JP2014177532A - Method for producing dichlorodiketopyrrolopyrrole pigment composition, dichlorodiketopyrrolopyrrole pigment composition, coloring composition for color filter, and color filter - Google Patents

Abstract

A color filter having a high brightness, a high contrast ratio, and a low viscosity for producing a pigment composition comprising a dichlorodiketopyrrolopyrrole pigment having an excellent degree of fineness and having a crystal form changed to an α-type transformation. It is an object to make it possible to provide a coloring composition.
Biaxial extinction includes a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, and at least one of resin (B) and resin-type dispersant (C). The problem is solved by a method for producing a dichlorodiketopyrrolopyrrole pigment composition characterized in that a β-type crystal transformation is transformed into an α-type crystal transformation by kneading using a Luder type kneader.
[Selection] Figure 1

Description

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  In order to achieve high brightness and high contrast, the primary particle size of the pigment particles is generally further refined and sized compared to the level normally used in printing inks, gravure inks, and colorants, It is necessary to maintain and disperse and stabilize a fine state in a solvent.

  The red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, has a diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment as a colorant. It is common to use pigments excellent in light resistance and heat resistance alone or in combination. Among the pigment types, in recent years, dichlorodiketopyrrolopyrrole pigment (CI Pigment Red 254) having an excellent spectral shape has been used as a main pigment from the viewpoint of brightness. Therefore, in order to achieve a red-colored pixel having a high brightness and a high contrast ratio, there is a demand for a technique that ensures the stability when the dichlorodiketopyrrolopyrrole pigment is refined, sized and dispersed.

  As a method for producing a finely divided dichlorodiketopyrrolopyrrole pigment, an acid paste method, a salt milling method, and the like have been proposed (Patent Documents 1 and 2). However, since the acid paste method uses concentrated sulfuric acid, there are concerns about safety, and the salt milling method requires the use of a specially micro-processed inorganic salt, and there is a process for removing the inorganic salt from the fine pigment. There is a cost constraint because it is necessary. Furthermore, since all of them are water-based pigment miniaturization, in the process of removing water, the pigments are dried and agglomerated, making it difficult to achieve high contrast and low viscosity of the dispersion.

  Furthermore, in order to achieve a high brightness and a high contrast ratio using a dichlorodiketopyrrolopyrrole pigment, it is necessary to consider the crystal form in addition to the particle diameter.

  In general, dichlorodiketopyrrolopyrrole pigments are known to have α-type and β-type crystal modifications (see, for example, Patent Document 5). Patent Document 5 defines a β-type crystal modification as a new crystal modification of a dichlorodiketopyrrolopyrrole pigment. In Patent Document 5, a known modification before the filing of the patent application is described as an α-type crystal modification. doing. It is also described that a β-type transformation can be obtained by synthesis of dichlorodiketopyrrolopyrrole. In addition, X-ray diffraction charts of α-type and β-type crystal transformations are also known (Non-patent Document 1). Generally, it is known that α-type transformation is a stable system and β-type transformation is an unstable system. It has been. When it is used for color filter applications, if α-type transformation and β-type transformation are mixed, the spectral shape of the coating film becomes poor and low brightness, so it is suitable for use as a color filter application. For this purpose, it is necessary to transfer the crystal modification of the dichlorodiketopyrrolopyrrole pigment to the α-type. The crystal form transition from the β-type crystal transformation to the α-type crystal transformation includes a crystal form transition by wet milling by a salt milling method (Patent Document 2), and a crystal form using a crystal form adjusting solvent by a reprecipitation method. Transition (Patent Documents 6 and 7), crystal-type transition under a thin film fluid (Patent Document 8), and the like, but depending on the solvent used, the contrast ratio is low due to crystal growth or pigment aggregation. Or problems such as poor stability occurred.

JP 2001-264528 A JP 2008-24873 A JP 58-210084 JP-A-5-222314 JP-A-8-48908 High Performance Pigments, WILEY-VCH, pp 174-175 JP 2011-46846 A JP 2011-68852 A Japanese Patent No. 4840835

An object of the present invention is to produce a pigment composition containing a dichlorodiketopyrrolopyrrole pigment having an excellent fineness and having a crystal form changed to an α-type transformation, which has high brightness, high contrast ratio, and low viscosity. It is possible to provide a coloring composition for a certain color filter.
In order to achieve this, (1) the dichlorodiketopyrrolopyrrole pigment is sufficiently transformed into the α-type crystal transformation, (2) the dichlorodiketopyrrolopyrrole pigment is refined, (3 It is necessary to solve the problems such as suppressing the crystal particle transition process and pigment particle growth during contact with the solvent, and (4) suppressing the dry aggregation of the pigment.

  As a result of extensive studies, the present inventors have determined that a crude dichlorodiketopyrrolopyrrole pigment and at least one of the resin (B) and the resin-type dispersant (C) are mixed with a biaxial extruder. High brightness, high contrast ratio, and low viscosity color containing dichlorodiketopyrrolopyrrole pigment with α-type transformation excellent in fineness by manufacturing method of dichlorodiketopyrrolopyrrole pigment composition kneaded using smelting equipment The present inventors have found that a pigment composition capable of providing a coloring composition for a filter can be obtained, and have reached the present invention.

  That is, the present invention provides a biaxial mixture of a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, and at least one of resin (B) and resin-type dispersant (C). The present invention relates to a method for producing a dichlorodiketopyrrolopyrrole pigment composition, wherein the β-type crystal transformation is crystallized to the α-type crystal transformation by kneading using an extruder type kneading apparatus.

  The present invention also relates to a method for producing the dichlorodiketopyrrolopyrrole pigment composition, wherein the resin (B) contains at least one of an acrylic resin and a rosin-modified maleic acid resin.

  Moreover, this invention relates to the manufacturing method of the said dichloro diketopyrrolopyrrole pigment composition characterized by including a pigment derivative (D) further.

  Further, the present invention provides the dichlorodi, wherein the dye base skeleton of the dye derivative (D) is one selected from the group consisting of a diketopyrrolopyrrole pigment skeleton, a thiazine pigment skeleton, and an azo pigment skeleton. The present invention relates to a method for producing a ketopyrrolopyrrole pigment composition.

In the present invention, the α-type crystallinity represented by the formula (1) of the crude dichlorodiketopyrrolopyrrole pigment is 0.08 or more and less than 0.9, and the formula (1) of the dichlorodiketopyrrolopyrrole pigment composition ( It relates to a method for producing the dichlorodiketopyrrolopyrrole pigment composition, wherein the α-type crystallinity shown in 1) is 0.9 or more and 1.0 or less.

Formula (1) α-type crystallinity = I _α / (I _α + I _β )

[In Formula (1),
In powder X-ray diffraction measurement using I _α ... CuKα ray, the intensity I 2 ··· 0.3 ° is the characteristic Bragg angle (2θ) of α-type crystal transformation I _β ... powder X using CuKα ray In the line diffraction measurement, the intensity is 27.0 ± 0.3 ° which is a characteristic Bragg angle (2θ) of β-type crystal transformation. ]

  The present invention also relates to the method for producing the dichlorodiketopyrrolopyrrole pigment composition, wherein the temperature of the biaxial extruder type kneader is in the range of 20 ° C to 100 ° C.

  Moreover, this invention relates to the dichloro diketopyrrolopyrrole pigment composition manufactured by the manufacturing method of the said dichloro diketopyrrolopyrrole pigment composition.

  The present invention also relates to a coloring composition for a color filter, wherein the dichlorodiketopyrrolopyrrole pigment composition further contains at least one of a photopolymerizable monomer and a photopolymerization initiator. .

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

  By using the method for producing a dichlorodiketopyrrolopyrrole pigment composition of the present invention, it is possible to provide a dichlorodiketopyrrolopyrrole pigment composition having an excellent degree of fineness and having a crystal form changed to α-type. By using the pigment composition of the present invention, it is possible to provide a coloring composition for a color filter having high brightness, high contrast ratio, and low viscosity. In addition, the use of a twin-screw extruder type kneading device gives the energy required for the finer pigment effect and the crystal form transition of dichlorodiketopyrrolopyrrole pigment due to the share of kneading, as well as continuous kneading. Since this is a process, productivity can be expected to be improved over conventional pigment refinement methods. Furthermore, at the time of kneading, at least one of resin (B) or resin-type dispersant (C) and kneading together with dichlorodiketopyrrolopyrrole pigment, dichlorodiketo is adsorbed and protected by the pigment. The effect of suppressing particle growth due to crystal type transition of pyrrolopyrrole pigment, particle growth due to solvent contact, and drying aggregation at the time of preparing a coating film is born. When a pigment dispersion is made, high contrast and low viscosity can be achieved.

It is an example of the diffraction pattern by powder X-ray diffraction of a crude diketopyrrolopyrrole pigment. It is the diffraction pattern which removed the background of the diffraction pattern of FIG.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” mentioned below means a color index (CI).

  The method for producing a dichlorodiketopyrrolopyrrole pigment composition of the present invention comprises a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, resin (B) and resin-type dispersant (C). At least one of them is kneaded using a biaxial extruder-type kneading apparatus, whereby the β-type crystal transformation is changed to the α-type crystal transformation.

<< Method for Producing Dichlorodiketopyrrolopyrrole Pigment Composition >>
The method for producing a dichlorodiketopyrrolopyrrole pigment composition of the present invention comprises a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, resin (B) and resin-type dispersant (C). A mixture containing at least one of them and, if necessary, the dye derivative (D) is kneaded using a biaxial extruder-type kneader, thereby converting the β-type crystal-transformed dichlorodiketopyrrolopyrrole pigment into α Crystal form transition to a type crystal modified dichlorodiketopyrrolopyrrole pigment.
Thereby, it can be set as the pigment composition containing the dichloro diketopyrrolopyrrole pigment which was excellent in the degree of refinement | miniaturization, and changed the crystal | crystallization type | mold to the alpha transformation.

<Biaxial extruder type kneading equipment>
By kneading with a biaxial extruder type kneading device, a sufficient energy load is applied to make the pigment finer and the pigment crystal type transition, and at the same time, the resin (B) or resin type dispersant ( By adsorbing and protecting C) to the pigment, there is an effect of suppressing crystal growth accompanying the crystal type transition.

  In addition, the twin-screw extruder type kneading device has more driving parts than the single-shaft kneading device, so it is easy to take a share, and it is possible to close gaps by using a closed kneading system. Kneading with a higher share is possible as compared with the apparatus, and it is suitable for refining pigments with crystal type transition as in the present invention.

  A twin-screw extruder type kneading apparatus is composed of a paddle, a screw, and a heater. Each paddle includes a paddle that transports the material, a paddle that stirs and mixes the material, and a paddle that transports the material in the opposite direction, and is configured by connecting them appropriately according to the purpose. However, the total length of the screw is limited by the extruder, and it is necessary to combine the paddles so that the intended process is continuously performed within the total length.

  In the above apparatus configuration, when the material is put into the biaxial extruder kneading apparatus from the hopper, it is heated by the heater and sent to the outlet side while being kneaded.

  As conditions for the biaxial extruder-type kneading apparatus, the temperature is preferably in the range of 20 to 200 ° C, and more preferably in the range of 20 to 100 ° C. When produced at a temperature lower than 20 ° C., the volatilization of the solvent is suppressed, and it becomes difficult for the kneaded product to be sheared, making it difficult for the resin adsorption to proceed. When it is produced at a temperature higher than 200 ° C., too much heat is applied, so that the resin component may be thermally denatured, leading to deterioration in quality.

Rotational speed of the extruder type kneading apparatus biaxial is preferably 70～360Min ^-1, more preferably from 150~210min ^-1.
When produced at a rotational speed slower than 70 min ⁻¹ , this leads to a decrease in productivity, and when produced at a rotational speed faster than 360 min ⁻¹ , the kneading time inside is short because the speed of feeding the kneaded product is too fast, Appropriate resin adsorption may not be performed, and it may be difficult to obtain target quality.

As conditions for the biaxial extruder type kneading apparatus, a temperature of 30 ° C. to 200 ° C. and a rotational speed of 70 to 360 min ⁻¹ are excellent in viscosity stability and a high quality color filter Is preferable because it can be obtained.

  Specifically, as a biaxial extruder type kneading device, for example, KRC kneader manufactured by Kurimoto Seiko Co., Ltd., Extruder manufactured by Nara Machinery Co., Ltd., Extruder manufactured by Miwa Co., Ltd., BCTA manufactured by Buehler type company, PRIO twin Etc.

<Crude dichlorodiketopyrrolopyrrole pigment mixture>
The mixture kneaded by the biaxial extruder-type kneading apparatus comprises at least a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal transformation and β-type crystal transformation, resin (B) and resin-type dispersant (C). Any one kind and a pigment derivative (D) as needed are included.

  The solid content concentration in 100% by weight of the mixture is preferably 30 to 95% by weight, and more preferably 50 to 90% by weight. When the solid content concentration is less than 30% by weight, it is difficult to apply an appropriate share for promoting resin adsorption. When the solid content concentration is more than 95% by weight, fluidity is difficult and kneading may not be performed properly.

  The pigment concentration in the solid content of 100% by weight of the mixture is preferably 40 to 95% by weight, more preferably 50 to 90% by weight. If it is less than 40% by weight, it is difficult to take a share for promoting the resin adsorption. If it is more than 90% by weight, the resin content for promoting the adsorption is small and it may be difficult to obtain the target quality.

<Crude dichlorodiketopyrrolopyrrole pigment>
The crude dichlorodiketopyrrolopyrrole pigment is a dichlorodiketopyrrolopyrrole pigment in which an α-type crystal modification and a β-type crystal modification are mixed. Specifically, C.I. I. And CI Pigment Red 254.

  In the present invention, a crude dichlorodiketopyrrolopyrrole pigment in which an α-type crystal modification and a β-type crystal modification are mixed is used as the crude pigment. The crude pigment may be a mixture of a separately produced α-type crystal modified crude dichlorodiketopyrrolopyrrole pigment and a β-type crystal modified crude dichlorodiketopyrrolopyrrole pigment, or the α-type crystal modified and β It may be produced by mixing a crude dichlorodiketopyrrolopyrrole pigment having a type crystal modification.

  Further, a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification used in the present invention, for example, oxalic acid diester and 4-chlorobenzonitrile in an organic solvent by a known method. It is possible to obtain the protonated alkali metal salt of the crude dichlorodiketopyrrolopyrrole pigment obtained by the reaction at 0 to 20 ° C. in a mixed solvent of methanol, water and acetic acid. Whether or not the crude dichlorodiketopyrrolopyrrole pigment has α-type and β-crystal modifications can be confirmed by powder X-ray diffraction measurement using CuKα rays. In other words, the characteristic Bragg angle (2θ) of the β-type crystal transformation of dichlorodiketopyrrolopyrrole is 27.0 ± 0.3 °, and the α crystal transformation shows almost no peak at this Bragg angle (2θ). Absent. The characteristic Bragg angle (2θ) of the α-type crystal transformation is 28.1 ± 0.3 °, and the β crystal transformation shows almost no peak at this Bragg angle (2θ). From this, by confirming the presence or absence of the Bragg angle of the diffraction pattern of the pigment obtained by X-ray diffraction measurement, the dichlorodiketopyrrolopyrrole pigment of α-type crystal modification and β-type crystal modification is contained in the crude pigment. It is easy to determine whether it exists.

(Α-type crystallinity)
In the present invention, the α-type crystallinity of the dichlorodiketopyrrolopyrrole pigment can be confirmed by the formula (1) using the Bragg angle (2θ) in powder X-ray diffraction measurement using CuKα rays.

Formula (1) α-type crystallinity = I _α / (I _α + I _β )

[In Formula (1),
In powder X-ray diffraction measurement using I _α ... CuKα ray, the intensity I 2 ··· 0.3 ° is the characteristic Bragg angle (2θ) of α-type crystal transformation I _β ... powder X using CuKα ray In the line diffraction measurement, the intensity is 27.0 ± 0.3 ° which is a characteristic Bragg angle (2θ) of β-type crystal transformation. ]

  In other words, the characteristic Bragg angle (2θ) of the β-type crystal transformation of dichlorodiketopyrrolopyrrole is 27.0 ± 0.3 °, and the α-type crystal transformation has almost no peak at this Bragg angle (2θ). can not see. The characteristic Bragg angle (2θ) of the α-type crystal transformation is 28.0 ± 0.3 °, and the β-type crystal transformation shows almost no peak at this Bragg angle (2θ). From this, by confirming the presence or absence of the Bragg angle of the diffraction pattern of the pigment obtained by X-ray diffraction measurement, the α-type crystal modification and β of the dichlorodiketopyrrolopyrrole pigment in the crude pigment and the pigment composition were confirmed. It can be easily confirmed whether or not the type crystal transformation exists.

  The measurement of powder X-rays is performed with a powder X-ray diffraction measurement device RINT2100 (manufactured by Rigaku Corporation) in accordance with Japanese Industrial Standard JIS K0131 (general rules for X-ray diffraction analysis). 1 and 2, the intensity I α of 28.1 ± 0.3 °, which is a characteristic Bragg angle (2θ) of the α-type crystal transformation, and the characteristic Bragg angle (2θ) of the β-type crystal transformation are used. A method of calculating the ratio Iβ / (Iα + Iβ) of the intensity I β of 27.0 ± 0.3 ° will be described more specifically.

  FIG. 1 shows an example of a diffraction pattern obtained by powder X-ray diffraction of a crude dichlorodiketopyrrolopyrrole pigment. FIG. 2 shows a diffraction pattern obtained by removing the background of the diffraction pattern of FIG. 1 and 2, the X axis is the Bragg angle (2θ), and the Y axis is the diffraction peak intensity (count). The background removal of the diffraction pattern in FIG. 1 is performed as usual, but the point to be particularly noted is how to obtain the background from around 23 ° to around 30 ° used for intensity ratio calculation. The background from about 23 ° to about 30 ° can be obtained by using the Bragg angle (2θ) of α-type crystal transformation, the lower angle side of 24.5 °, the vicinity of 24 ° and the Bragg angle of α-type crystal transformation ( A straight line in contact with the vicinity of 29 ° of the heel on the high angle side of 28.0 ° which is 2θ) was drawn, and the value on this straight line was removed as the background. For example, in FIG. 2, the intensity I α of 28.1 °, which is the characteristic Bragg angle (2θ) of the α-type crystal transformation, is 490, while it is the characteristic Bragg angle (2θ) of the β-type crystal transformation. The intensity Iβ of 0.0 is 600. In this case, the value of Iβ / (Iα + Iβ) is 0.55.

  The α-type crystallinity in the crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification is preferably 0.08 or more and less than 0.9, more preferably 0.1 or more and 0.85. Is less than.

  When the pregelatinized crystallinity of the crude dichlorodiketopyrrolopyrrole pigment is less than 0.08, it takes a long time for the crystal transition, and the contribution of particle growth that occurs simultaneously with the crystal transition may increase and the contrast ratio may decrease. . On the other hand, when the pregelatinized crystallinity of the crude dichlorodiketopyrrolopyrrole pigment is 0.9 or more, the crystal form is already stable before kneading, so there is no state change and the quality improvement by the kneading process may be small. .

<Resin (B)>
Examples of the resin (B) include thermoplastic resins, thermosetting resins, and the like, and the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is preferable that
By kneading the crude dichlorodiketopyrrolopyrrole pigment with the resin (B) using a biaxial extruder type kneader, the resin is adsorbed and protected on the dichlorodiketopyrrolopyrrole pigment, and the crystal form transition of the pigment This has the effect of suppressing crystal growth during drying and aggregation during drying.

  Usable resins include rosin, rosin derivative, rosin modified maleic acid resin, rosin modified phenolic resin, rubber derivative, protein derivative, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, polyvinyl acetate, epoxy resin, acrylic resin , Maleic acid resin, styrene resin, styrene-maleic acid copolymer resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, polyamide resin, polyimide resin, alkyd resin, rubber resin, celluloses, benzoguanamine resin, Mention may be made of urea resins.

  Of these, acrylic resin and rosin-modified maleic acid resin are particularly suitable. By using these, a dichlorodiketopyrrolopyrrole pigment composition having a high affinity with a dichlorodiketopyrrolopyrrole pigment and having a high pigment protection effect is suitable, having a high transmittance and good stability. it can.

  The weight average molecular weight (Mw) of the resin (B) is preferably 500 to 50000, more preferably 3000 to 30000. When the number average molecular weight is less than 500, the effect of steric repulsion due to pigment adsorption, the effect of compatibility with a pigment carrier, and the effect of compatibility with a pigment carrier and a solvent when using a solvent are small. It becomes difficult to prevent crystal growth and aggregation. If the number average molecular weight is 50,000 or more, the required amount of resin added increases, and the pigment concentration of the pigment composition may decrease.

  The content of the resin (B) is preferably 1 to 50 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the crude dichlorodiketopyrrolopyrrole pigment. When the blending amount of the resin (B) is less than 1 part by weight, the pigment protection effect may be insufficient because the amount is small, and when it exceeds 50 parts by weight, the pigment concentration during kneading is low, and the pigment The kneading effect may not be sufficient.

<Resin type dispersant (C)>
The resin-type dispersant (C) has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to form a colorant carrier for the colorant. It works to stabilize dispersion in the water. Resin-type dispersant (C), like resin (B), is adsorbed and protected on dichlorodiketopyrrolopyrrole pigment by kneading with crude dichlorodiketopyrrolopyrrole pigment, resulting in excessive crystal growth under solvent. Effective in inhibiting pigment aggregation. Resin-type dispersants are roughly classified into those having an acidic substituent and those having a basic substituent, and both are preferably used. When used as a color filter coloring composition, an acidic resin-type dispersant is used. An agent is preferable because it has excellent development characteristics.

  The content of the resin type dispersant (C) is preferably 1 to 50 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the crude dichlorodiketopyrrolopyrrole pigment. When the content of the resin-type dispersant is less than 1 part by weight, the pigment protective effect may be small because the amount is small. On the other hand, if it exceeds 50 parts by weight, the pigment concentration during kneading is low, and the kneading effect of the pigment may not be sufficient.

  As a weight average molecular weight of the resin type dispersing agent (C) used by this invention, 500-50000 are preferable normally, and 3000-30000 are especially more preferable. When the weight average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and the solvent when using a solvent are small. It may be difficult to prevent aggregation of the dispersion, and the viscosity of the dispersion may increase. If the weight average molecular weight is 50000 or more, the amount of resin added for dispersion increases, which may lead to a decrease in the pigment concentration in the coating film.

(Resin type dispersant having an acidic substituent)
As the resin type dispersant in the present invention, it is preferable to use a resin type dispersant having an acidic substituent. These resin-type dispersants have a pigment-affinity unit containing an acidic substituent that adsorbs to the dichlorodiketopyrrolopyrrole pigment and a unit compatible with the pigment carrier to protect the dichlorodiketopyrrolopyrrole pigment.・ It works to stabilize.

  The acid value of the resin type dispersant having an acidic substituent is preferably 200 mgKOH / g or less, more preferably 20 to 150 mgKOH / g, and most preferably 40 to 100 mgKOH / g, from the viewpoint of dispersion stability.

  In particular, when a dichlorodiketopyrrolopyrrole pigment, a resin-type dispersant having an acidic substituent, and a dye derivative having a basic substituent are used in combination, the dispersion is improved when the dispersion is obtained due to the enhancement of the pigment protection effect. It is preferable for exhibiting an excellent effect.

  The basic structure of the resin-type dispersant having an acidic substituent is not particularly limited, and general resins such as acrylic resins, polyester resins, polyether resins, urethane resins, silicone resins, epoxy resins, vinyl acetate resins, etc. Can be mentioned.

  Examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Further, trimellitic acid and / or pyromellitic acid partially esterified are preferably used. In some cases, an aromatic ring having two or more acidic substituents may be a unit having one acidic substituent by a plurality of direct bonds and / or linking groups. Especially, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule has more adsorbing groups to the colorant than a resin-type dispersant having zero or one carboxyl group in one molecule. This is preferable because it has a strong function of stabilizing the dispersion on the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be secured.

  Examples of the resin-type dispersant having an acidic substituent include those having an acidic substituent, an aromatic group, or the like in the main chain or terminal of a linear resin, or in the main chain or side chain of a comb-like resin, in a block or randomly. preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly ( An amide formed by a reaction between a lower alkyleneimine) and a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble High molecular compounds, polyesters, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  As a site | part with high affinity to a dispersion medium of the resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

  Examples of commercially available resin-type pigment dispersants having acidic functional groups include Solsperse 3000, Solsperse 21000, Solsperse 26000, Solsperse 36600, Solsperse 41000, Solsperse 44000, Solsperse 46000, Solsperse 55000 (manufactured by Abyssia); Disperse Big 108, Disperbic 110, Disperbic 111, Disperbic 112, Disperbic 116, Disperbic 142, Disperbic 180, Disperbic 2001, (manufactured by BYK Chemie); Disparon 3600N, Disparon 1850 (manufactured by Enomoto Kasei); PA111 (Ajinomoto Fine Techno Co., Ltd.); EFKA4401 and EFKA4550 (Efka Additives Co., Ltd.) It is, but not limited thereto.

  As the resin type dispersant having an acidic substituent, an acidic resin type dispersant having an aromatic carboxyl group is particularly preferable. A polymer having a hydroxyl group at one end, an aromatic tricarboxylic acid anhydride and / or an aromatic tetra Most preferably, the dispersant is obtained by reacting carboxylic dianhydride. Examples of such resin-type dispersants include Japanese Patent No. 40201050, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, and Japanese Patent Application Laid-Open No. 2010-223888. And exhibits excellent effects such as compatibility between fluidity and dispersibility.

  Among these, a preferable resin-type dispersant is a radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO2008 / 007776 pamphlet. A polyester dispersant produced by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in one terminal region with an acid anhydride group in tetracarboxylic dianhydride is preferable. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride. Color filter coloring compositions using these polyester dispersants are preferable because they are excellent in pigment dispersion stability, and are synthesized using the method described in WO2008 / 007776 pamphlet or the like. be able to.

A more preferable resin type dispersant includes a resin type dispersant represented by the following formula described in JP-A No. 2007-140487.
_{(HOOC-) m -R 4 - (} - COO - [- R 6 -COO-] q -R 5) t
[Wherein R ₄ is a tetravalent tetracarboxylic acid compound residue, R ₅ is a monoalcohol residue, R ₆ is a lactone residue, m is 2 or 3, q is an integer of 1 to 50, and t is (4 -M). ]

A coloring composition for a color filter using an acidic resin type dispersant having an aromatic carboxyl group has very excellent pigment dispersion stability.
As a structural unit of the side chain portion of the resin-type dispersant, for example,
Ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, and maleic acid;
As an ethylenically unsaturated monomer having no acidic group, for example,
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and lauryl (meth) acrylate;
Cycloaliphatic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate, and paracumylphenoxyethylene oxide-modified (meth) acrylate;
And alkoxypolyalkylene glycol (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate; and mixtures thereof.
Among these, from the viewpoint of developability, it is preferable to include an ethylenically unsaturated monomer having a carboxyl group. These ethylenically unsaturated monomers having an acidic functional group may be only one type or two or more types. Moreover, since hydrophilicity is high, it is preferable to contain alkoxy polyalkylene glycol (meth) acrylates with favorable stability and dispersibility.
The number of hydroxyl groups in one molecule of other polyol is not particularly limited as long as the desired dispersant can be synthesized, but diol is preferred. In particular, by reacting with tetracarboxylic dianhydride (d1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. If a polyol having more than two hydroxyl groups is used in a large amount, the main chain of the polyester will be branched to increase the complexity and shade, making it difficult to obtain a dispersion effect. From the viewpoint of pigment adsorptivity, tetracarboxylic dianhydride having two or more aromatic rings is a skeleton suitable for pigment adsorption and has the highest heat resistance and is preferable.

(Resin type dispersant having basic substituent)
As the resin-type dispersant (C) in the present invention, a resin-type dispersant having a base substituent is preferably used, and a resin-type dispersant having a basic substituent containing a nitrogen atom is preferably dichlorodiketopyrrolo. It is excellent in the protective effect of the pyrrole pigment and can be preferably used.

  The amine value of the resin-type dispersant having a base substituent is preferably 35 to 100 mgKOH / g. More preferably, it is 50-75 mgKOH / g. When the amine value is less than 35 mg KOH / g, the pigment may not be sufficiently adsorbed and the kneading effect may not be exhibited. When the amine value exceeds 100 mg KOH / g, dichlorodiketopiroro may be adsorbed or reacted with an acidic component in the pigment carrier. Adsorption efficiency with respect to the pyrrole pigment may deteriorate and the kneading effect may not be exhibited.

  Various types of resin-based dispersants such as vinyl-based, urethane-based, polyester-based, polyether-based, or polyamide-based resins can be used as the resin-type dispersant having a base substituent, but the resin design is easy and excellent in various resistances Vinyl monomer copolymer type is preferred, specifically, a copolymer resin of N, N-disubstituted amino group-containing vinyl monomer units, alkyl (meth) acrylate monomer units, and other vinyl monomer units. Is preferred.

  As N, N-disubstituted amino group-containing vinyl monomer units, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Examples thereof include N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, and N, N-diethylaminoethyl (meth) acrylamide, but are not necessarily limited thereto. These monomer units are adsorbed to the naphthol azo pigment (a1) as basic group-containing monomer units.

  As alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

  Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing vinyl monomers such as (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, etc. Amide group-containing vinyl monomers, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxime Alkoxymethyl group-containing vinyl monomers such as ru (meth) acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples thereof include vinyl ethers such as n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate, which are appropriately used according to the purpose, but are not necessarily limited thereto.

  Polymers having primary amino group-containing monomer units such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, or poly (aminomethylated) epoxy resin, polyester resin, acrylic resin Alternatively, a resin-type dispersant having a comb-shaped basic substituent modified with a polyether resin or the like can also be mentioned.

  Examples of commercially available resin-type dispersants having such base substituents include, for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000 of Big Chemie Japan. 2001, 2050, 2150, 2163, 2164, BYK-LPN6919, 21116, 21324, Nippon Lubrizol SOLPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100 , 35200, 37500, 38500, 39000, 53095, 56000, 71000, EFKA4300, 4330, 4046, 406 of Ciba Japan , 4080, Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Dye derivative (D)>
The pigment derivative is a compound represented by the following general formula (2), and there are those having a basic substituent and those having an acidic substituent.
General formula (2)
AB
A: Organic pigment residue B: Basic substituent or acidic substituent

  In the general formula (2), the organic pigment constituting the organic pigment residue of A includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine. Phthalocyanine pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indantron, pyranthrone, violanthrone, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, Examples thereof include thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  In the present invention, a dye derivative having a diketopyrrolopyrrole pigment skeleton, a thiazine pigment skeleton, or an azo pigment skeleton showing a strong affinity with a dichlorodiketopyrrolopyrrole pigment is preferable.

  In the general formula (2), examples of the basic substituent of B include substituents represented by the following general formula (3), general formula (4), general formula (5), and general formula (6). As an acidic substituent, the substituent shown by General formula (7) and General formula (8) is mentioned. When an acidic resin (B) such as an alkali-soluble acrylic resin or rosin-modified maleic acid is used, an enhancement of the resin adsorption protection effect by interaction can be expected, so that a basic substituent is preferable.

General formula (3)

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ₁ and R ₂ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ , R ₇ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituent Represents an optionally substituted phenyl group.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.

R: represents a substituent represented by the general formula (9) or a substituent represented by the general formula (10).
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the general formula (9) or a substituent represented by the general formula (10).

General formula (9)

General formula (10)

M: represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i: represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, substitution Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used to form the substituent represented by the general formula (3) to the general formula (6), the general formula (9), and the general formula (10) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropyl Amine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) Amine, dioctylamine, N, N-methyloctadecyl , Didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentyl N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetic acid, Ethyl isonicopetinate 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N -A And minopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. .

  The amine component used to form the sulfonic acid amine salt of the general formula (8) may be any of primary, secondary and tertiary amines and quaternary ammonium salts. For example, as the primary amine, Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, which may have side chains Examples thereof include amines such as amine, nonadecylamine, and eocosylamine, and unsaturated amines corresponding to the number of carbon atoms.

Secondary, tertiary amine and quaternary ammonium salts include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium Chloride, dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl Ammonium chloride, dimethyl hexade Le octadecyl ammonium chloride, and the like.
Further, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (7) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

<Organic solvent (E)>
The crude dichlorodiketopyrrolopyrrole pigment mixture of the present invention can contain an organic solvent (E) in order to ensure the fluidity of the mixture and increase the kneading degree. As the organic solvent (E), it is necessary to select a solvent having low pigment solubility in order to suppress crystal growth of the dichlorodiketopyrrolopyrrole pigment.

Examples of the organic solvent (E) include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N , N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec- Butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotarsia Libutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Cole monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol , Methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among these, glycols such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate from the viewpoint of suppressing crystal growth of the dichlorodiketopyrrolopyrrole pigment. Acetates are particularly preferred.

  The content of the solvent added at the time of kneading is preferably 3 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the crude dichlorodiketopyrrolopyrrole pigment. If it exceeds 50 parts by weight, an appropriate share will not be applied at the time of kneading, which may adversely affect the refinement and crystal transition of the dichlorodiketopyrrolopyrrole pigment. If it is 3 parts by weight or less, it is difficult to ensure fluidity. There is a case.

<< Method for Producing Dichlorodiketopyrrolopyrrole Pigment Composition >>
The dichlorodiketopyrrolopyrrole pigment composition obtained by the method for producing a dichlorodiketopyrrolopyrrole pigment composition of the present invention comprises a crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification. In the process of kneading with at least one of resin (B) and resin type dispersant (C) in a biaxial extruder type kneader, the transition from β-type crystal transformation to α-type crystal transformation occurs. At the same time, the resin (B) or the resin-type dispersant (C) is adsorbed on the pigment, and a more refined α-type crystal modification dichlorodiketopyrrolopyrrole pigment is obtained. Furthermore, since the particle growth occurs when the β-type crystal transformation proceeds to the α-type crystal transformation, if the aggregate of the crude dichlorodiketopyrrolopyrrole pigment contains the β-type crystal transformation, Since the flocculation of the pigment aggregate is further promoted, a highly sized α-type crystal modified dichlorodiketopyrrolopyrrole pigment is obtained.

  The α-type crystallinity of the diketopyrrolopyrrole pigment composition after kneading in a biaxial extruder type kneading apparatus is preferably 0.9 or more and 1.0 or less, more preferably 0.95 or more. 1.0 or less.

  If the α-type crystallinity is 0.9 or more, there is little mixing of β-type crystal-modified dichlorodiketopyrrolopyrrole pigment, the spectral shape when the colored composition coating film is made, and the lightness is also excellent. This is preferable.

<Coloring composition for color filter>
Since the diketopyrrolopyrrole pigment composition of the present invention is excellent in the degree of fineness and has a crystal form transferred to an α form, it can be suitably used for color filter applications.
When used as a coloring composition for a color filter, the diketopyrrolopyrrole pigment composition of the present invention is added to a two-roll mill in a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid. A diketopyrrolopyrrole pigment dispersion can be produced by fine dispersion using various dispersing means such as a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, the dichlorodiketopyrrolopyrrole pigment composition and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.

  At this time, in order to increase the transmittance, it is preferable to use a wet disperser using a medium, and there are horizontal and vertical types of cylindrical dispersers, and an annular type (annular type), for example, a ball mill , Various dispersers using media such as a sand mill, an attritor, and a vibration mill.

The rotary shafts of these wet dispersers are equipped with stirring blades having various shapes, and disk types, pin types, and the like are known. Among them, those equipped with rotor pins are more effective for the present invention. Preferred for greater prominence.
Moreover, as a media separation mechanism of this wet disperser, there are a centrifugal separation method, a slit method (gap separator method), a screen method, and the like, but a centrifugal separation method is preferable. This is because it is very difficult to manufacture slits or screens capable of separating minute media having a particle size of 0.3 mmφ or less because of machining accuracy, and there is a possibility of clogging when supplying a pigment composition. . In addition, when using fine media having a particle size of 0.3 mmφ or less, particularly 0.1 mmφ or less, the filtration rate becomes very slow when separating the fine media by a slit or screen method, This is because it is difficult to increase the supply amount.

Examples of the wet disperser having a rotor pin and a media separation mechanism by centrifugation include, for example, a super apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), an ultra apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), a DCP type pearl mill (manufactured by Eirich Co., Ltd.), and a pico glen mill. (Asada Iron Works Co., Ltd.).
Moreover, the media filling rate in the disperser with good dispersion efficiency is preferably 50 to 100%, more preferably 60 to 80%.

  The material of the media is not particularly limited, and commonly used glass, steel, stainless steel, ceramics, zircon, zirconia and the like can be mentioned. The media particle size is preferably 0.5 mmφ or less, more preferably 0.3 mmφ or less, and usually 0.01 mmφ or more in order to achieve fine dispersion, a sizing effect, and a high contrast ratio. is there. Furthermore, the preferable particle diameter of the media is 0.1 mmφ or less, and in particular, the use of micro media of 0.05 mmφ to 0.01 mmφ is preferable because the effect becomes very large.

  The diketopyrrolopyrrole pigment composition of the present invention has a fineness of 0.3 mmφ or less because the resin (B) or the resin-type dispersant (C) is adsorbed and protected on the diketopyrrolopyrrole pigment. Even when dispersed using a medium, the colored composition has low viscosity and excellent stability.

  Moreover, when using the coloring composition for color filters as a photosensitive coloring composition (resist material), it can prepare as a solvent developing type or an alkali developing type coloring composition. Solvent development type or alkali development type coloring composition includes the dichlorodiketopyrrolopyrrole pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent and other pigment dispersants. , And additives can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Other colorants>
In the present invention, in addition to the dichlorodiketopyrrolopyrrole pigment composition, other red pigments, orange pigments, yellow pigments, and dyes may be used in combination for adjusting the hue. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

  Examples of the red pigment that can be used in combination when the coloring composition for a color filter of the present invention is used for a red filter segment include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Red pigments such as 166, 168, 176, 177, 178, 179, 184, 185, 187, 200, 202, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, and 279 Can be used in combination. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 177, C.I. I. Pigment Red 242 is preferably used, and these may be used together.

Examples of orange pigments and yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, and 214, and the like.
Examples of the orange pigment include C.I. I. Pigment orange 38, 43, 71, or 73.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Orange 38 is preferable.

The dyes that can be used in combination are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes. Moreover, it may be in the form of a lake pigment obtained by lacquering these dyes.
Among these, use of a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye is preferable because of excellent hue.

Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like. Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these dyes, C.I., which is a rhodamine acid dye, is particularly excellent in terms of color developability, heat resistance and light resistance. I. Most preferably, Acid Red 52 is used.

<Binder resin>
The binder resin is a material in which a colorant is dispersed in a colorant carrier, and includes a thermoplastic resin, a thermosetting resin, etc., and is described in a kneaded material kneaded by the biaxial extruder type kneader described above. The same thing as resin (B) which was made is mentioned.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type coloring composition, it is preferable to use the alkali-soluble vinyl-type resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It may be used in combination. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to preferably disperse or dissolve the colorant, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used for a color filter coloring composition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the photosensitive coloring composition, a colorant adsorbing group and an alkali-soluble group during development are used. The balance of the aliphatic group and the aromatic group that act as affinity groups for the carboxyl group, the colorant carrier and the solvent is important for the dispersibility, penetrability, developability, and durability of the pigment. It is preferable to use a resin of ˜300 mg KOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 20 to 700 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances will be insufficient, and if it is more than 700 parts by weight, the concentration of the colorant will be low, and color characteristics may not be exhibited.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.
Here, the pigment derivative and the resin type dispersant are the same as the pigment derivative (D) and the resin type dispersant (C) described in the kneaded material kneaded by the biaxial extruder type kneader described above. Can be mentioned.

The content of the pigment derivative in the coloring composition is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the coloring agent in the coloring composition. If the content of the pigment derivative is less than 1 part by weight, the dispersion effect is insufficient, and if it is more than 20 parts by weight, the excess pigment derivative may affect the dispersion.
When adding a resin-type dispersant and a surfactant, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition. . When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.
As an organic solvent, the same thing as the organic solvent (E) described in the kneaded material knead | mixed with the biaxial extruder type kneading apparatus mentioned above is mentioned.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Since the organic solvent used for the coloring composition can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, it is 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent. It is preferable to use it in the quantity.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

《Color filter》
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a red coloring composition for a color filter of the present invention. It is preferable to use a product. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. It is a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, or 58. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or a yellow pigment 214 and the like can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter such as.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  Further, the acid value of the resin type dispersant, the weight average molecular weight (Mw) of the resin type dispersant and the resin, the acid value of the resin type dispersant, the average primary particle diameter of the pigment, and the contrast ratio of the coating film The measuring method is as follows.

<Acid value of resin-type dispersant>
The acid value of the resin-type dispersant was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin-type dispersant indicates the acid value of the solid content.

<Weight Average Molecular Weight (Mw) of Resin Type Dispersant and Resin>
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

<Measurement method of contrast ratio (CR) of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

  Subsequently, acrylic resin / solution, acidic resin type dispersant / solution, basic resin type dispersant / solution, crude dichlorodiketopyrrolopyrrole pigment, refined pigment, and pigment dispersion used in Examples and Comparative Examples, A method for producing the green photosensitive coloring composition and the blue photosensitive coloring composition will be described.

<Production of acrylic resin / solution>
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 40% by weight. Acrylic resin / solution was prepared by adding ether acetate.

<Production of acidic resin type dispersant / solution>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, as a first-stage synthesis, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate are charged with nitrogen gas. Replaced with. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted. Next, as the synthesis of the second stage, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst. Then, the mixture was reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. Thus, a resin-type dispersant / solution having a poly (meth) acrylate skeleton having an acid value per solid content of 42 mgKOH / g and a non-volatile content of 40% by weight with a weight average molecular weight of 9,800 and having an aromatic carboxyl group Got.

<Preparation of basic resin type dispersant / solution>
After removing the solvent from Big Chemie Japan's DISPERBYK2000 using an evaporator, the solvent was diluted with propylene glycol monomethyl ether acetate so that the nonvolatile content was 40% by weight to obtain a basic resin type dispersant / solution.

<Preparation of crude dichlorodiketopyrrolopyrrole pigment>
(Preparation of crude dichlorodiketopyrrolopyrrole pigment / SDPP-1)
In a 1 L stainless steel reaction vessel equipped with a reflux tube, 450 parts of tert-amyl alcohol dehydrated with molecular sieves and 30 parts of small-sized metal sodium were added in a nitrogen atmosphere and heated to 90 ° C. After 1 hour, the mixture was heated to 100 ° C. or higher, and while stirring, the molten metal sodium was vigorously stirred, and stirring was continued for 10 hours to dissolve the sodium metal and prepare an alcoholate solution. On the other hand, in a 500 ml glass flask, 120 parts of tert-amyl alcohol dehydrated with molecular sieve, 88 parts of diisopropyl oxalate and 100 parts of p-chlorobenzonitrile were added and dissolved by heating to 90 ° C. with stirring. A solution of the mixture was prepared. The heated solution of this mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt solution of a dichlorodiketopyrrolopyrrole pigment.

  To a 3 L glass jacketed reaction vessel, 600 parts of methanol, 600 parts of water and 117 parts of acetic acid were added and cooled to 0 ° C. While cooling this cooled mixture vigorously, the above obtained alkali metal salt solution of dichlorodiketopyrrolopyrrole pigment at 90 ° C. was cooled using a refrigerant so as to keep the temperature at 10 ° C. or lower. However, when added in small portions, a deep red suspension was formed. The suspension was vigorously stirred for 10 minutes, and then filtered using a Nutsche, and then washed with 300 parts of methanol cooled to 10 ° C. and 1000 ml of water. Subsequently, the crude crystal water paste was heat-treated at 80 ° C. for 24 hours using a vacuum dryer, and dried to a moisture content of less than 1% by weight. The yield was 106.6 parts. Then, it grind | pulverized with the hammer mill type grinder and obtained the crude dichloro diketopyrrolopyrrole pigment and SDPP-1 through a 5 mm screen. The pregelatinized crystallinity of this crude pigment was 0.74.

(Preparation of crude dichlorodiketopyrrolopyrrole pigment / SDPP-2)
To a 3 L glass jacketed reaction vessel, 600 parts of methanol, 600 parts of water and 117 parts of acetic acid were added and cooled to 0 ° C. While the cooled mixture was vigorously stirred, an alkali metal salt solution of 90 ° C. diketopyrrolopyrrole pigment produced in the same manner as the crude dichlorodiketopyrrolopyrrole pigment / SDPP-1 was added at 10 ° C. or less. While adding a small amount while cooling with a refrigerant so as to maintain the temperature, a deep red suspension was formed. The suspension was vigorously stirred for 1 hour, then filtered off using a Nutsche, and then washed with 300 parts of methanol cooled to 10 ° C. and 1000 ml of water. Subsequently, the crude crystal water paste was heat-treated at 80 ° C. for 24 hours using a vacuum dryer, and dried to a moisture content of less than 1% by weight. The yield was 108.4 parts. Then, it grind | pulverized with the hammer mill type grinder and obtained the crude dichloro diketopyrrolopyrrole pigment and SDPP-2 through a 5 mm screen. The pregelatinized crystallinity of this crude pigment was 0.42.

(Preparation of crude dichlorodiketopyrrolopyrrole pigment / SDPP-3)
To a 3 L glass jacketed reaction vessel, 600 parts of methanol, 600 parts of water and 117 parts of acetic acid were added and cooled to 0 ° C. While stirring this cooled mixture vigorously, an alkali metal salt solution of 90 ° C. dichlorodiketopyrrolopyrrole pigment produced in the same manner as crude dichlorodiketopyrrolopyrrole pigment • SDPP-1 was added at 10 ° C. When a small amount was added while cooling using a refrigerant so as to maintain the following temperature, a deep red suspension was formed. The suspension was cooled to 0 ° C. and stirred vigorously for 2 hours, followed by filtration using a Nutsche, and then washed with 300 parts of methanol cooled to 10 ° C. and 1000 ml of water. Subsequently, the crude crystal water paste was heat-treated at 80 ° C. for 24 hours using a vacuum dryer, and dried to a moisture content of less than 1% by weight. The yield was 109.8 parts. Then, it grind | pulverized with the hammer mill type grinder and obtained the crude dichloro diketopyrrolopyrrole pigment and SDPP-3 through a 5 mm screen. The pregelatinized crystallinity of this crude pigment was 0.16.

<Preparation of finer pigments>
(Miniaturized red pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Miniaturized green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Miniaturized yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Miniaturized blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB15: 6-1) was obtained.

(Miniaturized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple refined purple pigment (PV23-1) was obtained.

<Preparation of pigment dispersion>
(PR177 / pigment dispersion (PR177P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (PR177P-1) having a non-volatile component of 20% by weight was produced.

Refined red pigment (PR177-1): 12.0 parts acrylic resin / solution: 11.0 parts propylene glycol monomethyl ether acetate (PGMAC): 68.0 parts Basic resin type dispersant / solution: 9.0 parts

(PG58 pigment dispersion (P-24))
PG58 / Pigment Dispersion (P) in the same manner as Pigment Dispersion (PR177P-1) except that the refined PR177 Pigment (PR177-1) in the production method of Pigment Dispersion (PR177P-1) was changed to PG58-1. -24) was produced.

(PY150 / Pigment dispersion (P-25))
PY150 / Pigment Dispersion (P) in the same manner as Pigment Dispersion (PR177P-1) except that the refined PR177 Pigment (PR177-1) in the production method of Pigment Dispersion (PR177P-1) was changed to PY150-1. −25).

(PB15: 6, pigment dispersion (P-26))
PB15: 6 • Pigment in the same manner as the pigment dispersion (PR177P-1) except that the refined PR177 pigment (PR177-1) in the production method of the pigment dispersion (PR177P-1) was changed to PB15: 6-1 A dispersion (P-26) was produced.

(PV23 / Pigment dispersion (P-27))
PV23 / Pigment Dispersion (P) in the same manner as Pigment Dispersion (PR177P-1) except that the refined PR177 Pigment (PR177-1) in the production method of Pigment Dispersion (PR177P-1) was changed to PV23-1. -27) was produced.

<Method for producing green and blue photosensitive coloring composition>
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (RG-1).

PG58 / pigment dispersion (P-24): 32.0 parts PY150 / pigment dispersion (P-25): 18.0 parts Acrylic resin / solution: 7.5 parts Photopolymerizable monomer: 2.0 parts ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Dipentaerythritol hexaacrylate photopolymerization initiator (“OXE-02” manufactured by Ciba Japan): 1.5 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce a blue photosensitive coloring composition (RB-1).

PB15: 6, Pigment dispersion (P-26): 45.0 parts PV23, Pigment dispersion (P-27): 5.0 parts Acrylic resin / solution: 7.5 parts Photopolymerizable monomer: 1. 0 parts ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (“OXE-02” manufactured by Ciba Japan): 1.5 parts cyclohexanone: 39.0 parts

[Example 1]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-1)
A dichlorodiketopyrrolopyrrole pigment composition RGS-1 was prepared by kneading using a KRC kneader manufactured by Kurimoto Seiko Co., Ltd., which is a biaxial extruder type kneading apparatus, with the composition as shown below. The kneading conditions were a set temperature of 50 ° C. and a shaft rotation speed of 180 min ⁻¹ .

Crude dichlorodiketopyrrolopyrrole pigment composition / SDPP-1: 69.4 parts acrylic resin / solution: 30.6 parts

[Examples 2 to 13]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-2 to 13)
Dichlorodiketopyrrolopyrrole pigment compositions RGS-2 to 13 were prepared under the composition and blending amounts (parts by weight) shown in Tables 1 and 2 and the kneading conditions of a biaxial extruder type kneading apparatus. The chemical structure of the dye derivative used is shown in Table 2.

[Comparative Example 1]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-14)
Crude dichlorodiketopyrrolopyrrole pigment / SDPP-1 (69.4 parts), pulverized and dried sodium chloride with an average particle diameter of 20 μm (1500 parts), acidic resin type dispersant / solution (30.6 parts) are both 3 L kneader (manufactured by Inoue Seisakusho). ). The heating medium was controlled at 50 ° C., 280 parts of diethylene glycol was added, and after forming a good dough state, grinding was started. After grinding for 10 hours, the mixture was added to 10 times by weight of water and stirred to dissolve sodium chloride and diethylene glycol, followed by filtration and purification to separate the pigment. This wet cake containing water was heat-treated in an oven at 80 ° C. for 24 hours, dried to a moisture content of less than 1% by weight, pulverized with a hammer mill type pulverizer, and passed through a 5 mm screen to dichlorodiketopyrrolo. A pyrrole pigment RGS-14 was obtained.

[Comparative Example 2]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-15)
85 parts of crude dichlorodiketopyrrolopyrrole pigment, SDPP-1, 1500 parts of pulverized and dried sodium chloride having an average particle diameter of 20 μm, and 15 parts of rosin-modified maleic acid resin / Marquide 32 (manufactured by Arakawa Chemical Co., Ltd.) are both 3 L kneader ( Inoue Seisakusho). The heating medium was controlled at 50 ° C., 280 parts of diethylene glycol was added, and after forming a good dough state, grinding was started. After grinding for 10 hours, the mixture was added to 10 times by weight of water and stirred to dissolve sodium chloride and diethylene glycol, followed by filtration and purification to separate the pigment. This wet cake containing water was heat-treated in an oven at 80 ° C. for 24 hours, dried to a moisture content of less than 1% by weight, pulverized with a hammer mill type pulverizer, and passed through a 5 mm screen to dichlorodiketopyrrolo. A pyrrole pigment RGS-15 was obtained.

[Comparative Example 3]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-16)
Add 10 parts of crude dichlorodichlorodiketopyrrolopyrrole pigment / SDPP-1, 180 parts of propylene glycol monomethyl ether acetate, 20 parts of water, 2.65 parts of acidic resin type dispersant / solution and add at 40 ° C. Crystal transformation by aging in an organic solvent was performed by stirring for 3 hours using a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Next, the solution was concentrated by Nutsche filtration, and further ion-exchanged water was added for washing, and filtration was performed again to replace the solvent with water, thereby stopping the crystal transition due to aging. This was again concentrated by Nutsche filtration, and then dried in an oven at 100 ° C. for 2 hours to obtain a dichlorodiketopyrrolopyrrole pigment composition RGS-16.

[Comparative Example 4]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-17)
85 parts of crude dichlorodiketopyrrolopyrrole pigment / SDPP-1 and 22.5 parts of acidic resin type dispersant / solution were mixed and kneaded by hand to obtain dichlorodiketopyrrolopyrrole pigment composition RGS-17. .

[Comparative Example 5]
(Preparation of dichlorodiketopyrrolopyrrole pigment composition RGS-18)
85 parts of crude dichlorodiketopyrrolopyrrole pigment / SDPP-1 and 22.5 parts of an acidic resin type dispersant / solution were mixed and added to a 3 L kneader (manufactured by Inoue Seisakusho). The heat medium was controlled at 50 ° C. and kneaded for 1 hour to obtain a dichlorodiketopyrrolopyrrole pigment composition RGS-18.

<Evaluation of pigment composition>
Table 3 shows the evaluation results of the pregelatinized crystallinity and the average particle size of the colored compositions obtained in Examples and Comparative Examples.

  When the pigment composition using the biaxial extruder type kneader is compared before and after kneading, it can be seen that the crystal transition to α-type proceeds. In addition, as compared with the method of Comparative Example 4 in which the crude pigment was simply mixed with the resin-type dispersant, the finer pigment was advanced and the average primary particle size was small. In the aging of the method of Comparative Example 3, the effect of the crystal type transition was not so much seen, and in the method of Comparative Example 4 by the simple mixing, the crystal type transition was not seen.

In the salt milling methods of Comparative Examples 1 and 2, crystal transition to α-type and finer pigment can be achieved, but pigment aggregation occurs due to washing and drying steps to remove the salt used for finer processing. ing.
Further, in the method of Comparative Example 5 using a kneader as an apparatus used for crystal transition, the pigment was not sufficiently refined as compared with the case of using a biaxial extruder type kneader.

[Example 14]
(Preparation of dichlorodiketopyrrolopyrrole pigment dispersion (RP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (RP-1) whose non-volatile component is 20 weight% was produced.

Dichlorodiketopyrrolopyrrole pigment composition RGS-1: 14.1 parts acrylic resin / solution: 5.7 parts propylene glycol monomethyl ether acetate (PGMAC): 71.2 parts basic resin type dispersant / solution: 9.0 Part

[Examples 15 to 26, Comparative Examples 6 to 10]
(Preparation of dichlorodiketopyrrolopyrrole pigment dispersion RP-2 to 18)
RP-2 to 18 were produced in the same manner as RP-1, except that the dichlorodiketopyrrolopyrrole pigment composition / RGS-1 was changed to the pigment composition shown in Table 5.

[Example 18-2]
(Preparation of dichlorodiketopyrrolopyrrole pigment dispersion RP-5-2)
The following mixture was stirred and mixed to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.1 mm, and then 5.0 μm. The pigment dispersion (RP-5-2) whose non-volatile component is 20 weight% was produced.

Dichlorodiketopyrrolopyrrole pigment composition RGS-5: 14.1 parts acrylic resin / solution: 5.7 parts propylene glycol monomethyl ether acetate (PGMAC): 71.2 parts basic resin type dispersant / solution: 9.0 Part

<Evaluation of pigment dispersion>
A red coating film was prepared using the obtained dichlorodiketopyrrolopyrrole pigment dispersion (RP-1 to 18), and the contrast ratio (CR) and viscosity were evaluated by the following methods. The results are shown in Table 4.

(Evaluation of contrast ratio)
The pigment dispersion (RP-1 to 18) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to a chromaticity of x = 0.644 with a C light source after heat treatment at 220 ° C. The result of contrast ratio was determined according to the following criteria.

◎: 7000 or more ○: 6000 or more, less than 7000
Δ: 5000 or more and less than 6000 ×: less than 5000

(Evaluation of viscosity)
The viscosity of the pigment dispersion was measured at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). The evaluation criteria were as follows.

◎: Less than 10 mPa · s ○: 10 mPa · s or more, less than 20 mPa · s Δ: 20 mPa · s or more, less than 30 mPa · s ×: 30 mPa · s or more

From Table 4, it is shown that the crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, and at least one of resin (B) and resin-type dispersant (C) By kneading using a Luder type kneader, a high contrast ratio and a low viscosity can be achieved in the case of using a pigment composition in which the β-type crystal transformation is changed to the α-type crystal transformation. In particular, when the pigment derivative (D) was used in combination, it was remarkably effective for high contrast ratio and low viscosity.
In Example 18-2, by setting the media diameter at the time of dispersion to 0.1 mm, it was possible to obtain a composition having higher contrast and no problem with stability.

In the case of the salt milling kneader method of Comparative Examples 1 and 2, the α crystallinity of the pigment composition and the average particle size were fine, but washing and drying for removing the salt used for the finening Pigment aggregation has occurred depending on the process, and there was a problem in viscosity when a pigment dispersion was obtained.
The aging method of Comparative Example 3 has a problem in contrast ratio because particle growth occurs simultaneously with crystal growth. In the simple mixing of Comparative Example 4, since the miniaturization has not progressed, the low contrast ratio, and even when kneaded with a kneader, the miniaturization was insufficient, so the contrast ratio was lower than that of the example.

[Example 27]
(Red photosensitive coloring composition (RR-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (RR-1).

(Pigment dispersion) (Total 50 parts)
Diketopyrrolopyrrole pigment dispersion (RP-1): 25.0 parts PR177 / Pigment dispersion (PR177P-1): 25.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 1.5 parts PGMAC: 39.0 parts

[Examples 28 to 39, Comparative Examples 11 to 15]
(Red photosensitive coloring composition (RR-2 to 18))
A red photosensitive coloring composition (RR-2 to 18) is obtained in the same manner as the red photosensitive coloring composition (RR-1) except that the pigment dispersion (RP-1) is changed to the type shown in Table 5. It was. In each photosensitive coloring composition, a total of 50 parts of the pigment dispersion is divided into a coating film substrate for lightness evaluation of each coloring composition, where x = 0.658 and y = 0.325 in the C light source. The ratio of the pigment dispersion was adjusted so that 100 parts of a red photosensitive coloring composition was prepared.

<Evaluation of red photosensitive coloring composition>
Evaluation of the brightness and contrast ratio of the red coating film produced using the obtained red photosensitive coloring composition (RR-1-18) was performed by the following method. Table 5 shows the evaluation results.

(Evaluation of brightness)
The red photosensitive coloring composition (RR-1 to 18) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then further heated to 230 ° C. at 60 ° C. A coated substrate was produced such that the chromaticity of the substrate obtained by partial heating was x = 0.658 and y = 0.325 in a C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

◎ ... 19.2 or more ○ ... 19.0 or more, less than 19.2 Δ ... 18.8 or more, less than 19.0 × ... less than 18.8

(Evaluation of contrast ratio)
The contrast ratio was evaluated using the substrate on which the brightness was evaluated. The results are as shown in Table 5 and were determined according to the following criteria.

◎: 13000 or more ○: 12000 or more to less than 13000
Δ: 1100 or more and less than 12000 ×: less than 11000

  From Table 5, it can be seen that a sample with insufficient α-type crystallinity has low brightness. Contrast ratio was the same as the result of the pigment dispersion, and the effectiveness of the pigment composition using the biaxial extruder type kneader was proved also in the evaluation of the photosensitive coloring composition.

  The photosensitive compositions of Comparative Examples 11 and 12 had no problem with lightness and contrast ratio, but had poor stability and could not withstand practical use.

[Example 40]
(Color filter)
The red photosensitive coloring composition (RR-1) of the present invention was applied by spin coating to a glass substrate on which a black matrix was previously formed, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, the substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (RG-1) is used, the green coloring pixel layer is formed in the same manner as the red coloring pixel layer, and further the blue photosensitive coloring composition (RB-1) is used. A blue colored pixel layer was formed in the same manner as the red colored pixel layer to obtain a color filter. The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the colored composition of the present invention has high brightness and excellent contrast ratio, and the effect of the present invention has been proved.

Claims (9)

  Biaxial extruder-type kneading of crude dichlorodiketopyrrolopyrrole pigment mixed with α-type crystal modification and β-type crystal modification, and at least one of resin (B) and resin-type dispersant (C) A method for producing a dichlorodiketopyrrolopyrrole pigment composition, wherein the β-type crystal transformation is changed to the α-type crystal transformation by kneading using an apparatus.   The method for producing a dichlorodiketopyrrolopyrrole pigment composition according to claim 1, wherein the resin (B) contains at least one of an acrylic resin and a rosin-modified maleic resin.   The method for producing a dichlorodiketopyrrolopyrrole pigment composition according to claim 1 or 2, further comprising a dye derivative (D).   4. The dichlorodiketopyrrolo according to claim 3, wherein the dye base skeleton of the dye derivative (D) is one selected from the group consisting of a diketopyrrolopyrrole pigment skeleton, a thiazine pigment skeleton, and an azo pigment skeleton. A method for producing a pyrrole pigment composition. The α-type crystallinity represented by the formula (1) of the crude dichlorodiketopyrrolopyrrole pigment is 0.08 or more and less than 0.9, and the α represented by the formula (1) of the dichlorodiketopyrrolopyrrole pigment composition The method for producing a dichlorodiketopyrrolopyrrole pigment composition according to any one of claims 1 to 4, wherein the crystallinity of the mold is from 0.9 to 1.0.

Formula (1) α-type crystallinity = I _α / (I _α + I _β )

[In Formula (1),
In powder X-ray diffraction measurement using I _α ... CuKα ray, the intensity I 2 ··· 0.3 ° is the characteristic Bragg angle (2θ) of α-type crystal transformation I _β ... powder X using CuKα ray In the line diffraction measurement, the intensity is 27.0 ± 0.3 ° which is a characteristic Bragg angle (2θ) of β-type crystal transformation. ]   6. The production of a dichlorodiketopyrrolopyrrole pigment composition according to claim 1, wherein the operating temperature of the biaxial extruder type kneader is in the range of 20 ° C. to 100 ° C. 6. Method.   A dichlorodiketopyrrolopyrrole pigment composition produced by the method for producing a dichlorodiketopyrrolopyrrole pigment composition according to any one of claims 1 to 6.   The coloring composition for a color filter, wherein the dichlorodiketopyrrolopyrrole pigment composition according to claim 7 further contains at least one of a photopolymerizable monomer and a photopolymerization initiator.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 8 on a substrate.