattern obtained in (1), a diffraction pattern with the background removed is obtained. Here, the background removal method is to contact the lower Bragg angle (2θ) = 23.3 ° and the higher Bragg angle (2θ) = 29.7 ° of the measurement pattern. An operation is performed to draw a straight line and obtain a pattern obtained by removing the X-ray diffraction intensity value represented by the straight line from the X-ray diffraction intensity value obtained in (1).
(3) From the X-ray diffraction pattern obtained by removing the background determined in (2), the α-type crystallinity is calculated by the following formula.
α-type crystallinity = Iα / (Iα + Iβ)
Here, Iα is the diffraction intensity value after removing the background of the Bragg angle (2θ) = 28.1 ± 0.3 °, which is a characteristic diffraction peak of the α-type crystal transformation, and Iβ is the β-type crystal transformation. It is defined as a diffraction intensity value after removing the background of a diffraction peak in the vicinity of Bragg angle (2θ) = 27.0 ± 0.3 ° which is a characteristic diffraction peak.
(2) The color material dispersion according to (1), which is produced through the following steps [i] and [ii].
[[I] A dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent. A step of generating fine particles. ]
[[Ii] the [dichlorodiketopyrrolopyrrole pigment of fine particles obtained in the step i], is contacted with the following crystalline adjusting organic solvent in the presence of the particle growth inhibitor, dichlorodiketopyrrolopyrrole pigment To increase the α-type crystallinity of. ]
[Crystal type adjusting organic solvent: ether solvent, sulfoxide solvent, ester solvent, amide solvent, aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, nitrile solvent, halogen solvent, alcohol solvent, ketone System solvent, ionic liquid, carbon disulfide solvent, or a mixture thereof]
(3) The colorant dispersion according to (1) or (2), wherein the concentration of the pigment fine particles is 0.1 to 50% by mass .
(4) The color material dispersion according to any one of (1) to (3), wherein an average particle size of the pigment fine particles is 100 nm or less .
(5) The color material dispersion described in any one of (1) to (4), wherein the particle growth inhibitor is further represented by the following general formula (2).

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. R ³ and R ⁴ are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R ³ and R ⁴ is a substituted or unsubstituted alkyl group.)
(6) Pigment fine particles containing the dichlorodiketopyrrolopyrrole pigment according to any one of (1) to (5), which are produced through the following steps [i] and [ii]: The manufacturing method of the coloring material dispersion which contains.
[[I] A dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent. A step of generating fine particles. ]
[[Ii] the [dichlorodiketopyrrolopyrrole pigment of fine particles obtained in the step i], is contacted with the following crystalline adjusting organic solvent in the presence of the particle growth inhibitor, dichlorodiketopyrrolopyrrole pigment To increase the α-type crystallinity of. ]
[Crystal type adjusting organic solvent: ether solvent, sulfoxide solvent, ester solvent, amide solvent, aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, nitrile solvent, halogen solvent, alcohol solvent, ketone System solvent, ionic liquid, carbon disulfide solvent, or a mixture thereof]
(7) The pigment solution containing the dichlorodiketopyrrolopyrrole pigment is obtained by dissolving the dichlorodiketopyrrolopyrrole pigment in an organic solvent in the presence of a base. A method for producing a color material dispersion.
(8) The method for producing a color material dispersion according to (6) or (7), wherein the step [i] is performed in the presence of the particle growth inhibitor.
(9) The method for producing a color material dispersion according to any one of (6) to (8), wherein an average particle size of the pigment fine particles is 100 nm or less .
( 10 ) The method for producing a color material dispersion according to any one of (6) to (9), wherein the particle growth inhibitor is represented by the following general formula (2).

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. R ³ and R ⁴ are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R ¹ and R ² is a substituted or unsubstituted alkyl group.)
(1 1 ) The dichlorodiketopyrrole pigment fine particles produced in the step [i] are in a mixed state of β-type crystal transformation or β-type crystal transformation (6) to (1 0 ) The manufacturing method of the coloring material dispersion of any one of these.
(1 2 ) The method for producing a color material dispersion as described in any one of (6) to (1 1 ), wherein the step [ii] is performed in the absence of an attritor.
(1 3) the step of the [ii], any said drying the dichlorodiketopyrrolopyrrole pigment fine particles produced in step a [i] and performs no (6) - (1 2) A method for producing a color material dispersion according to claim 1.
(14) The method for producing a color material dispersion according to any one of (6) to (13), wherein the step [ii] is performed at −10 ° C. to 100 ° C.

By using the color material dispersion of the present invention, a high contrast can be realized when a color filter is used, and the viscosity of the dispersion as a raw material can be kept low.
By using the production method of the present invention, a dichlorodiketo having the desired α-type crystallinity and crystallite size under a mild condition that does not require an extra step and does not require a strong acid or high-temperature heating. The dispersion of a pyrrolopyrrole pigment can be prepared efficiently and at low cost, and has an excellent effect of being able to suitably cope with mass production.
In addition, the color material dispersion of the present invention is highly suitable for production as a color filter raw material, and has an excellent effect of realizing high contrast and good quality particularly when used as a color filter.

It is a X-ray-diffraction pattern figure which shows the result (typical example) which performed the powder X-ray-diffraction measurement using CuK (alpha) ray about the dichloro diketopyrrole pigment. It is the figure which removed the background from the X-ray-diffraction pattern figure of FIG. It is a figure which shows the X-ray-diffraction pattern figure (typical example) in the dichloro diketopyrrole pigment of the state of a beta type crystal modification substantially. It is the graph which showed the relationship of alpha excessiveness of the microparticles | fine-particles contained in the dispersion liquid prepared by the Example and the comparative example, and crystallite size.

Hereinafter, preferred embodiments of the present invention will be described, but the present invention should not be construed as being limited thereto.
The colorant dispersion of the present invention has a particle growth inhibitor and α-type crystallinity of 0.65 to 0.90, a crystallite size in the (-151) crystal plane direction of 6.0 to 13.0 nm, (111 ) It is characterized by containing fine particles of a dichlorodiketopyrrolopyrrole pigment having a crystallite size in the crystal plane direction in the range of 5.0 to 23.0 nm.

[Α-type crystallinity]
Conventionally, it has been proposed to use a dichlorodiketopyrrolopyrrole pigment having an α-type crystal modification in a color filter (see Patent Document 3). On the other hand, when the α-type crystallinity is suppressed as in the present invention, the color filter is made to have a high contrast, while the viscosity of the raw material dispersion is increased and the stability of the dispersion is impaired. It was done. Even when the α-type crystallinity is suppressed, the inventors set the crystallite size of the dichlorodiketopyrrole pigment within a specific range, and more preferably by coexisting a particle growth inhibitor in the predetermined plane direction. It was found that the viscosity of the dispersion liquid can be maintained at a low viscosity by setting the crystallite diameter within a specific range, and the present invention has been achieved. In addition, when a color filter is obtained by setting the α-type crystallinity within the above range, the α-type crystallinity exceeds the above range, for example, it is extremely high that cannot be realized if the α-type crystallinity exceeds the above range. Contrast can be realized. The reason is not clear. If the estimation is included, the interaction between the pigment particles that increases the viscosity of the dispersion when the α-type crystallinity is suppressed is due to the presence of the particle growth inhibitor or the crystallite size being set within a specific range. It can be reduced and a low-viscosity dispersion can be obtained.

  The color material dispersion of the present invention is [i] a step of bringing a pigment solution containing a dichlorodiketopyrrolopyrrole pigment dissolved in a solvent into contact with a poor solvent to produce fine particles of a dichlorodiketopyrrolopyrrole pigment, ii) The α-type crystallinity of the dichlorodiketopyrrolopyrrole pigment obtained by bringing the fine particles of the dichlorodiketopyrrolopyrrole pigment obtained in [i] above into contact with a crystal-type-adjusting organic solvent in the presence of a particle growth inhibitor. It is preferable that it has passed through the process which raises.

  In the present invention, the α-type crystallinity of the dichlorodiketopyrrolopyrrole pigment is not particularly limited as long as it is within the above range, but is preferably 0.68 to 0.80, more preferably 0.70 to 0.78. By making the α-type crystallinity not more than the above upper limit value, particle growth is suppressed and the color filter can be made high contrast. On the other hand, the viscosity of a dispersion liquid can be restrained low by setting it as the said lower limit or more. Regarding the crystal modification of the dichlorodiketopyrrolopyrrole pigment, for example, JP-A-58-210084 can be referred to for the α-type crystal modification, and JP-A-8-48908 can be referred to for the β-type crystal modification. be able to. Crystal transformation in the fine particles of the obtained dichlorodiketopyrrolopyrrole pigment can be confirmed by powder X-ray diffraction measurement using CuKα rays. In the present invention, the α-type crystallinity and crystallite size are as follows. It is defined as the value determined by the method.

○ Determination method of α-type crystallinity (1) Powder X-ray diffraction measurement using CuKα rays is performed on dichlorodiketopyrrole pigments. The measurement is performed in accordance with Japanese Industrial Standard JIS K03131 (general rules for X-ray diffraction analysis) in the range of Bragg angle (2θ) of 23 ° to 30 °. FIG. 1 illustrates an X-ray diffraction pattern.
(2) From the X-ray diffraction pattern obtained in (1), a diffraction pattern with the background removed is obtained. Here, the background removal method is to contact the lower Bragg angle (2θ) = 23.3 ° and the higher Bragg angle (2θ) = 29.7 ° of the measurement pattern. An operation is performed to draw a straight line and obtain a pattern obtained by removing the X-ray diffraction intensity value represented by the straight line from the X-ray diffraction intensity value obtained in (1). Explaining with illustrations (typical examples), the pattern obtained by removing the diffraction intensity represented by the straight line L in contact with the point A and the point B is obtained from the X-ray diffraction intensity value of FIG. The removed X-ray diffraction pattern is used. An example of the X-ray diffraction pattern with the background removed is shown in FIG.
(3) From the X-ray diffraction pattern obtained by removing the background determined in (2), the α-type crystallinity is calculated by the following formula.
α-type crystallinity = Iα / (Iα + Iβ)
Here, Iα is the diffraction intensity value after removing the background of the Bragg angle (2θ) = 28.1 ± 0.3 °, which is a characteristic diffraction peak of the α-type crystal transformation, and Iβ is the β-type crystal transformation. It is defined as a diffraction intensity value after removing the background of a diffraction peak in the vicinity of Bragg angle (2θ) = 27.0 ± 0.3 ° which is a characteristic diffraction peak. In the example of FIG. 2, the lengths of the lines L1 and L2 correspond to Iβ and Iα.

In the above definition, when the α-type crystallinity of the dichlorodiketopyrrole pigment is high, no clear diffraction peak is observed at the position of Bragg angle (2θ) = 27 ± 0.3 °, which is a characteristic of the β-type crystal. In this case, Iβ is defined as a diffraction intensity value of Bragg angle (2θ) = 27.0 ° after background removal. In addition, when the α-type crystallinity of the dichlorodiketopyrrole pigment is low, there is a case where a clear peak does not appear in the vicinity of 28.1 ° which is a characteristic of the α-type crystal. Is defined as the diffraction intensity value of Bragg angle (2θ) = 28.1 °.
In these definitions, even when the α-type crystallinity of the dichlorodiketopyrrole pigment is high and no clear peak is observed in the vicinity of the characteristic Bragg angle (2θ) = 27 ° of the β-type crystal, the value of Iβ is zero. Note that the α-type crystallinity value is never 1. This is because even if the diffraction peak derived from the β-type crystal does not exist at 27 °, the spread of the diffraction peak derived from the α-type crystal present on both sides of the diffraction peak takes 27 °. This is because it becomes a finite value. Similarly, even when the β-type crystallinity of the dichlorodiketopyrrole pigment is high and no clear peak is observed in the vicinity of the characteristic Bragg angle (2θ) = 28.1 ° of the α-type crystal, the value of Iα is Therefore, the α-type crystallinity value never becomes zero. This is because the flares on the high angle side of the diffraction peak derived from the β-type crystal existing in the vicinity of Bragg angle (2θ) = 27 ° take up to about 28.1 °, so the diffraction peak at 28.1 ° is finite. This is because it becomes a value.

In the present invention, the dichlorodiketopyrrole pigment is substantially in the β-type crystal transformation state when the powder X-ray diffraction measurement using CuKα ray is performed on the dichlorodiketopyrrole pigment powder. No diffraction peak in the black angle (2θ) = 28.1 ± 0.3 ° region, which is a characteristic X-ray diffraction peak, is observed, and a black angle (2θ) = 27 characteristic in the β-type crystal transformation state is not observed. It is defined as a state where a clear diffraction peak is observed at 0.0 ± 0.3 °. FIG. 3 shows an example of an X-ray diffraction pattern substantially in the β-type crystal transformation state.
When the dichlorodiketopyrrole pigment is substantially in the β-type crystal transformation state, the α-type crystallinity based on the above definition is the diffraction peak intensity in the vicinity of the Bragg angle (2θ) = 27 ° derived from the β-type crystal transformation and Although the diffraction peak intensity given by the spread of the Bragg angle (2θ) = 28.1 ° changes under reprecipitation conditions, it is not uniquely determined, but is usually in the range of 0.15 to 0.40.

Step [ii] Step of increasing α-type crystallinity In the present invention, the dichlorodiketopyrrolopyrrole pigment fine particles obtained by the reprecipitation method of step [i] as described below are used as a crystal-type adjusting organic solvent. The α-type crystallinity can be increased by contact. The reprecipitation method will be described later. Usually, the fine particles of the dichlorodiketopyrrolopyrrole pigment obtained by the reprecipitation method consist of a mixed state of α-type crystal modification and β-type crystal modification or a β-type crystal modification. The α-type crystallinity of the pigment fine particles obtained by the reprecipitation method varies depending on the reprecipitation conditions and coexisting materials described later, but is usually 0.15 to 0.55. In the present invention, the fine particles of the dichlorodiketopyrrolopyrrole pigment obtained by the reprecipitation method are preferably substantially in the β-type crystal modification, and the α-type crystallinity at this time is 0.15 to 0.40. It is preferable to use those as raw material fine particles in the step [ii]. From this viewpoint, it is preferable to set the difference in α-type crystallinity between 0.23 and 0.65 before and after the treatment in step [ii].

The crystalline form adjusting organic solvent, e ether solvents (e.g., tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate), sulfoxide solvents (e.g., dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane), ester solvents (Eg, ethyl acetate, acetic acid-n-butyl, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents (eg, toluene) , Xylene, etc.), aliphatic hydrocarbon solvents (eg, octane), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane, etc.), alcohol solvents (eg, methanol, Ethanol, n- Propanol, etc.), ketone solvents (e.g., methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), an ionic liquid (e.g., 1-ethyl-3-methylimidazolium tetrafluoroborate), carbon disulfide solvent or a mixture thereof, Is used .
Among these, ether solvents, ester solvents, alcohol solvents, ketone solvents, mixtures thereof, or mixtures of these with water are more preferable, and those having propylene glycol monomethyl ether acetate as a main component are particularly preferable. The poor solvent used here is also used as a dispersion medium in the preparation of the dispersion in the next step, but propylene glycol monomethyl ether acetate is a general-purpose solvent for the final dispersion, which improves cost performance by using it in both steps. To do.
In addition, since the fine particles of the dichlorodiketopyrrolopyrrole pigment used in the crystal type adjustment step are preferably used without being dried after being precipitated by the reprecipitation method, these organic solvents are used as the solvent for the crystal type adjustment step. A part of the good and poor solvents at the time of precipitation, water used for washing with water, or another solvent substituted for these may be mixed, and it is preferable that water is mixed. However, since the good solvent used at the time of reprecipitation may cause excessive particle growth, it is desirable not to coexist in the crystal type adjustment step.

  The conditions for bringing the fine particles of the dichlorodiketopyrrolopyrrole pigment into contact with the crystal-type-adjusting organic solvent are not particularly limited, but both are maintained while maintaining the stirring state so that the ratio of the crystal-type-adjusting organic solvent and the pigment fine particles does not become uneven. It is preferable to make it contact. Moreover, there is no restriction | limiting in particular in the temperature at the time of contact, Any temperature with which a crystal-type adjustment organic solvent maintains a liquid state is applicable preferably. When the temperature at the time of crystal type adjustment is high, it is preferable in that the time required to increase the α-type crystallinity is shortened. Then, since an excessively high temperature is not preferable, it is desirable to determine the temperature in consideration of the type of organic solvent used and the time required to increase the α-type crystallinity. Specifically, −10 ° C. to 100 ° C. is preferable, and 0 ° C. to 80 ° C. is more preferable. Further, the amount of the crystal-type adjusting organic solvent is not particularly limited, but if the amount of the organic solvent is too small, there is a concern about unevenness at the time of crystal-type adjustment or unintentional coalescence between pigment particles. It is preferable to use a crystal-type adjusting organic solvent in an amount such that the pigment concentration at the time of mold adjustment ranges from 0.1% to 50%. In addition, there is no particular limitation on materials other than the crystal-type adjusting organic solvent that coexists at the time of crystal-type adjustment, but it is preferable that a particle growth inhibitor described later coexists, and other materials include acid, base, inorganic Salts, viscosity modifiers, surfactants, antifoaming agents, polymer dispersing agents and the like may be included. When the base coexists, the rate of increase of the α-type crystallinity increases, but the particle growth is promoted. Therefore, it is desirable to adjust the crystal type adjustment time. Moreover, since the good solvent of the pigment used in the step [i] of the present invention may cause excessive particle growth, it is preferable not to coexist in the step [ii].

The step of increasing the α-type crystallinity in step [ii] of the present invention is preferably performed in the presence of a particle growth inhibitor. By performing an operation to increase the α-type crystallinity in the presence of a particle growth inhibitor, excessive particle growth when increasing the α-type crystallinity can be suppressed, and the crystallite size of the dichlorodiketopyrrole pigment Can be limited to the preferred range of the present invention. The particle growth inhibitor may be added at the same time as step [i] or at the same time as step [i] after completion of step [i] but before step [ii] is started. Moreover, after adding a particle growth inhibitor simultaneously with process [i], adding the same or another raw material before the start of process [ii] can also be performed preferably.
As the preferred type and amount of the particle growth inhibitor used in step [ii] of the present invention, preferred materials and amounts used can be used when they are contained in step [i] described below.

[Crystallite size]
In the present invention, the dichlorodiketopyrrolopyrrole pigment obtained by obtaining step [ii] has a crystallite size in the (-151) crystal plane direction of 6 nm to 13 nm, and 6 nm to 11.0. It is particularly preferable that the thickness is 6 nm or more and 9.0 nm or less. The crystallite size in the (111) crystal plane direction is 5.0 nm to 23 nm, preferably 5.0 nm to 20 nm, and particularly preferably 10 nm to 18 nm. By adjusting the crystallite size in the predetermined crystal plane direction of the dichlorodiketopyrrolopyrrole pigment within such a range, the viscosity of the dispersion when the α-type crystallinity is limited can be kept low.

  The mechanism by which the viscosity of the dispersion can be reduced by limiting the range of the crystallite size is not clear, but it is as follows, including estimation. The state in which (-151) crystal plane direction and (111) crystal plane direction both realize the above preferred range is that the main particle growth direction of the dichlorodiketopyrrolopyrrole pigment is grown by the particle growth inhibitor. It is considered that the state of inhibition, that is, the state of interaction with the additional layer of pigment molecules on the crystal surface is limited. This is presumed that the interaction between particles in these directions is also kept low, and as a result, the viscosity of the dispersion is reduced. In addition, when only one of the crystallite size is extremely suppressed, in addition to the increase in the interaction between particles in the weakly suppressed plane direction, the particles are easily anisotropic due to the anisotropic particle shape, It is assumed that the increase in the interaction between particles leads to an increase in viscosity. From the above viewpoint, the present invention is characterized in that both the crystallite size in the (−151) crystal plane direction and the (111) crystal plane direction of the crystal grain are set in a specific range.

○ Determination method of crystallite size (1) Similar to the determination method of α-type crystallinity, powder X-ray diffraction measurement using CuKα ray was performed for dichlorodiketopyrrole pigment, and the Bragg angle (2θ) was 23 ° to 30 °. Perform in the range of °. Further, the X-ray diffraction pattern with the background removed is calculated in the same manner as the method for determining the α-type crystallinity.
(2) From the X-ray diffraction pattern obtained by removing the background obtained in (1), a Bragg angle (2θ) derived from α-type crystal transformation = 24.6 ± 0.3 ° and a diffraction peak of 28.1 ± 0 For each diffraction peak near 3 °, find the half-width and Bragg angle (2θ) of the diffraction peak. The half-value width is calculated using four diffraction peaks existing in the above measurement range (three peaks in the vicinity of each of the Bragg angles 24.6 °, 25.6 °, 28.1 ° derived from α-type crystal transformation and β-type crystal transformation). It can be calculated by performing peak separation using a commercially available data analysis software. In the present invention, the value of the half-value width calculated by performing fitting using the data analysis software Igor Pro manufactured by Wave Metrics as a Voig function is used.
(3) The crystallite size is calculated from the half-width of the diffraction peak calculated in (2) and the Scherrer equation below.
D = Kλ / (10 × B × cos A)
B = Bobs-b
here,
D: Crystallite size (nm)
Bobs: full width at half maximum (rad) calculated in (2)
b: X-ray diffractometer angular resolution correction coefficient, half-value width (rad) when measuring standard silicon crystal. In the present invention, a standard silicon crystal was measured under the following apparatus configuration and measurement conditions, and b = 0.2.
A: Diffraction peak Bragg angle 2θ (rad)
K: Scherrer constant (defined as K = 0.94 in the present invention)
λ: X-ray wavelength (Å) (in the present invention, since it is CuKα ray, λ = 1.54)

The measurement conditions in the present invention are as follows.
X-ray diffractometer: RINT2500 manufactured by Rigaku Corporation
Goniometer: RINT2000 vertical goniometer manufactured by Rigaku Corporation Sampling width: 0.01 °
Step time: 1 second diverging slit: 2 °
Scattering slit: 2 °
Receiving slit: 0.6mm
Tube: Cu
Tube voltage: 55KV
Tube current: 280 mA

  As described above, in order to increase the crystallite size, (i) increase the temperature in the crystallization step, (ii) suppress the amount of the crystal growth inhibitor, (iii) delay the timing of addition, or (iv) the reaction One example is to increase the time. In order to relatively increase only the crystallite diameter in any one direction with respect to each of the (−151) plane direction and the (111) plane direction, the type, addition amount, and addition of the crystal growth inhibitor in the crystallization step It is effective to properly select the crystal growth solvent and the like. For example, in order to relatively increase the crystallite size in the (−151) direction, it is effective to increase the ratio of the growth inhibitor having a high growth suppression effect in the (111) plane direction. The compounds represented are mentioned as specific examples of this. Further, in order to relatively increase the crystallite size in the (111) plane direction, it is effective to increase the ratio of the growth inhibitor in the (-151) plane direction, and a quinacridone skeleton pigment derivative is an example of this. As mentioned.

[Other conditions]
In the present invention, the fine particles of the dichlorodiketopyrrolopyrrole pigment applied in the step [ii] are preferably used without being dried after being precipitated by the reprecipitation method, so that the dispersed state in the dispersion medium is maintained. It is preferred that Here, drying means that the concentration of the pigment fine particles is increased to 60% or more.

  In the present invention, the step [ii] is preferably performed in the absence of a grinding agent. Examples of the grinding material include media such as zirconia beads, glass beads, and agate balls, and water-soluble inorganic salts such as sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.

In the present invention, after increasing the α-type crystallinity of the fine particles of the dichlorodiketopyrrolopyrrole pigment in the above step [ii], washing treatment, addition of an adsorbing material, cooling, or the like is performed so as to prevent this from excessively increasing. It is preferable to perform the above-mentioned treatment. Although the specific procedure of the water washing treatment is not particularly limited, for example, an excess amount of water (ion-exchanged water or distilled water) having a mass 100 to 10,000 times that of the target pigment fine particles is used, and the above-mentioned pigment fine particles coexist with the pigment fine particles. The embodiment which pours a crystallization promotion organic solvent is mentioned. The temperature of the water used for this washing is preferably 0 to 30 ° C., and the atmospheric temperature during the washing is preferably 5 to 25 ° C. Moreover, as an adsorption material, the below-mentioned particle growth inhibitor, a dispersing agent, etc. can be used. The temperature at which the cooling treatment is performed is preferably set to a temperature lower by 10 ° C. or more than the temperature of step [ii], and specifically, is preferably in the range of −15 ° C. to 20 ° C.
The pigment concentration after these treatments can be increased by an operation such as concentration or drying, if necessary. There are no particular restrictions on the concentration or drying method, but when drying, in order to avoid excessive aggregation of pigment fine particles due to drying, freeze drying or after replacing the solvent with an organic solvent such as alcohol or acetone. It is preferable to perform drying, and it is also preferable to mix with a dispersant before drying.

  In the present invention, the concentration of the pigment fine particles in the dispersion when applied to the step [ii] is not particularly limited, but is preferably 0.1 to 50% by mass, and preferably 1 to 25% by mass. Is more preferable.

[Pigment fine particles]
Regarding the particle size of fine particles, there is a method of expressing the average size of the population by quantifying by a measurement method. There are corresponding median diameters, various average diameters (number average, length average, area average, mass average, volume average, etc.). In the present invention, the average particle diameter refers to the number average diameter unless otherwise specified. In the present invention, the average particle size of the pigment fine particles (primary particles) is preferably 100 nm or less, more preferably 75 nm or less, and particularly preferably 50 nm or less. Although a minimum is not specifically limited, It is practical that it is 3 nm or more.

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as an index representing the uniformity (monodispersity) of the particles, unless otherwise specified. In the present invention, the monodispersity of the pigment fine particles (primary particles) (in the present invention, the monodispersity means the degree of uniform particle size), that is, Mv / Mn is 1.0 to 2.0. Is more preferable, 1.0 to 1.8 is more preferable, and 1.0 to 1.5 is particularly preferable.

  Examples of the method for measuring the particle size of the organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus based on the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150, Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (both are trade names), and the like.

[Step [i] Reprecipitation method]
In the present invention, dichlorodiketopyrrolopyrrole pigment dissolved in a solvent is brought into contact with a poor solvent to produce dichlorodiketopyrrolopyrrole pigment fine particles. A dichlorodiketopyrrole pigment dissolved in a solvent means a dichlorodiketopyrrole pigment obtained by dissolving a previously synthesized dichlorodiketopyrrole pigment in a good solvent, and a dichlorodiketopyrrole pigment from a raw material in the synthesis solvent. It means both dichlorodiketopyrrole pigments that are dissolved in a synthesis solvent in the state of alkali metal salts or the like when synthesized and produced. At this time, the compatibility of the solvent (good solvent) for dissolving the dichlorodiketopyrrolopyrrole pigment and the poor solvent is preferably such that the amount of the good solvent dissolved in the poor solvent is 30% by mass or more, and 50% by mass or more. It is more preferable. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.

The good solvent is not particularly limited, but an organic acid (eg, formic acid, dichloroacetic acid, methanesulfonic acid, etc.), an organic base (eg, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, sodium methoxide, etc.) ), Aqueous solvents (for example, water, hydrochloric acid, aqueous sodium hydroxide), alcoholic solvents (for example, methanol, ethanol, n-propanol, etc.), ketone solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), Ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), Stealth solvents (for example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, And 1-ethyl-3-methylimidazolium tetrafluoroborate), a carbon disulfide solvent, or a mixture thereof.

  Among these, an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.

  Examples of the organic acid include, but are not limited to, sulfonic acid compounds, carboxylic acid compounds, acid anhydride compounds, and the like.

  Examples of the sulfonic acid compound include alkyl sulfonic acid, halogenated alkyl sulfonic acid, and aromatic sulfonic acid, and the alkyl chain and the aromatic ring may be unsubstituted or substituted.

  Specific examples of the sulfonic acid compound used in the present invention include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nona. Fluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, chlorobenzenesulfonic acid, aminobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid tetrahydrate, etc. It is done.

  Examples of the carboxylic acid compound include alkyl carboxylic acids, halogenated alkyl carboxylic acids, and aromatic carboxylic acids. The alkyl chain and the aromatic ring may be unsubstituted or substituted with the substituent T. Specific examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, difluoroacetic acid, dichloroacetic acid, dibromoacetic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, chlorodifluoroacetic acid , Cyanoacetic acid, phenoxyacetic acid, diphenylacetic acid, thioacetic acid, mercaptoacetic acid, mercaptopropionic acid, 2-chloropropionic acid, 2,2-dichloropropionic acid, 3-chloropropionic acid, 2-bromopropionic acid, 3-bromopropion Acid, 2,3-dibromopropionic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, isobutyric acid, 2-bromoisobutyric acid, cyclohexanecarboxylic acid, nitroacetic acid, phosphonoacetic acid, pyruvic acid, oxalic acid, propargyl Acid, trimethylammonium acetic acid Benzoic acid, tetrafluorobenzoic acid, pentafluorobenzoic acid, 2-chlorobenzoic acid, 2-fluorobenzoic acid, benzoyl formate, benzoylbenzoic acid, 2-dimethylaminobenzoic acid, 2,6-dihydroxybenzoic acid, picolinic acid, Citric acid, cysteine, sulfanilic acid, squaric acid and the like can be mentioned.

  In the present invention, in addition to carboxylic acid and sulfonic acid, an acid anhydride can be used as the acid, and specifically, acetic anhydride, propionic acid anhydride, trifluoromethanesulfonic acid anhydride, trichloro And acid anhydrides such as acetic anhydride. Examples of organic acids other than these include isopropyl phosphate, methyl phosphate, phenylphosphonic acid, ethylenediaminetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and methylenediphosphonic acid.

  As the organic acid, alkylsulfonic acid, alkylcarboxylic acid, halogenated alkylcarboxylic acid, and aromatic sulfonic acid are preferable, and methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid. Formic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable.

  Examples of organic bases include primary amines, secondary amines, tertiary amines, quaternary amines, anilines, piperidines, piperazines, amidines, formamidines, pyridines, Examples include, but are not limited to, guanidines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like. Among these, tertiary amines, quaternary amines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like are preferable.

  Specifically, aniline, 2-chloroaniline, 3-fluoroaniline, 2,4-difluoroaniline, 2-nitroaniline, N, N-diethylaniline, 2,6-diethylaniline, 2,4-dimethoxyaniline, p-phenylenediamine, pyridine, 2-aminopyridine, pyrimidine, pyridazine, pyrazine, 2,2-dipyridyl, pyrrolidine, piperidine, imidazole, pyrazole, thiazole, benzothiazole, oxazole, diazabicycloundecene, diazabicyclononene, Diazabicyclooctane, 1-cyanoguanidine, N, N′-diphenylguanidine, cyclohexylamine, butylamine, cyclopropylamine, t-butylamine, benzylamine, diisopropylamine, trimethylamine, triethylamine , Tributylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, morpholine, thiomorpholine, N-methylmorpholine, hexamethylphosphoramide, 1-methyl -4-piperidone, N- (2-aminoethyl) piperazine, ethylenediamine, diethylenetriamine, bis- (3-aminopropyl) ether, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium Examples include ethoxide and potassium t-butoxide.

  Among these, aniline, 2,4-difluoroaniline, pyridine, diazabicycloundecene, diazabicyclononene, diazabicyclooctane, triethylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethyl Ammonium hydroxide, tetrabutylammonium hydroxide, N-methylmorpholine, N- (2-aminoethyl) piperazine, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium -T-butoxide is preferred, 2,4-difluoroaniline, diazabicycloundecene, diazabicyclononene, tetrahydroquinoline, phenyltrimethylammonium Hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, N- methylmorpholine, sodium methoxide, potassium -t- butoxide preferred.

  More specific examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.

  More specifically, examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε -Caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

  There are no particular limitations on the preparation conditions for depositing the pigment fine particles, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  When the pigment is uniformly dissolved in a good solvent, generally, in the case of a pigment having an alkaline dissociable group in the molecule, there is no alkali, but there is no alkaline dissociable group, and a nitrogen atom to which a proton is easily added is present. It is preferred that acidity be used when there are many in the molecule. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  In addition to the organic base, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide can also be used as the base used when dissolving in an alkaline manner. The amount of the base used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and 1.0 Particularly preferred is ˜20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the pigment.

  In addition to the organic acid, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like can be used as an acid used when the acid is dissolved. The amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, It is particularly preferably 30 to 200 molar equivalents.

  When mixing an inorganic base or an inorganic acid with an organic solvent and using it as a good solvent for a pigment, the alkali or acid is completely dissolved, so it has a high solubility in some water or lower alcohol or other alkali or acid. A solvent can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

The pigment solution may contain the above pigment and other components as required in a good solvent.
Other components are not particularly limited, and preferred examples include acids (such as organic compounds having an acidic group) and bases (such as basic organic compounds). In particular, in the present invention, it is preferable to dissolve the dichlorodiketopyrrolopyrrole pigment in the presence of a base, and it is more preferable that the base is an organic base.

  In the present invention, as an organic base (an organic compound having a basic group), alkylamine, arylamine, aralkylamine, pyrazole derivative, imidazole derivative, triazole derivative, tetrazole derivative, oxazole derivative, thiazole derivative, pyridine derivative, pyridazine Derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives and the like are preferable, and alkylamine, arylamine and imidazole derivatives are preferable. Above all,

  As carbon number of the organic compound which has the said basic group, 6 or more are preferable, More preferably, it is 8 or more, More preferably, it is 10 or more. In the organic compound having a basic group, examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylbutylamine, t-amylamine, 3-aminoheptane, t-octylamine, 1,4 -Diaminobutane, 1,6-hexadiamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dibutylamine, dihexylamine, dioctylamine, bis (2- Tylhexyl) amine, didecylamine, N-methyloctadecylamine, triethylamine, tripropylamine, N, N-dimethylbutylamine, N-methyldibutylamine, tributylamine, tripentylamine, N, N-dimethylhexylamine, N, N- Dimethyloctylamine, N-maledioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N-methylcyclohexylamine, N, N, N ′, N ′, N '' -Pentamethyldiethyl Rentriamine, cyclohexylamine, cycloheptylamine, cyclohexylamine, cyclododecylamine, 1-adamandanamine and the like are preferable, preferably octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecamine Decylamine, tetradecylamine, octadecylamine, t-octylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N -Methyloctadecylamine, N, N-dimethyloctylamine, N-mail dioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexane Examples include diamine, N-methylcyclohexylamine, N, N, N ′, N ′, N ′ ′-pentamethyldiethylenetriamine, cyclododecylamine, 1-adamandanamine, and more preferably decylamine, undecylamine, Examples include dodecylamine, tridecylamine, tetradecylamine, didecylamine, N-methyloctadecylamine, N, N-dimethyldodecylamine, and tridodecylamine. Also suitable are organic polymer compounds having a basic group such as polyallylamine and polyvinylamine.

  As the arylamine, for example, N, N-dibutylaniline, 4-butylaniline, 4-pentylamine, 4-hexylamine, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4 -Tetradecylaniline, 4-hexadecylaniline, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, and the like, preferably 4-octylaniline, 4-decylaniline 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, etc., more preferably 4-decylaniline, 4 -Dodecylaniline, 4 Tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline.

  Examples of the imidazole derivative include 1- (10-hydroxydecyl) imidazole, 1-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and the like.

Moreover, as an organic compound which has the said basic group, the organic compound comprised by a basic group and a heterocyclic group is also preferable.
Examples of such an organic compound include 2-aminopyridine, 3-aminopyridine, 1- (2-aminophenyl) pyrrole, 5-aminopyrazole, 3-amino-5-methylpyrazole, 5-amino-1- Ethylpyrazole, 3-aminotriazole, 2-aminothiazole, 5-aminoindole, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, phthalimide, 5-aminobenzimidazolone N, N-dimethyl-5-aminobenzimidazolone, 5-aminouracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, aminopyrazine, 8-aminoquinoline, 3-aminoquinoline, 9-amino Acridine, ASTRA blue 6GLL (base Phthalocyanine derivative), 2-amino-anthraquinone, 3-amino-anthraquinone, acridone, N- acridone, quinacridone, NILE Red, and the like methylene violet naphthalimide is. Preferably, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone, 5-amino Uracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, 8-aminoquinoline, 3-aminoquinoline, 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoanthraquinone, 3-amino Anthraquinone, acridone, N-acridone, quinacridone, NILE red, methylene violet naphthalimide, and more preferably 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoan Laquinone, 3-aminoanthraquinone, acridone, N-acridone, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone , 5-aminouracil, 6-aminouracil, NILE red, and methylene violet naphthalimide.

  As the organic compound having a basic group, an organic compound composed of a basic group and a heterocyclic group is particularly preferable.

  The organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, and more preferably 0.05 to 15% with respect to the pigment. It is particularly preferable to be in the range of mass%.

  In addition to the above, pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified. The pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names), and the like. When a pigment derivative is used, the amount used is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 3 to 20% by mass, and 5 to 15% by mass with respect to the pigment. It is especially preferable that it is in the range.

  The poor solvent is not particularly limited, but the solubility of the dichlorodiketopyrrolopyrrole pigment in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. There is no particular lower limit to the solubility of the pigment in the poor solvent, but 0.0001% by mass or more is practical considering the commonly used one.

The poor solvent is not particularly limited, but an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), an alcohol solvent (for example, methanol, ethanol, n-propanol, etc.), a ketone solvent (for example, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents ( For example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents (examples) Toluene, xylene, etc.), aliphatic hydrocarbon solvents (eg, octane, etc.), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane, etc.), ionic liquids (eg, 1-ethyl-3
-Methylimidazolium tetrafluoroborate etc.), carbon disulfide solvent, or a mixture thereof is preferably mentioned.
Among these, an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous medium, an alcohol solvent, or a mixture thereof. Is particularly preferred.

The aqueous medium refers to water alone or water and water-soluble organic solvent or inorganic salt solution, for example, water, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol, and the like.

  Some are listed as specific examples of good solvents and those listed as poor solvents, but the same as the good solvent and the poor solvent are not combined, and the solubility in the good solvent is related to the pigment. The solubility should be sufficiently higher than the solubility in the poor solvent. For the pigment, for example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit on the difference in solubility between the good solvent and the poor solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used pigment.

  The state of the poor solvent is not particularly limited, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C. The viscosity of the pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  When mixing the pigment solution and the poor solvent, either of them may be added and mixed, but it is preferable to jet and mix the pigment solution into the poor solvent, in which the poor solvent is stirred It is preferable that The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number in mixing the pigment solution and the poor solvent, the particle diameter of the pigment nanoparticles that are deposited can be controlled. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In formula (1), Re represents the Reynolds number, ρ represents the density of the pigment solution [kg / m ³ ], U represents the relative velocity [m / s] when the pigment solution and the poor solvent meet, L represents the equivalent diameter [m] of the flow path or supply port where the pigment solution and the poor solvent meet, and μ represents the viscosity coefficient [Pa · s] of the pigment solution.

The equivalent diameter L refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the flow path. The equivalent diameter L is expressed by the following formula (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting a pigment solution into a poor solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the pigment solution and the poor solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the pigment solution is injected and mixed in a stationary poor solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the pigment solution is a value determined by the type of material selected, but is practically 0.8 to 2.0 kg / m ³ , for example. The viscosity coefficient μ of the pigment solution is also a value determined by the material used, the ambient temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

  The mixing ratio of the pigment solution and the poor solvent is preferably 1/50 to 2/3 by volume, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. The particle concentration in the liquid when organic fine particles are precipitated is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, with respect to 1000 ml of the solvent. Preferably it is the range of 50-25000 mg. Moreover, the preparation scale at the time of producing | generating microparticles | fine-particles is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

  In the present invention, in preparing the dispersion by depositing pigment fine particles in the step [i], a “particle growth inhibitor” may be contained in at least one of the pigment solution and the poor solvent, preferably in the pigment solution. . By using this particle growth inhibitor, it is preferable because the crystallite size is not increased carelessly and good performance can be further obtained as a color material for a color filter.

[Crystal growth inhibitor ]

The pigment derivative preferably used as a particle growth inhibitor in the present invention can be represented by the following general formula (1).
P- [X- (Y) k] n ... General formula (1)
(Wherein, P is to display the diketopyrrolopyrrole pigment compound residue or a quinacridone pigment compound residue, X is, the. Linking group represents a single bond or a divalent linking group, 1 to 100 carbon atoms A group consisting of 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, and further having a substituent even if unsubstituted. X is preferably an organic linking group, and specific examples of X include a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, — CONR _1- , -SO ₂ NR _1- , -NR ₁ CO-, -NR ₁ SO _2- (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), having a substituent An alkylene group having 18 or less carbon atoms, an alkyl group and a substituent. A phenyl group which may be, or triazine residue or .Y which may be mentioned combinations of these -NR 2 _{R 3,,} represents a sulfo group or a carboxyl group, hydrogen each independently of R ₂ and R ₃ An atom, an alkyl group, an alkenyl group, or a phenyl group which may have a substituent, or a heterocyclic ring formed integrally with R ₂ and R ₃ is represented, k represents an integer of 1 or 2. , N represents an integer of 1 to 4. In the present invention, the term “compound” or “agent” represented by a predetermined general formula refers to a compound that forms a salt in addition to the compound of the structural formula itself. Is meant to include its salts.

A diketopyrrolopyrrole derivative or a quinacridone derivative is used as the pigment derivative. In particular, diketopyrrolopyrrole derivatives are effective in suppressing crystal growth in the (111) crystal plane direction, and quinacridone derivatives are effective in suppressing crystal growth in the (-151) crystal plane direction. From this point of view, it is preferable to use a diketopyrrolopyrrole derivative and a quinacridone derivative in combination .

The growth inhibitor used in the present invention is preferably one represented by the following general formula (2).

In the formula, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. Among these, a hydrogen atom, a chlorine atom, a methyl group, a t-butyl group, or a phenyl group is preferable, and a hydrogen atom or a chlorine atom is more preferable.

R ³ and R ⁴ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. However, at least one of R ³ and R ⁴ represents a substituted or unsubstituted alkyl group.
In R ³ and R ⁴ , the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and may be linear, branched or cyclic. Specific examples of the group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl period, an isopropyl group, and an isobutyl group, and a methyl group, an ethyl group, a propyl group, and a pentyl group. preferable. It is preferable that R ¹ and R ² are not both methyl groups.

  When the alkyl group has a substituent, examples of the substituent include a halogen atom, aryl group, heterocyclic group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group , Heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl Fine heterocyclic azo group, an imido group or is preferably a combination thereof.

（式中、Ｑ^１はアルキル基又は芳香族基を表す。Ｑ^２は環状脂肪族又は芳香族基を表す。Ｑ^３はアルキル又は芳香族基を表す。Ｑ^４は芳香族基を表す。ｐは整数を表す。） R ³ and R ⁴ are preferably substituents represented by any of the following general formulas (R-1) to (R-4).

(Wherein Q ¹ represents an alkyl group or an aromatic group, Q ² represents a cyclic aliphatic group or an aromatic group, Q ³ represents an alkyl group or an aromatic group, and Q ⁴ represents an aromatic group. P Represents an integer.)

In the formula, Q ¹ is an alkyl group or an aromatic group (including an aryl group). Q2 is a cyclic aliphatic group or an aromatic group (including an aryl group). Q3 is an alkyl group or an aromatic group (including an aryl group). Q4 is an aromatic group (including an aryl group). Alkyl and aromatic are the same as those described above. p represents an integer and is preferably 1 to 3.
Specific examples of R ³ and R ⁴ are given below.

Although the example of the pigment derivative compound used suitably as the said crystal growth inhibitor is shown below, this invention is not limited by this. In addition, the following exemplary compound S-6 is a reference example.

When the crystal growth inhibitor is incorporated in the particles, the presence or absence of the crystal growth inhibitor can be determined by solid-state ¹³ C CP / MAS NMR measurement (AVANCE DSX-300 spectrometer manufactured by Bruker BioSpin Corporation and 4 mmΦ HFX CP / MAS probe). ). The solid ¹³ C CP / MAS NMR measurement can be performed as follows.
The pigment fine particle dispersion is subjected to suction filtration using a membrane filter (MILLIPORE cut size: 0.05 μm) to prepare a concentrated paste. The concentrated paste was set on a solid ¹³ C CP / MAS NMR sample stage, and based on the Goldman-Shen pulse sequence, ¹ H 90 ° pulse width 4.5 μs, waiting time for initial solvent selection 200 μs, CP contact time 1 ms Then, the measurement is performed by changing the spin diffusion time from 0.5 to 200 ms. The number of integrations is 4096, and the repetition time is 3 to 10 seconds with 5 times the ¹ H spin-lattice relaxation time of the sample as a guide. The rotation speed of magic angle spinning is 8000 to 10000 Hz depending on the sample.
The peak areas of the pigment and the dispersant are calculated by peak separation of the spectrum at each spin diffusion time, and the diffusion distance L assuming a one-dimensional diffusion model is L = 1.1 (tm) with respect to the spin diffusion time tm. ^{Using the 1/2} relationship, the particle structure is determined from a plot of peak area versus distance from solvent molecules.

[Polymer compound]
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like. Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

  When a polymer compound is used, the molecular weight is preferably 500 to 200000, and more preferably 1000 to 70000. In the present invention, the term “molecular weight” means a mass average molecular weight unless otherwise specified, and the molecular weight and the degree of dispersion are values measured by the following measuring methods.

○ Method for measuring molecular weight and degree of dispersion of polymer compound The molecular weight and degree of dispersion are measured using GPC (gel filtration chromatography) unless otherwise specified. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected together. Examples of the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone, but ether solvents such as tetrahydrofuran are preferred. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently. The measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C.

Specific conditions for molecular weight measurement are shown below.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Pre-column: TSKGUARDCOLUMN MP (XL)
6mm x 40mm (manufactured by Tosoh Corporation)
Sample side column: The following two columns are directly connected (all manufactured by Tosoh Corporation)
・ TSK-GEL Multipore-HXL-M 7.8mm × 300mm
Reference side column: Same as sample side column Temperature chamber temperature: 40 ° C
Moving bed: Tetrahydrofuran Sample-side moving bed flow rate: 1.0 mL / min Reference-side moving bed flow rate: 0.3 mL / min Sample concentration: 0.1% by weight
Sample injection volume: 100 μL
Data collection time: 16 minutes to 46 minutes after sample injection Sampling pitch: 300 msec

  The amount of the particle growth inhibitor used in step [i] is preferably in the range of 1 to 60% by mass with respect to the pigment in order to further improve the intended effect on the fine particles of the dichlorodiketopyrrolopyrrole pigment. More preferably, it is the range of 3-30 mass%, More preferably, it is the range of 5-20 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

[Concentration / solvent removal step]
In the present invention, in order to remove solvents, bases, salts and other unnecessary components unnecessary for the final product, it is desirable to remove these from the mixed liquid after precipitation of the pigment fine particles obtained in step [i]. The removal process of these unnecessary components is not particularly limited, but for example, a method of filtering with a filter, a method of precipitating pigment fine particles by centrifugation, a method of concentrating and extracting a pigment by adding an extraction solvent, and a phase containing unnecessary components Examples thereof include a phase separation method (so-called flushing method).
As the filter filtration device, for example, a device such as reduced pressure or pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.
Any device may be used as the centrifuge as long as the fine pigment particles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking a supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be given. Centrifugation conditions are preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable.
In addition, as a solvent removal step, a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.
In the method of extracting the pigment and separating it from the phase containing unnecessary components, the extraction solvent is not particularly limited as long as it is a solvent capable of extracting the pigment from the mixed liquid after the pigment fine particles are precipitated, and any of them can be preferably used. It is. As the extraction solvent, propylene glycol monomethyl acetate is particularly preferred because it can also serve as a solvent for increasing the α-type crystallinity and a solvent for dispersion in the step [ii] of the present invention.
In order to remove these unnecessary components from the mixed solution after the pigment is deposited, it is preferable to add a washing solvent such as water or methanol after the above operation and repeat the above operation again. Further, these unnecessary components can be removed preferably between step [i] and step [ii] of the present invention or after step [ii]. In order not to bring in a good solvent, it is preferable to carry out between step [i] and step [ii].

[Preparation of composition for color filter]
○ Solvent When the crystallization treatment is performed in a state where the good solvent and the poor solvent are contained, the good solvent and the poor solvent can be removed using the third solvent. Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or Aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
In the present invention, not only the above-mentioned third solvent but also a fourth solvent described later, a solvent different from both the good solvent and the poor solvent, which is a medium of the dispersion composition, is collectively referred to as “first solvent”. 3 solvent ".

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include methanol, ethanol, n-butanol, isobutanol and the like. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane.

  Of these, ethyl lactate, ethyl acetate, ethanol, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the good solvent or the poor solvent.

The timing of adding the third solvent is not particularly limited as long as it is after the pigment fine particles are precipitated, but may be added to the mixed liquid in which the fine particles are precipitated, or after removing a part of the solvent of the mixed liquid. It may be added, or all may be added after removal (concentration) in advance.
That is, the third solvent can be used as a substitution solvent, and the solvent component consisting of the good solvent and the poor solvent in the dispersion liquid in which the fine particles are precipitated can be substituted with the third solvent.
Alternatively, the third solvent can be added after the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder.

In addition, when a pigment dispersion composition to be described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( The solvent may be removed and powdered by the second removal). Thereafter, a pigment dispersant and / or a solvent can be added to obtain a desired pigment dispersion composition.
Alternatively, the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent and / or the pigment dispersant can be added to obtain a desired pigment dispersion composition.
The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the fine particles of the water-insoluble colorant.

  The fine particles of the pigment can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted.

  The concentration of fine particles in the dispersion composition of fine particles after redispersion is appropriately determined according to the purpose, but preferably the fine particles are preferably 2 to 30% by mass with respect to the total amount of the dispersion composition, and 4 to 20% by mass. It is more preferable that it is 5-15 mass%. When dispersed in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of pigment, etc., but the binder is preferably 1 to 30% by mass based on the total amount of the dispersion composition. 3 to 20% by mass is more preferable, and 5 to 15% by mass is particularly preferable. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

○ Dispersant In the present invention, when the pigment fine particles are redispersed in the third solvent, the aggregation state of the pigment fine particles is spontaneously solved in the third solvent without adding another dispersant or the like. It is preferable to have a property of dispersing in, and this property is referred to as “self-dispersible” or “self-dispersible”. However, in order to further improve the redispersibility in the present invention, a pigment dispersant or the like may be added during redispersion of the fine particles.

As a method of redispersing the fine particles in such an aggregated state, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs, so the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.
There are no particular limitations on the disperser used when dispersing the pigment nanoparticles by applying physical energy. Can be mentioned. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants can be added to the pigment dispersion composition as long as the effects of the present invention are not impaired.
Examples of pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like. The dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like. Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

  In the present invention, the pigment derivative (hereinafter also referred to as “pigment derivative type dispersant”) is derived from an organic pigment as a parent substance, and is manufactured by chemically modifying the parent structure, or It is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.

  Although not particularly limited, for example, a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like. The introduced pigment derivative is preferably used.

Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)” manufactured by Lubrizol (any) Also product name).
Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative.
Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

  The photocurable composition includes a dispersion composition of fine particles of the pigment, a photopolymerizable compound, and a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator system), preferably, Contains alkali-soluble resin. Hereinafter, each component of the photocurable composition will be described.

  The pigment fine particles and the method for producing the dispersion composition have already been described in detail. The content of fine particles in the photocurable composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content refers to the total composition excluding the organic solvent), and 20 -80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

○ Polymerizable compound The photopolymerizable compound (hereinafter sometimes referred to as polymerizable monomer or polymerizable oligomer) has two or more ethylenically unsaturated double bonds and is polyfunctionalized by addition polymerization upon irradiation with light. A monomer is preferred. Examples of such a photopolymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned. Further, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  The photopolymerizable compound may be used alone or in combination of two or more. The content of the photocurable composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

○ Polymerization initiator As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture expressing a photopolymerization initiation function by a combination of a plurality of compounds). Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbons described in US Pat. No. 2,722,512 Substituted aromatic acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones A combination of a benzothiazole compound described in Japanese Patent Publication No. 51-48516 and trihalomethyl-s -A triazine compound, a trihalomethyl-triazine compound described in U.S. Pat. No. 4,239,850, a trihalomethyloxadiazole compound described in U.S. Pat. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

  In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.

  The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced. The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the photocurable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

○ Alkali-soluble resin The alkali-soluble resin can be added at the time of preparing the photocurable composition or the inkjet ink for the color filter, but it should be added at the time of producing the fine particle dispersion composition or at the time of forming the fine particles. Is also preferable. The alkali-soluble resin can be added to both or one of the poor solvent for adding the pigment solution and the pigment solution to form pigment fine particles. Alternatively, it is also preferable to add an alkali-soluble resin solution at the time of forming fine pigment particles in a separate system.

  As the alkali-soluble resin, a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  The alkali-soluble resin may be used alone or may be used in the state of a composition used in combination with a normal film-forming polymer. The addition amount of pigment to 100 parts by mass of fine particles is 10 to 200 parts by mass. Generally, 25-100 mass parts is preferable.

  In addition, in order to improve the crosslinking efficiency, the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin, a thermosetting resin, or the like is also useful. Furthermore, as the alkali-soluble resin, a resin having a water-soluble atomic group in a part of the side chain can be used.

O Photocurable resin In a photocurable composition, you may use the organic solvent (4th solvent) for photocurable composition preparation other than the said component further. Examples of the fourth solvent include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons. Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or these More preferably, a mixture of
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
These solvents may be used alone or in combination of two or more. Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. As for content of an organic solvent, 10-95 mass% is preferable with respect to photocurable composition whole quantity.

  Moreover, it is preferable to contain an appropriate surfactant in the photocurable composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. As for content of surfactant, 5 mass% or less is preferable with respect to photocurable composition whole quantity.

  The photocurable composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less with respect to the total amount of the photocurable composition.

  In addition to the colorant (pigment), a colorant (dye, pigment) can be added to the photocurable composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the photocurable composition. Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the photocurable composition.

  The photocurable composition can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the photocurable composition whole quantity.

  In addition to the above additives, the photocurable composition may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like.

Inkjet ink The photocurable composition can be made into an inkjet ink by appropriately adjusting its composition. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing. Among them, the inkjet ink for the color filter is preferable.
The ink-jet ink is not particularly limited as long as it contains the pigment fine particles, and is preferably a medium containing a polymerizable monomer and / or a polymerizable oligomer containing the pigment fine particles. Here, as the polymerizable monomer and / or polymerizable oligomer, those described above for the photocurable composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

  As the ink jet head (hereinafter also simply referred to as a head), a normal one can be applied, and a continuous type and a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

  A preparation method in which a partition wall is prepared in advance and the ink is applied to a portion surrounded by the partition wall before the pixel forming step using the color filter inkjet ink described above is preferable. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

○ Coating Film The components contained in the coating film using the photocurable composition are the same as those already described. Moreover, although the thickness of the coating film using a photocurable composition can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and it is 1.0-3.0 micrometers. Is more preferable. In the coating film using this photocurable composition, the above-mentioned monomer or oligomer can be polymerized to form a polymerized film of the photocurable composition, and a color filter having the polymerized film can be produced (about production of a color filter) Will be described later.) Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

  In addition, although the said coating film can be formed by apply | coating and drying a photocurable composition with a normal coating method, in this invention, it is a slit which has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the photocurable composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and can be widely used for producing color filters. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using the slit-shaped nozzle already demonstrated. Preferred specific examples of the slit coater are the same as described above.

○ Color filter The color filter is preferably excellent in contrast. In the present invention, the term “contrast” means a value measured by a measurement method employed in Examples described later unless otherwise specified. The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter is used for a television, the chromaticity of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below (hereinafter referred to as “this”). In the invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

  A liquid crystal display device provided with a color filter has a high contrast and is excellent in descriptive power such as black spots, and the VA method is particularly preferable. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. The color filter can be used for a CCD device and exhibits excellent performance.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted. In the examples, “part” and “%” are based on mass unless otherwise specified.

(Example 1 and Comparative Example 1)
Pigment C.I. to 220 ml of dimethyl sulfoxide at room temperature I. Pigment Red 254 (trade name Irgazine Red 2030, manufactured by Ciba Specialty Chemicals Co., Ltd.), and 1.1 g of the pigment derivative compounds S-1 and S-2 as particle growth inhibitors, respectively, 21.5 ml of 25% aqueous solution of tetramethylammonium hydroxide was added and stirred. Thus, an organic pigment solution in which the pigment was dissolved in a good solvent was obtained.
Separately, 2000 ml of water containing 70 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.

  Here, the temperature of the organic pigment solution was controlled at 5 ° C., and the organic pigment solution was NP-KX-500 in the poor solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). An organic pigment solution and a poor solvent were brought into contact with each other by injecting using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to precipitate organic pigment fine particles. At this time, the injection of the organic pigment solution was carried out at a flow rate of 100 ml / min for 2 minutes at a flow rate of 100 ml / min, with the flow channel diameter and the supply port diameter of the liquid feed pipe set to 0.5 mm. Thus, dispersion 1-1S in which organic pigment fine particles were dispersed in a solvent was obtained.

  The pigment dispersion prepared by the above procedure is subjected to vacuum filtration with an aspirator using Nutsche and filter paper (Advantech Co., Ltd., No. 2 (trade name)) with a diameter of 9 cm, thereby containing a fine pigment material. Got. By repeating the procedure of dispersing the obtained paste in ion-exchanged water and filtering again, the paste was washed with water to remove the good solvent and water-soluble ions. The washing of the paste with water was repeated until the conductivity when the paste was dispersed to a pigment concentration of 5% was 1 ms / m or less.

  In this manner, a water paste having a solid content concentration of 30% containing the pigment and the particle growth inhibitor was prepared as water paste 1-1W. The X-ray diffraction of the pigment powder obtained by separately drying a part of 1-1W was measured to calculate the crystal transformation ratio of the pigment in 1-1W. From the X-ray diffraction pattern, no diffraction peak is observed at 28.1 ± 0.3 ° which is the characteristic Bragg angle (2θ) of α-type crystal-modified dichlorodiketopyrrole, while β-type crystal-modified dichlorodiketopyrrole is A strong diffraction peak was observed at a characteristic Bragg angle (2θ) of 27.0 ± 0.3 °, and the pigment in 1-1W was substantially a dichlorodiketopyrrole having a β-type crystal modification.

<Crystal conversion process>
GK-0222-10 type lamond stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) is added at a temperature of 40 ° C. with respect to 30 parts by mass of the water paste 1-1W. Crystal transformation was carried out by stirring for 3 hours. Next, after concentrating by Nutsche filtration, adding ion-exchanged water, washing with water, and repeating the filtration twice to stop the excessive progress of the crystal conversion by replacing the solvent with water, and again by Nutsche filtration. By concentrating, a water paste having a solid content concentration of 30% containing a dichlorodiketopyrrolopyrrole pigment having undergone crystal conversion was obtained, and this was designated as water paste 1-1CW. The obtained water paste 1-1CW was dried using an oven at 100 ° C. for 2 hours, and then pulverized to 180 μm or less with a mortar to obtain a powder. In this way, Sample 1-1P, which is a red powdery color material (hereinafter sometimes referred to as “pigment” or “pigment substance”) containing a dichlorodiketopyrrole pigment and a particle growth inhibitor, was obtained. . As a result of measuring X-ray diffraction of 1-1P by the above-mentioned method, 1-1P is a characteristic Bragg angle (2θ) of the dichlorodiketopyrrolopyrrole pigment of α-type crystal modification. 28.1 ± 0.3 ° A diffraction peak was observed, and it was confirmed that crystal conversion was proceeding by the above operation. Further, the α-type crystallinity, the (−151) plane crystallite size, and the (111) plane crystallite size were calculated from the obtained X-ray diffraction results by the above-described methods. The calculation results are shown in Table 1.

<Dye dispersion preparation process>
A dye dispersion 1-1D of the present invention was prepared by bead mill dispersion of a dye substance, a dispersant, and a solvent mixture having the following composition. Dispersion was performed with a sand grinder mill BSG-01 (manufactured by AIMEX) using zirconia beads having a diameter of 0.5 mm for 1 hour at 1500 rpm and then using zirconia beads having a diameter of 0.05 mm for 4 hours at 2500 rpm.
-------------------------------
Pigment derivative 1-1P 12.0 parts by weight Pigment derivative 1 0.75 parts by weight Pigment derivative 2 0.75 parts by weight Dispersant resin 1 8.1 parts by weight Propylene glycol monomethyl ether acetate 78.4 parts by weight --- -------------------------------
The structures of pigment derivatives 1 and 2 are shown below.

Dispersing resin 1: "Ajisper PB821" (trade name) manufactured by Ajinomoto Fine Techno Co., Ltd.
Amine value: 10 mgKOH / g
Acid value: 17 mg KOH / g

  As a result of observation with an electron microscope, the obtained pigment dispersion 1-1D was confirmed to contain fine pigment particles having a volume weighted average diameter of 20.0 nm (converted to the same volume sphere) and a coefficient of variation of 15%.

  Hereinafter, pigment fine particles were prepared in the same manner except that the conditions of the pigment fine particles were changed as shown in Table 1 below, and evaluated in the same manner.

The exemplified compound N-1 was synthesized as follows.
To a 1 L three-necked flask, 20 g of PR254, 400 mL of dimethyl sulfoxide, and 18.48 g of potassium tert-butoxy were added and dissolved by stirring at 60 degrees. To this liquid, 1.3 g of potassium iodide and 14.25 g of chloroacetanilide were added and stirred at 60 ° C. for 3 hours. The reaction solution was discharged into 1000 parts by mass of ice water containing 20 parts by mass of hydrochloric acid to precipitate a solid. The precipitate was washed with 2000 parts by mass of water, and then washed with 600 parts by mass of methanol to obtain Compound N-1. It was confirmed by H-NMR and MS that the compound was N-1. From H-NMR, it was confirmed that PR254: Compound N-1 (1): Compound N-1 (2) = 37: 62: 2.

<Evaluation>
The following evaluation was performed on the dispersion liquid 1-1D.
(1) Contrast evaluation The obtained pigment dispersion 1-1D was applied on a glass substrate so as to have a thickness of 2 μm to prepare a sample. Using a three-wavelength cold-cathode tube light source (trade name: FWL18EX-N, manufactured by Toshiba Lighting & Technology Corp.) as a backlight unit, two polarizing plates (polarizing plates manufactured by Sanritsu Co., Ltd.) This sample was placed between the product names: HLC2-2518), and the amount of transmitted light was measured when the polarization axis was parallel and when it was vertical, and the contrast was determined from the ratio (“1990 7th Color Optics”). Conference, 512 color display 10.4 "size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka" etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and light transmitted through this. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.

The contrast value obtained by the above was calculated | required as ratio with respect to the value of the below-mentioned dispersion liquid 1-2D, and the following ranking was performed.
8: Contrast ratio 10 times or more 7: Contrast ratio 9 times or more and less than 10 times 6: Contrast ratio 8 times or more and less than 9 times 5: Contrast ratio 7 times or more and less than 8 times 4: Contrast ratio 6 times or more and less than 7 times 3: Contrast Ratio 4 times or more and less than 6 times 2: contrast ratio 2 times or more and less than 4 times 1: contrast ratio less than 2 times

(2) Viscosity characteristics evaluation The viscosity characteristics of the obtained pigment dispersion were measured with a rotational viscometer (RE-85L viscometer [trade name] manufactured by Toki Sangyo Co., Ltd.) under the condition of 25 ° C. The following ranking was performed.
6: Viscosity value is less than 8 mPa · s. The best level.
5: Viscosity value of 8 mPa · s or more and less than 10 mPa · s. Very good level.
4: Viscosity value of 10 mPa · s or more and less than 15 mPa · s. Good level.
3: A viscosity value of 15 mPa · s or more and less than 20 mPa · s. Acceptable level.
2: Viscosity value of 20 mPa · s or more and less than 100 mPa · s. Problem level.
1: A viscosity value of 100 mPa · s or more. Extremely problematic level.

For the method of preparing the dye dispersion 1-1D, only the type of particle growth inhibitor, the addition amount, the addition time, and the crystal conversion conditions were changed as shown in Table 1, and the bead mill dispersion time was only optimized. Dispersions were prepared by different methods to obtain dye dispersions 1-2D to 1-25D. These dye dispersions were evaluated in the same manner as the dye dispersion 1-1D. The particle growth inhibitors used here are shown in Tables 1-1 and 1-2 below.
Similarly, with respect to the method for preparing the pigment dispersion 1-3D, the type, addition amount, addition timing, and crystal conversion conditions of the particle growth inhibitor were changed as shown in Table 1-1, and the bead mill dispersion time was further changed. A dispersion liquid was prepared by a method different only in the adjustment of dyes to obtain dye dispersion liquids 1-26D to 1-41D. The particle growth inhibitors used here are shown in Table 1-3 below.

From the results of Tables 1-1 and 1-2, the dyes in which the α-type crystallinity, (−151) plane crystallite size, and (111) plane crystallite size of the dichlorodiketopyrrole pigment were set within the scope of the present invention. It can be seen that in the dispersion, both the contrast characteristics and the viscosity characteristics tend to be good (see the comparison between the dispersion liquid sample of the example and the sample of the comparative example). Here, even if the α-type crystallinity is within the range of the present invention, a dispersion sample whose crystallite size does not satisfy the requirements of the present invention is inferior in contrast characteristics or viscosity characteristics (Sample 1- 11D and samples 1-15D).
In addition, the α-type crystallinity, the (−151) plane crystallite size, and the (111) plane crystallite size are within the preferred range of the present invention, that is, the equivalent α crystallinity, the (−151) plane crystallite size and In order to set the (111) plane crystallite size to a smaller value, it is effective to add a particle growth inhibitor at the time of dissolving the pigment and perform the crystal conversion step in the presence of the particle growth inhibitor. It can be seen (see comparison between dispersion sample 1-1D and sample 1-11D).
In particular, by using a dye derivative having a diketopyrrolopyrrole skeleton and a quinacridone skeleton, it is possible to effectively reduce both the (-151) crystallite size and the (111) crystallite size. It can be seen (see comparison between dispersion sample 1-1D and sample 1-15D or 1-16D).

  From the results shown in Table 1-3, when N-1 to N-6, which are preferable derivatives of the present invention, are used, (111) when the α-type crystallinity is set to the same level as compared with the case where these are not used (111 ) It can be seen that the surface crystallite size can be effectively suppressed (for example, refer to the comparison between Sample 1-18D and Sample 1-34D or 1-37D). At this time, the contrast and / or the viscosity were improved, and it was confirmed that the dispersion characteristics could be effectively improved by suppressing the (111) plane crystallite size.

  FIG. 4 shows the relationship (excerpt) between the pregelatinization rate and the crystallite size in the examples and comparative examples. In FIG. 4, the same plot symbol indicates a sample with the same type and amount of crystal growth inhibitor during crystal conversion. If there are multiple plots with the same symbol (plot shape), crystal growth It means that the type and amount of the inhibitor used are the same and the α-type crystallinity is changed by changing the temperature and / or time of crystal conversion. In the plot of the same symbol in FIG. 4, there is a tendency to rise to the right, that is, the crystallite size tends to increase as the α-type crystallinity increases. That is, the upward trend in the plot of FIG. 4 suggests that it is difficult to produce pigment fine particles in the lower right direction in the figure, where it is considered that it is easy to achieve both a decrease in dispersion viscosity and an increase in contrast. . At this time, by using crystal growth inhibitors S-1 and S-2 in combination with a sample that does not use a crystal growth inhibitor, the crystallite size is reduced while maintaining the same degree of α-type crystallinity. This is considered to indicate that the trade-off relationship between the decrease in dispersion viscosity and the increase in contrast is improved. Further, when S-4 and N-1 are used in combination as a crystal growth inhibitor, it can be seen that the crystallite size on the (111) plane can be particularly suppressed, which is more preferable. On the other hand, when S-1 alone is used as the crystal growth inhibitor, the crystallite size on the (-151) plane is reduced, while the crystallite size on the (111) plane is increased. When S-2 alone is used as the crystal growth inhibitor, the crystallite size on the (111) plane is reduced while the crystallite size on the (-151) plane is increased. These single use results are considered to indicate that excessive suppression of the growth of the specific crystal plane leads to promotion of the growth of the crystal plane which is not suppressed.

(Comparative Example 1A)
Furthermore, although the pigment dispersion was prepared based on the conventional technique as follows, it was confirmed that a product within the scope of the present invention could not be obtained.

(Comparative Example 1A-1)
An attempt was made to obtain the alkali metal salt solution of the dichlorodiketopyrrolopyrrole pigment in the same manner as in the example of Japanese Patent No. 4144655. However, precipitation of the pigment occurred and an alkali metal salt solution could not be obtained. Based on this result, an alkali metal salt solution of a dichlorodiketopyrrolopyrrole pigment was prepared by the method described later.

(Comparative Example 1A-2)
As shown below, by setting the poor solvent composition, particle formation conditions and crystal conversion conditions close to those in Examples 1 and 2 of Japanese Patent No. 4144655, and using isobutyl alcohol and caustic soda as the crystal conversion solvent, the dye substance 3-1P and dispersion 3-1D, pigment substance 3-2P, and dispersion 3-2D were prepared, respectively.

○ Preparation of Sample 3-1 Pigment C.I. was added to 308 ml of dimethyl sulfoxide at room temperature. I. Pigment Red 254 (trade name: Irgazine Red 2030, manufactured by Ciba Specialty Chemicals Co., Ltd.) 15.4 g was added, and 8.32 g of a sodium methoxide (28%) methanol solution was added and stirred. In this way, an alkali metal salt solution of a dichlorodiketopyrrolopyrrole pigment in which the pigment was dissolved in a good solvent was obtained, and this was heated to 90 ° C.
Separately from this, 600 g of methanol, 600 g of water and 2.6 g of acetic acid were added as a poor solvent, and a solution cooled to −10 ° C. was prepared. Into this, the previously obtained alkali metal salt solution of 90 ° C. diketopyrrolopyrrole pigment was added in small portions over about 60 minutes while cooling so that the temperature of the preparation liquid was always 0 ° C. or lower. Thus, a dispersion liquid in which organic pigment fine particles were dispersed in a solvent was obtained.

The pigment dispersion prepared by the above procedure was filtered off using Nutsche and filter paper, and then washed with 300 g of methanol cooled to 10 ° C. and 1000 ml of water. The obtained red paste was dispersed again in a mixture of 400 g of methanol and 400 g of water, and again filtered by using a Nutsche to obtain an aqueous paste of diketopyrrolopyrrole pigment, which was dried at 80 ° C. for 24 hours, By further pulverizing, a coarse crystal powder composed of a mixed crystal of α type and β type was obtained.
The obtained crude crystal powder was subjected to crystal conversion by adding 1500 g of isobutyl alcohol and 5.6 g of 25% aqueous sodium hydroxide solution to a solution cooled to 10 ° C. and stirring for 6 hours, and then adjusted the pH to 7 or less with acetic acid. Subsequently, Nutsche filtration was performed again, and this was washed by sequentially sprinkling 1000 g of methanol cooled to 10 ° C. and 1000 g of water, and dried to prepare a pigment substance 3-1P. Moreover, with respect to the preparation method of the pigment dispersion 1-1D of Example 1, the pigment substance was replaced with 3-1P, and further the dispersion time was optimized to obtain a dispersion 3-1D.

Preparation of Sample 3-2 Pigment C.I. was added to 308 ml of dimethyl sulfoxide at room temperature. I. Pigment Red 254 (trade name: Irgazine Red 2030, manufactured by Ciba Specialty Chemicals Co., Ltd.) 15.4 g was added, and 8.32 g of a sodium methoxide (28%) methanol solution was added and stirred. Thus, an alkali metal salt solution of a dichlorodiketopyrrolopyrrole pigment in which the pigment was dissolved in a good solvent was obtained, heated to 90 ° C., and then cooled to 75 ° C.
Separately from this, 600 g of methanol, 600 g of water and 6.76 g of acetic acid were added as a poor solvent, and a solution cooled to −10 ° C. was prepared. Into this, the alkali metal salt solution of the diketopyrrolopyrrole pigment of 75 ° C. obtained above was added little by little over about 120 minutes while cooling so that the temperature of the preparation solution was always 5 ° C. or less. Thus, a dispersion liquid in which organic pigment fine particles were dispersed in a solvent was obtained.

  The pigment dispersion prepared by the above procedure was separated by filtration using Nutsche and filter paper, and then washed by sprinkling 3000 g of methanol cooled to 0 ° C. and 1000 ml of water cooled to 5 ° C. Methanol was added to the obtained red paste to make a suspension with a methanol concentration of about 90%, and crystal conversion was performed by stirring at 5 ° C. for 3 hours. This was filtered with Nutsche, further washed with 1000 ml of water at 5 ° C., filtered, dried at 80 ° C. for 24 hours, and further pulverized to prepare coloring matter 3-2P. Moreover, with respect to the preparation method of the pigment dispersion liquid 1-1D of Example 1, the pigment substance was replaced with 3-2P, and further the dispersion time was optimized to obtain a dispersion liquid 3-2D.

For the pigment substances 3-1P and 3-2P, the α-type crystallinity, the (−151) plane crystallite size, and the (111) plane crystallite size were calculated by X-ray diffraction as in Examples 1 and 2. Further, the same evaluation as in Example 1 was performed on the pigment dispersions 3-1D and 3-2D. These results are shown in the table below.

  From the above table, it can be seen that the pigment substances 3-1P and 3-2P have crystallite sizes that are out of the scope of the present invention and their dispersion properties are not good.

(Example 2 and Comparative Example 2)
A dye dispersion was prepared by the method described below.
(Preparation of pigment dispersion 2-1D)
Before the crystal conversion step, the water paste 1-1W was dried and then pulverized. To 9 parts by mass of the obtained powder, 189 parts by mass of propylene glycol monomethyl ether acetate and 21 parts by mass of water were added, and the temperature was 40 ° C. A dye dispersion was prepared in the same manner as the dye dispersion 1-1D of Example 1 except that the crystal conversion was performed by stirring for 12 hours to obtain a dye dispersion 2-1D. At this time, after finishing the crystal change treatment, the sample was immediately washed with water so as to prevent excessive crystallization.

(Preparation of pigment dispersion 2-2D)
A pigment dispersion was prepared by the same method as that of the pigment dispersion 2-1D to obtain a pigment dispersion 2-2D. However, during the crystal conversion step, sand grinder mill BSG-01 [trade name] (manufactured by AIMEX) is used instead of ramond stirrer, and 10 parts by mass of conversion liquid using zirconia beads having a diameter of 0.5 mm as a grinding agent. Crystal conversion was carried out by using 40 parts by mass (bulk weight ratio of about 50%) and stirring at 1500 rpm for 16 hours while controlling at 40 ° C. At this time, after finishing the crystal change treatment, the sample was immediately washed with water so as to prevent excessive crystallization.

Evaluation similar to Example 1 was performed with respect to the obtained pigment dispersion liquid. The results are shown in Table 2. By drying before crystal conversion (Sample 2-1D) and using a milling agent (Sample 2-2D), the conversion process time for obtaining the same degree of α crystallinity is extended, and the contrast characteristics are further improved. There was a tendency to decrease. At this time, increases in the (−151) plane crystallite size and the crystal plane (111) plane crystallite size were observed, and it was considered that the decrease in contrast characteristics correlated with the decrease in crystallite size. Drying prior to the crystal conversion step can lead to agglomeration of the pigment particles, resulting in non-uniform crystal conversion, resulting in the formation of excessively grown particles by increasing the α crystallinity, leading to a decrease in contrast characteristics. It was estimated that there was sex. Moreover, it was estimated that the use of the milling agent resulted in a decrease in the efficiency of α crystallization due to the suppression of α crystallization or β crystallization due to destruction of α crystals.
From the comparison of these results with the results of the dye dispersion 1-1D, it is preferable not to perform a drying step before the crystal conversion step, and further to use no milling agent, whereby a dichlorodiketopyrrole pigment starting from β-type crystals Was able to be efficiently crystallized into α form even in the presence of pigment derivatives.

(Preparation of pigment dispersion 2-3D)
A pigment dispersion was prepared by the same method as that of the pigment dispersion 1-1D to obtain a pigment dispersion 2-3D. However, immediately after crystal conversion, it is rapidly cooled to 5 ° C., and when concentrated by Nutsche filtration, propylene glycol monomethyl ether acetate is added in place of ion-exchanged water and filtration is repeated twice to change the solvent to propylene glycol monomethyl ether acetate. After the replacement, a dye dispersion was immediately prepared without drying. At this time, the amount of propylene glycol monomethyl ether acetate added in the dye dispersion preparation step was adjusted so that the dye substance concentration in the finished dye dispersion was equal to that of the dye dispersion 1-1D. Evaluation similar to Example 1 was performed with respect to the obtained pigment dispersion liquid. Here, the α crystallinity and crystallite size were measured by adding water to a part of the dye dispersion after replacing the solvent with propylene glycol monomethyl ether acetate to completely stop crystal conversion and then drying. This was performed on the obtained pigment powder. The results are shown in Table 2. Dye dispersion 2-3D has improved contrast and viscosity characteristics over dye dispersion 1-1D, indicating that it is effective not to dry before preparing the dispersion. Further, it was confirmed that even if water washing was not performed after crystal conversion, the dispersion after the conversion was cooled and immediately dispersed, so that no adverse effects due to excessive crystallization were observed.

(Preparation of pigment dispersion 2D)
In contrast to the method of preparing the dye dispersion 2-1D, when the organic pigment solution is added to the poor solvent and the organic pigment fine particles are precipitated, the organic pigment solution supply rate is changed to a flow rate of 3.3 ml / min for about 60 minutes. A dye dispersion was prepared by a different method except that organic pigment fine particles were precipitated over time to obtain a dye dispersion 2-4D.

(Preparation of pigment dispersion 2-5D)
A dye dispersion was prepared by a method different from that for preparing the dye dispersion 2-4D, except that 2000 ml of methanol containing 70 ml of 1 mol / l hydrochloric acid was used as a poor solvent, and a dye dispersion 2-5D was obtained.
Evaluation similar to Example 1 was performed with respect to the obtained pigment dispersion liquid. The results are shown in Table 2. In the dye dispersions 2-4D and 2-5D, the crystal form before the crystal conversion operation was a mixed state of α-type and β-type, and a decrease in contrast characteristics was observed with respect to the dye dispersion 2-1D. At this time, increases in the (−151) plane crystallite size and the crystal plane (111) plane crystallite size were observed, and it was considered that the decrease in contrast characteristics correlated with the increase in the crystallite size. Operations such as lowering the precipitation rate and using a solvent as a poor solvent, which can already produce a part of the dichlorodiketopyrrole pigment in the α-type crystal form after pigment precipitation, lead to an increase in the particle size during pigment precipitation. Therefore, it is estimated that the crystallite size after crystal conversion also increased and caused a decrease in contrast characteristics. From these results, it was shown that the β-type is more preferable as the crystal form of the dichlorodiketopyrrole pigment at the time of pigment particle precipitation.

(Preparation of pigment dispersion 2-6D)
In contrast to the method of preparing the pigment dispersion 2-3D, the pigment dispersion is obtained by a method different from the method of performing solvent extraction (so-called flashing method) instead of Nutsche filtration before crystal conversion, and further changing the crystal conversion time. It was made and it was set as the pigment dispersion 2-6D. The procedure of washing with solvent extraction was as follows. After obtaining a dispersion 1-1S in which organic pigment fine particles were dispersed in a solvent, 40% by weight of propylene glycol monomethyl ether acetate was added to 1-1S and stirred for 5 minutes. By allowing the obtained dispersion to stand in a separating funnel, the solvent composition mainly consists of propylene glycol monomethyl ether acetate, the upper layer containing the pigment, and the solvent composition mainly consists of water and DMSO. Separated into lower layers not containing. By discarding the lower layer, unnecessary salts and DMSO contained in the dispersion 1-1S were discarded. Next, after adding 160% by weight of ion-exchanged water to the remaining upper layer and stirring for 5 minutes, it was left to stand again in a separatory funnel to mainly consist of propylene glycol monomethyl ether acetate as a solvent composition. The upper layer containing the pigment and the solvent composition mainly composed of water were separated into the lower layer containing almost no pigment, and unnecessary salts were discarded by discarding the lower layer.
Thus, pigment dispersion 2-6W having been desalted was obtained. 2-6W was a pigment dispersion composed of about 85% propylene glycol monomethyl ether acetate and about 15% water as a solvent composition. The obtained 2-6W was aged at 40 ° C. for 1 hour for crystal conversion, then immediately cooled to 5 ° C., and the solvent was replaced with propylene glycol monomethyl ether acetate by Nutsche filtration in the same manner as in the dispersion 2-3D. By carrying out, a dispersion 2-6D was obtained. Evaluation similar to Example 1 was performed with respect to the obtained pigment dispersion liquid. Here, the α crystallinity and crystallite size were measured by adding water to a part of the dye dispersion after replacing the solvent with propylene glycol monomethyl ether acetate to completely stop crystal conversion and then drying. This was performed on the obtained pigment powder. The results are shown in Table 2. It was confirmed that the present invention is also effective when desalting and pigment extraction are performed by the flushing method.

(Preparation of pigment dispersion 2-7D)
A pigment dispersion was prepared by the same method as that of the pigment dispersion 1-1D to obtain a pigment dispersion 2-7D. However, when drying the water paste 1-1CW that had undergone crystal conversion, drying was performed by freeze-drying instead of drying at 100 ° C. for 2 hours using an oven. Table 2 shows the results of evaluation similar to Example 1 performed on the obtained pigment dispersion. Dye dispersion 2-7D showed improved contrast and viscosity characteristics over dye dispersion 1-1D, indicating that it was effective to perform drying by freeze-drying. Similarly, dye dispersions were prepared for the samples 1-26D to 1-41D, and good production suitability and product performance were confirmed in the present invention.

(Example 3 and Comparative Example 3)
<Create color filter>
As a result of producing a color filter by the following procedure using the dye dispersion 2-3D obtained in Example 2, a good contrast is obtained as a color filter, and the dye dispersion of the present invention is suitably used for a color filter. I confirmed that I can do it.

[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 3 below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K1 was obtained.

[Table 3]
--------------------------------------
K pigment dispersion 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization start Agent A 0.16 parts by mass Surfactant 1 0.044 parts by mass -------------------------------- ------

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials, Inc., 100-fold diluted solution) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

  The colored photosensitive resin composition K1 is first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone and binder 2 , Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s- Triazine) and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass / dispersant (compound J1) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio, molecular weight 38,000) 27 parts by massPropylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 1>
・ Megafuck F-780-F (trade name: manufactured by Dainippon Ink & Chemicals, Inc.)
: Composition is C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ 40 parts by mass and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ Copolymer with 5 parts by mass (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]
A heat-treated pixel R was formed in the same process as the formation of the black (K) image using the colored photosensitive resin composition R1 having the composition shown in Table 4 below on the substrate on which the image K was formed. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 4]
--------------------------------------
R pigment dispersion 2-1D 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA liquid 3.8 parts by mass Part 2-Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.06 parts by mass ----------- --------------------------

<R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate <Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, propylene glycol monomethyl ether acetate 73 parts by mass

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition shown in Table 5 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 5]
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 2.5 parts by mass DPHA solution 3 0.5 part by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by weight ----------- --------------------------

<G pigment dispersion 1>
GT-2 (trade name: manufactured by FUJIFILM Electronics Materials)
<Y pigment dispersion 1>
CF yellow-EX3393 (trade name: manufactured by Mikuni Color Co., Ltd.)

[Formation of blue (B) pixels]
Using the colored photosensitive resin composition B1 having the composition shown in Table 6 below on the substrate on which the image K, the pixel R, and the pixel G are formed, heat treatment is performed in the same process as the formation of the black (K) image. Pixel B was formed. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.

Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 6]
--------------------------------------
B Pigment Dispersion 1 (CIPB 15: 6) 8.6 parts by mass V Pigment Dispersion 2 (CIPB 15: 6 + CIPV 23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA solution 4.0 Parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 0.06 parts by mass -------------------- -----------------

<B pigment dispersion 1>
CF Bull-EX3357 (trade name: manufactured by Mikuni Color Co., Ltd.)
<B pigment dispersion 2>
CF Bull-EX3383 (trade name: manufactured by Mikuni Color Co., Ltd.)
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

[Production of ITO electrodes]
The glass substrate on which each pixel is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed to complete the color filter A1.

Claims (14)

A colorant dispersion containing a particle growth inhibitor represented by the following general formula (1) and pigment fine particles containing a dichlorodiketopyrrolopyrrole pigment , wherein the colorant dispersion is defined by the following (1) to (3): The α-type crystallinity of the pigment fine particles is 0.65 to 0.90, the crystallite size in the (-151) crystal plane direction is 6.0 to 13.0 nm, and the crystallite size in the (111) crystal plane direction is A colorant dispersion characterized by having a range of 5.0 to 23.0 nm.
P- [X- (Y) k] n ... General formula (1)
(In the formula, P represents a diketopyrrolopyrrole pigment compound residue or a quinacridone pigment compound residue. X represents a single bond or a divalent linking group. Y represents —NR ₂ R ₃ , a sulfo group, or a carboxyl group. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group, which may have a substituent, or R ₂ and R ₃ formed integrally. (K represents an integer of 1 or 2. n represents an integer of 1 to 4.)
(1) Powder X-ray diffraction measurement using CuKα rays is performed on the dichlorodiketopyrrole pigment. The measurement is performed in accordance with Japanese Industrial Standard JIS K03131 (general rules for X-ray diffraction analysis) in the range of Bragg angle (2θ) from 23 ° to 30 °.
(2) From the X-ray diffraction pattern obtained in (1), a diffraction pattern with the background removed is obtained. Here, the background removal method is to contact the lower Bragg angle (2θ) = 23.3 ° and the higher Bragg angle (2θ) = 29.7 ° of the measurement pattern. An operation is performed to draw a straight line and obtain a pattern obtained by removing the X-ray diffraction intensity value represented by the straight line from the X-ray diffraction intensity value obtained in (1).
(3) From the X-ray diffraction pattern obtained by removing the background determined in (2), the α-type crystallinity is calculated by the following formula.
α-type crystallinity = Iα / (Iα + Iβ)
Here, Iα is the diffraction intensity value after removing the background of the Bragg angle (2θ) = 28.1 ± 0.3 °, which is a characteristic diffraction peak of the α-type crystal transformation, and Iβ is the β-type crystal transformation. It is defined as a diffraction intensity value after removing the background of a diffraction peak in the vicinity of Bragg angle (2θ) = 27.0 ± 0.3 ° which is a characteristic diffraction peak. The color material dispersion according to claim 1, wherein the color material dispersion is produced through the following steps [i] and [ii].
[[I] A dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent. A step of generating fine particles. ]
[[Ii] the [dichlorodiketopyrrolopyrrole pigment of fine particles obtained in the step i], is contacted with the following crystalline adjusting organic solvent in the presence of the particle growth inhibitor, dichlorodiketopyrrolopyrrole pigment To increase the α-type crystallinity of. ]
[Crystal type adjusting organic solvent: ether solvent, sulfoxide solvent, ester solvent, amide solvent, aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, nitrile solvent, halogen solvent, alcohol solvent, ketone System solvent, ionic liquid, carbon disulfide solvent, or a mixture thereof] The color material dispersion according to claim 1 or 2, wherein the concentration of the pigment fine particles is 0.1 to 50% by mass . The color material dispersion according to any one of claims 1 to 3, wherein an average particle diameter of the pigment fine particles is 100 nm or less . The said particle growth inhibitor is further represented by the following general formula (2), The coloring material dispersion of any one of Claims 1-4 characterized by the above-mentioned.

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. R ³ and R ⁴ are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R ³ and R ⁴ is a substituted or unsubstituted alkyl group.) The colorant dispersion containing pigment fine particles containing the dichlorodiketopyrrolopyrrole pigment according to any one of claims 1 to 5, wherein the colorant dispersion is produced through the following steps [i] and [ii]: Manufacturing method.
[[I] A dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent. A step of generating fine particles. ]
[[Ii] the [dichlorodiketopyrrolopyrrole pigment of fine particles obtained in the step i], is contacted with the following crystalline adjusting organic solvent in the presence of the particle growth inhibitor, dichlorodiketopyrrolopyrrole pigment To increase the α-type crystallinity of. ]
[Crystal type adjusting organic solvent: ether solvent, sulfoxide solvent, ester solvent, amide solvent, aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, nitrile solvent, halogen solvent, alcohol solvent, ketone System solvent, ionic liquid, carbon disulfide solvent, or a mixture thereof]   The colorant dispersion according to claim 6, wherein the pigment solution containing the dichlorodiketopyrrolopyrrole pigment is obtained by dissolving the dichlorodiketopyrrolopyrrole pigment in an organic solvent in the presence of a base. Manufacturing method.   8. The method for producing a color material dispersion according to claim 6, wherein the step [i] is performed in the presence of the particle growth inhibitor. The method for producing a color material dispersion according to any one of claims 6 to 8, wherein an average particle diameter of the pigment fine particles is 100 nm or less . The method for producing a color material dispersion according to any one of claims 6 to 9, wherein the particle growth inhibitor is represented by the following general formula (2).

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. R ³ and R ⁴ are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R ¹ and R ² is a substituted or unsubstituted alkyl group.) Wherein [i] fine particle dichlorodiketopyrrolopyrrole pyrrole pigment is produced in step a it is, in any one of claims 6-1 0, which is a β-type crystalline mixed state or β-type crystal modification of modification The manufacturing method of the coloring material dispersion of description. The method of producing a color material dispersion according to any one of claims 6 to 11, wherein the step [ii] is performed in the absence of a grinding agent. Wherein the step of [ii], the [i] according the generated dichlorodiketopyrrolopyrrole pigment fine particles in any one of claims 6 to 1 2, which comprises carrying out without drying in the step A method for producing a color material dispersion.   The method for producing a color material dispersion according to any one of claims 6 to 13, wherein the step [ii] is performed at -10 ° C to 100 ° C.

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