TW201802592A - Color resin composition for color filter, pigment dispersion liquid, color filter and display device - Google Patents

Abstract

The present invention provides a color resin composition for a color filter, which can form a red pixel that satisfies a specific chromaticity and a specific retardation. Disclosed is a color resin composition for a color filter, the composition comprising: a pigment containing a red pigment represented by the following general formula (1); a dispersant containing a copolymer having a constitutional unit represented by the following general formula (2); a pigment derivative; an alkali soluble resin; a monomer, an initiator; and a solvent, wherein the pigment derivative contains one or more selected from a pigment derivative having a diketopyrrolopyrrole skeleton and a pigment derivative having an azo lake skeleton, and when a color layer of the color resin composition is formed, a chromaticity (x, y) of the color layer measured by a C light source satisfies 0.630 ≤ x ≤ 0.665 and 0.326 ≤ y ≤ 0.335, and a retardation (Rth) of a light with a wavelength of 620 nm in a thickness direction of the color layer, is -30 nm or more and 120 nm or less: (the symbols in the formulae are as disclosed in the specification.).

Description

Colored resin composition for color filter, pigment dispersion, color filter, and display device

The present invention relates to a colored resin composition for a color filter, a pigment dispersion liquid, a color filter, and a display device.

In recent years, with the development of personal computers and the development of personal computers for mobile use, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablets) has also increased, and the market for liquid crystal displays has been expanding. Further, recently, an organic light-emitting display device such as an organic EL display which is highly self-illuminating and has high visibility is also a highly anticipated new-generation image display device. In view of the performance of these image display devices, it is strongly expected that the contrast and color reproducibility are improved to further improve the image quality and reduce the power consumption.

Conventional display devices are mostly sRGB (IEC61966-2-1) according to the international standard for color space. However, the demand for display devices that correspond to Adobe RGB having a wider color reproduction area than sRGB is being demanded because it is closer to the performance of the object and requires further enhancement of color reproducibility. The AdobeRGB specification is defined by the color space advocated by Adobe Systems, and the three primary colors of AdobeRGB are defined for the chromaticity coordinates x and y of the XYZ chromaticity system as follows. The AdobeRGB specification is characterized by a width in the green direction compared to the sRGB specification. Wide color reproduction area.

Red: x=0.64; y=0.34

Green: x=0.21; y=0.71

Blue: x=0.15; y=0.06

Furthermore, a corresponding specification of DCI (Digital Cinema Initiatives) specifications having a wide color reproduction area in the red and green directions is also required as compared with sRGB.

Here, the color filter used in the liquid crystal display device is generally provided with: a substrate; a coloring layer formed on the substrate and composed of a color pattern of three primary colors of red, green, and blue; and a method of distinguishing each coloring pattern a light blocking portion on the substrate.

The formation method of such a coloring layer is known, for example, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like. Among them, a pigment dispersion method having an average excellent characteristic is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

In the red pigment, a pyrrolopyrroledione pigment excellent in heat resistance and light resistance (for example, Patent Documents 1 to 3) is widely used.

On the other hand, a specific problem of the liquid crystal display device is a problem of dependence of viewing angle due to refractive index anisotropy of the liquid crystal cell and the polarizing plate. The problem of the dependence of the viewing angle is a problem in which the color tone and contrast of the image to be viewed change when the liquid crystal display device is viewed from the front and when viewed from the oblique direction. The problem of such viewing angle characteristics has become more important with the large screen of liquid crystal display devices in recent years.

In order to improve the problem of such viewing angle dependence, a method of assembling a retardation film in a liquid crystal display device has been widely used. However, since the color filters used in the liquid crystal display device have different phase differences depending on the color patterns of the respective colors of the colored layer, When the retardation film described above is used, there is a problem that the difference in phase difference between the coloring patterns of the respective colors cannot be compensated, and it is difficult to completely solve the problem of the dependence of the viewing angle.

The color filter for liquid crystal display disclosed in Patent Document 4 is a color filter in which at least a red pixel, a green pixel, and a blue pixel are disposed on a transparent substrate; wherein the green pixel is composed of a retardation adjusting agent A cured product of the colored composition is formed. However, the technique of Patent Document 4 causes the concentration of the pigment in the pixel to decrease, and the target color tone cannot be achieved.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2013-14750

Patent Document 2: International Publication No. 2012/102399

Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-155232

Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-185985

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a colored resin composition for a color filter which can form a red pixel which satisfies a specific chromaticity and a specific phase difference, and a pigment dispersion liquid for preparing the colored resin composition, A color filter that satisfies a specific chromaticity and a specific phase difference, and a display device using the color filter.

The colored resin composition for a first color filter of the present invention contains a pigment containing a red pigment represented by the following general formula (1), and contains the following general formula (2); a dispersant, a pigment derivative, an alkali-soluble resin, a monomer, a starter, and a solvent which constitute a copolymer of the unit; wherein The pigment derivative contains one or more selected from the group consisting of a pigment derivative having a pyrrolopyrroledione skeleton and a pigment derivative having an azo lake skeleton; When the coloring layer of the colored resin composition is formed, the chromaticity (x, y) of the colored layer measured by the C light source satisfies 0.630 ≦ x ≦ 0.665, 0.326 ≦ y ≦ 0.335, and the light is in the thickness direction of the colored layer. The optical phase difference (Rth) at a wavelength of 620 nm is -30 nm or more and 120 nm or less.

(一般式(1)中，R¹及R²係各自獨立為4-氯苯基或4-溴苯基。)

(In the general formula (1), R ¹ and R ² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

(一般式(2)中，R¹¹係表示氫原子或甲基；Q係表示2價連接基；R¹²係表示碳數1~8之伸烷基、依 -[CH(R¹⁵)-CH(R¹⁶)-O]_x-CH(R¹⁵)-CH(R¹⁶)-或-[(CH₂)_y-O]_z-(CH₂)_y-所示之2價有機基；R¹³及R¹⁴係各自獨立表示亦可被取代的鏈狀或環狀烴基、或R¹³與R¹⁴相互鍵結形成環狀結構。R¹⁵及R¹⁶係各自獨立為氫原子或甲基。

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure, and each of R ¹⁵ and R ¹⁶ is independently a hydrogen atom or a methyl group.

The x system represents an integer from 1 to 18, the y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18. )

The colored resin composition for a second color filter of the present invention contains a pigment containing the red pigment represented by the above general formula (1), a dispersant containing a copolymer having the structural unit represented by the above general formula (2), a pigment derivative, an alkali-soluble resin, a monomer, a starter, and a solvent; wherein the pigment derivative is derived from a pigment derivative having a pyrrolopyrroledione skeleton and a pigment having an azo lake skeleton One or more selected from the above; the pigment further contains one or more pigments selected from the group consisting of a red pigment, an orange pigment, and a yellow pigment different from the red pigment shown in the above general formula (1); In the coloring layer of the colored resin composition, the chromaticity (x, y) of the colored layer measured by the C light source satisfies 0.630 ≦ x ≦ 0.665, 0.295 ≦ y ≦ 0.360, and the wavelength of light in the thickness direction of the colored layer is 620 nm. The light phase difference (Rth) is -30 nm or more and 120 nm or less.

The colored resin composition for a color filter of the present invention preferably has a block portion having a structural unit represented by the above general formula (2) from the viewpoints of pigment dispersibility and dispersion stability. And a block portion having a structural unit represented by the following general formula (3); the structural unit represented by the above general formula (3) contains from methacrylic acid, 2-hydroxyethyl methacrylate, and methyl group One or more constituent units selected from the group consisting of benzyl acrylate.

(一般式(3)中，R²¹係氫原子或甲基；Q'係直接鍵結或2價連接基；R²²係烴基、-[CH(R²³)-CH(R²⁴)-O]_x-R²⁵或-[(CH₂)_y-O]_z-R²⁵所示1價基。R²³及R²⁴係各自獨立為氫原子或甲基；R²⁵係氫原子、烴基、-CHO、-CH₂CHO、或-CH₂COOR²⁶所示1價基；R²⁶係氫原子或碳數1~5之烷基。

(In general formula (3), R ²¹ is a hydrogen atom or a methyl group; Q' is a direct bond or a divalent linking group; R ²² is a hydrocarbon group, -[CH(R ²³ )-CH(R ²⁴ )-O] _X- R ²⁵ or -[(CH ₂ ) _y -O] _z -R ²⁵ represents a monovalent group. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group; R ²⁵ is a hydrogen atom, a hydrocarbon group, -CHO And a monovalent group represented by -CH ₂ CHO or -CH ₂ COOR ²⁶ ; and a hydrogen atom of R ²⁶ or an alkyl group having 1 to 5 carbon atoms.

The above hydrocarbon group may have a substituent.

The x system represents an integer from 1 to 18, the y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18. )

In the colored resin composition for a color filter of the present invention, the red pigment represented by the above general formula (1) preferably contains the following chemical formula (1-1) from the viewpoint of satisfying a desired color tone and phase difference. The red pigment and the red pigment represented by the following chemical formula (1-2) are shown.

[Chemical 5]

In the colored resin composition for a color filter of the present invention, the alkali-soluble resin preferably contains a polyamidoquinone imine resin having a carboxyl group from the viewpoint of easily reducing the absolute value of the phase difference.

The colored resin composition for a color filter of the present invention preferably has a void from the inside of the colored layer and suppresses color unevenness due to light diffused reflection when the colored layer is viewed obliquely. It contains at least two lanthanide initiators, and more preferably contains an antioxidant.

Further, the colored resin composition for a second color filter of the present invention preferably contains the CI pigment yellow from the viewpoint of satisfying a desired color tone and phase difference and easily reducing the absolute value of the phase difference. 185.

The pigment dispersion liquid of the present invention contains a pigment containing the red pigment represented by the above general formula (1), a dispersant containing a copolymer of the structural unit represented by the above general formula (2), a pigment derivative, and a solvent; In addition, the pigment derivative is one or more selected from the group consisting of a pigment derivative having a pyrrolopyrroledione skeleton and a pigment derivative having an azo lake skeleton.

The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate; wherein at least one of the colored layers is a color filter according to any one of claims 1 to 5. A cured product of a colored resin composition is used.

Furthermore, the display device provided by the present invention is characterized in that the color is provided Filter.

According to the present invention, it is possible to provide a colored resin composition for a color filter which can form a red pixel which satisfies a specific chromaticity and a specific phase difference, and a pigment dispersion liquid for preparing the colored resin composition, which satisfy a specific chromaticity and a specific phase A poor color filter and a display device using the color filter.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of a display device of the present invention.

Fig. 3 is a schematic cross-sectional view showing another example of the display device of the present invention.

In the following, the colored resin composition for a color filter of the present invention, the pigment dispersion liquid for coloring the coloring resin composition for color filter, the color filter, and the display device will be described in detail in order.

Further, in the present invention, the light system covers electromagnetic waves of wavelengths of visible and non-visible regions, and radiation, and the radiation system covers, 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, the "(meth)acrylyl group" means a propylene group and a methacryl group, respectively, and the "(meth)acrylate" means an acrylate and a methacrylate, respectively.

[Colored resin composition for color filter]

The colored resin composition for a first color filter of the present invention contains a pigment containing a red pigment represented by the following general formula (1), and contains a composition represented by the following general formula (2). a coloring resin composition of a dispersant, a pigment derivative, an alkali-soluble resin, a monomer, a starter, and a solvent of a copolymer of the unit, wherein the pigment derivative contains a pigment having a pyrrolopyrroledione skeleton One or more selected from the group consisting of a derivative and a pigment derivative having an azo lake skeleton; and the chromaticity (x, y) measured by the C light source when the colored layer of the colored resin composition is formed It is 0.630 ≦ x ≦ 0.665 and 0.326 ≦ y ≦ 0.335, and the optical phase difference (Rth) of light having a wavelength of 620 nm in the thickness direction of the colored layer is -30 nm or more and 120 nm or less.

(一般式(1)中，R¹及R²係各自獨立為4-氯苯基或4-溴苯基。)

(In the general formula (1), R ¹ and R ² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

(一般式(2)中，R¹¹係表示氫原子或甲基；Q係表示2價連接基；R¹²係表示碳數1~8之伸烷基、依 -[CH(R¹⁵)-CH(R¹⁶)-O]_x-CH(R¹⁵)-CH(R¹⁶)-或-[(CH₂)_y-O]_z-(CH₂)_y-所示之2價有機基；R¹³及R¹⁴係各自獨立表示亦可被取代的鏈狀或環狀烴基、或由R¹³與R¹⁴相互鍵結形成環狀結構。R¹⁵及R¹⁶係各自獨立為氫原子或甲基。

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group.

The x system represents an integer from 1 to 18, the y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18. )

In addition, the colored resin composition for a second color filter of the present invention contains a pigment containing the red pigment represented by the above general formula (1) and a copolymer containing the constituent unit represented by the above general formula (2). a coloring resin composition of a dispersing agent, a pigment derivative, an alkali-soluble resin, a monomer, a starter, and a solvent, wherein the pigment derivative contains a pigment derivative having a pyrrolopyrroledione skeleton, and One or more selected from the group consisting of pigment derivatives having an azo lake skeleton; the pigment further containing a red pigment, an orange pigment, and a yellow pigment different from the red pigment represented by the above general formula (1) One or more kinds of pigments; when the coloring layer of the colored resin composition is formed, the chromaticity (x, y) of the colored layer measured by the C light source satisfies 0.630 ≦ x ≦ 0.665, 0.295 ≦ y ≦ 0.360, and The optical phase difference (Rth) of light at a wavelength of 620 nm in the thickness direction of the colored layer is -30 nm or more and 120 nm or less.

According to the present invention, a red pigment represented by the above general formula (1), a dispersant containing a copolymer having the structural unit represented by the above general formula (2), and a specific pigment derivative are used in combination, in the general formula. (1) In the dispersion step of the red pigment shown, the specific pigment derivative is adsorbed on the surface of the finely pigmented pigment to improve the affinity between the nitrogen atom in the constituent unit represented by the general formula (2) of the dispersant. Properties, which are excellent in both pigment dispersibility and dispersion stability, when forming the coloring layer of the colored resin composition, The chromaticity (x, y) measured by the C light source satisfies 0.630 ≦ x ≦ 0.665 and 0.326 ≦ y ≦ 0.335, and the optical phase difference (Rth) of light at a wavelength of 620 nm in the thickness direction of the colored layer becomes -30 nm or more. And 120 nm or less, or the chromaticity (x, y) measured by the C light source of the above colored layer satisfies 0.630 ≦ x ≦ 0.665, 0.295 ≦ y ≦ 0.360, and the optical phase difference of light at a wavelength of 620 nm in the thickness direction of the colored layer (Rth) ) is -30 nm or more and 120 nm or less.

The colored resin composition for a color filter of the present invention contains at least a pigment, a dispersant, an alkali-soluble resin, a monomer, a starter, and a solvent, and can be further improved without impairing the effects of the present invention. Contains other ingredients. Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail in order.

<pigment>

(一般式(1)中，R¹及R²係各自獨立為4-氯苯基或4-溴苯基。) In the present invention, the pigment contains at least the red pigment represented by the following general formula (1):

(In the general formula (1), R ¹ and R ² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

Since the colored resin composition for a color filter of the present invention contains the above specific pigment, a colored layer having a specific chromaticity and a specific phase difference can be formed.

The red pigment represented by the above general formula (1) is specifically exemplified by the following The red pigments of the formula (1-1) to the chemical formula (1-3) may be used alone or in combination of two or more.

In the present invention, from the viewpoint of adjusting the chromaticity and the phase difference to a desired value, it is preferred to use a red pigment represented by the chemical formula (1-1) and a red pigment represented by the chemical formula (1-2).

In the present invention, the red pigment represented by the chemical formula (1-1) is used in combination, and In the case of the red pigment represented by the chemical formula (1-2), the blending ratio is not particularly limited. When the chromaticity (x, y) is in the range of 0.630 ≦ x ≦ 0.665, 0.326 ≦ y ≦ 0.335, the phase difference is adjusted to be lower than 10, the red pigment represented by the chemical formula (1-1), and the chemical formula (1) -2) The quality of the red pigment shown is preferably 100:0~60:40, and more preferably 100:0~75:25. Further, when the chromaticity (x, y) is in the range of 0.630 ≦ x ≦ 0.665, 0.326 ≦ y ≦ 0.335, and the phase difference is adjusted to 10 to 120, the red pigment represented by the chemical formula (1-1), and the chemical formula ( 1-2) The quality of the red pigment shown is better than 60:40~0:100, and more preferably 45:55~15:85.

Further, from the viewpoint of lowering the absolute value of the phase difference and increasing the contrast, it is preferred to use a red pigment represented by the chemical formula (1-1). In this case, the red pigment represented by the chemical formula (1-1) is contained in 100 parts by mass of the total amount of the red pigment, preferably 40 parts by mass or more, more preferably 50 parts by mass or more.

(other pigments)

In the present invention, other pigments different from the red pigment represented by the general formula (1) may be used in combination within the range which does not impair the effects of the present invention. Among them, it is preferable to contain one or more pigments selected from other red pigments, orange pigments, and yellow pigments.

The yellow pigment may be, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 150 Derivative pigments, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and the like. C.I. Pigment Yellow 150 and its derivative pigments are disclosed in Japanese Laid-Open Patent Publication No. 2001-354869, JP-A-2005-325350, and JP-A-2007-25687 No. 2007-23287, JP-A-2007-23288, and JP-A-2008-24927 are available.

The yellow pigment is preferably C.I. Pigment Yellow 185 from the viewpoint of satisfying a desired color tone and phase difference and easily reducing the absolute value of the phase difference. Further, when C.I. Pigment Yellow 185 is contained, since the coloring power is high, there is an advantage that the pigment concentration can be easily lowered and the plate making property can be improved.

The red pigment may be, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 147, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 184, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 221, 224, 226, 242, 243, 245, 255, 264, 265, 269, 272, etc.

Further, the orange pigment may be, for example, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71 , 73, etc.

When the red pigment represented by the general formula (1) is used in combination with other pigments, the blending ratio is not particularly limited, and from the viewpoint of chromaticity and phase difference, the general formula (1) is based on 100 parts by mass of the total amount of the pigment. The red pigment shown is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 50 parts by mass or more.

The average dispersed particle size of the pigment used in the present invention is in accordance with the used pigment The type of the material varies, but is preferably in the range of 10 nm or more and 100 nm, more preferably 15 nm or more and 60 nm or less. When the average dispersed particle diameter of the pigment is within the above range, a display device including the color filter produced using the resin composition of the present invention can be made highly contrasted and of high quality.

Although the average dispersed particle diameter of the pigment is smaller within the above range, the contrast can be improved, but the absolute value of the phase difference tends to be large. Therefore, it is best to consider the desired phase difference and contrast and then choose the average dispersed particle size. In particular, the red pigment represented by the general formula (1-1) tends to have a large absolute value of the phase difference even if the particle diameter is excessively reduced, and the average dispersed particle diameter is preferably from the viewpoint of lowering the absolute value of the phase difference. 40nm~60nm.

Further, the average dispersed particle diameter of the pigment in the colored resin composition is a dispersed particle diameter of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size analyzer. The particle size measurement by the laser light scattering particle size analyzer is performed by appropriately diluting the colored resin composition to a concentration (for example, 1000 times or the like) measurable by a laser light scattering particle size distribution analyzer using a solvent used for the colored resin composition. Further, a laser light scattering particle size distribution analyzer (for example, Nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.) can be used for measurement at 23 ° C by dynamic light scattering. The average dispersed particle diameter herein means a volume average particle diameter.

<Pigment Derivative>

In addition, the coloring resin composition for a color filter of the present invention further includes a viewpoint of excellent dispersibility and dispersion stability in terms of adjusting the phase difference and the luminance to a specific range. One or more pigment derivatives selected from the group consisting of pigment derivatives having a pyrrolopyrroledione skeleton and pigment derivatives having an azo lake skeleton. The absolute value of the phase difference can be reduced by appropriately selecting the pigment derivative.

Further, examples of the pyrrolopyrroledione skeleton include C.I. Pigment Red 254, 255, 264, and 272, and such halogen-substituted pigments. Among them, C.I. Pigment Red 254 and 272 are preferable. Further, examples of the azo lake pigment skeleton include C.I. Pigment Red 48 and the like.

In the present invention, a pyrrolopyrroledione derivative represented by the following general formula A, an amidated pyrrolopyrroledione derivative represented by the general formula B, and the following general formula are preferably used. One or more pigment derivatives are selected from the sulfonated pyrrolopyrroledione derivative represented by C and the derivative having an azo lake pigment skeleton represented by the following general formula D.

(一般式A中，Ar係亦可具有下述取代基A'的伸芳基。)

(In the general formula A, the Ar system may have an extended aryl group of the following substituent A'.)

(取代基A'中，R⁴係碳原子數1~5的伸烷基；X係磺酸基、磺酸鹽、或{-SO₂NH-(CH₂)_n-NR'R"}所示磺醯胺基，而R'及R"係各自獨立的氫原子、碳數1~20之亦可被取代的飽和或不飽和烷基或芳基，或R'與R"鍵結並與鄰接的氮原子一起形成亦可進一步含有氮、氧、或 硫原子的雜環；n係1~6的整數。)

(Substituent A', R ⁴ is an alkylene group having 1 to 5 carbon atoms; X-based sulfonic acid group, sulfonate, or {-SO ₂ NH-(CH ₂ ) _n -NR'R"} a sulfonamide group, and R' and R" are each independently a hydrogen atom, a saturated or unsaturated alkyl or aryl group having a carbon number of 1 to 20 which may be substituted, or R' and R" bonded and The adjacent nitrogen atoms together form a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom; n is an integer of 1 to 6.)

(一般式B中，R'及R"係各自獨立的氫原子、碳數1~20之亦可被取代的飽和或不飽和烷基或芳基，或R'與R"鍵結並與鄰接的氮原子一起形成亦可進一步含有氮、氧、或硫原子的雜環；複數R⁵係各自獨立的氫原子、碳原子數1~4之烷基、碳原子數6~12之芳基、鹵原子、或取代基{-CONH-(CH₂)_n-NR'R"}；n係1~6的整數，m係1~4的整數。)

(In general formula B, R' and R" are each independently a hydrogen atom, a saturated or unsaturated alkyl or aryl group having 1 to 20 carbon atoms which may be substituted, or R' and R" bonded and adjacent to each other. The nitrogen atoms together form a heterocyclic ring which may further contain a nitrogen, oxygen, or sulfur atom; the plural R ⁵ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom or a substituent {-CONH-(CH ₂ ) _n -NR'R"}; n is an integer of 1 to 6, and m is an integer of 1 to 4.

(一般式C中，X係從由磺酸基、-SO₂NH-(CH₂)_n-NR'R"、-SO₂NH-(CH₂)_n-COOH、-SO₂NH-(CH₂)_n-SO₃H、及磺酸鹽所構成群組中選擇1種以上，而R'及R"係各自獨立的氫原子、碳數1~20之亦可被取代的飽和或不飽和烷基或芳基，或R'與R"鍵結並與鄰接的氮原子一起形成亦可進一步含有氮、氧、或硫原子的雜環；複數 R⁶係各自獨立的氫原子、碳原子數1~4之烷基、碳原子數6~12之芳基、鹵原子、或取代基X；n係1~6的整數，m係1~4的整數。)

(In general formula C, X is derived from sulfonic acid groups, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One or more selected from the group consisting of _n- SO ₃ H and a sulfonate, and R' and R" are independent hydrogen atoms, and carbon atoms 1 to 20 may be substituted or unsaturated. An alkyl group or an aryl group, or R' and R" are bonded together with a contiguous nitrogen atom to form a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom; a plurality of independent R ⁶ groups each independently have a hydrogen atom or a carbon atom An alkyl group of 1 to 4, an aryl group having 6 to 12 carbon atoms, a halogen atom or a substituent X; an integer of 1 to 6 for n, and an integer of 1 to 4 for m.)

(一般式D中，X係從由磺酸基、-SO₂NH-(CH₂)_n-NR'R"、-SO₂NH-(CH₂)_n-COOH、-SO₂NH-(CH₂)_n-SO₃H、及磺酸鹽所構成群組中選擇1種，而R'及R"係各自獨立的氫原子、碳數1~20之亦可被取代的飽和或不飽和烷基或芳基，或R'與R"鍵結並與鄰接的氮原子一起形成亦可進一步含有氮、氧、或硫原子的雜環；n係1~6的整數，m係1~4的整數。)

(In general formula D, X is derived from sulfonic acid groups, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One of _n -SO ₃ H and sulfonate groups is selected, and R' and R" are independent hydrogen atoms, and saturated or unsaturated alkyl groups having 1 to 20 carbon atoms may be substituted. a group or an aryl group, or a combination of R' and R" and a contiguous nitrogen atom, which may further contain a nitrogen, oxygen, or sulfur atom; n is an integer of 1 to 6, m is 1 to 4; Integer.)

The aryl group of the above general formula A is not particularly limited, and is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a stretching phenyl group, a stretching naphthyl group, and a stretching phenyl group.

Examples of the alkylene group having 1 to 5 carbon atoms of R ⁴ include a methylene group, an exoethyl group, a propyl group, a butyl group, and a pentyl group.

啉乙基、哌啶丙基、甲哌啶 丙基、二乙胺基己基、二乙胺基乙氧基丙基、二乙胺基丁基、二甲胺基戊基、N-N-甲基-月桂基-胺基丙基、2-乙基己胺基乙基、硬脂胺基乙基、油基胺乙基等。 Further, in the sulfonamide group represented by {-SO ₂ NH-(CH ₂ ) _n -NR'R"}, the introduced amine component (-(CH ₂ ) _m -NR'R") Specific examples thereof include piperidinylmethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, and piperidin. Pyridylethyl, meperidine ethyl,

Phenylethyl, piperidinylpropyl, piperidinylpropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminopentyl, NN-methyl- Lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, and the like.

R ⁵ of the general formula B represents, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, or a substituent {-CONH-(CH ₂ ) _n -NR 'R'}.

The alkyl group having 1 to 4 carbon atoms of R ⁵ may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. Examples of the aryl group having 6 to 12 carbon atoms of R ⁵ include a phenyl group, a naphthyl group, and a biphenyl group. The halogen atom of R ⁵ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among them, a chlorine atom or a bromine atom is preferred.

In the general formula B, the introduced amine component (-(CH ₂ ) _m -NR'R") of the substituent {-CONH-(CH ₂ ) _n -NR'R"} may be, for example, the above general formula A. The same is illustrated in the middle. In the general formula B, the substitution position of the substituent {-CONH-(CH ₂ ) _n -NR'R"} is not particularly limited as long as it has at least one in the molecule, and any of the aromatic rings having R ⁵ The hydrogen atom may be substituted, and R ⁵ may be substituted. Further, when R ⁵ is an aryl group, the hydrogen atom of the aromatic ring constituting the aryl group may be substituted.

In general formula C, R ⁶ carbon atoms, an alkyl group of 1 to 4 carbon atoms, an aryl group of 6 to 12, a halogen atom, with each line in the general formula R ⁵ B is the same.

In the general formula C, the substituent X may be the same as in the general formula A. In the general formula C, the substitution position of the substituent X is not particularly limited as long as at least one molecule is contained in the molecule, and any hydrogen atom having an aromatic ring of R ⁶ may be substituted, and R ⁶ may be substituted. . Further, when R ⁶ is an aryl group, the hydrogen atom of the aromatic ring constituting the aryl group may be substituted.

Furthermore, in the general formula D, the substituent X may be the same as the general formula A. kind. In the general formula D, the substitution position of the substituent X is not particularly limited.

(一般式(C-1)中，n係1~4的整數，m係1或2的整數；R'及R"係各自獨立的氫原子、亦可具有取代基的碳原子數1~4之烷基或芳基。) The sulfonated pyrrolopyrroledione derivative represented by the general formula C is preferably from the viewpoint of enhancing the dispersibility and dispersion stability by interaction with the red pigment represented by the general formula (1). The compounds of the general formula (C-1) to (C-4) are as follows:

(In the general formula (C-1), n is an integer of 1 to 4, m is an integer of 1 or 2; R' and R" are each independently a hydrogen atom, and may have a substituent having 1 to 4 carbon atoms. Alkyl or aryl.)

(一般式(C-2)中，m係1或2的整數；R"'係碳原子數1~20之烷基。另外，取代基SO₃ ^-係亦可取代於Cl的位置。)

(In general formula (C-2), m is an integer of 1 or 2; R"' is an alkyl group having 1 to 20 carbon atoms. Alternatively, the substituent SO ₃ ^- may be substituted for the position of Cl.)

(一般式(C-3)中，m係1或2的整數，取代基SO₃H係亦可取代於Cl的位置。) [Chem. 19] General formula (C-3)

(In the general formula (C-3), m is an integer of 1 or 2, and the substituent SO ₃ H may be substituted for the position of Cl.)

(化學式(C-4)中，X係從由磺酸基、-SO₂NH-(CH₂)_n-NR'R"、-SO₂NH-(CH₂)_n-COOH、-SO₂NH-(CH₂)_n-SO3H、及磺酸鹽所構成群組中選擇1種；R'及R"係各自獨立的氫原子、碳數1~20之亦可被取代的飽和或不飽和脂肪族烴基或芳香族烴基，或與鄰接的氮原子一起形成亦可進一步含有氮、氧、或硫原子的雜環；n係各自獨立的1~6之整數。m係1~4的整數。)

(In the chemical formula (C-4), X is derived from a sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH One of the group consisting of -(CH ₂ ) _n -SO3H and a sulfonate; R' and R" are each independently a hydrogen atom, and a saturated or unsaturated aliphatic group having a carbon number of 1 to 20 may be substituted. a hydrocarbon group or an aromatic hydrocarbon group or a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom together with an adjacent nitrogen atom; n is an independent integer of 1 to 6. m is an integer of 1 to 4.

A preferred specific example of the above pigment derivative is, for example, a compound represented by the following chemical formula: [Chemical Formula 21] Chemical Formula 1

Chemical formula 5

As the other pigment derivative, the sulfonated quinophthalone derivative represented by the following general formula E may be further combined. By using a sulfonated quinophthalone derivative in combination, a colored resin composition having more excellent pigment dispersibility can be prepared.

[化28]

(In general formula E, X is derived from sulfonic acid groups, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One of _n -SO ₃ H and sulfonate groups is selected, and R' and R" are independent hydrogen atoms, and saturated or unsaturated fatty acids having 1 to 20 carbon atoms may be substituted. a hydrocarbon group or an aromatic hydrocarbon group or a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom together with an adjacent nitrogen atom; n is an independent integer of 1 to 6. m is an integer of 1 to 4.

The X system in the general formula E can be the same as X in the above general formula C. From the viewpoint of pigment dispersibility, it is preferred to be the following Chemical Formula 8:

In the colored resin composition for a color filter of the present invention, a sulfonated pyrrolopyrroledione pigment is preferably used from the viewpoint of lowering the absolute value of the phase difference and improving the pigment dispersibility and dispersion stability. derivative. From the viewpoint of enhancing the dispersibility of the pigment, it is preferred to use a sulfonated pyrrolopyrroledione derivative and a sulfonated quinophthalone derivative in combination. Further, from the viewpoint of suppressing the precipitation derived from the pyrrolopyrroledione pigment by suppressing hydrogen bonding, it is more preferable to use a ruthenium imide to alkylate a pyrrolopyrroledione derivative.

When the pigment derivative is used, the content ratio of the pigment derivative is preferably from 1 to 25 parts by mass, more preferably from 1 to 15 parts by mass, particularly preferably from 3 to 10 parts by mass, per 100 parts by mass of the pigment.

<dispersant>

In the present invention, a polymer having the structural unit represented by the above general formula (2) is used as the dispersant. The constituent unit represented by the above general formula (2) has a basic function and functions as a site to which the pigment is adsorbed.

In the colored resin composition for a color filter of the present invention and the pigment dispersion liquid, by using a polymer having a structural unit represented by the general formula (2) as a dispersing agent, the adsorption property to the pigment and the pigment dispersibility can be improved. With dispersion stability.

[Chem. 30] General formula (2)

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group.

The x system represents an integer from 1 to 18, the y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18. )

In the general formula (2), Q is a divalent linking group. The divalent linking group of Q may, for example, be an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group, or an ether group having 1 to 10 carbon atoms (-R'- OR "-: R' and R" are each independently an alkyl group), and combinations thereof.

Among them, from the viewpoint of dispersibility, the Q of the general formula (2) preferably includes a -CONH- group or a -COO- group divalent linking group.

The divalent organic group R ¹² of the above general formula (2) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ¹⁵ )-CH(R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH ( R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -. The above-mentioned alkylene group having 1 to 8 carbon atoms may be either linear or branched.

R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group.

The above R ¹² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and R ^{12 is more} preferably a methylene group, an ethyl group, a propyl group or a butyl group. It is a methylene group and an ethyl group.

The cyclic structure in which R ¹³ and R ^{14 in the} above general formula (2) are bonded to each other may, for example, be a nitrogen-containing heterocyclic monocyclic ring having a five- to seven-membered ring or a combined ring in which the two are condensed. The nitrogen-containing heterocyclic ring is preferably not aromatic, and is more preferably a saturated ring.

The repeating unit represented by the above general formula (2) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or diethylaminoethyl (meth)acrylate. (meth)acrylate containing an alkyl-substituted amino group, such as diethylaminopropyl (meth)acrylate; dimethylaminoethyl(meth)propenylamine, dimethylaminopropyl ( (Meth) propenylamine or the like containing an alkyl-substituted amine group such as methyl)propenylamine. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl group are preferably used. (Meth)propenylamine.

In the polymer having the structural unit represented by the above general formula (2), the structural unit represented by the general formula (2) preferably contains three or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is more preferable to contain 3 to 100, particularly good to contain 3 to 50, and optimal to contain 3 to 30.

In the polymer having the structural unit represented by the above general formula (2), it is preferred from the viewpoint of further improving the pigment adsorption property, the pigment dispersion stability, the development residue, and the solvent resolubility at the salt formation site. One or more compounds selected from the group consisting of the compounds represented by the general formulas (I) to (III) below, and at least a part of the terminal nitrogen sites of the structural unit represented by the above general formula (2) Form a salt.

[化31]

(In the general formula (I), R ^{a is a} linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a methyl group having a carbon number of 1 to 4 a propylene fluorenyl group. In the general formula (II), R ^b , R ^{b '} and R ^b" are each independently a hydrogen atom, an acidic group or an ester group thereof, and may have a substituent having a carbon number of 1 to 20 a chain, a branched chain or a cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR ^f , and the R ^f group may have a carbon number of a substituent 1~ a straight chain, a branched chain or a cyclic alkyl group of 20, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a methyl group having a carbon number of 1 to 4 (methyl group) a propylene group; a X-type chlorine atom, a bromine atom, or an iodine atom. In the general formula (III), R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, a linear chain having a carbon number of 1 to 20, or a branched chain or a cyclic alkyl group, a vinyl group, a phenyl group or a benzyl group which may also have a substituent, or OR ^e , and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or an alkylene group having a carbon number of 1 to 4 a (meth) acrylonitrile group, wherein at least one of R ^c and R ^d contains a carbon atom.

In the above general formulas (I) to (III), R ^a , R ^b , R ^{b '} , R ^b" , R ^c , R ^d , R ^e and R ^{f have} a linear number of 1 to 20 or a branched chain or The cyclic alkyl group may be either a straight chain or a branched chain, and may also have a cyclic structure. Preferably, for example, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms is used. More preferably, it is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

Further, R ^a , R ^c , R ^d , and R ^e may be a substituent of a phenyl group or a benzyl group which may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms and a fluorenyl group. Alkoxy groups, etc.

In the case of R ^b , R ^{b '} , R ^{b "} and R ^f , a substituent of a phenyl group or a benzyl group which may have a substituent, for example, an acidic group or an ester group thereof, and a carbon number of 1 to 5 Alkyl, decyl, decyloxy and the like.

Further, R ^b , R ^{b '} , R ^{b "} and R ^f may have a substituent of a straight chain, a branched chain or a cyclic alkyl group having 1 to 20 carbon atoms or a vinyl group. For example, an acidic group or an ester group thereof, a phenyl group, a decyl group, a decyloxy group and the like.

In the case of R ^b , R ^{b '} , R ^{b "} and R ^f , the acidic group means a group which is acidic when a proton is released in water. Specific examples of the acidic group include a carboxyl group (-COOH) and a sulfonate. (-SO ₃ H), phosphinyl (-P(=O)(OH) ₂ ), phosphonic acid subunit (>P(=O)(OH)), boric acid (-B(OH) ₂ ) , boronic acid group (> BOH) and the like, such as for example carboxymethylcellulose may foundation (-COO ^-) and the like as the hydrogen atoms dissociated anions, may also be formed with alkali metal ions such as sodium ion, potassium ion salt of the acid salt.

Further, examples of the acid group of the acid group include a carboxylate (-COOR), a sulfonate (-SO ₃ R), a phosphate (-P(=O)(OR) ₂ ), and (>P ( =O)(OR)), borate ester (-B(OR) ₂ ), borane ester (>BOR) (borinate ester), and the like. Among them, the acid group ester group is preferably a carboxylate (-COOR) from the viewpoint of dispersibility and dispersion stability. In addition, the R-based hydrocarbon group is not particularly limited, and is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of dispersibility and dispersion stability.

The compound of the above formula (II) preferably has a carboxyl group, a boric acid group, a boronic acid group, or an anion thereof from the viewpoints of dispersibility, dispersion stability, alkali developability, and suppression of development residue. And one or more of the above-mentioned alkali metal salts and the above-mentioned esters, and more preferably have a carboxyl group, a carboxyl group, or a carboxyl group. A functional group selected from the group consisting of an acid base and a carboxylate.

In the case where the compound of the above formula (II) has an acidic group and an ester group (hereinafter referred to as an acidic group or the like), the side of the acidic group and the side of the halogen atom of the compound and the terminal nitrogen are both capable of terminal nitrogen sites. The salt is formed, but it is presumed that the terminal nitrogen moiety and the halogen atom side hydrocarbon can form a salt more stably than when a salt is formed from the terminal nitrogen moiety and the acidic group. Further, it is presumed that the dispersibility and the dispersion stability are improved by adsorbing the pigment at the salt-forming site where the stability exists.

In the case where the compound of the above formula (II) has the above acidic group or the like, the acidic group or the like may have two or more. When the acid group or the like has two or more, the plurality of acidic groups or the like may be the same or different. The number of the acidic groups and the like of the compound of the above formula (II) is preferably 1 to 3, more preferably 1 to 2, and particularly preferably one.

In at least one of R ^a in the above general formula (I), R ^b , R ^{b '} and R ^b′ of the above general formula (II), and R ^c and R ^d in the above general formula (III) At least one of them has an aromatic ring, and is excellent in affinity between a skeleton of a pigment to be described later, and excellent in pigment dispersibility and dispersion stability, and a coloring composition excellent in contrast can be obtained. Preferably.

The molecular weight of one or more compounds selected from the group consisting of the above general formulas (I) to (III) is preferably 1,000 or less, more preferably 50 to 800, from the viewpoint of improving pigment dispersibility. More preferably, the system is 50~400, and the better is 80~350, and the best is 100~330.

The compound represented by the above general formula (I) may, for example, be benzenesulfonic acid, ethylenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid or mono-n-propylsulfuric acid. Further, a hydrate such as p-toluenesulfonic acid monohydrate can also be used. on The compound represented by the general formula (II) may, for example, be methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide or iodine. Ethyl chloride, n-butane chloride, hexane chloride, octane chloride, dodecyl chloride, tetradecane chloride, hexadecane chloride, phenethyl chloride, chlorotoluene, Bromotoluene, iodine toluene, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodobenzene Benzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid, and the like. The compound represented by the above general formula (III) may, for example, be monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid, diphenylphosphoric acid, phenylphosphinic acid, phenylphosphonic acid or dimethyl Acryloxyethyl acid phosphate and the like.

Among the groups of the above general formulas (I) to (III), from the viewpoint of particularly excellent dispersion stability, it is preferred to use phenylphosphinic acid, phenylphosphonic acid, dimethyl propylene oxide. One or more selected from the group consisting of ethyl acid phosphate, dibutyl phosphoric acid, chlorotoluene, bromotoluene, ethylene sulfonic acid, and p-toluenesulfonic acid monohydrate, and more preferably from phenylphosphinium One or more selected from the group consisting of acid, phenylphosphonic acid, chlorotoluene, bromotoluene, and p-toluenesulfonic acid monohydrate.

In addition, from the viewpoint of improving the development residue suppressing effect by the combination of the block copolymer having an acid value described later, it is preferred to use a general formula having an acidic group and an ester group thereof ( The compound shown by II), wherein, more preferably, it is used from α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid One or more selected from the group consisting of 4-iodophenylbenzoic acid.

In the polymer having the structural unit represented by the general formula (2), the content of one or more compounds selected from the group consisting of the above general formulas (I) to (III) is the same as the general formula (2). The terminal nitrogen portion of the constituent unit is formed to form a salt, and thus is relative to one The terminal nitrogen moiety 1 mol of the constituent unit represented by the general formula (2), and one or more compounds selected from the group consisting of the general formulas (I) to (III) are preferably 0.01 mol or more. The best is 0.1 moles or more, the best is 0.2 moles or more, and the best is 0.3 moles or more. If it is more than the above lower limit value, the effect of improving the dispersibility of the pigment caused by the salt formation can be easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, more preferably 0.7 m or less, and most preferably 0.6 m or less. When it is at most the above upper limit value, it is excellent in both the development adhesiveness and the solvent resolubility.

In addition, one or more compounds may be selected from the group consisting of the above-described general formulas (I) to (III), and one type may be used alone or two or more types may be used in combination. When two or more types are combined, the total content is preferably within the above range.

The polymer having the structural unit represented by the general formula (2) preferably further contains a solvent-affinitive site from the viewpoint of improving dispersibility. The solvent affinity site is preferably a solvent which is polymerizable with a monomer derived from the structural unit represented by the general formula (2) and has an ethylenically unsaturated bond, and is appropriately formulated in a solvent affinity manner. Choose to use. As a standard, it is preferred to introduce a solvent affinity site in such a manner that the solubility of the solvent to be used in combination is 50 (g/100 g solvent) at 23 ° C.

The polymer used in the present invention is preferably a block copolymer or a viewpoint of improving pigment dispersibility, dispersion stability, and heat resistance of a resin composition, and capable of forming a high-luminance and high-contrast coloring layer. A graft copolymer, more preferably a block copolymer. The following is a detailed description of a particularly preferred block copolymer.

[block copolymer]

When the block containing the structural unit represented by the above general formula (2) is referred to as an A block, The structural unit represented by the above general formula (2) of the A block has a basic function and functions as a site to which the pigment is adsorbed. In addition, at least a part of the terminal nitrogen sites of the structural unit represented by the general formula (2) and the one or more compounds selected from the group consisting of the general formulas (I) to (III) form a salt. The salt forming portion functions as a portion that strongly adsorbs the pigment. On the other hand, the B block which does not contain the structural unit represented by the above general formula (2) functions as a block having solvent affinity. Therefore, the block copolymerization system used in the present invention functions as a pigment dispersant by supporting the A block adsorbed by the pigment and the B block function having solvent affinity.

{A block}

The A block contains the block of the structural unit represented by the above general formula (2), and since the structural unit represented by the above general formula (2) is as described above, it will not be described herein.

In the A block containing the structural unit represented by the general formula (2), the structural unit represented by the general formula (2) preferably contains three or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is more preferable to contain 3 to 100, particularly good to contain 3 to 50, and optimal to contain 3 to 30.

The constituent unit represented by the general formula (2) may have a function as a pigment adsorption site, and may be composed of one type or two or more types of constituent units.

The A block may have a constituent unit other than the constituent unit represented by the general formula (2) within the range of the object of the invention, and may be a constituent unit capable of copolymerizing with the constituent unit represented by the general formula (2). It can be included. For example, the basic block portion may contain a constituent unit other than the constituent unit represented by the general formula (2), and specifically, for example, a constituent unit represented by the general formula (3) described later.

In the A block of the block copolymer before salt formation, the general formula (2) is shown as a single The content ratio of the element is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, particularly preferably 100% by mass based on the total mass of the total constituent unit of the A block. The reason for this is that the higher the ratio of the constituent units represented by the general formula (2), the higher the adsorption force to the pigment, and the better the dispersibility and dispersion stability of the block copolymer. Further, the content ratio of the above-mentioned constituent unit is calculated from the packing mass at the time of synthesis of the A block having the structural unit represented by the general formula (2).

In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (2) is based on the total structural unit of the block copolymer from the viewpoint of good dispersibility and dispersion stability. The total mass is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass. Further, the content ratio of each constituent unit in the above block copolymer is calculated from the packing mass at the time of synthesis of the block copolymer before salt formation.

In addition, the constituent unit represented by the general formula (2) may be one type or one or more types of constituent units as long as it has affinity with a pigment.

{B block}

The B block system does not contain a block of the structural unit represented by the above general formula (2). It is preferable that the B block is appropriately selected from a monomer which can be copolymerized with a monomer derived from the structural unit represented by the general formula (2) and which has an unsaturated double bond, and a solvent is used in a solvent-compatible manner. . As a standard, it is preferred to introduce a B block in such a manner that the solubility of the solvent to be used in combination at a temperature of 23 ° C is 20 (g / 100 g of solvent).

The constituent unit constituting the B block may, for example, be a monomer which can be copolymerized with a monomer derived from a structural unit represented by the general formula (2) and has an unsaturated double bond, and is preferably a general formula (3) ) The constituent unit shown: [Chem. 32]

(In general formula (3), R ²¹ is a hydrogen atom or a methyl group; Q' is a direct bond or a divalent linking group; R ²² is a hydrocarbon group, -[CH(R ²³ )-CH(R ²⁴ )-O] _X- R ²⁵ or -[(CH ₂ ) _y -O] _z -R ²⁵ represents a monovalent group. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group; R ²⁵ is a hydrogen atom, a hydrocarbon group, -CHO And a monovalent group represented by -CH ₂ CHO or -CH ₂ COOR ²⁶ ; and a hydrogen atom of R ²⁶ or an alkyl group having 1 to 5 carbon atoms.

The above hydrocarbon group may have a substituent.

The x system represents an integer from 1 to 18, the y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18. )

In the general formula (3), Q' is a direct bond or a divalent link. The term "direct bonding" means that Q' does not have an atom, that is, C (carbon atom) in the general formula (3), and R ²² is not bonded via another atom. The divalent linking group can be the same as Q in the general formula (2). Among them, Q' is preferably a direct bond, a divalent linking group including a -CONH- group or a -COO- group, from the viewpoint of solubility in an organic solvent.

In the general formula (3), R ²² is a hydrocarbon group, -[CH(R ²³ )-CH(R ²⁴ )-O] _x -R ²⁵ or -[(CH ₂ ) _y -O] _z -R ²⁵ .

The hydrocarbon group of R ²² is preferably 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.

The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic. Either.

The alkenyl group having 2 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. Examples of such an alkenyl group include a vinyl group, an allyl group, and an allyl group. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of reactivity of the obtained polymer, it is preferred to have a double bond at the terminal of the alkenyl group.

Examples of the substituent of the aliphatic hydrocarbon such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

The aryl group may, for example, be a phenyl group, a biphenyl group, a naphthyl group, a tolyl group or a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.

Further, examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14.

The substituent of the aromatic ring such as an aryl group or an aralkyl group may, for example, be a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include an alkenyl group, a nitro group, and a halogen atom.

Further, the above preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ²² , x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2; y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably Line 2 or 3. z is an integer of 1 to 18, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.

The hydrocarbon group of the above R ²⁵ may be the same as those shown by the above R ²² .

R ²⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be any of a linear chain, a branched chain, or a cyclic chain.

Further, R ²² in the structural unit represented by the above general formula (3) may be the same or different from each other.

The above-mentioned R ^{22 is} preferably selected so as to have a good compatibility with a solvent to be described later. Specifically, for example, a glycol ether acetate system for a solvent of a colored resin composition for a general color filter is used as the solvent. When a solvent such as an ether system or an ester system is used, a methyl group, an ethyl group, an isobutyl group, a n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.

Further, the above R ²² may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group or an isocyanate group, or may be substituted in the above block, without hindering the dispersion property of the block copolymer. After the synthesis is carried out, the compound having the above substituent is further reacted to form the above substituent.

In the present invention, from the viewpoint of dispersibility of the pigment and dispersion stability, the constituent unit represented by the above general formula (3) preferably contains methacrylic acid, 2-hydroxyethyl methacrylate, and methyl group. One or more constituent units are selected from the group consisting of benzyl acrylate.

The number of constituent units constituting the B block is not particularly limited, and it is preferably from 10 to 300, more preferably from 10 to 100, from the viewpoint of effectively functioning the solvent affinity portion and the pigment adsorption site and improving the pigment dispersibility. 10 to 70 special and excellent.

In the B block of the block copolymer, the content ratio of the structural unit represented by the above general formula (3) is based on the total mass of the total constituent units of the B block from the viewpoint of enhancing the solvophilic property and the pigment dispersibility. It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass. Further, the content ratio of the above constituent units is calculated from the packing quality at the time of synthesizing the B block.

In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the above general formula (3) is based on the total constituent unit of the block copolymer from the viewpoint of improving pigment dispersibility and dispersion stability. The total mass is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. Further, the content ratio of the above constituent unit is calculated from the mass of the block copolymer before salt formation at the time of synthesis.

The B block system may be a device that functions as a solvophilic moiety, and the constituent unit may be appropriately selected. The structural unit represented by the above general formula (3) may be composed of only one type, or may be composed of two or more types. The constituent unit. The two or more constituent units contained in the B block may be randomly arranged in the block.

The weight average molecular weight Mw of the above-mentioned copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and particularly preferably from 3,000 to 12,000, from the viewpoint of good pigment dispersibility and dispersion stability.

Here, the weight average molecular weight (Mw) is determined by a gel permeation chromatography (GPC) based on a standard polystyrene conversion value.

Further, in the present invention, the weight average molecular weight Mw of the block copolymer is determined by a GPC (Gel Penetration Chromatography Analyzer) based on a standard polystyrene conversion value. The measurement system used HTC-8120GPC manufactured by Tosoh Co., Ltd., and the elution solvent was N-methylpyrrolidone with 0.01 mol/liter lithium bromide added, and the calibration curve was set to Mw377400, 210500 using polystyrene standards. , 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (all of which are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (made by Tosoh Co., Ltd.), and two tubes are used for measuring the column system. TSK-GEL ALPHA-MX (Tosoh Corporation) was implemented.

In the present invention, the block arrangement of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The method for producing the above block copolymer is not particularly limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method.

Further, the method for producing the salt block copolymer is, for example, a polymer having the structural unit represented by the above general formula (2) dissolved or dispersed in a solvent, and further added from the above general formula (I). (III) One or more kinds of compounds are selected from the group consisting of, and stirring is carried out, and a method of performing heating is required.

Further, in the polymer having the structural unit represented by the above general formula (I), the terminal nitrogen moiety of the structural unit represented by the general formula (2) and the general formula (I) to (III) The case where a salt or more is selected from the group to form a salt, and the ratio can be confirmed by a known method such as NMR.

<alkali soluble resin>

The alkali-soluble resin of the present invention has an acidic group and can be appropriately selected from those having a function as a binder resin and soluble in a developer used in pattern formation, particularly an alkali developer.

In the present invention, the acid value of the alkali-soluble resin is not particularly limited. The alkali-soluble resin is preferably a resin having an acid value of 30 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of improving the stability of the dispersion stability and the like, and improving the heat resistance of the colored layer obtained by the resin composition.

Further, the acid value of the present invention means a value obtained by potentiometric titration according to JIS K 0070:1992, which is used for neutralizing the solid content of 1 g of KOH.

The preferred alkali-soluble resin of the present invention is a resin having a carboxyl group as an acidic group, and specific examples thereof include an acrylic copolymer having a carboxyl group, an epoxy (meth)acrylate resin having a carboxyl group, and a polycondensation having a carboxyl group. Amidoxime resin, and the like.

Among these, a particularly preferred side chain having a carboxyl group and further having a photopolymerizable functional group such as an ethylenically unsaturated bond group in the side chain. Photopolymerizable functional group The film strength of the formed cured film is increased. To the resin having a carboxyl group, for example, an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group is added, and an alkali-soluble resin having a side chain introduced into an ethylenically unsaturated bond group can be obtained.

Further, the alkali-soluble resin selected from the group consisting of the carboxyl group-containing acrylic copolymer, the carboxyl group-containing epoxy acrylate resin, and the carboxyl group-containing polyamidoximine resin may be used in combination. 2 or more types.

The acryl-based copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer with another ethylenically unsaturated monomer.

Specific examples of the carboxyl group-containing acryl-based copolymer are, for example, those described in JP-A-2013-029832, and specific examples thereof include methyl (meth)acrylate and ethyl (meth)acrylate. An ethylenically unsaturated monomer having no carboxyl group such as styrene, and a copolymer of one or more selected from the group consisting of (meth)acrylic acid and an anhydride thereof. Further, a polymer obtained by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above-mentioned copolymer, and introducing an ethylenically unsaturated bond, etc., may be exemplified. Not limited to these.

The monomer having no carboxyl group preferably has a hydrocarbon ring. By containing a large hydrocarbon ring in the colored layer, the solvent resistance and heat resistance of the obtained colored layer can be improved.

The hydrocarbon ring system may, for example, be an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or a combination thereof, and the hydrocarbon ring may have, for example, an alkyl group, a carbonyl group or a carboxyl group. a substituent such as an oxycarbonyl group, a decylamino group, a hydroxyl group, a nitro group, an amine group or a halogen atom.

The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher group.

烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪 族烴環；苯、萘、蒽、菲、茀等芳香族烴環；聯苯基、聯三苯、二苯甲烷、三苯甲烷、茋等鏈狀多環；懸掛(cardo)結構(9,9-二芳基茀)等。 Specific examples of the hydrocarbon ring include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending.

An aliphatic hydrocarbon ring such as alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) or adamantane; an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene or anthracene; biphenyl group; A chain polycyclic ring such as terphenyl, diphenylmethane, triphenylmethane or anthracene; a cardo structure (9,9-diarylfluorene).

From the viewpoint of improving heat resistance and adhesion of the colored layer, and enhancing the luminance of the obtained colored layer, it is preferred to contain an aliphatic hydrocarbon ring as a hydrocarbon ring.

The alkali-soluble resin is preferably a crosslinked cyclic hydrocarbon ring having an aliphatic hydrocarbon ring having a structure in which two or more rings share two or more atoms.

烷、異

烷、金剛烷、三環[5.2.1.0(2,6)]癸烷、三環[5.2.1.0(2,6)]癸烯、三環戊烯、三環戊烷、三環戊二烯、二環戊二烯；該等基之一部分被取代基所取代的基。 Specific examples of the crosslinked cyclic hydrocarbon ring may, for example, be as follows:

Alkane, different

Alkane, adamantane, tricyclo[5.2.1.0(2,6)]decane, tricyclo[5.2.1.0(2,6)]nonene, tricyclopentene, tricyclopentane, tricyclopentadiene Dicyclopentadiene; a group in which one of the groups is substituted by a substituent.

The substituent may, for example, be an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amine group or a halogen atom.

The carbon number of the crosslinked cyclic hydrocarbon ring is preferably 5 or more, and more preferably 7 or more, from the viewpoint of compatibility with other materials and solubility to an alkali developer. The upper limit is preferably 12 or less, more preferably 10 or less.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer 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 obtained coating film to the alkali developing solution is lowered, resulting in difficulty in pattern formation. In addition, when the copolymerization ratio exceeds 50% by mass, when the image is developed by the alkali developer, the pattern is likely to be detached from the substrate, or the film surface tends to be rough.

The acid value of the carboxyl group-containing copolymer is preferably 30 mgKOH/g or more and 200 mgKOH/g or less, more preferably 50 mgKOH/g or more and 150 mgKOH/g or less. It is particularly preferably 60 mgKOH/g or more and 120 mgmgKOH/g or less.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably in the range of 3,000 to 20,000. If it is less than 1,000, the function of the binder after hardening may be remarkably lowered. If it exceeds 50,000, it may be difficult to form a pattern when it is developed by an alkali developer.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin was measured using polystyrene as a standard material and THF as an eluent, and was determined by Shodex GPC System 21H (Shodex GPC System-21H).

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and is preferably an epoxy (methyl) obtained by reacting an epoxy compound with a reaction product containing an unsaturated monocarboxylic acid and an acid anhydride. Acrylate compound.

The acid value of the carboxyl group-containing epoxy (meth) acrylate resin is preferably 30 mgKOH/g or more and 200 mgKOH/g or less, more preferably 50 mgKOH/g or more and 150 mgKOH/g or less, and particularly preferably 60 mgKOH/g or more. 120 mg mgKOH / g or less.

An epoxy compound having an epoxy group (meth) acrylate resin having a carboxyl group, a monocarboxylic acid containing an unsaturated group, and an acid anhydride can be appropriately selected from known ones.

In addition, the carboxyl group-containing polyamidoximine resin is not particularly limited, and is preferably 90 mgKOH/g or more, more preferably 110 mgKOH/g or more, and particularly preferably 130 mgKOH/g or more from the viewpoint of developability. . On the other hand, the acid value of the carboxyl group-containing polyamidoximine resin is preferably 300 KOH mg/g or less, more preferably 250 KOH mg/g from the viewpoint of suppressing water permeation and excellent stability of the colored resin composition. the following.

Carboxy polyamine quinone imine resin, which can be obtained from the formation of brightness and contrast It is preferable to have a repeating unit represented by the following general formula (A) from the viewpoint of a colored layer which is excellent in developability and which inhibits water permeation after development, and is preferably a colored resin composition. Polyamidoximine resin.

(In the general formula (A), a residue of a divalent aliphatic diisocyanate which is independent of each other in the Ra system; and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3); The structural unit represented by the general formula (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The plural Ra, Rb and Rc present in the amine imine resin may be the same or different, and at least one of Rb is a structural unit represented by the following general formula (B1) or (B2); Rc and resin At least one of the ends contains an acidic group, and n represents the number of repeating units, and is 1 or more.

[化35]

(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) And (C10), wherein R is independently an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue having a carbon number of 6 to 20 which may have a substituent. The Re is independently derived from the alcohol compound. Residues of hydroxyl groups removed.)

a residue of an aliphatic diisocyanate of the repeating unit represented by the above formula (A), an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue having a carbon number of 6 to 20 which may have a substituent, An aromatic or aliphatic tricarboxylic acid or a tetracarboxylic acid which may have a substituent of an aliphatic diisocyanate or a carbon number of 6 to 20 may be appropriately selected. It is not limited to the following examples.

烷二異氰酸酯(NBDI)、氫化二苯甲烷二異氰酸酯等。Ra係從更加提升著色層輝度、且抑制發生水滲透的觀點而言，較佳係各自獨立的2價環式脂肪族二異氰酸酯類之殘基。Ra係從更加提升著色層輝度、且抑制發生水滲透的觀點而言，較佳係異佛爾酮二異氰酸酯的殘基。 The divalent aliphatic diisocyanate may, for example, be a linear aliphatic diisocyanate or a cyclic aliphatic diisocyanate such as hexamethylene diisocyanate (HDI) or trimethylhexamethylene diisocyanate (HTMDI). ), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate (HTDI), hydrogenated xylene diisocyanate (HXDI),

Alkyl diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate, and the like. From the viewpoint of further enhancing the luminance of the colored layer and suppressing the occurrence of water permeation, Ra is preferably a residue of each of the independent divalent cyclic aliphatic diisocyanates. The Ra system is preferably a residue of isophorone diisocyanate from the viewpoint of further enhancing the luminance of the colored layer and suppressing the occurrence of water permeation.

The aromatic tricarboxylic anhydride which may have a substituent of 6 to 20 carbon atoms may, for example, be trimellitic anhydride or naphthalene-1,2,4-tricarboxylic anhydride. Further, examples of the aliphatic tricarboxylic anhydride having a carbon number of 6 to 20 which may have a substituent include a linear aliphatic tricarboxylic anhydride and a cyclic aliphatic tricarboxylic anhydride, and examples thereof include propane tricarboxylic anhydride and cyclohexane. An alkane tricarboxylic anhydride, methylcyclohexane tricarboxylic anhydride, cyclohexene tricarboxylic anhydride, methylcyclohexene tricarboxylic anhydride, and the like.

Further, examples of the aromatic or aliphatic tetracarboxylic anhydride having a carbon number of 6 to 20 which may have a substituent include pyromellitic dianhydride and diphenyl ketone-3,3',4,4'- Tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, and the like.

A polyamidoximine resin having a repeating unit represented by the above general formula (A) can be produced, for example, by referring to International Publication No. 2015/008744.

The above polyamidoximine resin preferably contains an unsaturated double bond group from the viewpoint of forming a coloring layer which is improved in brightness and contrast, and a film rate which can increase the coloring layer. In the carboxyl group of the polyamidoximine resin, an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group is added, and an ethylenically unsaturated bond group can be introduced.

The alkali-soluble resin used in the present invention is a carboxyl group-containing polyamidoximine resin, and it is preferred to contain a poly group having a repeating unit represented by the above general formula (A) from the viewpoint of easily reducing the absolute value of the phase difference. Amidoxime resin.

Furthermore, the alkali-soluble resin used in the present invention can form a coloring layer with improved brightness and contrast under the absolute value of the phase difference, and improve the stability and solvent resolubility of the colored resin composition. From the viewpoint of the above, it is preferred to contain an acrylic copolymer having an acid value of 50 KOHmg/g or more and a polyacrylamide imine resin having a carboxyl group.

The alkali-soluble resin used for the coloring resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and it is composed of a colored resin for a color filter. The total amount of the solid content of the substance, the alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. When the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained. Further, when the content of the alkali-soluble resin is more than the above upper limit, film roughness and pattern defect may occur during development. Case. Further, the solid portion of the present invention includes all liquid substances other than the above solvent, and also includes a liquid polyfunctional monomer.

<monomer>

The monomer used for the colored resin composition for a color filter is not particularly limited as long as it can be polymerized by a photoinitiator described later, and a compound having an ethylenically unsaturated double bond is usually used. It has an acryl fluorenyl group or a methacryl fluorenyl group. Further, it is preferred to contain a polyfunctional (meth) acrylate having two or more ethylenically unsaturated double bonds.

Such a polyfunctional (meth) acrylate may be appropriately selected from known conventionally known ones. Specific examples thereof include those described in JP-A-2013-029832.

These (meth) acrylates may be used singly or in combination. Use two or more types. Further, when the colored resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds. Particularly preferred are poly(meth)acrylates of a trihydric or higher polyhydric alcohol, and such dicarboxylic acid modified materials, and specific examples thereof include trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth) acrylate, pentaerythritol tri(meth) acrylate succinic acid modification, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate An ester, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like. Among them, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like is more preferable.

The content of the above-mentioned monomer used for the colored resin composition for a color filter is not particularly limited, and the monomer is preferably 5 to 60 by mass based on the total amount of the solid content of the colored resin composition for a color filter. %, more preferably in the range of 10 to 40% by mass. When the monomer content is less than the above lower limit, the photocuring may not be sufficiently performed, and the exposed portion may be eluted during development; and if the monomer content is more than the above upper limit, the alkali developability may be lowered. The possibility.

Further, particularly in the case where the pigment concentration is high, in order to improve the developing solubility, it is preferable to further contain an alkylene oxide-modified monomer, and specifically, for example, trimethylolpropane PO-modified triacrylate, and three Hydroxymethylpropane EO modified triacrylate, isomeric cyanuric acid EO modified triacrylate, diglycerin EO modified acrylate, and the like. Among them, particularly preferred are diglycerin EO modified acrylate, trimethylolpropane EO modified triacrylate.

In addition, the term "EO modification" means a block structure having an ethylene oxide unit (-CH ₂ -CH ₂ -O-); the so-called "PO modification" means having a propylene oxide unit (-CH ₂ - Block structure of CH(CH ₃ )-O-).

The amount of the alkylene oxide-modified monomer to be added can be appropriately adjusted, and it is preferably added in an amount of from 5 to 100% by mass based on the total amount of the monomer in terms of balance between development solubility and hardenability.

<starting agent>

The photoinitiator used for the coloring resin composition is not particularly limited, and may be used alone or in combination of two or more kinds of various photoinitiators known in the art. Specific examples are, for example, those described in JP-A-2013-029832.

The photoinitiator may be used alone or in combination of two or more. The photoinitiator preferably contains an oxime ester photoinitiator from the viewpoint of suppressing the occurrence of pattern defects and suppressing the effect of causing water permeation. When a dispersing agent having an acid value is used, water permeation tends to occur particularly. However, when an oxime ester-based photoinitiator is combined, water permeation can be suppressed and it is suitable for use. In addition, "water permeation" means a water stain phenomenon such as water permeation after washing with pure water after alkali development. Since such "water permeation" disappears after post-baking, it does not pose a problem as a product. However, when the appearance of the pattern surface is examined after development, the excellent spot is detected abnormally, and the normal product cannot be distinguished. Problems with abnormal products. Therefore, if the inspection sensitivity of the inspection apparatus is lowered during the visual inspection, the result is that the yield of the final color filter product is lowered, which poses a problem.

The oxime ester-based photoinitiator is preferably an aromatic ring, and a more preferred accessory has an aromatic ring from the viewpoint of reducing contamination of the colored resin composition for a color filter due to decomposition products or contamination of the device. Condensed ring, especially good with benzene ring and heterocyclic ring Healing.

The oxime ester photoinitiator can be derived from 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzamide), ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-acetyl), Japanese Patent Laid-Open No. 2000-80068, JP-A-2001 The oxime ester photoinitiator described in the above-mentioned Japanese Patent Publication No. 233-842, No. 2010-527339, JP-A-2010- 527 338, and the like. For commercial use, for example, IRGACURE OXE-01, IRGACURE OXE-02, IRGACURE OXE-03 (all of which are manufactured by BASF) having an carbazole skeleton; ADEKA ARKLSN-1919, ADEKA ARKLS NCI-831 (all of which are ADEKA company); TR-PBG-304, TR-PBG-326 (all of which are manufactured by Changzhou Strong Electronic New Materials Co., Ltd.); ADEKA ARKLS NCI-930 (made by ADEKA) with diphenyl sulfide skeleton; TR-PBG -345, TR-PBG-3057 (all of which are manufactured by Changzhou Power Electronic New Material Co., Ltd.); TR-PBG-365 (manufactured by Changzhou Power Electronic New Material Co., Ltd.) with a skeleton.

In particular, from the viewpoint of luminance, an oxime ester photoinitiator having a diphenyl sulfide skeleton or an anthracene skeleton is preferably used. Further, from the viewpoint of sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used.

In addition, from the viewpoint of easily improving the development resistance and improving the effect of suppressing the occurrence of water permeation, it is preferred to use two or more kinds of oxime ester-based photoinitiators in combination. In particular, from the viewpoint of easily increasing the luminance and high heat resistance, it is preferred to use two kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton or an oxime ester system of a diphenyl sulfide skeleton. A photoinitiator and an oxime ester photoinitiator having an anthracene skeleton. Further, from the viewpoint of excellent sensitivity and brightness, it is preferred to use an oxime ester photoinitiator of a carbazole skeleton, an oxime ester photoinitiator having an anthracene skeleton or a diphenyl sulfide. Ester-based photoinitiator.

啉基丙烷-1-酮(例如IRGACURE 907、BASF公司製)、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮(例如IRGACURE 369、BASF公司製)、4,4'-雙(二乙胺基)二苯基酮(例如HICURE ABP、川口藥品製)等。 Further, from the viewpoint of enhancing the sensitivity, it is preferred to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator. The reason for this is that since the photoinitiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen matting agent in the molecule, radicals generated from the initiator are not easily deactivated by oxygen, which may improve sensitivity. The above commercially available photoinitiator having a tertiary amine structure may, for example, be 2-methyl-1-(4-methylthiophenyl)-2-

Lolinylpropan-1-one (for example, IRGACURE 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-

Polinylphenyl)-1-butanone (for example, IRGACURE 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, HICURE ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

The content of the photoinitiator used in the coloring resin composition for a color filter is not particularly limited, and the photoinitiator is preferably 0.1 to the total amount of the solid content of the colored resin composition for a color filter. 12% by mass, more preferably 0.6 to 8% by mass. When the content is less than the above lower limit, photohardening is not sufficiently performed, and the exposed portion is eluted at the time of development; on the other hand, if it is more than the above upper limit, yellowing of the obtained colored layer is obtained. Enhanced, there are cases where the brightness is lowered.

<solvent>

The solvent used in the present invention is not particularly limited as long as it does not react with each component in the colored resin composition and can dissolve or disperse the organic solvent. The solvent may be used singly or in combination of two or more.

Specific examples of the solvent include alcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxylated alcohol; methoxyethoxyethanol and ethoxyethoxyethanol; Keben alcohol solvent; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, methyl hydroxypropionate , ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, An ester solvent such as ethyl lactate or cyclohexanol acetate; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), glycolic acid acetate solvent such as 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyacetate Carbopol acetate solvent such as ethoxyethyl ester, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); propylene glycol diacetate, 1,3-butylene glycol diacetate Diacetate such as ester; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol A glycol ether solvent such as monomethyl ether or dipropylene glycol dimethyl ether; aprotic oxime such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone Amine solvent; lactone solvent such as γ-butyrolactone; cyclic ether solvent such as tetrahydrofuran; unsaturated hydrocarbon solvent such as benzene, toluene, xylene or naphthalene; N-heptane, N-hexane, N-octyl Saturated hydrocarbon solvent such as alkane; toluene, two An organic solvent such as an aromatic hydrocarbon such as toluene. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, or an ester solvent is preferably used from the viewpoint of solubility with other components. In particular, the solvent used in the present invention is preferably derived from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, butyl carbitol acetic acid, from the viewpoints of solubility to other components and coating suitability. a group consisting of ester (BCA), acetic acid-3-methoxy-3-methyl-1-butyl ester, ethyl 3-ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate Select one or more of the groups.

In the present invention, it is preferred to use ethyl 3-ethoxypropionate or 3-methoxy-3-methylbutyl acetate at a boiling point of 150 ° C to 200 ° C, when the pigment concentration is 30%. In the above case, the high boiling point solvent preferably contains 0 to 40% by mass of the total solvent, and more preferably 0 to 30% by mass. If the high boiling point solvent content is within the above range, by improving the resolubility, even if the pigment is highly concentrated, the developability and resolubility are good. Effect.

<arbitrarily added ingredients>

In the colored resin composition for a color filter, various additives may be contained as needed.

The additive may, for example, be a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a adhesion promoter, or the like, in addition to an antioxidant.

Further, a color material such as a dye may be contained within a range that does not impair the effects of the present invention.

The colored resin composition for a color filter of the present invention preferably further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include a hindered phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and an oxime-based antioxidant, and are preferably blocked from the viewpoint of heat resistance. Phenolic antioxidants. For example, a latent antioxidant as described in International Publication No. 2014/021023 can also be used.

The hindered phenolic antioxidant is, for example, neopentyl alcohol oxime [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation) 1,3,5-gin(3,5-di-t-butyl-4-hydroxybenzyl)iso-cyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-gin ( 4-hydroxy-3,5-di-t-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis(6-t-butyl-4-methyl) (trade name: SUMIRAIZA-MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGAMOD 195, BASF system) and so on. Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX) is preferred. 1010, made by BASF).

In the colored resin composition for a color filter of the present invention, when the photosensitive coloring resin composition is combined with the above-described oxime ester-based photoinitiator and an antioxidant, it is less likely to occur during development by the multiplication effect. It is preferable that the peeling and the damage caused by the development during the development are caused by the fact that the colored layer is not easily caused by the diffuse reflection of light when viewed from the oblique direction. Since the colored resin composition for a color filter of the present invention contains the red pigment, the pigment concentration tends to be high, and it is preferable to contain it in combination from the viewpoint of the above problems.

The content of the antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the total solid content in the colored resin composition. When it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the above-described oxime ester photoinitiator, the antioxidant content is 100 parts by mass based on the total amount of the above oxime ester photoinitiator, and the antioxidant is preferably 1 part by mass or more and 250. It is more preferably 3 parts by mass or more and 80 parts by mass or less, and particularly preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the above range, the effect of the above combination is excellent.

Specific examples of the surfactant and the plasticizer are, for example, those described in JP-A-2013-029832.

染料、酞菁染料、 靛藍染料等。 Further, the dye system can be appropriately selected from known dyes, and specific examples thereof include an azo dye, an anthraquinone dye, and a triphenylmethane dye.

Dyes, phthalocyanine dyes, indigo dyes, and the like.

<Bonding ratio of each component in the colored resin composition for color filter>

The total content of the pigment is preferably a ratio of 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total amount of the solid content of the colored resin composition for a color filter.

When the color filter is colored to a predetermined thickness (usually 1.0 to 5.0 μm), the colored layer has a sufficient color density. In addition, when it is at most the above upper limit value, a coloring layer which is excellent in storage stability, has sufficient hardness, and has adhesion to a substrate can be obtained. In particular, when a high pigment concentration colored layer is formed, the pigment content is preferably 15 to 65 mass%, more preferably 25 to 60 mass%, based on the total amount of the solid content of the colored resin composition for a color filter. Proportional blending.

Further, the content of the dispersant is not particularly limited as long as the pigment can be uniformly dispersed. For example, the total amount of the solid content of the colored resin composition for the color filter can be 1 to 40 mass. %. Further, the total amount of the solid content of the colored resin composition for a color filter is preferably blended in a ratio of 2 to 30% by mass, more preferably 3 to 25% by mass. When it is more than the above lower limit value, the dispersibility of the pigment and the dispersion stability are excellent, and the coloring resin composition for a color filter is more excellent in storage stability. Moreover, when it is below the said upper limit, the developability is favorable. In particular, when a high pigment concentration colored layer is formed, the dispersant content is preferably 2 to 25% by mass, more preferably 3 to 20% by mass, based on the total amount of the solid content of the colored resin composition for a color filter. The ratio of blending. In addition, when the mass of the dispersing agent is in the form of a salt block copolymer, the block copolymer before the salt formation and one or more selected from the group consisting of the above general formulas (I) to (III) The total mass of the compounds.

In addition, the solvent content may be appropriately set within a range in which the coloring layer can be formed with high precision. The total amount of the colored resin composition for the color filter containing the solvent is usually preferably in the range of 55 to 95% by mass, more preferably 65 to 88% by mass. When the solvent content is within the above range, the coating property is excellent.

<Coloring layer of colored resin composition for color filter>

When the colored resin composition for a first color filter of the present invention is used to form a colored layer of the colored resin composition, color measurement is performed using a C light source, and in the XYZ chromaticity system of JIS Z8701:1999, the chromaticity coordinate system x = 0.630 to 0.665, y = 0.326 to 0.335, and the phase difference (Rth) of light having a wavelength of 620 nm in the thickness direction of the colored layer is -30 nm or more and 120 nm or less.

Among them, from the viewpoint of improving color reproducibility, it is preferable to form a cured film in the range of x=0.640~0.665 and y=0.326~0.335, and a better system can form x=0.650~0.665, y=0.326~ A cured film in the range of 0.335.

The phase difference (Rth) of the light having a wavelength of 620 nm in the thickness direction of the colored layer is preferably -30 nm or more and 60 nm or less, more preferably -20 nm or more and 45 nm or less, and particularly preferably -10 nm or more and 20 nm or less.

Further, the contrast of the colored layer is preferably 4,000 or more, more preferably 5,000 or more, and particularly preferably 6,000 or more. By using the red pigment represented by the above chemical formula (1-1), the phase difference in the range of chromaticity (x, y) of 0.630 ≦ x ≦ 0.665 and 0.326 ≦ y ≦ 0.335 is less increased, and luminance and contrast can be improved.

In the colored resin composition for a second color filter of the present invention, the pigment further contains one of a red pigment, an orange pigment, and a yellow pigment different from the red pigment represented by the above general formula (1). Above pigment, and when forming When coloring the coloring layer of the resin composition, color measurement is performed using a C light source. In the XYZ chromaticity system of JIS Z8701:1999, the chromaticity coordinate system x=0.630 to 0.665, y=0.295 to 0.360, and the thickness direction of the colored layer The phase difference (Rth) of the light having a wavelength of 620 nm is -30 nm or more and 120 nm or less.

Among them, from the viewpoint of improving color reproducibility, it is preferable to form a cured film in the range of x=0.630~0.665 and y=0.315~0.340, and a better system can form x=0.640~0.665, y=0.315~ A cured film in the range of 0.335.

The phase difference (Rth) of the light having a wavelength of 620 nm in the thickness direction of the colored layer is preferably -30 nm or more and 60 nm or less, more preferably -20 nm or more and 45 nm or less, and particularly preferably 0 nm or more and 10 nm or less.

Further, the contrast of the colored layer is preferably 4,000 or more, more preferably 5,000 or more, and particularly preferably 6,000 or more. By using the red pigment represented by the above chemical formula (1-1), the phase difference in the range of chromaticity (x, y) of 0.630 ≦ x ≦ 0.665 and 0.295 ≦ y ≦ 0.360 is less increased, and luminance and contrast can be improved.

Further, the thickness of the colored layer is preferably 0.5 to 5 μm, more preferably 1 to 3 μm.

In the retardation (Rth) of the colored layer in the present invention, for example, a refractive index at an arbitrary wavelength is measured using a phase difference layer measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS Co., Ltd.), and can be calculated by the following formula.

Rth=((Nx+Ny)/2-Nz)d

Nx: in-plane slow axis refractive index

Ny: in-plane fast axis refractive index

Nz: refractive index in the thickness direction

d: film thickness (nm)

The thickness of the colored layer is not particularly limited, but is preferably 1 to 3 μm.

<Method for Producing Colored Resin Composition for Color Filter>

The method for producing the colored resin composition for a color filter of the present invention is not particularly limited. For example, the pigment containing the red pigment represented by the above general formula (1) and the constituent unit represented by the above general formula (2) are contained. An alkali-soluble resin, a monomer, a photoinitiator, and other components as needed may be added to the dispersant of the copolymer and the pigment dispersion liquid of the solvent, and may be obtained by mixing using a known mixing means. Alternatively, by using the above dispersant, a dispersion of a red pigment represented by the general formula (1) and a pigment dispersion of other pigments as needed, and each dispersion, an alkali-soluble resin, a monomer, and a photoinitiator are separately prepared. And other components as needed may be obtained by mixing using a known mixing means.

The method for producing the pigment dispersion liquid is not particularly limited as long as it is a method in which the pigment is dispersed in a solvent to obtain a pigment dispersion liquid.

In the preparation of the dispersion, the pigment can be dispersed using a conventionally known disperser.

Specific examples of the dispersing machine include, for example, a roller mill such as a twin roll machine and a three roll machine; a ball mill such as a ball mill or a vibrating ball mill; a bead mill such as a paint regulator, a continuous disc bead mill, and a continuous ring bead mill; machine. The preferred dispersion condition of the bead mill is preferably 0.03 to 3.0 mm, more preferably 0.05 to 2.0 mm.

Specifically, for example, pre-dispersion is carried out using 2.0 mm zirconia beads having a large bead diameter, and then 0.1 mm zirconia beads having a small bead diameter are used for formal dispersion. Further, after dispersion, it is preferred to carry out filtration using a 0.5 to 2 μm filter.

[Color Filter]

The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, wherein at least one of the colored layers has a cured product of the colored resin composition for the color filter of the present invention. The color layer.

The color filter of the present invention is described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention is provided with a substrate 1, a light blocking portion 2, and a coloring layer 3.

(colored layer)

At least one of the coloring layers used in the color filter of the present invention is a cured layer of the colored resin composition for a color filter of the present invention, and a colored layer formed by curing the colored resin composition.

The colored layer is usually formed in an opening of a light-shielding portion on a substrate to be described later, and is usually composed of a three-color or more colored pattern.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration of the colored resin composition for a color filter, the viscosity, and the like, and is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, according to the method described below.

First, the colored resin composition for a color filter of the present invention is applied to a colored resin composition by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed on a substrate to be described later. Among them, a spin coating method or a die coating method is preferably used.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to a mask having a predetermined pattern, and an alkali-soluble resin, a monomer, or the like is photopolymerized to form a cured coating film. Examples of the light source used for the 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 in accordance with the light source used, the thickness of the coating film, and the like.

Further, in order to promote the polymerization reaction after the exposure, heat treatment may be performed. The heating conditions are appropriately selected in accordance with the blending ratio of each component in the colored resin composition for a color filter to be used, the thickness of the coating film, and the like.

Next, development treatment is carried out using a developing solution, and the unexposed portion is removed by dissolution to form a coating film in a desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. A surfactant or the like may be appropriately added to the alkali solution. Further, the development method can be carried out by a general method.

After the development treatment, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition for the color filter is dried to form a colored layer. Further, after the development treatment, heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected in accordance with the use of the coating film.

(lighting part)

The light-shielding portion of the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be used in the same manner as a general color filter used as a light-shielding portion.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light shielding portion may be a metal thin film which is subjected to chromium or the like by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing, for example, light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in the resin binder. Contain When the resin layer of the light-blocking particles is used, for example, a method of patterning by development using a photosensitive photoresist, a method of patterning using an inkjet ink containing light-shielding particles, and a thermal transfer of a photosensitive photoresist can be employed. Method etc.

The film thickness of the light-shielding portion is about 0.2 to 0.4 μm in the case of a metal thin film, and is about 0.5 to 2 μm when the black pigment is dispersed or dissolved in the binder resin.

(substrate)

As the substrate, a transparent substrate or a germanium substrate to be described later is used, and an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on the substrates.

The transparent substrate of the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, for example, a non-flexible transparent rigid material such as quartz glass, an alkali-free glass, or a synthetic quartz plate; or a transparent transparent film such as a transparent resin film, an optical resin plate, or a flexible glass; material.

The thickness of the transparent substrate is not particularly limited, and may be, for example, about 100 μm to 1 mm in combination with the use of the color filter of the present invention.

Further, in the color filter of the present invention, in addition to the substrate, the light shielding portion, and the coloring layer, for example, a protective layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, and the like may be formed.

[display device]

The display device of the present invention is characterized in that the color filter of the present invention described above is provided. The configuration of the display device of the present invention is not particularly limited, and can be appropriately selected from known display devices such as a liquid crystal display device, an organic light-emitting display device, and the like. According to the present invention, even if it is a lateral electric field type liquid crystal display device, it is possible to suppress various display failures such as disorder of liquid crystal alignment due to electrical characteristics of green pixels, branding due to shift of the threshold value of the switch, and thus it is suitable for liquid crystal. Display device.

<Liquid crystal display device>

A liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

A liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic view showing an example of a display device of the present invention, and a schematic view showing an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention is provided with a color filter 10, an opposite substrate 20 having a TFT array substrate, and the like, and between the color filter 10 and the opposite substrate 20 The liquid crystal layer 30 is formed.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may be a known configuration of a liquid crystal display device in which a color filter is generally used.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Such a driving method may be, for example, a TN method, an IPS method, an OCB method, or an MVA method. The invention preferably adopts any of these methods.

Further, the counter substrate can be appropriately selected in accordance with the driving method of the liquid crystal display device of the present invention.

Furthermore, the liquid crystal system constituting the liquid crystal layer can be combined with the driving of the liquid crystal display device of the present invention. Various methods, such as various liquid crystals having different dielectric anisotropy, and mixtures thereof.

As a method of forming the liquid crystal layer, a method employed in a method of manufacturing a general liquid crystal cell, for example, a vacuum injection method, a liquid crystal dropping method, or the like can be used.

<Organic light-emitting display device>

An organic light-emitting display device of the present invention is characterized by comprising the color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing another example of the display device of the present invention, and is a schematic view showing an example of an organic light-emitting display device. As illustrated in FIG. 3, the organic light-emitting display device 100 of the present invention is provided with a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

The method of laminating the organic light-emitting body 80 is, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter. A method of bonding an organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 71, and the cathode 76 of the organic light-emitting body 80, and other structures can be suitably used. The organic light-emitting display device 100 manufactured in this manner can also be applied to, for example, a passively driven organic EL display, and can also be applied to an active-drive organic EL display.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be used as a known configuration of an organic light-emitting display device in which a color filter is generally used.

[Examples]

Hereinafter, an exemplary embodiment of the present invention will be specifically described. However, the present invention is not limited by the description.

(Production Example 1: Production of Dispersant I)

(1) Synthesis of block copolymer I

PTFE: 250 parts by mass and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-port separable flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet tube, a mechanical stirrer, and a digital thermometer. Fully perform nitrogen substitution. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Further, B block was used as a monomer, 2.22 parts by mass of E-methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 2-ethyl methacrylate. 12.8 parts by mass of hexyl ester (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA), used for addition. The funnel dripped for 60 minutes. After 30 minutes, 26.6 parts by mass of dimethylaminoethyl methacrylate (DMMA) belonging to the monomer for the A block was dropped over 20 minutes. After the reaction for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration, vacuum drying, and diluted with PGMEA to obtain a 30% by mass solid solution. 32.5 parts by mass of water was added, and the temperature was raised to 100 ° C to carry out a reaction for 7 hours, and the structural unit derived from EEMA was deprotected to obtain a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, and subjected to purification by filtration and vacuum drying to obtain an A block containing a structural unit represented by the general formula (2), and a carboxyl group-derived monomer. Constituent unit and solvophilic Block B copolymer block I. The block copolymer I obtained in accordance with the above was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730.

(2) Synthesis of salt block copolymer I (dispersant I)

In a 100 mL round bottom flask, the block copolymer I was dissolved in 42.12 parts by mass of PGMEA: 10.0 parts by mass, and 0.53 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) belonging to the compound of the above general formula (III) was added ( The compound of the above formula (III) is stirred with a reaction temperature of 30 ° C for 20 hours with respect to the DMMA unit of the block copolymer I, 0.20 mol, to obtain a solid block copolymer of 20% by mass. I (dispersant I) solution.

(Production Example 2: Production of Dispersant II)

The salt type block copolymer II (dispersant II) was obtained in the same manner as in Production Example 1 except that the amount of the monomer was changed as shown in the following Table 1.

(Production Example 3: Production of Dispersant III)

In Production Example 1, instead of the synthetic block copolymer I, Disperbyk LPN6919 (acrylic dispersant, 60% solid content, manufactured by BYK-Chemie Co., Ltd.) (amine value: 120 mgKOH/g, solid content: 60% by mass) was prepared. Next, in (2) of Production Example 1, the salt block copolymer III was obtained in the same manner as in (2) of Production Example 1, except that the substituted block copolymer I was used instead of the above-mentioned LPN6919. Dispersant III).

(Production Example 4: Production of Dispersant IV)

In (I) of Production Example 1, except that the type and amount of the monomer were changed as shown in Table 1 below, The block copolymerization IV was obtained in the same manner as in (1) of Production Example 1. Then, in a 100 mL round bottom flask, the block copolymer IV: 10.0 parts by mass was dissolved in PGMEA: 42.56 parts by mass, and 0.64 parts by mass of benzyl chloride (manufactured by Kanto Chemical Co., Ltd.) belonging to the salt-forming component was added ( The block copolymer was stirred at a reaction temperature of 80 ° C for 12 hours with respect to a DMMA unit of 0.3 equivalent) to prepare a salt block copolymer solution IV having a solid content of 20% by mass.

In addition, the abbreviations in Table 1 are as follows:

(Production Example 5: Production of alkali-soluble resin A)

A mixture of 40 parts by mass of BzMA, MMA: 15 parts by mass, MAA: 25 parts by mass, and 3 parts by mass of azoisobutyronitrile (AIBN) was dropped into the PGMEA 150 at 100 ° C for 3 hours under a nitrogen stream. Parts by mass in the polymerization tank. After the completion of the dropwise addition, the mixture was further heated at 100 ° C for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7,000.

Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heating was carried out at 110 ° C for 10 hours. The reaction of the carboxylic acid group of the main chain methacrylic acid with the epoxy group of glycidyl methacrylate was carried out to obtain an alkali-soluble resin A solution. In the reaction, in order to prevent polymerization of glycidyl methacrylate, air is bubbled in the reaction solution. Again, the reaction is followed by measuring the acid number of the solution. The obtained alkali-soluble resin A solution was obtained by introducing a side chain having an ethylenic double bond into a main chain formed by copolymerization of BzMA, MMA, and MAA, and the solid content was 40% by mass and the acid value was 74 mgKOH/g. The weight average molecular weight is 12,000.

(Production Example 6: Production of alkali-soluble resin B)

15 parts by mass of styrene (St), 5 parts by mass of cyclohexyl methacrylate (CHMA), 23.9 parts by mass of MMA, 26.9 parts by mass of MAA, and 3 parts by mass of azoisobutyronitrile (AIBN) Under a nitrogen stream, it was dropped at 100 ° C for 3 hours in a polymerization tank filled with 150 parts by mass of PGMEA. After the completion of the dropwise addition, heating was further carried out at 100 ° C for 3 hours to obtain a polymer solution.

Next, 29.2 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heating was carried out at 110 ° C for 10 hours. And the carboxylic acid group of the main chain methacrylic acid is The reaction with an epoxy group of glycidyl methacrylate gives an alkali-soluble resin B solution. In the reaction, in order to prevent polymerization of glycidyl methacrylate, air is bubbled in the reaction solution. Again, the reaction is followed by measuring the acid number of the solution. The obtained alkali-soluble resin B solution is a resin obtained by copolymerization of St, CHMA, MMA, and MAA, and a resin having a side chain having an ethylenic double bond is introduced using GMA, and the solid content is 40% by mass and the acid value is 77 mgKOH. /g, weight average molecular weight of 17600.

(Production Example 7: Production of alkali-soluble resin C (polyamidoximine resin))

In a flask equipped with a stirring device, a thermometer, and a condenser, 1086 parts by mass of PGMEA and IPDI3N (iso-isocyanate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) were added in an amount of 587.3 parts by mass (0.80). Mole) and 499.1 parts by mass (2.52 mole parts) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were heated to 140 °C. The reaction is carried out under foaming. The reaction was carried out at this temperature for 8 hours. In the system, a pale yellow liquid was obtained, and the characteristic absorption was measured by infrared spectroscopy. As a result, it was confirmed that 2270 cm ^-1 which absorbed the characteristic of the isocyanate group completely disappeared, and the absorption of the quinone imine group was observed at 1780 cm ^-1 and 1720 cm ^-1 .

After cooling to 110 ° C, 1.2 parts by mass of p-methoxyphenol, 153.5 parts by mass of glycidyl methacrylate (GMA) (1.08 mole parts), and 9.6 parts by mass of triethylamine were added, and the temperature was adjusted at 110 ° C for 15 hours. Addition reaction. When the characteristic absorption was measured by infrared spectroscopy, it was confirmed that the absorption of 1860 cm ^{-1 which} is characteristic absorption of the acid anhydride group was completely disappeared. The acid value was 148 KOH mg/g in terms of solid content, and the molecular weight was an average molecular weight of 5,000 in terms of polystyrene. Further, the concentration of the resin component was 51.3% by mass. This was made into an alkali-soluble resin C solution. The obtained alkali-soluble resin C solution was a polyamidoximine resin having a carboxyl group, and a resin having a side chain of an ethylenic double bond was introduced using GMA.

(Examples 1 to 16: Preparation of Pigment Dispersion)

According to the composition shown in the following Table 2, 100 parts by mass of a pigment, a dispersant, a pigment derivative, an alkali-soluble resin, a pigment dispersant, a solvent, and a particle diameter of 2.0 mm of zirconia balls were respectively charged into the melon. In the squeeze bottle, the pre-crushing system was shaken for 1 hour using a paint stirrer (made by Asada Iron Works Co., Ltd.), and then the zirconia balls having a particle diameter of 2.0 mm were taken out, and the quality of the zirconia balls having a particle diameter of 0.1 mm was added. In the same manner, the main crushing was carried out for 6 hours using a paint shaker, and the pigment dispersion liquids of Examples 1 to 16 were obtained.

(Comparative Examples 1 to 2: Preparation of Comparative Pigment Dispersion)

A pigment, a dispersant, a solvent, and the like were each mixed so as to have a composition shown in the following Table 2 to obtain a comparative pigment dispersion.

The chemical formula numbers in Table 2 correspond to the respective chemical formulas described in the pigment and pigment derivative terms. Further, in Table 2, R177 represents C.I. Pigment Red 177, and Y150 represents C.I. Pigment Yellow 150.

(Example 17: Preparation of colored resin composition)

The following components were mixed to prepare a colored resin composition.

‧ Pigment dispersion of Example 1 (solid content 21.5% by mass): 48.3 parts by mass

‧ Alkali-soluble resin A (BzMA/MMA/MAA/GMA=40/15/25/20% by mass, weight average molecular weight 12,000, PGMEA solution, solid content 40% by mass): 6.0 parts by mass

‧Photocurable polyfunctional monomer (Aronix M-305, manufactured by Toagosei): 5.6 parts by mass

‧Photopolymerization initiator (BASF, IRGACURE 907): 1.07 parts by mass

‧Photopolymerization initiator (manufactured by BASF, IRGACURE 369): 1.34 parts by weight

‧Photosensitizer (4,4'-bis(dimethylamino)diphenyl ketone): 0.27 parts by weight

‧Interactive surfactant (DIC (manufactured by the company), MEGAFAC R-08MH): 0.9 parts by mass

‧PGMEA: 36.5 parts by mass

(Examples 18 to 39: Preparation of Colored Resin Composition)

In the preparation of the colored resin composition, the coloring resin compositions of Examples 18 to 39 were prepared in the same manner as in Example 17 except that the blending amounts of the respective components were changed as shown in Tables 3 and 4 below.

In addition, among the components described in Tables 3 and 4 below, the first appearance is as follows:

‧Photocurable polyfunctional monomer (EO modification) (Aramid M-350)

‧ Lanthanide photopolymerization initiator (made by ADEKA, ADEKA ARKLS N-1919)

(Comparative Example 3)

In the above Example 18, the pigment dispersion liquid of Comparative Example 2 was used instead of the pigment dispersion liquid of Example 1, and the blending amount of each component was changed as shown in Table 3 below, and the rest were in accordance with the examples. 18 The coloring resin composition of Comparative Example 3 was prepared in the same manner.

In addition, since the results of the evaluation of the stability over time of Comparative Example 1 were gelatinized, the preparation of the colored resin composition could not be performed.

[Evaluation]

<Evaluation of Dispersion Stability of Pigment Dispersion>

The pigment dispersion liquids of the examples and the comparative examples were each stored at room temperature (25 ° C), and the viscosity was measured after one day of storage and one month after the preparation. The viscosity was measured by a vibrating viscometer (VM-200T2 manufactured by SEKONIC) at 25.0 ± 1.0 ° C, and the value after 30 seconds from the start of measurement was used.

The viscosity after 1 day of dispersion was compared with the viscosity after storage for 1 month, and the viscosity was changed to 2% or less, and the viscosity change was 5% or less, and the viscosity was rated as "A". Those who have changed by more than 5% and less than 10% are rated as "B", and those who have changed by more than 10% are rated as "C". The results are shown in Table 2. If the viscosity changes within 10%, it is considered to be excellent in dispersion stability and is a practical range.

<Optical characteristic evaluation>

The colored resin composition obtained in each of the examples and the comparative examples was applied to a glass substrate by a spin coater and then baked to a desired color (red colored layer: x=0.630 under a C light source). (NH TECHNO GLASS (shares) system, "NA35"). After heating and drying on a hot plate at 80 ° C for 3 minutes, ultraviolet rays of 60 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. Then, baking was performed for 25 minutes in a 230 ° C clean oven, and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored film were measured. The comparison was carried out by using the "Comparative Measuring Device CT-1B" manufactured by Hiroshima Electric Co., Ltd.; the chromaticity and the luminance were measured by using "Microscopic Spectrometry Apparatus OSP-SP200" manufactured by Olympus Co., Ltd.

<Evaluation of phase difference (Rth)>

The color layer retardation is based on the thickness direction retardation (Rth) calculated by the following equation. The retardation (Rth) was measured using a phase difference layer measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS Co., Ltd.). The measurement wavelength of the red colored layer was measured at 620 nm.

Rth=((Nx+Ny)/2-Nz)d

Nx: in-plane slow axis refractive index

Ny: in-plane fast axis refractive index

Nz: refractive index in the thickness direction

d: film thickness (nm)

<developability evaluation (development time)>

The colored resin compositions obtained in the examples and the comparative examples were applied to a 100 mm × 100 mm glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.) using a spin coater at a thickness of 0.7 mm, and then heated. The plate was dried at 80 ° C for 3 minutes to form a coloring layer having a thickness of 2.5 μm. The colored layer was irradiated with an ultraviolet ray of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was subjected to a shower development using a 0.05 mass% potassium hydroxide aqueous solution of an alkali developer. The development completion time at this time is set as an index of developability.

A: development time ~ 20 seconds

B: Development time 20~40 seconds

C: development time is 1 or more

<Color spot>

The colored resin compositions obtained in the examples and the comparative examples were applied to a 100 mm × 100 mm glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.) using a spin coater at a thickness of 0.7 mm, and then heated. The plate was dried at 60 ° C for 3 minutes, and the number of revolutions was adjusted so as to become the film thickness described in the table after baking, thereby forming a colored layer. The colored layer was irradiated with an ultraviolet ray of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 80 μm and a mask width of 160 μm. The glass plate on which the colored layer was formed was subjected to a shower development using a 0.05% by mass aqueous potassium hydroxide solution of an alkali developer for 60 seconds. Next, the substrate on which the colored substrate was baked in a clean oven at 230 ° C for 30 minutes was used, and the color unevenness of the colored layer was visually observed under a light projector, and the edge portion of the colored layer in the range of 50 mm × 50 mm was measured by an optical microscope. The number of gaps.

(Color spot evaluation benchmark)

AA: no color spots, no edge gaps

A: There is no stain, and the gap at the edge is less than 20

B: Part of the observed color spots

C: Spots were observed in all

If the stain evaluation standard is AA, A or B, it is practical, but if the evaluation result is A or even AA, the effect is more excellent.

(Examples 40 to 43: Preparation of Pigment Dispersion)

Pigments, dispersants, pigment derivatives, alkali-soluble resins, pigment dispersants, and solvents were mixed according to the composition shown in Table 5 below, and the pigments of Examples 40 to 43 were obtained in the same manner as in Example 1. Dispersions.

[table 5]

The chemical formula numbers in Table 5 correspond to the respective chemical formulas described in the pigment and pigment derivative terms. Further, in Table 5, R177 represents C.I. Pigment Red 177, Y150 represents C.I. Pigment Yellow 150, and Y185 represents C.I. Pigment Yellow 185.

(Examples 51 to 58: Preparation of colored resin composition)

In the preparation of the colored resin composition described above, the colored resin compositions of Examples 51 to 58 were prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6 below.

In addition, among the components described in Table 6 below, the first appearance is as follows:

‧ Lanthanide photopolymerization initiator (made by ADEKA, ADEKA ARKLS NCI-930)

‧ Lanthanide photopolymerization initiator (manufactured by Changzhou Power Electronic New Material Co., Ltd., TR-PBG-3057)

‧Antioxidants (BASF, IRGANOX1010)

(Examples 59 to 60: Preparation of pigment dispersion and coloring resin composition)

The pigment, the dispersant, the pigment derivative, the alkali-soluble resin, the pigment dispersant, and the solvent were each mixed in the same manner as in Example 2, and the formal crushing of Example 59 was carried out by using a paint shaker for 24 hours. The dispersion was carried out, and the main crushing of Example 60 was carried out for 3 hours using a paint shaker, and each of the pigment dispersion liquids was obtained in the same manner as in Example 2.

The coloring resin compositions of Examples 59 and 60 were prepared in the same manner as in Example 18 except that the pigment dispersions of Examples 59 and 60 were used. With respect to the colored resin compositions of Examples 59 and 60, the evaluation of the phase difference and the comparison was carried out in the same manner as in Example 18. The evaluation results are shown in Table 7.

(Examples 61 to 62: Preparation of pigment dispersion liquid and coloring resin composition)

A pigment, a dispersant, a pigment derivative, an alkali-soluble resin, a pigment dispersant, and a solvent were mixed in the same manner as in Example 1, and the official crushing of Example 61 was carried out for 24 hours using a paint shaker. The dispersion was carried out, and the main crushing of Example 62 was carried out in the same manner as in Example 1 except that the dispersion was carried out for 3 hours using a paint shaker.

The colored resin compositions of Examples 61 and 62 were prepared in the same manner as in Example 17 except that the pigment dispersions of Examples 61 and 62 were used. With respect to the colored resin compositions of Examples 61 and 62, the evaluation of the phase difference and the comparison was carried out in the same manner as in Example 17.

Further, the colored resin composition of each of the examples was diluted 1000 times with PGMEA, and a laser light scattering particle size distribution analyzer (for example, Nanotrac particle size distribution manufactured by Nikkiso Co., Ltd.) was used. The measurement apparatus UPA-EX150) measured the average dispersed particle diameter at 23 ° C by a dynamic light scattering method.

The results of each evaluation are shown in Table 7.

[Results finishing]

From the results of Tables 3 and 4, it is known to use a pigment containing a red pigment represented by the general formula (1), a dispersant containing a copolymer having a structural unit represented by the general formula (2), and a pyrrole-containing compound. The pigment dispersion liquids of Examples 1 to 16 in which one or more pigment derivatives are selected from the pigment derivatives of the pyrrolidone skeleton and the pigment derivative having an azo lake skeleton are excellent in stability over time. The pigment dispersions of Examples 10 and 11 in which a sulfonated pyrrolopyrroledione derivative and a sulfonated quinophthalone derivative are used in combination are particularly excellent in stability over time.

a pigment containing a red pigment represented by the general formula (1), a dispersant containing a copolymer having a structural unit represented by the general formula (2), and a pigment derivative containing a pyrrolopyrroledione skeleton, and Among the pigment derivatives of the azo lake skeleton, one of the pigment derivatives of Examples 17 to 28 and the coloring resin compositions of Examples 32 to 39 are selected, and the colored layer color (x, y) is satisfied. 0.630≦x≦0.665, 0.326≦y≦0.335, and the optical phase difference (Rth) of the light at a wavelength of 620 nm in the thickness direction of the colored layer is -30 nm or more. Below 120 nm.

Further, one or more pigments selected from the group consisting of a pigment containing a red pigment represented by the general formula (1) and a red pigment, an orange pigment, and a yellow pigment different from the red pigment shown in the general formula (1) are used. In the colored resin compositions of Examples 27 to 31, the coloring layer chromaticity (x, y) of the coloring layer satisfies 0.630 ≦ x ≦ 0.665, 0.295 ≦ y ≦ 0.360, and light having a wavelength of 620 nm in the thickness direction of the colored layer is achieved. The phase difference (Rth) is -30 nm or more and 120 nm or less.

As is clear from the results of Table 6, when Y185 is used as the yellow pigment, the absolute value of the phase difference tends to be small. Since Y185 has an asymmetric molecular structure, it is estimated that the phase difference is not easily large.

Further, when Example 54 is compared with Example 55, Example 32, and Example 57, and Example 33 and Example 58, respectively, it is found that if a polyamidoximine resin is contained as an alkali-soluble resin, it can be lowered. The absolute value of the phase difference.

Further, when Example 32 is compared with Example 57, Example 33 and Example 58, it is found that if a polyamidoximine resin is contained as an alkali-soluble resin and at least two kinds of diphenyl sulfide skeletons are contained The lanthanide initiator has a tendency to increase the brightness.

Further, it has been found that when at least two kinds of lanthanide initiators are contained and further contain an antioxidant, even if the pigment concentration is increased, the occurrence of color spots at the edge portion can be easily suppressed.

As is apparent from the results of Table 7, in the case of the red pigment represented by the chemical formula (1-2), the smaller the average primary particle diameter of the pigment, the higher the contrast, but the larger the absolute value of the phase difference tends to be. On the other hand, the red pigment represented by the general formula (1-1) has a tendency to increase the absolute value of the phase difference even if the particle diameter is excessively reduced, and in particular, from the viewpoint of reducing the absolute value of the phase difference, the average The primary particle diameter is preferably 40 nm to 60 nm.

Claims (12)

A colored resin composition for a color filter comprising: a pigment containing a red pigment represented by the following general formula (1); a dispersant containing a copolymer of a constituent unit represented by the following general formula (2); and a pigment a derivative, an alkali-soluble resin, a monomer, a starter, and a solvent; the above pigment derivative contains a pigment derivative having a pyrrolopyrroledione skeleton and a pigment derivative having an azo lake skeleton One or more types are selected; when the coloring layer of the colored resin composition is formed, the chromaticity (x, y) of the colored layer measured by the C light source satisfies 0.630 ≦ x ≦ 0.665, 0.326 ≦ y ≦ 0.335, and light The optical phase difference (Rth) at a wavelength of 620 nm in the thickness direction of the colored layer is -30 nm or more and 120 nm or less; (In the general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl); [Chemical 2] General formula (2) (In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure; R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group; Indicates an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. The colored resin composition for a color filter according to claim 1, wherein the copolymerization system has a block portion having a structural unit represented by the above general formula (2), and has the following general formula (3); a block portion constituting the unit; the constituent unit represented by the above general formula (3) contains one selected from the group consisting of methacrylic acid, 2-hydroxyethyl methacrylate, and benzyl methacrylate. The above constituent unit; (In general formula (3), R ²¹ is a hydrogen atom or a methyl group; Q' is a direct bond or a divalent linking group; R ²² is a hydrocarbon group, -[CH(R ²³ )-CH(R ²⁴ )-O] _x -R ²⁵ or -[(CH ₂ ) _y -O] _z -R ²⁵ represents a monovalent group; R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group; R ²⁵ is a hydrogen atom, a hydrocarbon group, -CHO a monovalent group represented by -CH ₂ CHO or -CH ₂ COOR ²⁶ ; a hydrogen atom of R ²⁶ or an alkyl group having 1 to 5 carbon atoms; the above hydrocarbon group may have a substituent; and x represents an integer of 1 to 18; The y system represents an integer from 1 to 5, and the z system represents an integer from 1 to 18). The colored resin composition for a color filter according to claim 1, wherein the red pigment represented by the above formula (1) contains a red pigment represented by the following chemical formula (1-1) and the following chemical formula (1-2) Red pigment shown; A coloring resin composition for a color filter according to claim 1, wherein the alkali is The soluble resin contains a polyamidoximine resin having a carboxyl group. The colored resin composition for a color filter according to claim 1, wherein the above initiator contains at least two oxime-based initiators and further contains an antioxidant. A colored resin composition for a color filter comprising: a pigment containing a red pigment represented by the following general formula (1); a dispersant containing a copolymer of a constituent unit represented by the following general formula (2); and a pigment a derivative, an alkali-soluble resin, a monomer, a starter, and a solvent; the above pigment derivative contains a pigment derivative having a pyrrolopyrroledione skeleton and a pigment derivative having an azo lake skeleton One or more selected ones of the above pigments, the pigments further comprising one or more pigments selected from the group consisting of red pigments, orange pigments, and yellow pigments different from the red pigment shown in the above formula (1); When the coloring layer of the composition is used, the chromaticity (x, y) measured by the C light source satisfies 0.630 ≦ x ≦ 0.665, 0.295 ≦ y ≦ 0.360, and the light phase of the light at a wavelength of 620 nm in the thickness direction of the colored layer. The difference (Rth) is -30 nm or more and 120 nm or less; (In general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl); [Chem. 7] General formula (2) (In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure; R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group; Indicates an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. The coloring resin composition for a color filter according to claim 6, wherein the pigment contains C.I. Pigment Yellow 185. The colored resin composition for a color filter according to claim 6, wherein the alkali-soluble resin contains a polyamidoximine resin having a carboxyl group. The colored resin composition for a color filter according to claim 6, wherein the above initiator contains at least two oxime-based initiators and further contains an antioxidant. A pigment dispersion liquid, which is a pigment dispersion liquid for preparing a colored resin composition for a color filter according to any one of claims 1 to 9, which comprises: a pigment containing a red pigment represented by the following general formula (1), a dispersant, a pigment derivative, and a solvent containing a copolymer having a structural unit represented by the following general formula (2); the pigment derivative contains a pigment derivative having a pyrrolopyrroledione skeleton, and an azo group One or more selected from the pigment derivatives of the lake skeleton; (In general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl); (In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; and R ¹² represents an alkylene group having 1 to 8 carbon atoms, and -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ¹³ And R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, or R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure; R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group; Indicates an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. A color filter having at least a substrate and being disposed on the substrate The coloring layer is characterized in that at least one of the colored layers is a cured product of the colored resin composition for a color filter according to any one of claims 1 to 9. A display device characterized by having a color filter having a request item 11.