JP2013064065A - Crystal deposition inhibitor precursor, pigment dispersion, red resin composition for color filter and method for producing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystal deposition inhibitor precursor which can inhibit deposition of pigment aggregate on the surface of a colored layer (coating film) at a high-temperature heating process in the production process of color filter, can achieve high contrast, and hardly causes increase of phase difference in the colored layer.SOLUTION: This crystal deposition inhibitor precursor is expressed by chemical formula (1), where in chemical formula (1), Arepresents Cl, Br, methyl, sulfo or phenyl; m denotes an integer of 0-5, provided that when m is an integer of ≥2, a plurality of As each may be the same or different; Band Beach independently H or a group represented by chemical formula (2), at least one of Band Bis the group represented by chemical formula (2); PCy is a condensed ring group which may have a substituent or contain a heteroatom, or a multi-cyclic compound group represented by chemical formula (3). In chemical formula (2), Rrepresents a hydrocarbon group optionally having a substituent.

Description

  The present invention uses a crystal precipitation inhibiting precursor, a pigment dispersion containing the crystal precipitation inhibiting precursor and a red resin composition for a color filter, and a red resin composition for a color filter containing a crystal precipitation inhibiting precursor. The present invention relates to a method for manufacturing a color filter.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light that has passed through a color filter is directly colored into the colors of the pixels that make up the color filter, and the light of those colors is synthesized to form a color image. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters.

The color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and made of red, green, and blue colored patterns, and a light-shielding portion formed on the transparent substrate so as to partition each colored pattern. And have.
As a method for forming such a colored layer, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

  Pigment dispersions used in the pigment dispersion method are widely studied in order to realize many requirements such as high brightness and high contrast of color filters in addition to dispersibility and dispersion stability of pigments. Has been. One of the attempts is a method using a pigment derivative.

On the other hand, the liquid crystal display device has a problem of viewing angle dependency due to the refractive index anisotropy of the liquid crystal cell and the polarizing plate as a specific problem. This problem of viewing angle dependency is a problem that the color and contrast of an image that is visually recognized change when the liquid crystal display device is viewed from the front and when viewed from an oblique direction. Such a problem of viewing angle characteristics has become more serious with the recent increase in the screen size of liquid crystal display devices.
In order to improve such a viewing angle dependency problem, a method of incorporating a retardation film into a liquid crystal display device has been widely used. However, since the color filter used in the liquid crystal display device has a different phase difference depending on the coloring pattern of each color of the colored layer, when the above retardation film is used, the difference in the retardation of each color coloring pattern is compensated. It is difficult to completely solve the problem of viewing angle dependency.
Therefore, in order to improve the problem of the viewing angle dependency of the liquid crystal display, it is required to make the phase difference value of each colored layer itself close to zero also in the color filter.

  In Patent Document 1, as a pigment dispersion composition that is excellent in pigment dispersibility and stability and can form a colored film with excellent contrast, a diketopyrrolopyrrole pigment, a phthalimide alkylated diketopyrrolopyrrole, and a phthalimide alkyl A pigment dispersion composition containing quinacridone and an organic solvent is disclosed. However, according to the technique of Patent Document 1, since the phthalimide alkylated pigment derivative is hardly soluble in the solvent, the pigment dispersibility and dispersion stability are lowered, and therefore the contrast is lowered, as in the comparative example described later. There is a problem that the phase difference of the obtained colored film becomes large.

  In Patent Document 2, the structure of a dye that dissolves in an organic solvent is used. By using as a colorant a compound that changes its structure by heating and forms a pigment, storage stability over time, ejection stability at a nozzle, redissolution It is described that an ink-jet ink having both the property of a dye-type ink, which is a property, and the property of a pigment-type ink, which is an excellent light resistance of a recorded matter, is obtained.

  In Patent Document 3, by using a specific organic pigment precursor compound as a raw material, the particle size of an organic pigment obtained by converting the compound is extremely small, the particle size distribution peak is sharp, monodispersibility and solvent dispersion stability. It describes that it can be made into the organic pigment fine particle with high property.

Patent Document 4 describes a soluble chromophore having a detachable soluble group. It is described that the chromophore has high solubility and can be blended with a substrate at a relatively high concentration, so that high color strength can be achieved.
However, the ink compositions described in Patent Documents 2 to 4 have insufficient contrast when used as color filter applications. Further, no attention has been paid to the retardation of the colored layer.

JP 2009-251586 A JP-A-11-293166 JP 2010-83926 A Japanese Patent No. 4558106

The present inventors have advanced the miniaturization of diketopyrrolopyrrole pigments by strengthening dispersion, and by using such miniaturized diketopyrrolopyrrole pigments, high brightness and high contrast are achieved. It was found that a red colored layer (coating film) was obtained.
However, in the refined diketopyrrolopyrrole pigment, with the miniaturization of the diketopyrrolopyrrole pigment, after the high-temperature heating process in the color filter manufacturing process, pigment crystals or aggregates are formed on the coating surface. (Hereinafter, in the present invention, this phenomenon may be referred to as crystal precipitation). When such pigment crystals or aggregates are deposited on the surface of the coating film as foreign matter, the color filter cannot be used as a defective product.

The present inventors have found that by using a combination of a diketopyrrolopyrrole pigment and a specific crystal precipitation inhibitor, it is possible to solve the above problem of pigment aggregates being deposited on the coating film surface. Got.
However, it has been found that a coating film formed using a resin composition in which a diketopyrrolopyrrole pigment and a specific crystal precipitation inhibitor are combined has a problem that the phase difference becomes large.

  The present invention has been made under such circumstances, and can suppress the precipitation of pigment aggregates on the surface of the colored layer (coating film) during the high-temperature heating process in the color filter manufacturing process, thereby achieving high contrast. A crystal precipitation inhibitor precursor that is capable of preventing the retardation of the colored layer from being increased, the pigment aggregates being suppressed during the high-temperature heating process, and a high-contrast colored layer with a small retardation can be produced. Pigment dispersion with excellent dispersibility and dispersion stability, and color filters with excellent dispersibility and dispersion stability that are capable of producing colored layers with high contrast and small phase difference, with the prevention of pigment aggregate precipitation during high-temperature heating processes It is an object of the present invention to provide a method for producing a color filter from which a red resin composition for use and a colored layer having a high contrast and a small phase difference are obtained.

As a result of intensive studies to achieve the above object, the present inventors have found a specific crystal precipitation inhibitor precursor that is soluble in a solvent and generates a crystal precipitation inhibitor by the action of heat or light. It has been found that by using this, the precipitation of pigment aggregates is suppressed during the high-temperature heating step, and a red resin composition for a color filter capable of producing a colored layer having a high contrast and a small phase difference can be obtained.
The present invention has been completed based on such knowledge.

  The crystal precipitation inhibitor precursor according to the present invention is a compound represented by the following chemical formula (1).

（化学式（１）中、Ａ^１は、塩素原子、臭素原子、メチル基、スルホ基、又はフェニル基を表し、ｍは０〜５の整数を表し、ｍが２以上の整数の場合、複数のＡ^１は、それぞれ同一であっても異なっていてもよい。Ｂ^１及びＢ^２は、それぞれ独立に、水素原子、又は下記化学式（２）で表される基であり、Ｂ^１及びＢ^２の少なくとも１つは下記化学式（２）で表される基である。ＰＣｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい縮合環基、又は、下記化学式（３）で表される多環式化合物基である。）

(In the chemical formula (1), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of a ¹ is good .B ¹ and B ² be different even in the same, respectively, each independently, a hydrogen atom, or a group represented by the following chemical formula (2), the B ¹ and B ² At least one is a group represented by the following chemical formula (2): PCy is a condensed ring group which may have a substituent and may contain a hetero atom, or the following chemical formula (3). It is a polycyclic compound group represented.)

（化学式（２）中、Ｒ^１は、置換基を有してもよい炭化水素基を表す。）

(In the chemical formula (2), R ¹ represents a hydrocarbon group which may have a substituent.)

（化学式（３）中、Ｘは、直接結合又はメチレン基を表し、Ｃｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい環式化合物基を表し、ｎは、１〜５の整数を表し、ｎが２以上の整数の場合、複数のＸ−Ｃｙは、それぞれ同一であっても異なっていてもよい。Ａ^２は、塩素原子、臭素原子、メチル基、又はスルホ基を表し、ｎ’は０〜４の整数を表し、ｎ’が２以上の整数の場合、複数のＡ^２は、それぞれ同一であっても異なっていてもよい。但し、ｎ＋ｎ’は１〜５の整数である。）

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.)

In the chemical formula (1), when B ¹ and B ² are groups represented by the chemical formula (2), a pigment layer and a dispersion stability are improved, and a colored layer having a high contrast and a small phase difference is obtained. It is preferable because it can be manufactured.

The pigment dispersion according to the present invention contains the crystal precipitation inhibitor precursor according to the present invention, a diketopyrrolopyrrole pigment, a pigment dispersant, and a solvent.
The red resin composition for a color filter according to the present invention contains a crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, a pigment dispersant, a curable binder component, and a solvent. .

  In the pigment dispersion and the red resin composition for a color filter of the present invention, the crystal precipitation inhibitor precursor is 0.5 to 20 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment. It is preferable from the viewpoint of improving the pigment dispersibility and dispersion stability, and capable of producing a colored layer having a high contrast and a small phase difference.

A method for producing a color filter according to the present invention is a method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
Applying a red resin composition for a color filter according to the present invention on a transparent substrate to form a red resin composition layer; and
Forming a red resin composition layer on the transparent substrate using the red resin composition for a color filter;
The red resin composition layer is used as a crystal precipitation inhibitor represented by the following chemical formula (4) by desorbing B ¹ and / or B ² in the crystal precipitation inhibitor precursor represented by the chemical formula (1). And a step of forming a red colored layer.

（化学式（４）中、Ａ^１は、塩素原子、臭素原子、メチル基、スルホ基、又はフェニル基を表し、ｍは０〜５の整数を表し、ｍが２以上の整数の場合、複数のＡ^１は、それぞれ同一であっても異なっていてもよい。ＰＣｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい縮合環基、又は、下記化学式（３）で表される多環式化合物基である。）

(In the chemical formula (4), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of A ¹ may be the same as or different from each other, and PCy may have a substituent, a condensed ring group that may contain a hetero atom, or a group represented by the following chemical formula (3). A polycyclic compound group.)

（化学式（３）中、Ｘは、直接結合又はメチレン基を表し、Ｃｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい環式化合物基を表し、ｎは、１〜５の整数を表し、ｎが２以上の整数の場合、複数のＸ−Ｃｙは、それぞれ同一であっても異なっていてもよい。Ａ^２は、塩素原子、臭素原子、メチル基、又はスルホ基を表し、ｎ’は０〜４の整数を表し、ｎ’が２以上の整数の場合、複数のＡ^２は、それぞれ同一であっても異なっていてもよい。但し、ｎ＋ｎ’は１〜５の整数である。）

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.)

The method for producing a color filter of the present invention includes a step of forming a red resin composition layer using the red resin composition for a color filter,
Exposing the red resin composition layer through a mask;
The red resin composition layer after the exposure is developed and heated to form a red colored layer having a predetermined pattern.

The method for producing a color filter of the present invention includes a step of selectively attaching the red resin composition for a color filter to a predetermined region on a transparent substrate by an inkjet method to form a red resin composition layer;
And a step of curing the red resin composition layer by heating to form a red colored layer having a predetermined pattern.

  According to the present invention, precipitation of pigment aggregates on the surface of the colored layer (coating film) can be suppressed during the high-temperature heating process in the color filter manufacturing process, high contrast can be achieved, and the retardation of the colored layer can be achieved. Precipitating agent for crystal precipitation that is difficult to increase, pigment aggregation is suppressed during high-temperature heating process, and a colored layer with high contrast and small phase difference can be produced, and pigment dispersion with excellent dispersibility and dispersion stability Liquid, high-contrast red resin composition for color filters, which suppresses the precipitation of pigment aggregates during heating, can produce a colored layer with high contrast and small phase difference, and has excellent dispersibility and dispersion stability. Thus, it is possible to provide a method for producing a color filter that can obtain a colored layer having a small phase difference.

It is the schematic which shows an example of the color filter manufactured by the photolithographic system. It is the schematic which shows an example of the color filter manufactured by the inkjet system.

  Hereinafter, the crystal precipitation inhibitor precursor of the present invention, the pigment dispersion, the red resin composition for color filter, and the method for producing a color filter using the red resin composition for color filter will be described in order.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.
In the present invention, as the retardation of the colored layer, retardation in the thickness direction (Rth) calculated by the following formula was used as an index.
Rth = ((Nx + Ny) / 2−Nz) d
Nx: Refractive index in the in-plane slow axis direction Ny: Refractive index in the in-plane fast axis direction Nz: Refractive index in the thickness direction d: Film thickness (nm)

[Crystal precipitation inhibitor precursor]
The crystal precipitation inhibitor precursor according to the present invention is a compound represented by the following chemical formula (1).

（化学式（１）中、Ａ^１は、塩素原子、臭素原子、メチル基、スルホ基、又はフェニル基を表し、ｍは０〜５の整数を表し、ｍが２以上の整数の場合、複数のＡ^１は、それぞれ同一であっても異なっていてもよい。Ｂ^１及びＢ^２は、それぞれ独立に、水素原子、又は下記化学式（２）で表される基であり、Ｂ^１及びＢ^２の少なくとも１つは下記化学式（２）で表される基である。ＰＣｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい縮合環基、又は、下記化学式（３）で表される多環式化合物基である。）

(In the chemical formula (1), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of a ¹ is good .B ¹ and B ² be different even in the same, respectively, each independently, a hydrogen atom, or a group represented by the following chemical formula (2), the B ¹ and B ² At least one is a group represented by the following chemical formula (2): PCy is a condensed ring group which may have a substituent and may contain a hetero atom, or the following chemical formula (3). It is a polycyclic compound group represented.)

（化学式（２）中、Ｒ^１は、置換基を有してもよい炭化水素基を表す。）

(In the chemical formula (2), R ¹ represents a hydrocarbon group which may have a substituent.)

（化学式（３）中、Ｘは、直接結合又はメチレン基を表し、Ｃｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい環式化合物基を表し、ｎは、１〜５の整数を表し、ｎが２以上の整数の場合、複数のＸ−Ｃｙは、それぞれ同一であっても異なっていてもよい。Ａ^２は、塩素原子、臭素原子、メチル基、又はスルホ基を表し、ｎ’は０〜４の整数を表し、ｎ’が２以上の整数の場合、複数のＡ^２は、それぞれ同一であっても異なっていてもよい。但し、ｎ＋ｎ’は１〜５の整数である。）

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.)

The crystal precipitation inhibitor precursor according to the present invention is a precursor that desorbs B ¹ and / or B ² by the action of heat or light to generate a crystal precipitation inhibitor represented by the following chemical formula (4). is there.

（化学式（４）中、Ａ^１は、塩素原子、臭素原子、メチル基、スルホ基、又はフェニル基を表し、ｍは０〜５の整数を表し、ｍが２以上の整数の場合、複数のＡ^１は、それぞれ同一であっても異なっていてもよい。ＰＣｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい縮合環基、又は、下記化学式（３）で表される多環式化合物基である。）

(In the chemical formula (4), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of A ¹ may be the same as or different from each other, and PCy may have a substituent, a condensed ring group that may contain a hetero atom, or a group represented by the following chemical formula (3). A polycyclic compound group.)

（化学式（３）中、Ｘは、直接結合又はメチレン基を表し、Ｃｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい環式化合物基を表し、ｎは、１〜５の整数を表し、ｎが２以上の整数の場合、複数のＸ−Ｃｙは、それぞれ同一であっても異なっていてもよい。Ａ^２は、塩素原子、臭素原子、メチル基、又はスルホ基を表し、ｎ’は０〜４の整数を表し、ｎ’が２以上の整数の場合、複数のＡ^２は、それぞれ同一であっても異なっていてもよい。但し、ｎ＋ｎ’は１〜５の整数である。）

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.)

  Each symbol in the chemical formula (4) is the same as that in the chemical formula (1).

  By using the crystal precipitation inhibitor precursor according to the present invention, pigment aggregation and crystal growth are suppressed during the high-temperature heating process in the color filter manufacturing process, and precipitation of pigment aggregates on the coating film surface is suppressed. High contrast can be achieved, and an increase in the retardation of the colored layer can be suppressed.

By using the crystal precipitation inhibitor precursor of the present invention, the effect of exhibiting the above effects is estimated as follows, although it is not yet elucidated.
In preparing the pigment dispersion, the pigment can be refined by increasing the dispersion time of the pigment in the solvent. In the case of using a pigment dispersant, the pigment dispersant can be appropriately adsorbed on the surface of the finely exposed pigment to stabilize the pigment in the solvent, and the pigment can be more uniformly refined. Is estimated to be possible. As a result, a coating film with improved contrast can be obtained.
However, after the uniformly refined pigment is made into a coating film, when a high temperature of 200 ° C. is applied to the coating film in the heating process in the color filter manufacturing process, the thermal movement of the pigment dispersant adsorbed on the pigment causes It is presumed that the adsorption of the pigment dispersant is weakened, the cohesive force between the finely exposed pigment surfaces is strengthened, and the pigment aggregate is precipitated.
The present inventors have found that by using a combination of a pigment and a specific crystal precipitation inhibitor, pigment crystals or aggregates do not precipitate even at high temperature heating, and a high-contrast coating film can be formed. . However, the resin composition in which the pigment and the specific crystal precipitation inhibitor are combined has insufficient pigment dispersibility and dispersion stability, and the coating film formed using the resin composition has a retardation. It turns out that the problem that becomes large arises.

  The crystal precipitation inhibitor precursor represented by the chemical formula (1) has at least one substituent represented by the chemical formula (2). By having the substituent, the crystal precipitation inhibitor precursor is improved in solubility in a solvent. For this reason, it is presumed that the pigment dispersibility and dispersion stability are improved without inhibiting the dispersibility as compared with the pigment dispersion using the crystal precipitation inhibitor itself having low solubility in the solvent.

Since the conventional crystal precipitation inhibitor is hardly soluble in a solvent, the surplus forms a hydrogen bond in NH of the diketopyrrolopyrrole skeleton and crystal grows, so that the phase difference is estimated to increase. Also, the conventional crystal precipitation inhibitor crystals have anisotropy that increases the phase difference with respect to the diketopyrrolopyrrole crystals and are hardly soluble in the solvent, so that they cannot act on the diketopyrrolopyrrole pigment surface. It is presumed that the coarser one increases the phase difference.
On the other hand, since the crystal precipitation inhibitor precursor represented by the chemical formula (1) has at least one substituent represented by the chemical formula (2) and has high solubility, before heating or exposure, It dissolves in a solvent without crystallization or agglomeration, and produces a crystal precipitation inhibitor having low solvent solubility upon heating or exposure.
According to this mechanism, unlike the conventional crystal precipitation inhibitor, crystals of the crystal precipitation inhibitor are not formed before heating or exposure. At the same time, hydrogen bonds can be efficiently formed with the outermost surface of the diketopyrrolopyrrole pigment. Further, it is presumed that the increase in retardation is suppressed because the crystallization inhibitor that forms a hydrogen bond on the outermost surface of the diketopyrrolopyrrole pigment has a crystal structure along the diketopyrrolopyrrole crystal type.
In addition, since the crystal precipitation inhibitor is generated in a cured film having low fluidity, it is difficult for them to approach each other, crystallization of the crystal precipitation inhibitor does not proceed, and as a result, the phase difference is difficult to increase. Presumed.

Furthermore, in the present invention, one of the two aromatic rings of the crystal precipitation inhibitor obtained by the action of heat or light has a bulky structure. The bulky structure is presumed to inhibit the lamination of pigments and hydrogen bonding on the pigment surface. However, it is presumed that the pigment derivative having two bulky structures is difficult to adsorb on the pigment surface due to the bulky structure. It is presumed that the crystal precipitation inhibitor of the present invention has only one bulky structure, so that it is easily adsorbed on the pigment surface and can efficiently suppress crystal precipitation.
From the above, by using the crystal precipitation inhibitor precursor of the present invention, it is possible to suppress the precipitation of pigment aggregates on the surface of the colored layer (coating film) during the high-temperature heating process in the color filter manufacturing process, It is presumed that high contrast of the color filter can be achieved and the phase difference of the colored layer is difficult to increase.
Hereinafter, the crystal precipitation inhibitor precursor of the present invention will be described.

In the chemical formula (1), A ¹ substituted with a phenyl group is a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group. In the case of the specific substituent, the effect of the present invention is not greatly hindered.
The phenyl group of the chemical formula (1) preferably has no substituent (m = 0). When there is no substituent such as chlorine in the phenyl group, the steric hindrance on the side that acts on the red pigment having the diphenyl diketopyrrolopyrrole skeleton is small, and more on the surface of the primary particle of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. Since it can be hydrogen-bonded or adsorbed, it has a great effect of suppressing pigment crystal precipitation during heating at high temperatures.
The A ¹ when having a substituent A ^1, among them chlorine atom, be a bromine atom, or a methyl group, steric hindrance is small, from the viewpoint that does not interfere with the adsorption to the pigment.

At least one of B ¹ and B ² in the chemical formula (1) is a group represented by the chemical formula (2). Among them, both B ¹ and B ² are groups represented by the chemical formula (2) from the viewpoint that solubility in a solvent is improved, pigment dispersibility and dispersion stability are excellent, and a phase difference is small. Is preferred.

In the chemical formula (2), if the hydrocarbon group in R ¹ is highly soluble in the solvent to be used and — (C═O) O—R ¹ is eliminated by the action of heat or light, particularly It is not limited. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group, and may further have a substituent. The alkyl group and the cycloalkyl group may be saturated or unsaturated. . When (-C = O) O-R ¹ is desorbed by heat, it is desorbed by heating at 100 to 230 ° C. from the point that a crystal precipitation inhibitor is efficiently generated by the production process of the present invention. It is preferable that it is desorbed by heating at 120 to 200 ° C.

The alkyl group is not particularly limited, but an alkyl group having 1 to 18 carbon atoms is preferable. The alkyl group may be linear or branched. For example, methyl group, ethyl group, n-propyl group, n-butyl group, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, hexadecyl group and the like can be mentioned. You may have unsaturated bonds, such as a double bond and a triple bond.
The substituent that the alkyl group may have is not particularly limited. Examples thereof include a hydroxy group, an alkoxy group, an alkylthio group, a dialkylamino group, a halogen atom, and an aryl group. Examples of the alkyl group substituted with an aryl group include a benzyl group. Moreover, as an alkyl group by which the alkoxy group was substituted, a methoxyalkyl group, 2-methoxy-ethoxyalkyl group, etc. are mentioned, for example.

Although the said cycloalkyl group does not have a restriction | limiting in particular, A C3-C18 cycloalkyl group is preferable. Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, and may have an unsaturated bond such as a double bond or a triple bond, and may be monocyclic or polycyclic. either will do.
The substituent that the cycloalkyl group may have is not particularly limited. For example, a C1-C5 alkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogenoalkyl group, an aryl group, a halogen atom, etc. are mentioned.

The aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable. For example, a phenyl group, a naphthyl group, a biphenyl, an anthryl group, etc. are mentioned.
The substituent that the aryl group may have is not particularly limited. For example, a cycloalkyl group, a C1-C5 alkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group, etc. are mentioned.

  Although there is no restriction | limiting in particular as the alkoxy group which the said hydrocarbon group may have as a substituent, A C1-C8 alkoxy group is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, A 2-ethylhexyloxy group, a 2-methoxy-ethoxy group, etc. are mentioned.

  The alkylthio group that the hydrocarbon group may have as a substituent is not particularly limited, but an alkylthio group having 1 to 4 carbon atoms is preferable. Examples thereof include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a methylethylthio group.

  Although there is no restriction | limiting in particular as a dialkylamino group which the said hydrocarbon group may have as a substituent, A C2-C8 dialkylamino group is preferable. Examples thereof include a dimethylamino group, a methylethylamino group, a diethylamino group, and a dibutylamino group.

  Examples of the halogen atom that the hydrocarbon group may have as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The aryl group that the hydrocarbon group may have as a substituent is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, a biphenyl, and an anthryl group. Can be mentioned. The aryl group may further have a substituent.

  The alkyl group having 1 to 5 carbon atoms that the hydrocarbon group may have as a substituent may be linear or branched. As a linear alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group and the like.

  The alkoxyalkyl group that the hydrocarbon group may have as a substituent is not particularly limited, but is preferably an alkoxyalkyl group having 1 to 8 carbon atoms, such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group. Group, ethoxyethyl group, methoxypropyl group and the like.

  The halogenoalkyl group that the hydrocarbon group may have as a substituent is not particularly limited, but is preferably a halogenoalkyl group having 1 to 8 carbon atoms, such as a chloromethyl group, a dichloromethyl group, or a trichloromethyl group. Group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 1,2-dichloroethyl group 1,1,2,2-tetrachloroethyl group and the like.

  Although there is no restriction | limiting in particular as a cycloalkyl group which the said hydrocarbon group may have as a substituent, A C3-C18 cycloalkyl group is preferable. Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, and may have an unsaturated bond such as a double bond or a triple bond, and may be monocyclic or polycyclic. either will do. The cycloalkyl group may further have a substituent.

In the chemical formula (1), PCy is a condensed ring group or a polycyclic compound group represented by the chemical formula (3). That is, PCy has a structure in which two or more rings are condensed, a structure in which they are directly bonded, or a structure in which they are bonded through a methylene group. When two or more rings are condensed, the ring structure is rigid, and even when the two or more rings are bonded directly or via a methylene group, Since the interaction is large and the ring structure is strongly fixed at a stable position by mutual hydrogen atoms and steric hindrance, it is presumed to be rigid.
The crystal precipitation inhibitor precursor represented by the chemical formula (1) has a high affinity with the diketopyrrolopyrrole pigment, but is rigid like PCy near the diketopyrrolopyrrole ring in the compound of the chemical formula (1). It is presumed that aggregation of the pigment adsorbed with the crystal precipitation inhibitor precursor is suppressed due to the presence of a bulky group. In the crystal precipitation inhibitor precursor of the present invention, the rigid structure of PCy hardly moves even at high temperature heating, and the compound represented by the chemical formula (4) functions as a crystal precipitation inhibitor at the high temperature heating step. It is estimated to be.

  In the chemical formula (1), the condensed ring group in PCy refers to the remaining atomic group obtained by removing one hydrogen atom from the condensed ring compound. The condensed ring in the condensed ring group is not particularly limited, and for example, condensed polycyclic aromatic hydrocarbons such as naphthalene, tetralin, indene, fluorene, anthracene, phenanthrene; benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone And condensed polycyclic heterocycles such as quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like, and these condensed rings may further have a substituent.

  Examples of the substituent that the condensed ring group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

  In the chemical formula (3), the cyclic compound group in Cy refers to the remaining atomic group obtained by removing one hydrogen atom from the cyclic compound. The cyclic compound in the cyclic compound group is not particularly limited. For example, in addition to benzene, a 5-membered heterocyclic ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole; pyran, pyrone, pyridine, pyridazine, 6-membered heterocycles such as pyrimidine and pyrazine; condensed polycyclic aromatic hydrocarbons such as naphthalene, tetralin, indene, fluorene, anthracene and phenanthrene; benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline and acridine And condensed polycyclic heterocycles such as phthalazine, quinazoline and quinoxaline, and these cyclic compound groups may further have a substituent.

  Examples of the substituent that the cyclic compound group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

  The substitution number n of X-Cy is an integer of 1 to 5, of which an integer of 1 to 3 is preferable, an integer of 1 or 2 is more preferable, and 1 is more preferable.

In the chemical formula (3), A ² substituted with a phenyl group is a chlorine atom, a bromine atom, a methyl group, or a sulfo group. In the case of the specific substituent, the effect of the present invention is not greatly hindered. Among them, the phenyl group in the chemical formula (3) preferably has no substituent A ² (n ′ = 0).

  Specific examples of the crystal precipitation inhibitor precursor according to the present invention are shown below, but the present invention is not limited thereto.

  The solubility of the crystal precipitation inhibitor precursor of the present invention in a solvent is not particularly limited. Among these, the solubility at 23 ° C. is excellent for at least one of the solvents used in the pigment dispersion described later from the viewpoint that pigment dispersibility and dispersion stability are excellent and precipitation of pigment aggregates can be efficiently suppressed during high-temperature heating. It is preferably 0.2 g / 100 g or more, and more preferably 0.34 g / 100 g or more.

<Method for Producing Crystal Precipitation Inhibitor Precursor>
The manufacturing method of the crystal precipitation inhibitor precursor represented by the chemical formula (1) is not particularly limited. For example, a method of introducing the group represented by the chemical formula (2) into the asymmetric diketopyrrolopyrrole derivative can be mentioned.

(Synthesis of asymmetric diketopyrrolopyrrole derivatives)
The method for producing the asymmetric diketopyrrolopyrrole derivative is not particularly limited. Examples thereof include a method of introducing a group represented by -X-Cy in the chemical formula (3) into a specific diketopyrrolopyrrole pigment, and a method of reacting a specific pyrrolinone and benzonitrile. A method for introducing a group represented by -X-Cy in the chemical formula (3) into a specific diketopyrrolopyrrole pigment is described in detail in, for example, JP-T-2004-501911, and refer to this. Can do. A method of reacting a specific pyrrolinone with benzonitrile is described in detail in, for example, European Patent Application Publication No. 0184982, and can be referred to.

(Synthesis of crystal precipitation inhibitor precursor)
The asymmetric diketopyrrolopyrrole derivative obtained by the above-described method and the compound represented by the following chemical formula (5) in an aprotic organic solvent in the presence of a base as a catalyst, By reacting at 10 to 100 ° C. for 2 to 8 hours, the crystal precipitation inhibitor precursor represented by the chemical formula (1) can be obtained.

（化学式（５）中、Ｒ^１’及びＲ^１’’は、それぞれ独立に置換基を有してもよい炭化水素基である。）

(In the chemical formula (5), R ^{1 ′} and R ^{1 ″} are each independently a hydrocarbon group which may have a substituent.)

In the chemical formula (5), R ^{1 ′} and R ^{1 ″} can be the same as R ¹ in the chemical formula (2).

  The aprotic organic solvent is not particularly limited. For example, ethers such as tetrahydrofuran or dioxane; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; acetonitrile, benzonitrile, N, N-dimethylformamide, N, N- Dipolar aprotic solvents such as dimethylacetamide, nitrobenzene, N-methylpyrrolidone; Halogenated aliphatics such as trichloroethane; Aromatic hydrocarbons such as benzene, toluene, xylene, anisole or chlorobenzene; Pyridine, picoline or quinoline And aromatic N-heterocyclic compounds.

  The base used as the catalyst is not particularly limited. Of these, organic bases such as diazabicyclooctene, diazabicycloundecene, and 4-dimethylaminopyridine are preferable.

  In the synthesis of the crystal precipitation inhibitor precursor, the crystal precipitation inhibitor represented by the chemical formula (1) is appropriately adjusted by appropriately adjusting the molar ratio of the asymmetric diketopyrrolopyrrole derivative and the compound represented by the chemical formula (5). The number of introduced groups represented by the chemical formula (2) in the precursor can be controlled.

  When one group represented by the chemical formula (2) is introduced, the compound represented by the chemical formula (5) is used in an amount of 0.8 to 10.0 molar equivalents with respect to the asymmetric diketopyrrolopyrrole derivative. It is more preferable to use 0.8 to 1.2 molar equivalents. If it is in the said range, the production | generation of a by-product can be suppressed and the reaction yield of the crystal precipitation inhibitor precursor in which one group represented by Chemical formula (2) was introduce | transduced can be improved.

  In addition, when two groups represented by the chemical formula (2) are introduced, the compound represented by the chemical formula (5) is preferably used in an amount of 2 to 80 molar equivalents with respect to the asymmetric diketopyrrolopyrrole derivative. 10 to 70 molar equivalents are more preferable. If it is in the said range, the production | generation of a by-product can be suppressed and the reaction yield of the crystal precipitation inhibitor precursor in which two groups represented by Chemical formula (2) were introduced can be improved.

  Moreover, the addition amount of a base is not specifically limited. From the viewpoint of improving the reaction yield, it is preferably used in an amount of 0.05 to 0.5 molar equivalents, more preferably 0.1 to 0.2 molar equivalents, relative to the asymmetric diketopyrrolopyrrole derivative.

  Although the reaction temperature in the said reaction does not have a restriction | limiting in particular, Usually, it is about 0-120 degreeC, and it is preferable that it is 10-40 degreeC from the point which suppresses a side reaction. Moreover, there is no restriction | limiting in particular in the reaction pressure of the said reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable. The reaction time in the above reaction may vary depending on the amount of synthesis, reaction temperature, etc., and thus cannot be generally specified, but is usually set in the range of 2 to 80 hours, preferably 5 to 20 hours.

  The crystal precipitation inhibitor precursor according to the present invention generates a crystal precipitation inhibitor and suppresses the precipitation of pigment aggregates in the high-temperature heating process in the color filter manufacturing process. The crystal precipitation inhibitor precursor of the present invention can be suitably used as a crystal precipitation inhibitor for diketopyrrolopyrrole pigments.

[Pigment dispersion]
The pigment dispersion according to the present invention contains the crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, a pigment dispersant, and a solvent.

  In the pigment dispersion of the present invention, by using a combination of the crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, and a pigment dispersant, aggregation and crystal growth of the pigment are suppressed during the high-temperature heating step, Precipitation of pigment aggregates on the coating surface is suppressed, a colored layer with high contrast and small phase difference can be produced, and a pigment dispersion excellent in dispersibility and dispersion stability can be obtained.

The pigment dispersion according to the present invention contains a crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, a pigment dispersant, and a solvent as essential components, and other components as necessary. It may be contained.
Hereinafter, each component of the pigment dispersion of the present invention will be described in order. Since the crystal precipitation inhibitor precursor can be the same as described above, description thereof is omitted here.

<Diketopyrrolopyrrole pigment>
The diketopyrrolopyrrole pigment used in the present invention has a structure represented by the following formula (6).

（化学式（６）中、Ａ^３及びＡ^４は、それぞれ独立に、ハロゲン原子、メチル基、エチル基、ｔｅｒｔ−ブチル基、フェニル基、Ｎ，Ｎ−ジメチルアミノ基、トリフルオロメチル基、シアノ基を表し、ｋ及びｋ’はそれぞれ独立に０〜５の整数を表し、ｋ及びｋ’がそれぞれ２以上の整数の場合、複数のＡ^３及びＡ^４は、それぞれ同じであっても異なっていてもよい。）

(In the chemical formula (6), A ³ and A ⁴ are each independently a halogen atom, methyl group, ethyl group, tert-butyl group, phenyl group, N, N-dimethylamino group, trifluoromethyl group, cyano group. K and k ′ each independently represent an integer of 0 to 5, and when k and k ′ are each an integer of 2 or more, a plurality of A ³ and A ⁴ are the same or different. May be good.)

  In the chemical formula (6), k and k ′ are each independently an integer of 0 to 5. Among these, k and k ′ are each preferably an integer of 0 to 3 and k and k ′ are each independently 0 or 0 from the viewpoint of achieving high contrast and easy adjustment of red color suitable for a color filter. More preferably, it is an integer of 1.

Among the diketopyrrolopyrrole pigments, among others, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73 is preferable, and C.I. I. Pigment red 254, C.I. I. More preferably, it is CI Pigment Red 255.
The diketopyrrolopyrrole pigments can be used singly or in combination of two or more.

The average primary particle size of the diketopyrrolopyrrole pigment used in the present invention is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter. From the viewpoint of improving the contrast, it is preferably in the range of 10 to 50 nm, and more preferably in the range of 10 to 30 nm. When the average primary particle diameter of the pigment is in the above range, the color filter can be made to have high contrast and high quality.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, with respect to 100 or more particles, the volume (mass) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

  The diketopyrrolopyrrole pigment used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Commercially available diketopyrrolopyrrole pigments may also be used.

  In the pigment dispersion of the present invention, the pigment content is not particularly limited. Usually, the pigment content is preferably in the range of 7 to 17% by mass and 9 to 15% by mass with respect to the total amount of the pigment dispersion including the solvent.

In the pigment dispersion of the present invention, the crystal precipitation inhibitor precursor represented by the chemical formula (1) can be used alone or in combination of two or more.
In the pigment dispersion of the present invention, the content of the crystal precipitation inhibitor precursor represented by the chemical formula (1) is not particularly limited. Among these, from the viewpoint of efficiently suppressing the precipitation of the pigment during the high-temperature heating step and forming a high-contrast colored layer, the crystal precipitation inhibitor represented by the chemical formula (1) with respect to 100 parts by mass of the pigment. The content of the precursor is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass.

<Pigment dispersant>
In the present invention, the pigment dispersant is not particularly limited, and known ones can be used. For example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

  The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diamino Examples thereof include amines having a hydroxy group such as tan, 1,4-bis (2-hydroxyethyl) piperazine and 1- (2-hydroxyethyl) piperazine, and others such as nipecotamide, isonipecotamide, and nicotinamide. A compound can be mentioned.

  Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

Examples of the pigment dispersant used in the present invention include a block copolymer type or graft copolymer (comb type) type polymer pigment dispersant in which a pigment adsorption site and a solvent affinity site are functionally separated in the molecule. It is preferable from the viewpoint of the pigment dispersibility of the ketopyrrolopyrrole pigment.
As the above-mentioned graft copolymer type polymer pigment dispersant, for example, a salt-type graft copolymer described in JP 2010-85647 A can be preferably used.

  The pigment dispersant used in the present invention has, among other things, a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), Further, a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound and / or a halogenated hydrocarbon form a salt is preferable.

［式（Ｉ）及び式（ＩＩ）中、Ｒ^２は、水素原子又はメチル基、Ｒ^３及びＲ^４は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^５は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数が１〜５のアルキル基である。上記アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ置換基を有していても良い。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。ｍは３〜２００の整数、ｎは１０〜２００の整数を示す。］

[In Formula (I) and Formula (II), R ² is a hydrogen atom or a methyl group, R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - a divalent group represented, ^{R 5} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH A monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]

  In the present invention, the contrast is particularly improved by combining a diketopyrrolopyrrole pigment, the crystal precipitation inhibitor precursor, and a pigment dispersant made of the specific salt-type block copolymer as a pigment dispersant. In addition, while achieving the demand for high brightness and high contrast, it is possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step.

  The pigment dispersant comprising such a specific salt-type block copolymer includes the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II). And a salt-forming block is formed by a salt-type block copolymer in which the amino group of the structural unit (1) and the organic acid compound and / or halogenated hydrocarbon form a salt. The structural unit (1) has particularly strong adsorptivity to the diketopyrrolopyrrole pigment, while the structural unit (2) has solubility in the solvent. When such a pigment dispersant is used, by increasing the dispersion time in the solvent, the pigment dispersant is appropriately adsorbed on the finely exposed pigment surface while the specific pigment is miniaturized, and the solvent is removed. It is presumed that the pigment in the inside can be stabilized, and the specific pigment can be more finely divided. As a result, a coating film with improved contrast can be obtained.

<Block copolymer>
The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II).
In the general formula (I), ^{R 2} represents a hydrogen atom or a methyl group, ^{R 3} and ^{R 4} each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ³ and R ⁴ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — ** is a divalent group. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various kinds. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, if x, y, and z are within the above ranges, the color filter pigment dispersion of the present invention has excellent pigment dispersibility.
As said A, a C1-C8 alkylene group is preferable and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

In the general formula (II), R ⁵ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) —. _O] x -R ⁸ or _- indicates a _{[(CH 2) y -O]} z -R 8.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group. , An aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or a linear, branched, or cyclic group having 1 to 5 carbon atoms. It is an alkyl group.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms of ^{R 8,} and alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the ^{R 5.}
In the above R ⁵ , x, y and z are as described in A above.
In addition, R ⁵ in the repeating unit (2) represented by the general formula (II) may be the same as or different from each other.

In the present invention, as R ⁵ , it is preferable to use those having excellent solubility in the solvent described later, and specifically, it varies depending on the repeating unit constituting the block copolymer. When the solvent is an ether alcohol acetate solvent, an ether solvent, an ester solvent or the like generally used as a solvent for a color filter, a methyl group, an ethyl group, an n-butyl group, 2- An ethylhexyl group, a benzyl group and the like are preferable.
Here, the reason for setting R ⁵ in this way is that the repeating unit (2) containing R ⁵ has good solubility in the solvent, and the amino group of the repeating unit (1) is described later. The salt-forming site formed by the organic acid compound and / or the halogenated hydrocarbon having a high adsorptivity to the pigment can make the dispersibility and stability of the pigment particularly excellent. Because it can.

Furthermore, R ⁵ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. Alternatively, after the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent. Moreover, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a block copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a block copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

  The ratio m / n of the number of units m of the structural unit (1) and the number of units n of the structural unit (2) used in the present invention is preferably within the range of 0.01 to 1, preferably 0.05 to More preferably, it is in the range of 0.5. When the ratio m / n is within the above range, the adsorptivity to the pigment is good, the solubility with the solvent by the structural unit (2) is not lowered, and the dispersibility and stability of the pigment are lowered. There is nothing to do.

  Regarding the molecular size of the block copolymer used in the present invention, the number m of the repeating unit (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number n of the repeating units (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when m and n are within the above ranges, the solvent-soluble part and the solvent-insoluble part act effectively, and the pigment dispersion for the color filter of the present invention has excellent pigment dispersibility. Can be. Furthermore, the mass average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed.

  The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

  The binding order of the block copolymer used in the present invention is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the pigment. However, it is preferable that the repeating unit (1) is bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of repeating unit (1) -repeating unit (2), or repeating unit (1) -repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of repeating unit (1) -repeating unit (2) are preferred. The reason is that it is excellent in the adsorptivity with respect to a pigment, and also the aggregation of pigment dispersants using such a block copolymer can be effectively suppressed.

  In the case where two or more structural units (1) and structural units (2) are included, a block copolymer in which the structural units (1), the structural units (2 ′), and the structural units (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ')-structural unit (1 ")-structural unit (2), or structural unit (1')-structural unit (1")-structural unit (2 ') -The block copolymer etc. which couple | bonded in order of the structural unit (2 ") may be sufficient.

<Organic acid compound>
An amino group contained in the structural unit (1) of the block copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); Examples of the organic acid compound that forms a salt include an organic phosphoric acid compound having a structure represented by the following general formula (III) and / or an organic sulfonic acid compound having a structure represented by the above general formula (IV). It is done.

［式（ＩＩＩ）及び式（ＩＶ）中、Ｒ^ａ及びＲ^ａ’はそれぞれ独立に、水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ａ’’で示される１価の基であり、Ｒ^ａ及びＲ^ａ’のいずれかは炭素原子を含む。Ｒ^ａ’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｂは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ｂ’で示される１価の基である。Ｒ^ｂ’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、又は−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｃ及びＲ^ｄは、それぞれ独立に水素原子又はメチル基であり、Ｒ^ｅは、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^ｆで示される１価の基であり、Ｒ^ｆは水素原子又は炭素数１〜５のアルキル基である。
Ｒ^ａ、Ｒ^ａ’、及びＲ^ｂにおいて、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｓは１〜１８の整数、ｔは１〜５の整数、ｕは１〜１８の整数を示す。］

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

  In the present invention, by using the organic acid compound and / or the halogenated hydrocarbon described later, the pigment dispersant can be made excellent in pigment dispersibility and stability. Furthermore, when an organic acid compound is used, the salt forming site has high solubility in an alkaline aqueous solution at the time of alkali development in a color filter manufacturing process by a photolithography method, so that it has excellent alkali developability. It can be. As the particle size of the pigment becomes smaller, a large amount of pigment dispersant is required, which may cause problems such as reduced alkali developability and increased residue. In such a case, the possibility of such a problem occurring can be reduced.

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described above for R ⁵ . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include alkenyl groups, nitro groups, and halogen atoms in addition to linear or branched alkyl groups having 1 to 4 carbon atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or It is a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms of the above ^{R e} are as indicated by ^{R 5} described above, an alkenyl group, an aralkyl group having 2 to 18 carbon atoms, an aryl group, said ^{R a} and R ^{a '} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^a ″ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R. ^e is a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.} In addition, when R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the general formula (IV), R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —. _O] s ^-R _e, - shows a _{[(CH 2) t -O]} u -R e, or -O-R ^{b '.}
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.}

When R ^b is —O—R ^b ′, it becomes an acidic sulfate. R ^b ′ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
In R ^b and R ^b ′, each of an alkyl group, an alkenyl group, an aralkyl group, and an aryl group may have a substituent.
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e, - [(CH ₂ ) _t— O] _u —R ^e is as described above for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are as described above for R ^a , R ^a, and R ^{a ″} .
In said ^Rb and ^Rb ', s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} described above.

As the organic acid compound represented by the general formula (III), R ^a and R ^{a ′} in the general formula (III) each independently have a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a substituent. Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} is a methyl group, ethyl Group, aryl group or aralkyl group which may have a substituent, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) and _{^{t -O] u -R e, R}} c and ^{R d} are each independently a hydrogen atom or a methyl group Ri, from the viewpoint of can be made of those ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) a = CH ₂ is excellent in pigment dispersibility.

Moreover, as an organic acid compound represented by general formula (IV), ^Rb in general formula (IV) is a methyl group, an ethyl group, the aryl group which may have a substituent, an aralkyl group, a vinyl group. , An allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{b ′} R ^{b ′} is a methyl group, an ethyl group, an aryl group or an aralkyl group optionally having a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , wherein R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e In which —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH ₂ has excellent pigment dispersibility It is preferable from the point which can be made.

Of these, organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' From the viewpoint of pigment dispersibility, it preferably has an aromatic ring. At least one of R ^a , R ^{a ′} and R ^{a ″} , or R ^b or R ^{b ′} , an aryl group or aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of pigment dispersibility. In the general formula (III), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

Further, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the general formula (III) and the general formula (IV) include carbon (P) and sulfur (S). A compound in which atoms are directly bonded is preferable, and R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl A monovalent group represented by a group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , R ^a and Any of R ^{a ′} preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.

The organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups at the time of exposure and post-baking when forming a colored layer using the red resin composition for a color filter of the present invention described later, It becomes possible to polymerize the curable binder component contained in the red resin composition for a color filter of the present invention, and the pigment dispersant can be stably present in the colored layer of the color filter. . When a liquid crystal display device is manufactured using such a color filter, the pigment dispersant can be prevented from bleeding out to the liquid crystal layer or the like.

  In addition, since the organic acid compound contains a polymerizable group, the polymerizable groups of the organic acid compound can be polymerized before being used for forming the colored layer, and as a result, the pigment dispersant has a high molecular weight. Therefore, at the time of alkali development for forming a colored layer in the color filter production process by a photolithography method, the red resin composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability.

  In addition, the organic acid compound represented by the said general formula (III) and general formula (IV) can be used individually by 1 type or in combination of 2 or more types.

<Halogenated hydrocarbon>
The halogenated hydrocarbon used in the present invention is a block copolymer having the above-mentioned repeating unit (1) represented by the general formula (I) and the repeating unit (2) represented by the general formula (II). A salt is formed with the amino group of the repeating unit (1).
In the present invention, by using the above-mentioned halogenated hydrocarbon, the salt-forming site produced by the pigment dispersant is excellent in adsorptivity to the pigment, so that it can exhibit high dispersibility, and at the same time, the dispersant Heat resistance and alkali resistance can be increased.

Examples of the halogenated hydrocarbon include those in which any one of a chlorine atom, a bromine atom and an iodine atom is substituted with a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. . Among these, a halogenated hydrocarbon in which one of the hydrogen atoms of the hydrocarbon is substituted with a halogen atom is preferable from the viewpoint of forming a salt with the pigment dispersant and improving the pigment dispersibility.
The halogenated hydrocarbon may be linear, branched or cyclic. The number of carbon atoms is preferably 1-18, and more preferably 1-7.

  Among the halogenated hydrocarbons, examples of the halogenated alkyl include those having 1 to 18 carbon atoms, but are not particularly limited. Specifically, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, etc. Can be mentioned. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Further, examples of the aralkyl group of the halogenated aralkyl include those having 7 to 18 carbon atoms, but are not particularly limited. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, pyridylmethyl bromide and the like.

  Among these, at least one selected from the group consisting of benzyl halide, allyl halide, and methyl halide is easy to form a salt, and the formed salt-forming site has excellent adsorptivity to the pigment. This is preferable.

  The content of the organic acid compound and / or halogenated hydrocarbon in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited. It is about 0.01-2.0 molar equivalent with respect to the tertiary amino group represented by (I), More preferably, it is 0.1-1.0 molar equivalent. In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using 2 or more types of the said organic acid compound and / or halogenated hydrocarbon together, content which added these should just be in the said range.

<Manufacture of pigment dispersant made of salt type block copolymer>
As a method for producing the block copolymer of the pigment dispersant, the repeating unit (1), the repeating unit (2), the amino group of the repeating unit (1), and the organic The method is not particularly limited as long as it can produce a salt formed with an acid compound and / or a halogenated hydrocarbon. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the organic acid is dissolved in the solvent. A salt-type block copolymer can be produced by adding a compound and / or a halogenated hydrocarbon and stirring (heating as necessary). Further, at the time of pigment dispersion, a salt type block copolymer is obtained by adding a copolymer having the above repeating unit (1) and repeating unit (2) and the above organic acid compound and / or halogenated hydrocarbon. May be manufactured.

  The polymerization means is not particularly limited as long as it is a means capable of polymerizing the above repeating unit (1) and repeating unit (2) in a desired number to obtain a desired molecular weight, and has a vinyl group. A method generally used for polymerization of a compound can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, in particular, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, the molecular weight, the molecular weight distribution, etc. can be easily set in a desired range, so that the dispersibility of the pigment dispersant can be made uniform.

  In the pigment dispersion of the present invention, one type of pigment dispersant may be used, or two or more types may be used in combination. In addition, the content is not particularly limited as long as the pigment can be uniformly dispersed, and for example, 10 to 150 parts by mass can be used with respect to 100 parts by mass of the pigment. Furthermore, it is preferable to mix | blend in the ratio of 15-45 mass parts with respect to 100 mass parts of pigments, and it is preferable to mix | blend especially in the ratio of 15-40 mass parts. If the content of the pigment dispersant is within the above range, the pigment can be uniformly dispersed.

(solvent)
The pigment dispersion according to the present invention contains a solvent for dispersing the pigment. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent that does not react with each component in the pigment dispersion and can dissolve or disperse them.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate , Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxy Cellosolve acetate solvents such as til acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Ether solvents such as monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene and xylene , Unsaturated hydrocarbon solvents such as naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Organic solvents such as system solvents can be mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion of the present invention is prepared by using the solvent as described above usually at a ratio of 60 to 85% by mass with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity increases and the pigment dispersibility tends to decrease. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

(Other ingredients)
If necessary, the pigment dispersion liquid of the present invention may further contain a pigment dispersion auxiliary resin and other components.
Examples of the pigment dispersion auxiliary resin include alkali-soluble resins exemplified by a resin composition described later. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other.
The pigment dispersion of the present invention may contain other pigments as long as the effects of the present invention are not impaired. Examples of other pigments include other red pigments and yellow pigments used for adjusting the pigment dispersion to a desired color. About the pigment used in such a case, the thing similar to the pigment illustrated by the red resin composition for color filters mentioned later can be used.
Moreover, as long as the effect of this invention is not impaired, the other pigment dispersant may be included.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.
Moreover, as long as the effect of this invention is not impaired, the other pigment derivative may be included.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention can be prepared by mixing the above-described crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, a pigment dispersant in a solvent, and dispersing the mixture using a known disperser. it can.
When preparing the dispersion, the method of mixing each component is not particularly limited. For example, after each of the diketopyrrolopyrrole pigment and the crystal precipitation inhibitor precursor is dispersed or dissolved, Or a solution may be mixed, and a diketopyrrolopyrrole pigment and a crystal precipitation inhibitor precursor may be co-dispersed.
Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.05 to 1.0 mm.

  Specifically, pre-dispersion is performed with 1 to 2 mm zirconia beads having a relatively large bead diameter, and further main dispersion is performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 to 0.1 μm after dispersion.

  In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. For example, when a paint shaker is used so that the average dispersed particle diameter of the pigment is about 15 to 50 nm. Is preferably 5 to 50 hours from the viewpoint of realizing high contrast by refining the pigment.

  In this way, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a red resin composition for a color filter having excellent pigment dispersibility.

[Red resin composition for color filter]
The red resin composition for a color filter according to the present invention contains the crystal precipitation inhibitor precursor according to the present invention, a diketopyrrolopyrrole pigment, a curable binder component, and a solvent. .

The red resin composition for a color filter of the present invention is a combination of the crystal precipitation inhibitor precursor, a diketopyrrolopyrrole pigment, a pigment dispersant, and a curable binder component. Precipitation of pigment aggregates is suppressed, a colored layer having a high contrast and a small phase difference can be produced, and a red resin composition for a color filter excellent in dispersibility and dispersion stability can be obtained.
Hereinafter, the component used for such a red resin composition for color filters of this invention is demonstrated.
The components that can be contained in the pigment dispersion according to the present invention can be the same as those described in the section of the pigment dispersion, and thus the description thereof is omitted here.

(Curing binder component)
The red resin composition for a color filter according to the present invention contains a curable binder component in order to impart film formability and adhesion to a surface to be coated, and to impart sufficient hardness to the coating film. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
Examples of the curable binder component include a photocurable binder component including a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

When the red resin composition for a color filter according to the present invention can be selectively attached in a pattern on a substrate to form a colored layer, for example, when used in an ink jet method, the developability of the curable binder component Is not necessary. In this case, a known thermosetting binder component, a photocurable binder component, or the like used when forming the color filter coloring layer by an inkjet method or the like can be appropriately used.
On the other hand, when a photolithography method is used when forming the colored layer, a photosensitive binder component having alkali developability is preferably used.
Hereinafter, the photosensitive binder component and the thermosetting binder component suitable for use in the ink jet system will be described in detail, but the curable binder component is not limited to these.

(1) Photosensitive binder component Examples of the photosensitive binder component include a positive type photosensitive binder component and a negative type photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin and a system containing an o-quinonediazide group-containing compound as a photosensitizing component, and examples of the alkali-soluble resin include a polyimide precursor.

  As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator will be specifically described.

<Alkali-soluble resin>
The alkali-soluble resin has a carboxyl group in the side chain, acts as a binder resin, and is suitably selected and used as long as it is soluble in a developer used for pattern formation, particularly preferably in an alkali developer. be able to.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photosensitive resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, disi Lopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. 1 type or more and (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and dimer of acrylic acid (for example, Toagosei Chemical Co., Ltd. M -5600), itaconic acid, crotonic acid Maleic acid, fumaric acid, vinyl acetate, a copolymer consisting of one or more selected from these anhydrides can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by mass, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

  One type of alkali-soluble resin may be used, or two or more types may be used in combination, and the content thereof is usually 100 parts by mass of the pigment contained in the red resin composition for color filters. It is in the range of 10 to 1000 parts by mass, preferably in the range of 20 to 500 parts by mass. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the pigment becomes relatively low and sufficient coloring is achieved. The concentration may not be obtained.

<Multifunctional monomer>
The polyfunctional monomer used in the red resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator described later. A compound having two or more is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.

  Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol di (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, triethylene glycol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, Methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, Bifunctional (butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate) Data) acrylate and the like.

  Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacrylic) Roxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol La (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the photocurable red resin composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. It is preferable to use poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Succinic acid modification of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) Dipentae modified acrylate succinate Sri Tall hexa (meth) acrylate are preferable.
Although there is no restriction | limiting in particular in content of the said polyfunctional monomer, Usually, about 5-500 mass parts with respect to 100 mass parts of said alkali-soluble resin, Preferably it is the range of 20-300 mass parts. If the content of the polyfunctional monomer is less than the above range, the photocuring may not proceed sufficiently, and the exposed part may be eluted. There is a risk.

<Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator used in the red resin composition for color filters of this invention, It can select suitably from various photoinitiators known conventionally. For example, aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, benzoin such as methylbenzoin, ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria Reel imidazole dimer 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) Halomethyloxadiazole compounds such as 1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl Ru-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldipheny Sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy -Cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2 -(4-morpholinyl) -1-propanone and the like can be mentioned. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  Content of a photoinitiator is about 0.01-100 mass parts normally with respect to 100 mass parts of said polyfunctional monomers, Preferably it is 5-60 mass parts. If the content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the colored layer may not have sufficient hardness. There may be a case where the content of the pigment or the like in the solid content of the composition is relatively reduced, and a sufficient coloring density cannot be obtained.

(2) Thermosetting binder component As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst that can accelerate the thermosetting reaction is used. It may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Moreover, you may use further the polymer which has no polymerization reactivity in itself.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is suitably used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

<Compound having two or more thermosetting functional groups in one molecule>
As an epoxy compound which is a polymer having a relatively high molecular weight that is usually used as a curable binder component (hereinafter sometimes referred to as “binder epoxy compound”), at least the structural unit represented by the following formula (V) and the following: A polymer composed of a structural unit represented by the formula (VI) and having two or more glycidyl groups can be used.

（Ｒ^２１は水素原子または炭素数１〜３のアルキル基であり、Ｒ^２２は炭素数１〜１２の炭化水素基である。）

(R ²¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ²² is a hydrocarbon group having 1 to 12 carbon atoms.)

（Ｒ^２３は水素原子又は炭素数１〜１０のアルキル基である。）

^{(R 23} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

By using the structural unit represented by the formula (V) as the structural unit of the binder epoxy compound, sufficient hardness and transparency can be imparted to the cured coating film formed from the resin composition of the present invention. In the formula (V), R ²¹ is preferably hydrogen or a methyl group. R ²² is a hydrocarbon group having 1 to 12 carbon atoms, and may be a linear aliphatic, alicyclic, or aromatic hydrocarbon group, and an additional structure such as a double bond, carbon It may contain a hydrogen group side chain, a spiro ring side chain, an intra-ring bridged hydrocarbon group, and the like.

  Specific examples of the monomer for deriving the structural unit represented by the above formula (V) include methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, i -Butyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl Examples include (meth) acrylate, para-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenyl (meth) acrylate, and the like.

The structural unit represented by the formula (VI) is used for introducing an epoxy group (epoxy reaction point) into the polymer. The resin composition containing the polymer is excellent in storage stability, and does not easily increase in viscosity during storage and discharge operations. One of the reasons is that the epoxy group in formula (VI) is a glycidyl group. It is estimated that.
In formula (VI), R ²³ is preferably hydrogen or a methyl group. Specific examples of the monomer for deriving the structural unit represented by the formula (VI) include glycidyl (meth) acrylate, and glycidyl methacrylate (GMA) is particularly preferable.

  The polymer may be a random copolymer or a block copolymer. The polymer may contain main chain constituent units other than those of formula (V) or formula (VI) as long as the performance required for each detail of the color filter, such as hardness and transparency, can be ensured. Good. Specific examples of such a monomer include acrylonitrile and styrene.

  The content of the structural unit of formula (V) and the structural unit of formula (VI) in the binder epoxy compound is preferably in the range of 10:90 to 90:10. When the amount of the structural unit of the formula (1) is more than the above ratio of 10:90, there is a possibility that the reaction point of curing decreases and the crosslinking density is lowered, whereas the structural unit of the formula (2) If the amount is more than the above ratio 90:10, the bulky skeleton may be reduced and curing shrinkage may be increased.

  The mass average molecular weight of the binder epoxy compound is preferably 3,000 or more, particularly 4,000 or more, when expressed in terms of polystyrene-equivalent weight average molecular weight. This is because if the molecular weight of the binder epoxy compound is too smaller than 3,000, physical properties such as strength and solvent resistance required for the cured layer as the details of the color filter are likely to be insufficient. On the other hand, the mass average molecular weight of the binder epoxy compound is preferably 20,000 or less, more preferably 15,000 or less when expressed in terms of polystyrene-equivalent weight average molecular weight. If the molecular weight is more than 20,000, the viscosity is likely to increase, and the stability of the ejection amount and the straightness of the ejection direction when ejecting from the ejection head by the inkjet method may be deteriorated, and the stability of long-term storage It is because there is a possibility that it may become worse. The binder epoxy compound can be synthesized by a method described in paragraph No. 0148 of JP-A-2006-106503, for example.

  The thermosetting binder is an epoxy compound having two or more epoxy groups in one molecule (hereinafter sometimes referred to as “polyfunctional epoxy compound”) having a molecular weight smaller than that of the binder epoxy compound. May be used. Especially, it is preferable to use the said binder-type epoxy compound and the said polyfunctional epoxy compound together as mentioned above. In this case, the polystyrene equivalent mass average molecular weight of the polyfunctional epoxy compound is preferably 4,000 or less, and particularly preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the resin composition, epoxy groups are replenished in the resin composition, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased.

  Among polyfunctional epoxy compounds, it is preferable to use an epoxy compound having four or more epoxy groups in one molecule in order to increase the crosslink density of the acid-epoxy reaction. In particular, when the mass average molecular weight of the binder epoxy compound is set to 10,000 or less in order to improve the discharge performance from the inkjet discharge head, the strength and hardness of the cured layer are likely to decrease. It is preferable to add a tetrafunctional or higher polyfunctional epoxy compound to the resin composition to sufficiently increase the crosslinking density.

  The polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, Bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy Resin, trifunctional epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A included Polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  More specifically, bisphenol A type epoxy resins such as trade name Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resins such as trade name YDF-175S (manufactured by Tohto Kasei Co., Ltd.), trade name YDB-715 ( Brominated bisphenol A type epoxy resin such as Toto Kasei Co., Ltd., Bisphenol S type epoxy resin such as EPICLON EXA1514 (Dainippon Ink Chemical Co., Ltd.), hydroquinone such as YDC-1312 (Toto Kasei Co., Ltd.) Type epoxy resin, naphthalene type epoxy resin such as trade name EPICLON EXA4032 (manufactured by Dainippon Ink and Chemicals), biphenyl type epoxy resin such as trade name Epicoat YX4000H (made by Japan Epoxy Resin), trade name Epicoat 157S70 (Japan Epoch) Bisphenol A type novolak epoxy resin such as Xylen Resin), brand name Epicoat 154 (Japan Epoxy Resin Co., Ltd.), brand name YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), phenol novolac type epoxy resin, brand name YDCN-701 Cresol novolak type epoxy resin (made by Toto Kasei Co., Ltd.), dicyclopentadiene phenol type epoxy resin such as EPICLON HP-7200 (made by Dainippon Ink & Chemicals, Inc.), trade name Epicoat 1032H60 (made by Japan Epoxy Resin Co., Ltd.) Such as trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin such as trade name VG3101M80 (manufactured by Mitsui Chemicals), and tetraphenylolethane type such as trade name Epicoat 1031S (made by Japan Epoxy Resin Co., Ltd.) Xi resin, tetrafunctional epoxy resin such as trade name Denacol EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.), hydrogenated bisphenol A type epoxy resin such as trade name ST-3000 (manufactured by Toto Kasei Co., Ltd.) Glycidyl ester type epoxy resin such as Japan Epoxy Resin Co., Ltd., glycidyl amine type epoxy resin such as trade name YH-434 (manufactured by Tohto Kasei Co., Ltd.), and glyoxal type epoxy resin such as trade name YDG-414 (manufactured by Toto Kasei Co., Ltd.) Examples include alicyclic polyfunctional epoxy compounds such as trade name Epolide GT-401 (manufactured by Daicel Chemical Industries) and trade name EHPE3150 (manufactured by Daicel Chemical Industries), and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC). be able to. Further, if necessary, a trade name Neotote E (manufactured by Toto Kasei Co., Ltd.) can be mixed as an epoxy reactive diluent.

  The blending ratio of the binder epoxy compound and the polyfunctional epoxy compound blended as necessary is 10 to 80 parts by mass of the binder epoxy compound and 10 to 60 parts by mass of the polyfunctional epoxy compound in mass ratio. It is preferable to mix, it is more preferable to mix 20-60 parts by mass of the binder epoxy compound and 20-50 parts by mass of the polyfunctional epoxy compound, and 30-40 parts by mass of the binder epoxy compound. It is particularly preferable to blend the epoxy compound in a proportion of 25 to 35 parts by mass.

<Curing agent>
The thermosetting binder used in the present invention is usually combined with a curing agent. As the curing agent, for example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used.
Specific examples of polycarboxylic anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbaric anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.
Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.

  These curing agents can be used singly or in combination of two or more. The compounding amount of the curing agent used in the present invention is usually in the range of 1 to 100 parts by mass, preferably 100 parts by mass, preferably 100 parts by mass of the component containing the epoxy group (the total amount of the binder epoxy compound and the polyfunctional epoxy compound). Is 5 to 50 parts by mass. If the blending amount of the curing agent is less than 1 part by mass, curing may be insufficient and a tough coating film may not be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 mass parts, there exists a possibility that the adhesiveness with respect to the board | substrate of a coating film may be inferior.

<Catalyst>
In order to improve the hardness and heat resistance of the cured layer, a catalyst that can accelerate the thermosetting reaction between acid and epoxy may be added to the thermosetting binder. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds described in JP-A-4-218561 can be used.
The thermal latent catalyst is usually blended at a ratio of about 0.01 to 10.0 parts by mass with respect to a total of 100 parts by mass of the compound having two or more thermosetting functional groups in one molecule and the curing agent. .

(solvent)
The red resin composition for a color filter according to the present invention contains a solvent in order to disperse the pigment and dissolve the curable binder component. The solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the resin composition and can dissolve or disperse them.
Examples of the solvent used in the resin composition of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate , Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxy Cellosolve acetate solvents such as til acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Ether solvents such as monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene and xylene , Unsaturated hydrocarbon solvents such as naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Organic solvents such as system solvents can be mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

  In particular, when the red resin composition of the present invention is used as an ink-jet ink, the ink viscosity does not increase suddenly and clogging does not occur, and the ejection performance is improved without adversely affecting the straightness and stability of ejection. Therefore, the boiling point is 180 ° C. to 260 ° C., particularly 210 ° C. to 260 ° C., and the vapor pressure at room temperature (especially in the range of 18 ° C. to 25 ° C.) is 0.5 mmHg (66.7 Pa) or less, particularly 0.1 mmHg ( It is preferable to use a solvent component of 13.3 Pa) or less as the main solvent. For example, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, and diethyl succinate. It can be illustrated. The “main solvent” is a solvent that occupies 50% by mass or more of the total amount of the solvent. The main solvent is desirably used in the highest possible mixing ratio, specifically 70% by mass or more, preferably 90% by mass or more.

  While these main solvents are slow to dry, they are excellent in intermittent ejection properties in ink jets. On the other hand, since the drying is slow at the time of coating film formation, there may be a problem in production efficiency. In addition, a lower boiling solvent may be mixed. Other co-solvents preferably used in combination with the main solvent include, for example, glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol diethyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate; diethylene glycol monomethyl ether Glycol oligomer ethers such as diethylene glycol monomethyl ether acetate; glycol oligomer ether esters such as ethyl acetate, aliphatic or aromatic esters such as propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; Alkoxycarboxylic esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; such as ethyl acetoacetate Tricarboxylic acid esters; alcohols or phenols such as ethanol, isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole; alkoxy such as 2-ethoxyethanol and 1-methoxy-2-propanol Examples include alcohols; glycol oligomers such as diethylene glycol and tripropylene glycol; alkoxy alcohol esters such as 2-ethoxyethyl acetate; ketones such as acetone and methyl isobutyl ketone.

(Optional additive)
The red resin composition for a color filter of the present invention may contain various additives as necessary within a range that does not impair the object of the present invention.
For example, as long as the effect of the present invention is not impaired, another pigment derivative may be further contained. Such a pigment derivative is a compound having a role of imparting a functional group to the pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to the pigment at the time of pigment dispersion, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the pigment surface, so that the surface of the pigment has polarity, so that the affinity between the dispersant and the pigment is increased. It is considered that the dispersibility and dispersion stability can be secured.

In addition, examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Among these, surfactants that can be used include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Examples include glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

(Other pigments)
The red resin composition for a color filter of the present invention may contain other pigments as long as the effects of the present invention are not impaired. Examples of other pigments include other red pigments and yellow pigments used to adjust the red resin composition for color filters to a desired color.

  Examples of other red pigments used as other pigments include C.I. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. And CI Pigment Red 265.

  Examples of yellow pigments used as other pigments include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. And CI Pigment Yellow 175.

(Mixing ratio of each component in red resin composition for color filter)
The total content of the pigment and the pigment derivative as a whole, including the crystal precipitation inhibitor precursor and the diketopyrrolopyrrole system, is more preferably 5 to 65% by mass with respect to the total solid content of the red resin composition for color filters. Is preferably blended at a ratio of 10 to 50% by mass. If the amount of the pigment is too small, the transmission density when the red resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) may be insufficient. If the amount of the pigment is too large, There is a risk that the properties as a coating film such as adhesion to the substrate when the red resin composition for color filter is applied and cured on the substrate, surface roughness of the cured film, coating film hardness, etc., Further, since the ratio of the amount of the dispersant used for dispersing the pigment in the red resin composition for a color filter is increased, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the content of the pigment dispersant is not particularly limited as long as the pigment can be uniformly dispersed. For example, 10 to 150 parts by mass with respect to 100 parts by mass of the pigment is used. it can. Furthermore, it is preferable to mix | blend in the ratio of 15-80 mass parts with respect to 100 mass parts of pigments, and it is preferable to mix | blend especially in the ratio of 20-70 mass parts. The total content of the pigment dispersant is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 40% by mass, based on the total solid content of the red resin composition for color filters. Preferably there is. When the content is less than 1% by mass with respect to the total solid content of the red resin composition for color filters, it may be difficult to uniformly disperse the pigment, and when the content exceeds 50% by mass May cause a decrease in curability and developability.
The total amount of the curable binder component is preferably 24 to 94% by mass, and preferably 40 to 90% by mass with respect to the total solid content of the red resin composition for a color filter.
Further, the content of the solvent is not particularly limited as long as the colored layer can be accurately formed. The total amount of the red resin composition for a color filter containing the solvent is usually preferably in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass. When the content of the solvent is within the above range, the coating property can be excellent.

(Manufacture of red resin composition for color filters)
As a method for producing a red resin composition for a color filter, the above-described crystal precipitation inhibitor precursor and diketopyrrolopyrrole pigment, a pigment dispersant, a curable binder component, and various additive components used as desired. Any method can be used as long as it can be uniformly dissolved or dispersed in a solvent, and is not particularly limited, and can be prepared by mixing using a known mixing means.
As a method for preparing the resin composition, for example, (1) the above pigment dispersion, the pigment and the crystal precipitation inhibitor precursor are added to a solvent and dispersed using a disperser, thereby dispersing the pigment dispersion described above. After preparing the liquid, a method of adding and mixing the curable binder component and various additive components used as desired, and (2) adding the above pigment dispersant and pigment to the solvent, (1), after adding a crystal precipitation inhibitor precursor, creating a pigment dispersion, and adding and mixing a curable binder component and various additive components used as desired. 3) A method in which the above-mentioned pigment, a crystal precipitation inhibitor precursor, a pigment dispersant, a curable binder component, and various additive components used as desired are simultaneously charged and mixed in a solvent, and (4) Face above in solvent A dispersant, a curable binder component, was added and various additive components optionally used, were mixed, and the like method of mixing this was added pigment and crystallization inhibitor precursors.
Among these methods, the method (1) is preferable from the viewpoint that the aggregation of the pigment can be effectively prevented and the pigment can be uniformly dispersed.

[Color filter manufacturing method]
A method for producing a color filter according to the present invention is a method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
Forming a red resin composition layer on the transparent substrate using the red resin composition for a color filter of the present invention;
The red resin composition layer is used as a crystal precipitation inhibitor represented by the following chemical formula (4) by desorbing B ¹ and / or B ² in the crystal precipitation inhibitor precursor represented by the chemical formula (1). And a step of forming a red colored layer.

（化学式（４）中、Ａ^１は、塩素原子、臭素原子、メチル基、スルホ基、又はフェニル基を表し、ｍは０〜５の整数を表し、ｍが２以上の整数の場合、複数のＡ^１は、それぞれ同一であっても異なっていてもよい。ＰＣｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい縮合環基、又は、下記化学式（３）で表される多環式化合物基である。）

(In the chemical formula (4), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of A ¹ may be the same as or different from each other, and PCy may have a substituent, a condensed ring group that may contain a hetero atom, or a group represented by the following chemical formula (3). A polycyclic compound group.)

（化学式（３）中、Ｘは、直接結合又はメチレン基を表し、Ｃｙは、置換基を有していてもよく、ヘテロ原子を含んでいてもよい環式化合物基を表し、ｎは、１〜５の整数を表し、ｎが２以上の整数の場合、複数のＸ−Ｃｙは、それぞれ同一であっても異なっていてもよい。Ａ^２は、塩素原子、臭素原子、メチル基、又はスルホ基を表し、ｎ’は０〜４の整数を表し、ｎ’が２以上の整数の場合、複数のＡ^２は、それぞれ同一であっても異なっていてもよい。但し、ｎ＋ｎ’は１〜５の整数である。）

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.)

  Each symbol in the chemical formula (4) is the same as that in the chemical formula (1).

According to the method for producing a color filter of the present invention, by heating or exposing the red resin composition layer, the pigment precipitation inhibitor precursor B ¹ and / or B ² represented by the chemical formula (1) is obtained. Since it is detached and the crystal precipitation inhibitor represented by the chemical formula (4) is generated, precipitation of pigment aggregates on the surface of the colored layer (coating film) can be suppressed during the high-temperature heating process in the color filter manufacturing process. A colored layer having a high contrast and a small phase difference can be obtained.

It is during pre-baking that B ¹ and / or B ² in the crystal precipitation inhibitor precursor represented by the chemical formula (1) is eliminated and the crystal precipitation inhibitor represented by the chemical formula (4) is generated. Although it may be at the time of post-baking or at the time of exposure, it is preferable that a crystal precipitation inhibitor is generated at the time of post-baking from the viewpoint of efficiently suppressing the precipitation of the pigment.

As a method for producing such a color filter of the present invention, for example, a step of forming a red resin composition layer on a transparent substrate using the red resin composition for a color filter, and the red resin composition layer And a step of exposing through a mask and a step of developing and heating the red resin composition layer after the exposure to form a red colored layer having a predetermined pattern. A method for producing a color filter, a step of selectively attaching the red resin composition for a color filter to a predetermined region on a transparent substrate by an inkjet method to form a red resin composition layer, and the red resin composition And a step of curing the layer by heating to form a red colored layer having a predetermined pattern. Method for producing a filter can be preferably used.
Hereinafter, a method for manufacturing a color filter by a photolithography method and a method for manufacturing a color filter by an inkjet method will be described in order.

(Color filter manufacturing method by photolithography)
When manufacturing a color filter by a photolithographic method, let the red resin composition for color filters of the said this invention be the photosensitive resin composition using the said photocurable binder component. First, the red resin composition for a color filter is applied on a transparent substrate described later using an application means such as a spin coat method to form a wet coating film.
Next, after drying the red resin composition layer using a hot plate or oven, the layer is exposed to light through a mask having a predetermined pattern. It is made to photopolymerize and it is set as the cured film of a red resin composition. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the red resin composition for color filter to be used, the thickness of the coating film, and the like.

Next, the red resin composition layer after exposure is developed using a developer, and unexposed portions are dissolved and removed, thereby forming a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development processing, the developer is usually washed and the cured film having a predetermined pattern of the red resin composition for color filter is dried. In addition, it is preferable to heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to a curable binder component, it selects suitably. As described above, a red colored layer having a predetermined pattern is formed. Other colored layers can be formed in the same manner.

(Inkjet color filter manufacturing method)
When producing a color filter by an inkjet method, first, a resin composition for a color filter is prepared which contains the red resin composition for a color filter of the present invention and, if necessary, a pigment for each color. Then, a color filter resin composition of a corresponding color is selectively attached to the colored layer forming region of each color defined by the pattern of the light-shielding portion on the surface of the transparent substrate to form an ink layer. . In addition, when the red resin composition manufactured by this invention is used, the said ink layer corresponds to a red resin composition layer. In this ink spraying process, the red resin composition for a color filter of the present invention uses a soluble crystal precipitation inhibitor precursor, so that it does not easily increase in viscosity at the tip of the inkjet head, and has good ejection properties. maintain. The inkjet method can also spray the resin composition for each color filter on the substrate at the same time using a plurality of heads, so that the working efficiency is higher than when a colored layer is formed for each color by a method such as printing. Can be improved.
Next, the ink layer of each color is dried and prebaked as necessary, and then cured by heating or exposure as appropriate. When the ink layer is appropriately heated or exposed, the crosslinking element of the curable resin contained in the color filter resin composition of each color causes a crosslinking reaction, and each ink layer is cured to form a colored layer. As described above, a red colored layer having a predetermined pattern is formed.

<Color filter>
The color filter obtained by the production method of the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram illustrating an example of a color filter manufactured by a photolithography method, and FIG. 2 is a schematic diagram illustrating an example of a color filter manufactured by an ink jet method. According to FIGS. 1 and 2, the color filter 10 obtained by the manufacturing method of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
If the colored layer in the color filter obtained by the method for producing a color filter of the present invention includes a red colored layer formed by curing using the above-described red resin composition for a color filter of the present invention, in particular, Although it is not limited, it is usually formed of a colored pattern that is formed in an opening of a light shielding part on a transparent substrate, which will be described later, and includes three or more colored layers.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the red resin composition for a color filter, but is usually preferably in the range of 1 to 5 μm.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the light-shielding part can be formed by any method that can pattern the light-shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method and the like using a resin composition for a color filter for a light shielding part can be exemplified.

  In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

  In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the red resin composition for a color filter for a light-shielding part containing a black colorant and a photosensitive resin, and further, a sensitizer and an improved coatability as necessary. An agent, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be added.

  On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Method, printing method and the like.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and 0.5 to 3.0 μm in the case where the black colorant is dispersed or dissolved in the binder resin. Set by degree.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

  The color filter obtained by the production method of the present invention has high contrast and can be suitably used for various display devices. Among them, the color filter obtained by the production method of the present invention has a small phase difference and can be suitably used particularly for a liquid crystal display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

(Comparative Synthesis Example 1: Synthesis of Pigment Derivative A)
While maintaining 5 ° C. or less in 320 g of 98.5% concentrated sulfuric acid, 1.02 g of paraformaldehyde and 5.00 g of phthalimide were alternately added over 10 minutes and stirred at 5 ° C. or less for 1 hour. Subsequently, 8.0g of PR255 (CI pigment red 255) was added over 10 minutes, keeping at 5 degrees C or less, and it stirred at 2-5 degrees C for 6 hours. The reaction mixture was poured into ice water (ice 870 g, water 450 g), stirred for 30 minutes, and the precipitate was filtered off. The obtained wet cake was washed with warm water of 40 to 60 ° C. and filtered, and this was repeated until the pH of the filtrate became 2 or more. The finally obtained wet cake was dried with a vacuum dryer at 80 ° C. to obtain pigment derivative A represented by the following chemical formula (7). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 1: Synthesis of Crystal Precipitation Inhibitor Precursor A)
To 100 ml of tetrahydrofuran, 4.07 g of pigment derivative A obtained in Comparative Synthesis Example 1 was added and stirred at room temperature. To this suspension, 0.17 g of dimethylaminopyridine and 11.19 g of di-tert-butyl dicarbonate were added, and the solution was stirred overnight at room temperature. The solvent of the obtained orange brown solution was distilled off, washed with n-hexane and filtered. It dried with the 80 degreeC vacuum dryer, and obtained the crystal precipitation inhibitor precursor A (yellowish brown crystal | crystallization) (n = 1 included) represented by following Chemical formula (8). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 2: Synthesis of Crystal Precipitation Inhibitor Precursor B)
To 100 ml of tetrahydrofuran, 4.07 g of pigment derivative A obtained in Comparative Synthesis Example 1 was added, and 0.17 g of dimethylaminopyridine was added to this suspension. In 100 ml of tetrahydrofuran, 1.98 g of di-tert-butyl dicarbonate was dissolved, and this was slowly added dropwise over 30 minutes and stirred overnight at room temperature. The solvent of the resulting fluorescent orange brown solution was distilled off, washed with n-hexane and filtered. It dried with the 80 degreeC vacuum dryer, and obtained the crystal precipitation inhibitor precursor B (brown crystal | crystallization) (n = 1 included) represented by following Chemical formula (9). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 3: Synthesis of Crystal Precipitation Inhibitor Precursor C)
In Synthesis Example 1, the same operation as in Synthesis Example 1 was carried out except that 8.85 g of diethyl dicarbonate was used instead of di-tert-butyl dicarbonate, and a crystal precipitation inhibitor represented by the following chemical formula (10) Precursor C (including n = 1) was obtained. The molecular weight of the target product was confirmed by TOF-MS.

(Comparative Synthesis Example 2: Synthesis of pigment derivative B)
28.8 g of PR255 was added to 315 g of 96% sulfuric acid at 35 ° C. 9.6 g of 3,5-dimethyl-pyrazole was added at 40 ° C. or lower, and then 3.0 g of paraformaldehyde was gradually added. The mixture was stirred at 40 ° C. for 2 hours, poured into 1500 ml of ice water, and stirred for 1 hour. The precipitate was filtered off and washed with warm water. The wet cake was vacuum-dried at 80 degrees to obtain pigment derivative B (red crystals) (including n = 1) represented by the following chemical formula (11). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 4: Synthesis of Crystal Precipitation Inhibitor Precursor D)
In Synthesis Example 1, instead of Pigment Derivative A, the same operation as in Synthesis Example 1 was performed except that 3.60 g of Pigment Derivative B obtained in Comparative Synthesis Example 2 was used. As a result, a crystal precipitation inhibitor precursor D (including n = 1) was obtained. The molecular weight of the target product was confirmed by TOF-MS.

(Comparative Synthesis Example 3: Synthesis of Pigment Derivative C)
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 15.07 parts of 1- (4-cyanophenyl) -2,5-dimethylpyrrole was added to the alkoxide, and 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was added to the alkoxide solution heated to 100 ° C. 17.7 parts were gradually added. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain pigment derivative C (including n = 1) represented by the following chemical formula (13). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 5: Synthesis of Crystal Precipitation Inhibitor Precursor E)
In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that 3.47 g of Pigment Derivative C obtained in Comparative Synthesis Example 3 was used instead of Pigment Derivative A, and represented by the following chemical formula (14). A crystal precipitation inhibitor precursor E (including n = 1) was obtained. The molecular weight of the target product was confirmed by TOF-MS.

(Comparative Synthesis Example 4: Synthesis of Pigment Derivative D)
In Synthesis Example 1, C.I. I. Except having used 2.62g of pigment red 255, it carried out similarly to the synthesis example 1, and obtained the pigment derivative D represented by following Chemical formula (15). The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 1: Preparation of dispersant / binder resin solution)
3. In a 225 mL mayonnaise bottle, 66.9 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), pigment dispersant (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 135 mgKOH / g, solid content 60% by mass) 83 parts by mass and 14.7 parts by mass of the binder resin A were dissolved. To the mixed solution, 0.3 part by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.3 molar equivalent with respect to the tertiary amino group of the block copolymer) is added and stirred at room temperature for 30 minutes. Thus, a dispersant / binder resin solution was prepared.
The pigment dispersant (trade name: BYK-LPN6919, manufactured by Big Chemie) is composed of a repeating unit (1) represented by the above general formula (I) and a repeating unit represented by the above general formula (II) ( 2). Furthermore, in Production Example 1, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

Example 1
(1) Preparation of pigment dispersion liquid To 84 parts by mass of the dispersant / binder resin solution prepared in Production Example 1, C.I. I. Pigment Red 254 (average primary particle size 30 nm) 15.36 parts by mass and 0.64 parts by mass of the crystal precipitation inhibitor precursor A obtained in Synthesis Example 1 were mixed, and 2 mm zirconia was applied using a paint shaker (manufactured by Asada Tekko). The pigment dispersion liquid of Example 1 was obtained by dispersing with beads for 1 hour and further with 0.1 mm zirconia beads for 24 hours.

(2) Preparation of red resin composition for color filter 59.6 parts by mass of pigment dispersion A obtained above and alkali-soluble resin (binder resin A, solid content 44% by mass) 2.49 parts by mass, 3-4 1.87 parts by mass of functional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.), photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1 -On (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) 0.26 parts by mass, photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- 1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) 0.58 parts by mass, photosensitizer: 2,4 diethylthioxanthone (product) Name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) 0.20 parts by mass, solvent: 40.4 parts by mass of a binder composition consisting of 35.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) Then, pressure filtration was performed to obtain a red resin composition for a color filter of Example 1.

(Examples 2-5, Comparative Examples 1-5)
In Example 1, instead of the crystal precipitation inhibitor precursor A obtained in Synthesis Example 1, the crystal precipitation inhibitors B to E obtained in Synthesis Examples 2 to 5 and Comparative Synthesis Examples 1 to 4 were obtained. The same operations as in Example 1 were performed except that pigment derivatives A to D were used, respectively, to obtain red resin compositions for color filters of Examples 2 to 5 and Comparative Examples 1 to 4. Moreover, in Example 1, except having not used the crystal precipitation inhibitor precursor A obtained in Synthesis Example 1, the same operation as in Example 1 was performed to obtain a red resin composition for a color filter of Comparative Example 5. It was.

[Dispersibility / storage stability evaluation]
For the pigment dispersions obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the shear viscosity at a shear rate of 60 rpm was measured immediately after dispersion and after standing at 40 ° C. for 1 week, respectively. For the viscosity measurement, “MCR301” manufactured by Nippon Siebel Hegner Co., Ltd. was used.
The results are shown in Table 1.

[Evaluation of brightness and contrast]
Each of the red resin compositions for color filters of Examples 1 to 5 and Comparative Examples 1 to 5 was used on a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. And applied. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (red colored layer) was obtained by irradiating ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity x = 0.653. The glass plate on which the red colored layer was formed was post-baked for 30 minutes in a 230 ° C. clean oven to obtain a red colored substrate. The contrast, chromaticity (x, y) and luminance (Y) of the substrate before and after post-baking were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectral light measuring device OSP-SP200” manufactured by Olympus Corporation.
The contrast retention was calculated by the following formula from the contrast before post-baking and the contrast after post-baking. The results are shown in Table 2.

［位相差の評価］
着色層の位相差は、以下の式で計算される厚み方向のリタデーション（Ｒｔｈ）を指標とした。
リタデーション（Ｒｔｈ）は、位相差層測定装置（ＡＸＯＭＥＴＲＩＣＳ社製Ａｘｏｓｃａｎ^ＴＭ Ｍｕｅｌｌｅｒ Ｍａｔｒｉｘ Ｐｏｌａｒｉｍｅｔｅｒ）を用い、赤色着色層の測定波長は６２０ｎｍで測定した。結果を表１に示す。
Ｒｔｈ＝（（Ｎｘ＋Ｎｙ）／２−Ｎｚ）ｄ
Ｎｘ：面内遅相軸方向の屈折率
Ｎｙ：面内進相軸方向の屈折率
Ｎｚ：厚み方向の屈折率
ｄ：膜厚（ｎｍ）

[Evaluation of phase difference]
The retardation of the colored layer was determined using the retardation in the thickness direction (Rth) calculated by the following formula as an index.
Retardation (Rth) was measured using a retardation layer measuring device (Axoscan ^™ Mueller Matrix Polarimeter manufactured by AXOMETRICS) at a measurement wavelength of 620 nm. The results are shown in Table 1.
Rth = ((Nx + Ny) / 2−Nz) d
Nx: Refractive index in the in-plane slow axis direction Ny: Refractive index in the in-plane fast axis direction Nz: Refractive index in the thickness direction d: Film thickness (nm)

[Evaluation of heat resistance]
The red resin compositions for color filters of Examples 1 to 5 and Comparative Examples 1 to 5 were each applied on a glass substrate having a thickness of 0.7 mm using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer to obtain a red colored substrate having a pattern formed thereon.
The red colored substrate on which the pattern was formed was post-baked for 30 minutes in a clean oven at 230 ° C., and further post-baked for 30 minutes in a clean oven at 260 ° C., and the presence or absence of precipitation of pigment aggregates was confirmed on the pattern coating film. . The results are shown in Table 1.
(Heat resistance evaluation criteria)
(Double-circle): It did not precipitate.
○: Slightly precipitated.
Δ: Precipitated.
X: It considerably precipitated.

[Summary of results]
The red colored layer formed using the red resin composition for a color filter of Comparative Example 5 which does not contain a crystal precipitation inhibitor precursor and a crystal precipitation inhibitor has a small phase difference, but a pigment aggregate during the heating process. Precipitated considerably, the contrast retention was low, and the contrast was low.
Since the red colored layer of Comparative Example 4 containing Pigment Derivative D that produces a pigment by heating does not contain a crystal precipitation inhibitor, like in Comparative Example 5, a pigment aggregate precipitates, and the contrast retention rate Was low and the contrast was low.
Although the red colored layer formed from the red resin composition for a color filter of Comparative Example 1 containing the pigment derivative A which is a crystal precipitation inhibitor is improved in heat resistance as compared with Comparative Examples 4 and 5, The phase difference has increased.
The red colored layer formed from the red resin composition for color filter of Examples 1 to 3 containing the crystal precipitation inhibitor precursor that produces the pigment derivative A by heating is Comparative Example 1 containing the pigment derivative A in advance. It was revealed that the heat resistance was further improved, the contrast retention was high, the contrast was improved, and the phase difference was difficult to increase as compared with the red colored layer.
When comparing Comparative Example 2 containing pigment derivative B, which is another crystal precipitation inhibitor, and Example 4 containing crystal precipitation inhibitor precursor D that produces pigment derivative B by heating, When comparing Comparative Example 3 containing pigment derivative C, which is another crystal precipitation inhibitor, and Example 5 containing crystal precipitation inhibitor precursor E that produces pigment derivative C by heating, It has been clarified that the use of the crystal precipitation inhibitor precursor has a higher contrast retention rate, the contrast is improved, and the phase difference is less likely to increase than when the crystal precipitation inhibitor itself is used.
From the above results, by using the crystal precipitation inhibitor precursor according to the present invention, it is possible to suppress the precipitation of pigment aggregates on the surface of the colored layer during the high-temperature heating process in the color filter manufacturing process, and the high contrast of the color filter. It has been clarified that the increase in the retardation of the colored layer can be suppressed.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter

Claims (9)

A crystal precipitation inhibitor precursor represented by the following chemical formula (1).

(In the chemical formula (1), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of a ¹ is good .B ¹ and B ² be different even in the same, respectively, each independently, a hydrogen atom, or a group represented by the following chemical formula (2), the B ¹ and B ² At least one is a group represented by the following chemical formula (2): PCy is a condensed ring group which may have a substituent and may contain a hetero atom, or the following chemical formula (3). It is a polycyclic compound group represented.)

(In the chemical formula (2), R ¹ represents a hydrocarbon group which may have a substituent.)

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.) The crystal precipitation inhibitor precursor according to claim 1, wherein B ¹ and B ² in the chemical formula (1) are groups represented by the chemical formula (2).   A pigment dispersion comprising the crystal precipitation inhibitor precursor according to claim 1, a diketopyrrolopyrrole pigment, a pigment dispersant, and a solvent.   The pigment dispersion liquid according to claim 3, wherein the crystal precipitation inhibitor precursor is 0.5 to 20 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment.   A red resin composition for a color filter, comprising the crystal precipitation inhibitor precursor according to claim 1, a diketopyrrolopyrrole pigment, a pigment dispersant, a curable binder component, and a solvent.   The red resin composition for a color filter according to claim 5, wherein the crystal precipitation inhibitor precursor is 0.5 to 20 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment. A method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
Forming a red resin composition layer on the transparent substrate using the red resin composition for a color filter according to claim 5;
The red resin composition layer is used as a crystal precipitation inhibitor represented by the following chemical formula (4) by desorbing B ¹ and / or B ² in the crystal precipitation inhibitor precursor represented by the chemical formula (1). And a step of forming a red colored layer.

(In the chemical formula (4), A ¹ represents a chlorine atom, a bromine atom, a methyl group, a sulfo group, or a phenyl group, m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of A ¹ may be the same as or different from each other, and PCy may have a substituent, a condensed ring group that may contain a hetero atom, or a group represented by the following chemical formula (3). A polycyclic compound group.)

(In the chemical formula (3), X represents a direct bond or a methylene group, Cy represents a cyclic compound group which may have a substituent and may contain a hetero atom, and n represents 1 Represents an integer of ˜5, and when n is an integer of 2 or more, the plurality of X-Cy groups may be the same or different, and A ² represents a chlorine atom, a bromine atom, a methyl group, or a sulfo group. Represents a group, and n ′ represents an integer of 0 to 4, and when n ′ is an integer of 2 or more, a plurality of A ² may be the same or different, provided that n + n ′ is 1 to (It is an integer of 5.) Forming a red resin composition layer on the transparent substrate using the red resin composition for a color filter according to claim 5;
Exposing the red resin composition layer through a mask;
The method for producing a color filter according to claim 7, further comprising: developing and heating the red resin composition layer after the exposure to form a red colored layer having a predetermined pattern. A step of selectively attaching the red resin composition for a color filter according to claim 5 or 6 to a predetermined region on a transparent substrate by an inkjet method to form a red resin composition layer;
The method for producing a color filter according to claim 7, further comprising a step of curing the red resin composition layer by heating to form a red colored layer having a predetermined pattern.

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