TWI713710B - 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, a color filter, and a display device.

In recent years, with the development of personal computers and special mobile personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet computers) has also increased, and the market for liquid crystal displays is expanding. In addition, recent organic light-emitting display devices such as organic EL displays with high visibility using self-luminescence are also a new generation of image display devices that have attracted much attention. In view of the performance of these image display devices, it is strongly expected that the contrast and color reproducibility will be improved to further enhance the image quality and reduce the power consumption.

Most conventional display devices are based on sRGB (IEC61966-2-1) according to the international standard of color space. However, because of the demand for closer real-world performance and further improvement of color reproducibility, the requirements for display devices corresponding to AdobeRGB, which has a wider color reproducing area than sRGB, are increasing. The AdobeRGB specification is defined by the color space advocated by Adobe Systems. The three primary colors of AdobeRGB are defined as follows for the chromaticity coordinates x and y of the XYZ chromaticity system. The AdobeRGB specification is characterized by a wide range 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

In addition, the corresponding specifications of the DCI (Digital Cinema Initiatives, Digital Cinema Initiatives) specification, which has a wider color reproduction area in the red and green directions than sRGB, are also required.

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 coloring patterns of the three primary colors of red, green, and blue; and formed in a way to distinguish the coloring patterns The shading part on the substrate.

Known methods for forming such colored layers include: pigment dispersion, dyeing, electrodeposition, printing, etc. Among them, from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, etc., the pigment dispersion method with excellent characteristics on average is most widely used.

For the red pigment series, diketopyrrolopyrrole pigments having excellent heat resistance and light resistance are widely used (for example, Patent Documents 1 to 3, etc.).

On the other hand, the unique problem of the liquid crystal display device lies in the problem of viewing angle dependence caused by the refractive index anisotropy of the liquid crystal cell and the polarizing plate. The problem of the viewing angle dependence is that when the liquid crystal display device is viewed from the front and when viewed from an oblique direction, the color tone and contrast of the viewed image change. This problem of viewing angle characteristics has become more important with the large screens of liquid crystal display devices in recent years.

In order to improve the dependence of the viewing angle, a method of assembling a retardation film in a liquid crystal display device is widely used. However, because the color filter used in the liquid crystal display device has a different phase difference depending on the color pattern of each color of the colored layer, When the above-mentioned retardation film is used, there is a problem that it is impossible to compensate for the difference in the retardation of the colored patterns of each color, and it is quite difficult to completely solve the problem of viewing angle dependence.

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

[Prior Technical Literature] [Patent Literature]

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

Patent Document 2: International Publication No. 2012/102399

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

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

The present invention has been completed in view of the foregoing facts, and its object is to provide a colored resin composition for a color filter that can form red pixels satisfying a specific chromaticity and a specific phase difference, and a pigment dispersion for preparing the colored resin composition, A color filter meeting a specific chromaticity and a specific phase difference, and a display device using the color filter.

The colored resin composition for the first color filter of the present invention contains: a pigment containing a red pigment represented by the following general formula (1), and containing a pigment represented by the following general formula (2) Dispersants, pigment derivatives, alkali-soluble resins, monomers, initiators, and solvents of the copolymer of the constituent units; among them, The above-mentioned pigment derivative contains at least one selected from a pigment derivative having a diketopyrrolopyrrole skeleton and a pigment derivative having an azo lake skeleton; When forming the colored layer of the colored resin composition, the chromaticity (x, y) of the colored layer measured by 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 retardation (Rth) at a wavelength of 620nm is -30nm or more and 120nm 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 general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl.)

(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 general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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.

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

The second colored resin composition for color filters of the present invention contains: a pigment containing a red pigment represented by the above general formula (1), a dispersant containing a copolymer having a structural unit represented by the above general formula (2), Pigment derivatives, alkali-soluble resins, monomers, initiators, and solvents; wherein the above-mentioned pigment derivatives contain pigment derivatives having a diketopyrrolopyrrole skeleton and pigments derived from an azo lake skeleton One or more selected from among the above-mentioned pigments; the above-mentioned pigment further contains one or more selected from among red pigments, orange pigments, and yellow pigments that are different from the red pigment represented by the above general formula (1); For 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 620nm The optical phase difference (Rth) is above -30nm and below 120nm.

The colored resin composition for a color filter of the present invention is based on the viewpoint of pigment dispersibility and dispersion stability. The copolymer preferably has: a block portion having a structural unit represented by the general formula (2) , And a block part with the structural unit represented by the following general formula (3); the structural unit represented by the above general formula (3) contains a mixture of methacrylic acid, 2-hydroxyethyl methacrylate, and methyl One or more structural 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 is} 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, and -CHO , -CH ₂ CHO, or -CH ₂ COOR ^{26 is} a monovalent group; R ²⁶ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms.

The above-mentioned hydrocarbon group may have a substituent.

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

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

[化5]

In the colored resin composition for color filters of the present invention, from the viewpoint that the absolute value of the retardation can be easily reduced, the alkali-soluble resin is preferably a polyamide resin having a carboxyl group.

The colored resin composition for a color filter of the present invention is preferably the above-mentioned initiator from the viewpoints that voids are unlikely to occur in the colored layer and the color unevenness caused by the diffuse reflection of light when the colored layer is viewed obliquely is suppressed It contains at least two oxime-based initiators, and more preferably contains antioxidants.

Furthermore, the colored resin composition for the second color filter of the present invention is preferably a pigment containing CI Pigment Yellow from the viewpoint of satisfying the required hue and retardation and easily reducing the absolute value of the retardation 185.

The pigment dispersion of the present invention contains: a pigment containing a red pigment represented by the above general formula (1), a dispersant containing a copolymer having a structural unit represented by the above general formula (2), a pigment derivative, and a solvent; Among them, the above-mentioned pigment derivative contains at least one selected from a pigment derivative having a diketopyrrolopyrrole skeleton and a pigment derivative having an azo lake skeleton.

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate; wherein at least one of the coloring layers is the color filter described in any one of claims 1 to 5 Use hardened colored resin composition.

Furthermore, the display device provided by the present invention is characterized by having the above-mentioned color Filter.

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

1‧‧‧Substrate

2‧‧‧Shading part

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧Opposite substrate

30‧‧‧Liquid crystal layer

40‧‧‧LCD device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧hole injection layer

73‧‧‧Electric tunnel transport layer

74‧‧‧Light-emitting layer

75‧‧‧Electron injection layer

76‧‧‧Cathode

80‧‧‧Organic luminous body

100‧‧‧Organic light emitting display device

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

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

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

Hereinafter, the colored resin composition for color filters of the present invention, the pigment dispersion for preparing the colored resin composition for color filters, the color filter, and the display device will be described in order in detail.

In addition, in the present invention, the light system covers electromagnetic waves of visible and non-visible wavelengths and radiation, and the radiation system covers, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less, and electron beams.

In the present invention, "(meth)acryl" refers to acrylic and methacryl, respectively, and "(meth)acrylate" refers to acrylate and methacrylate, respectively.

[Colored resin composition for color filter]

The colored resin composition for the first color filter of the present invention contains: a pigment containing a red pigment represented by the following general formula (1), and containing a composition represented by the following general formula (2) The coloring resin composition of a copolymer of a unit, a pigment derivative, an alkali-soluble resin, a monomer, an initiator, and a solvent, wherein the pigment derivative contains a pigment having a diketopyrrolopyrrole skeleton One or more selected among derivatives and pigment derivatives with an azo lake skeleton; when forming the colored layer of the colored resin composition, the colored layer is measured with a C light source (x, y) It satisfies 0.630≦x≦0.665 and 0.326≦y≦0.335, and the optical retardation (Rth) of the wavelength 620nm of the light in the thickness direction of the colored layer is -30nm or more and 120nm 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 general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl.)

(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 general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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.

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

Furthermore, the second colored resin composition for color filters of the present invention contains: a pigment containing a red pigment represented by the above general formula (1), and a copolymer containing a structural unit represented by the above general formula (2) The coloring resin composition of a dispersant, a pigment derivative, an alkali-soluble resin, a monomer, a starter, and a solvent, wherein the pigment derivative contains a pigment derivative with a diketopyrrolopyrrole skeleton, and One or more selected from pigment derivatives having an azo lake skeleton; the above-mentioned pigment further contains a red pigment, an orange pigment, and a yellow pigment that are different from the red pigment represented by the above general formula (1) One or more pigments; when forming the colored 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 optical retardation (Rth) of the wavelength 620nm of the light in the thickness direction of the colored layer is -30nm or more and 120nm or less.

According to the present invention, by combining 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), and a specific pigment derivative, In the dispersing step of the red pigment shown in (1), the above-mentioned specific pigment derivative is adsorbed on the surface of the micronized pigment to increase the affinity with the nitrogen atom in the structural unit represented by the general formula (2) of the dispersant Performance, excellent pigment dispersibility and dispersion stability, when forming the colored 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, 0.326≦y≦0.335, and the optical retardation (Rth) at a wavelength of 620nm in the thickness direction of the colored layer is -30nm or more And below 120nm, or the chromaticity (x, y) of the colored layer measured by C light source satisfies 0.630≦x≦0.665, 0.295≦y≦0.360, and the optical retardation (Rth ) Be -30nm or more and 120nm or less.

The colored resin composition for color filters of the present invention contains at least: a pigment, a dispersant, an alkali-soluble resin, a monomer, an initiator, and a solvent. It can go further within a range that does not impair the effects of the present invention. Contains other ingredients. Hereinafter, each component of the colored resin composition for color filters 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 system contains at least a red pigment represented by the following general formula (1):

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

Since the colored resin composition for color filters of the present invention contains the above-mentioned specific pigment, it can form a colored layer having a specific chromaticity and a specific phase difference.

The specific system of the red pigment represented by the above general formula (1) can be, for example, the following The red pigment represented by the formula (1-1) to the chemical formula (1-3) can be used alone or in combination of two or more.

In the present invention, from the viewpoint that chromaticity and phase difference can be adjusted to desired values, it is preferable to use the red pigment represented by the chemical formula (1-1) and the red pigment represented by the chemical formula (1-2) in combination.

In the present invention, the red pigment represented by the chemical formula (1-1) is used in combination with 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 within the range of 0.630≦x≦0.665, 0.326≦y≦0.335, and the phase difference is adjusted to be less than 10, the red pigment shown in the chemical formula (1-1) and the chemical formula (1) -2) The quality of the red pigment shown is better than 100:0~60:40, more preferably 100:0~75:25. In addition, when the chromaticity (x, y) is within the range of 0.630≦x≦0.665 and 0.326≦y≦0.335, when 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 pigments shown is better than 60:40~0:100, and more preferably 45:55~15:85.

Furthermore, from the viewpoint of reducing the absolute value of the retardation and increasing the contrast, it is preferable to use the red pigment represented by the chemical formula (1-1). In this case, the red pigment represented by the chemical formula (1-1) is based on 100 parts by mass of the total amount of red pigment, preferably at least 40 parts by mass, more preferably at least 50 parts by mass.

(Other paints)

In the present invention, other pigments different from the red pigment represented by the general formula (1) can also be used in combination within a range that 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.

Examples of yellow pigments include: 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, etc. C.I. Pigment Yellow 150 and its derivative pigments are based on Japanese Patent Publication No. 2001-354869, Japanese Patent Publication No. 2005-325350, and Japanese Patent Application Publication No. 2007-25687 No. Bulletin, JP 2007-23287 Bulletin, JP 2007-23288 Bulletin, and JP 2008-24927 Bulletin are available.

The yellow pigment system is preferably C.I. Pigment Yellow 185 from the viewpoint of meeting the required hue and phase difference and being able to easily reduce the absolute value of the phase difference. In addition, when C.I. Pigment Yellow 185 is contained, because of its high tinting power, it also has the advantages of easily reducing the pigment concentration and improving plate-making properties.

Examples of red pigments include: 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, 63:1, 63:1, 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.

Furthermore, the orange pigment series can include, 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. From the viewpoint of chromaticity and retardation, the general formula (1 The red pigment shown in) is preferably at least 10 parts by mass, more preferably at least 20 parts by mass, particularly preferably at least 50 parts by mass.

The average dispersed particle diameter of the pigment used in the present invention is based on the pigment used. The type of the material varies, but it is preferably in the range of 10 nm or more and 100 nm, more preferably in the range of 15 nm or more and 60 nm or less. When the average dispersed particle diameter of the pigment is within the above-mentioned range, a display device equipped with a color filter manufactured using the resin composition of the present invention can be made of high contrast and high quality.

Although the average dispersed particle diameter of the pigment within the above range is smaller, the contrast can be improved, but the absolute value of the phase difference tends to increase. Therefore, it is best to consider the required phase difference and comparison before selecting the average dispersion particle size. Especially related to the red pigment represented by the general formula (1-1), the absolute value of the phase difference tends to increase even if the particle size is excessively reduced. Among them, from the viewpoint of reducing the absolute value of the phase difference, the average dispersed particle size is preferably 40nm~60nm.

In addition, the average dispersed particle diameter of the pigment in the colored resin composition is the dispersed particle diameter of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured with a laser light scattering particle size distribution analyzer. The particle size measurement by the laser light scattering particle size analyzer is to use the solvent used in the colored resin composition to properly dilute the colored resin composition to a concentration that can be measured by the laser light scattering particle size analyzer (for example, 1000 times, etc.). Using a laser light scattering particle size distribution analyzer (for example, Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.), the measurement can be performed at 23° C. by the dynamic light scattering method. The average dispersed particle diameter here refers to the volume average particle diameter.

<Pigment Derivatives>

Furthermore, the colored resin composition for color filters of the present invention further contains from the viewpoint that the phase difference and brightness are adjusted to be within a specific range and the pigment dispersibility and dispersion stability are excellent. One or more pigment derivatives selected from pigment derivatives with a diketopyrrolopyrrole skeleton and pigment derivatives with an azo lake skeleton. By appropriately selecting the pigment derivative, the absolute value of the phase difference can be reduced.

In addition, the diketopyrrolopyrrole skeleton system may include, for example, C.I. Pigment Red 254, 255, 264, 272, and these halogen-substituted pigments, among which C.I. Pigment Red 254, 272 is preferred. In addition, examples of the azo lake pigment skeleton system include C.I. Pigment Red 48 and the like.

In the present invention, it is preferable to use an alkylated diketopyrrolopyrrole derivative represented by the following general formula A, an aminated diketopyrrolopyrrole derivative represented by general formula B, and the following general formula One or more pigment derivatives are selected from the sulfonated diketopyrrolopyrrole 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 general formula A, Ar may also have an arylene group having 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。)

(In the substituent A', R ⁴ is an alkylene having 1 to 5 carbon atoms; X is a sulfonic acid group, sulfonate, or {-SO ₂ NH-(CH ₂ ) _n -NR'R"} Shows a sulfonamide group, and R'and R" are each independent hydrogen atom, a saturated or unsaturated alkyl or aryl group with 1 to 20 carbon atoms that can also be substituted, or R'and R" are bonded and combined with Adjacent nitrogen atoms together form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; 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 independently hydrogen atoms, saturated or unsaturated alkyl or aryl groups with 1 to 20 carbon atoms and optionally substituted, or R'and R" are bonded and adjacent to each other The nitrogen atoms together form a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms; the plural R ⁵ are each independent hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an aryl group with 6 to 12 carbon atoms, Halogen atom or 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 group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) Select one or more from the group consisting of _n -SO ₃ H and sulfonate, and R'and R" are independent hydrogen atoms, saturated or unsaturated, with 1-20 carbon atoms, which can also be substituted Alkyl group or aryl group, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; plural R ⁶ are independent hydrogen atoms and carbon atoms An alkyl group of 1 to 4, an aryl group of 6 to 12 carbon atoms, a halogen atom, or the substituent X; n is an integer of 1 to 6, and m is an integer of 1 to 4.)

(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 group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) Choose one from the group consisting of _n -SO ₃ H and sulfonate, and R'and R" are independent hydrogen atoms, saturated or unsaturated alkanes with 1 to 20 carbon atoms that can be substituted Group or aryl group, or R'and R" are bonded together with the adjacent nitrogen atom to form a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms; n is an integer from 1 to 6, and m is from 1 to 4 Integer.)

The arylene group of the above general formula A is not particularly limited, and is preferably an arylene group having 6 to 12 carbon atoms. Specific examples include phenylene, naphthylene, and biphenylene.

Examples of the alkylene group having 1 to 5 carbon atoms for R ⁴ include methylene, ethylene, propylene, butylene, and pentylene.

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。 Furthermore, in the sulfonamide group represented by {-SO ₂ NH-(CH ₂ ) _n -NR'R"} in X, the introduced amine component (-(CH ₂ ) _m -NR'R") Specific examples of the system include piperidine methyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidine Pyridine ethyl, mepiridin ethyl,

Alline ethyl, piperidine propyl, mepiperidine propyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminopentyl, NN-methyl- Lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, etc.

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

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁵ include methyl, ethyl, propyl, and butyl. Examples of the aryl group having 6 to 12 carbon atoms in R ⁵ include phenyl, naphthyl, and biphenyl. Examples of the halogen atom system for R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom or a bromine atom is preferable.

In the general formula B, the introduced amine component (-(CH ₂ ) _m -NR'R") of the substituent {-CONH-(CH ₂ ) _n -NR'R"} can be, for example, the same as the above general formula A The same as exemplified in. In general formula B, the substitution position of the substituent {-CONH-(CH ₂ ) _n -NR'R"} is not particularly limited, as long as there is at least one in the molecule, any of the aromatic rings having R ⁵ The hydrogen atom may be substituted, and R ⁵ may be substituted. In addition, 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 that of the general formula A. In general formula C, the substitution position of the substituent X is not particularly limited, as long as there is at least one in the molecule, any hydrogen atom of the aromatic ring with R ⁶ can also be substituted, and R ⁶ can also be substituted . In addition, 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 can be the same as that in the general formula A kind. In 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 diketopyrrolopyrrole derivative represented by the general formula C is preferably based on the interaction with the red pigment represented by the general formula (1) to improve the dispersibility and dispersion stability. The compounds represented by general formulas (C-1)~(C-4):

(In the general formula (C-1), n is an integer of 1 to 4, and m is an integer of 1 or 2; R'and R" are independent hydrogen atoms, and the number of carbon atoms that may have substituents is 1 to 4的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 the general formula (C-2), m is an integer of 1 or 2; R"' is an alkyl group with 1 to 20 carbon atoms. In addition, the substituent SO ₃ ^- may be substituted at 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。) [化19] General formula (C-3)

(In general formula (C-3), m is an integer of 1 or 2, and the substituent SO ₃ H may be substituted at 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 from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH -(CH ₂ ) _n -SO3H, and sulfonate, select one from the group; R'and R" are independent hydrogen atoms, saturated or unsaturated fats with 1 to 20 carbon atoms that can be substituted Group hydrocarbon group or aromatic hydrocarbon group, or together with the adjacent nitrogen atom to form a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms; n is an independent integer of 1 to 6. m is an integer of 1 to 4.)

Preferable specific examples of the above-mentioned pigment derivatives include, for example, compounds represented by the following chemical formula: [化21] chemical formula 1

[Chemical formula 25] Chemical formula 5

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

[化28]

(In general formula E, X is derived from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) Choose one from the group consisting of _n -SO ₃ H and sulfonate, and R'and R" are independent hydrogen atoms, saturated or unsaturated fats with 1 to 20 carbon atoms that can be substituted Group hydrocarbon group or aromatic hydrocarbon group, or together with the adjacent nitrogen atom to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; 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 may be the same as the X in the above general formula C. From the viewpoint of pigment dispersibility, the following chemical formula 8 is preferred:

In the colored resin composition for color filters of the present invention, it is preferable to use a sulfonated diketopyrrolopyrrole pigment from the viewpoint of reducing the absolute value of the retardation and improving the dispersibility and dispersion stability of the pigment derivative. From the viewpoint of improving pigment dispersibility, it is preferable to use a sulfonated diketopyrrolopyrrole derivative and a sulfonated quinacridone derivative in combination. In addition, from the viewpoint of suppressing the precipitation derived from the diketopyrrolopyrrole pigment by inhibiting the hydrogen bond, it is more preferable to use an imine-alkylated diketopyrrolopyrrole derivative.

When a pigment derivative is used, relative to 100 parts by mass of the pigment, the content of the pigment derivative is preferably 1-25 parts by mass, more preferably 1-15 parts by mass, and particularly preferably 3-10 parts by mass.

<Dispersant>

In the present invention, the dispersant system uses a polymer having a structural unit represented by the general formula (2). The structural unit represented by the above general formula (2) has basicity and functions as a site for adsorbing the pigment.

The colored resin composition and the pigment dispersion for the color filter of the present invention, by using a polymer having a structural unit represented by the general formula (2) as a dispersant, can improve the adsorption performance of the pigment and the pigment dispersion And dispersion stability.

[化30] General formula (2)

(In general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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.

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

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

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

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

From the viewpoint of dispersibility, the above-mentioned R ¹² is preferably an alkylene having 1 to 8 carbon atoms. Among them, R ^{12 is more} preferably a methylene, ethylene, propylene, or butylene group. Department of methylene and ethylene.

The cyclic structure formed by R ¹³ and R ^{14 of the} above general formula (2) bonded to each other can include, for example, a five- to seven-membered nitrogen-containing heterocyclic monocyclic ring, or a comprehensive ring formed by condensation of these two. The nitrogen-containing heterocyclic ring is preferably not aromatic, and it is more preferably a saturated ring.

The repeating unit system represented by the above general formula (2) includes, for example: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate , (Meth)acrylic acid diethylaminopropyl ester and other (meth)acrylates containing alkyl substituted amino groups, etc.; dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl ( (Meth)acrylamide and the like containing alkyl substituted amino groups. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to use dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl. (Meth)propenylamide.

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 3 or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, the more preferable system contains 3 to 100, the particularly preferable system contains 3 to 50, and the best system contains 3 to 30.

Among the polymers having the structural unit represented by the above general formula (2), it is preferred from the viewpoints of further enhancing the pigment adsorption at the salt formation site, pigment dispersion stability, suppression of development residue, and excellent solvent resolubility At least one part of the terminal nitrogen site of the structural unit represented by the above general formula (2) and one or more compounds selected from the group consisting of compounds represented by the following general formulas (I) to (III) Form salt.

[化31]

(In general formula (I), R ^{a is a} linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -OR ^e , and R ^e is a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl or benzyl group which may have a substituent, or a (methyl) ) Propylene group. In general formula (II), R ^b , R ^b' , and R ^b" are each independent hydrogen atom, acidic group or ester group thereof, and may have a substituent with a carbon number of 1-20 Chain, branched chain or cyclic alkyl group, vinyl group which may have substituents, phenyl group or benzyl group which may also have substituents, or -OR ^f , and R ^f system may also have substituent carbon number 1~ 20 linear, branched or cyclic alkyl groups, vinyl groups which may also have substituents, phenyl or benzyl groups which may also have substituents, or (methyl) ) Allyl; X is a chlorine atom, a bromine atom, or an iodine atom. In general formula (III), R ^c and R ^d are independent hydrogen atoms, hydroxyl groups, straight or branched chains with 1 to 20 carbon atoms or Cyclic alkyl, vinyl, phenyl or benzyl which may also have substituents, or -OR ^e , and R ^e is a linear, branched or cyclic alkyl with 1 to 20 carbons, vinyl, or A phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. Among them, at least one of R ^c and ^Rd contains a carbon atom.)

The aforementioned general formula (I) ~ (III), the carbon number of ^{R a, R b, R b} ', R b ", R c, R d, R e and of R ^f linear 1 to 20, the branched or The cyclic alkyl group may be either linear or branched, and may also contain a cyclic structure. Preferred examples include linear, branched or cyclic alkyl groups with 1 to 15 carbon atoms. More preferably, it is a linear, branched or cyclic alkyl group with 1 to 8 carbon atoms.

Furthermore, R ^a , R ^c , R ^d , and R ^e may have a substituted phenyl or benzyl substituent. Examples include alkyl groups with 1 to 5 carbon atoms, acyl groups, Oxo and so on.

Among R ^b , R ^b' , R ^b" , and R ^f , the substituents of phenyl or benzyl may also have substituents. Examples include acidic groups or their ester groups, and those with 1 to 5 carbon atoms Alkyl, acyl, acyl and the like.

In addition, R ^b , R ^b' , R ^b" , and R ^f may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituent of a vinyl group, which may be For example, acidic group or its ester group, phenyl group, acyl group, acyloxy group, etc.

In R ^b , R ^b' , R ^b" , and R ^f , the acidic group refers to a group that releases protons in water and becomes acidic. Specific examples of the acidic group include: carboxyl (-COOH), sulfonic acid Group (-SO ₃ H), phosphinyl group (-P(=O)(OH) ₂ ), phosphonic acid subunit (>P(=O)(OH)), boronic acid group (-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.

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

The compound of the above general formula (II), from the viewpoints of dispersibility, dispersion stability, alkali developability, and suppression of development residue, preferably has anions from carboxyl group, boronic acid group, boronic acid group, etc. And these alkali metal salts and these esters select one or more functional groups, and more preferably have a carboxyl group, a carboxyl group, and a carboxyl group. A functional group selected from acid bases and carboxylic acid esters.

In the case of the acidic group and its ester group (hereinafter referred to as acidic group, etc.) possessed by the compound of the above general formula (II), the acidic group and the like and halogen atom-side hydrocarbons possessed by the compound are capable of interacting with the terminal nitrogen site A salt is formed, but it is estimated that the terminal nitrogen site and the halogen atom-side hydrocarbon can form a salt more stably compared to the case where the terminal nitrogen site and the acidic group form a salt. Moreover, by adsorbing the pigment at the salt formation site where stability exists, it is estimated that the dispersibility and dispersion stability will be improved.

When the compound of the aforementioned general formula (II) has the aforementioned acidic group and the like, the aforementioned acidic group and the like may have two or more. When there are two or more of the acidic groups, etc., the plural of the acidic groups may be the same or different. The number of the acidic groups and the like possessed by the compound of the general formula (II) is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

In the above general formula (I) in ^Ra , at least one of R ^b , R ^b'and R ^b" in the above general formula (II), and R ^c and R ^d in the above general formula (III) At least one of them is the case where it has an aromatic ring. From the viewpoint of enhancing the affinity with the skeleton of the pigment described later, as well as having excellent pigment dispersibility and dispersion stability, a coloring composition with excellent contrast can be obtained. Better.

The molecular weight of one or more compounds selected from the group consisting of the above general formulas (I) to (III), from the viewpoint of improving pigment dispersibility, is preferably 1000 or less, and more preferably 50 to 800, The best is 50~400, the best is 80~350, and the best is 100~330.

The compound system represented by the above general formula (I) includes, for example, benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, mono-n-propylsulfuric acid and the like. In addition, hydrates such as p-toluenesulfonic acid monohydrate can also be used. on The compounds represented by the general formula (II) include, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, and iodine. Ethyl chloride, n-butane chloride, hexane chloride, octane chloride, dodecane chloride, tetradecane chloride, hexadecane chloride, phenethyl chloride, chlorotoluene, Bromotoluene, iodotoluene, 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-bromophenyl acetate, 3-(bromomethyl)phenylboronic acid, etc. The compound system represented by the above general formula (III) may include, for example, monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenyl phosphinic acid, phenyl phosphonic acid, and dimethyl phosphoric acid. Allyl oxyethyl acid phosphate, etc.

Among the groups formed by the above general formulas (I) to (III), from the viewpoint of particularly excellent dispersion stability, it is preferable to use phenylphosphinic acid, phenylphosphonic acid, and dimethylacryloyloxy Ethyl acid phosphate, dibutyl phosphoric acid, chlorotoluene, bromotoluene, ethylene sulfonic acid, and p-toluene sulfonic acid monohydrate are selected from one or more types. Among them, it is more preferable to use phenylphosphine Choose one or more from the group consisting of acid, phenylphosphonic acid, chlorotoluene, bromotoluene, and p-toluenesulfonic acid monohydrate.

Furthermore, from the viewpoint of excellent dispersion stability and improved development residue suppression effect by combining with a block copolymer having an acid value described later, it is preferable to use a general formula having an acidic group and its ester group ( II) The compound shown in, among them, it is more preferable to use α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid Choose one or more from the group consisting of, and 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), because it will be in accordance with the general formula (2) It shows that the terminal nitrogen site of the constituent unit forms a salt, so it is relative to one The terminal nitrogen site of the structural unit represented by the general formula (2) is 1 mol, and one or more compounds selected from the group consisting of the above general formulas (I) to (III) are preferably 0.01 mol or more, more The best is more than 0.1 mol, the best is more than 0.2 mol, and the best is more than 0.3 mol. If it exceeds the above lower limit, the effect of improving the dispersibility of the pigment due to salt formation can be easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, particularly preferably 0.7 mol or less, and most preferably 0.6 mol or less. If it is not more than the above upper limit, it can have excellent development adhesion and solvent resolubility.

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

From the viewpoint of enhancing the dispersibility, the polymer having the structural unit represented by the general formula (2) preferably further contains a portion having solvent affinity. The solvent affinity site is preferably selected from monomers that can be polymerized with the monomers that derive the structural unit represented by the general formula (2) and have ethylenic unsaturated bonds, and the solvent is appropriately blended in a way that has solvent affinity. Choose to use. As a standard, it is preferable to introduce the solvent affinity site in a manner that the solubility of the polymer to the combined solvent at 23° C. reaches 50 (g/100g solvent) or more.

The polymer used in the present invention is from the viewpoint of improving pigment dispersibility, dispersion stability and heat resistance of the resin composition, and can form a high-brightness and high-contrast colored layer. Among them, block copolymers or Graft copolymers, more preferably block copolymers. The following is a detailed description of particularly preferred block copolymers.

[Block copolymer]

If the block containing the structural unit represented by the above general formula (2) is referred to as the A block, then The structural unit represented by the general formula (2) of the A block has basicity and functions as a site for adsorbing a pigment. In addition, when at least a part of the terminal nitrogen site of the structural unit represented by the general formula (2) forms a salt with one or more compounds selected from the group consisting of the general formulas (I) to (III), The salt-forming part will function as a part where the pigment is more strongly adsorbed. On the other hand, the B block that does not contain the structural unit represented by the above general formula (2) functions as a block having solvent affinity. Therefore, the block copolymer system used in the present invention shares the functions of the A block adsorbed by the pigment and the B block having solvent affinity, and functions as a pigment dispersant.

{A block}

The A block is a block containing the structural unit represented by the above general formula (2). Since the structural unit represented by the above general formula (2) is as described above, it will not be repeated here.

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 3 or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, the more preferable system contains 3 to 100, the particularly preferable system contains 3 to 50, and the best system contains 3 to 30.

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

The A block is within the scope of achieving the purpose of the invention, and may have structural units other than the structural unit shown in general formula (2), if it is a structural unit that can be copolymerized with the structural unit shown in general formula (2) It can contain. For example, the basic block part may contain structural units other than the structural unit represented by general formula (2), and specific examples include structural units represented by general formula (3) described later.

In the A block of the block copolymer before the salt is formed, the composition unit represented by the general formula (2) The content of the metabolites is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 100% by mass relative to the total mass of the total structural units of the A block. The reason for this is that the higher the ratio of the structural unit represented by the general formula (2), the higher the adsorption force for the pigment, and the better the dispersibility and dispersion stability of the block copolymer can be achieved. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass when the A block having the structural unit represented by the general formula (2) is synthesized.

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

In addition, the structural unit system represented by the general formula (2) has only to have affinity with the pigment, and may be composed of one type or may contain two or more types of structural units.

{B block}

The B block is a block that does not contain the structural unit represented by the above general formula (2). The B block is preferably selected from the monomers that can be copolymerized with the monomers that derive the structural units represented by the general formula (2) and have unsaturated double bonds, and the solvents are appropriately selected and used in a solvent-philic manner. . As a standard, it is preferable to introduce the B block in such a way that the solubility of the copolymer to the combined solvent at 23° C. reaches 20 (g/100g solvent) or more.

The structural unit system constituting the B block includes, for example, a monomer that can be copolymerized with the monomer deriving the structural unit represented by the general formula (2) and has an unsaturated double bond. Among them, the following general formula (3 ) Shows the structural unit: [化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 is} 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, and -CHO , -CH ₂ CHO, or -CH ₂ COOR ^{26 is} a monovalent group; R ²⁶ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms.

The above-mentioned hydrocarbon group may have a substituent.

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

In general formula (3), Q'is a direct bond or a divalent linking group. The so-called "direct bonding" means that Q'does not have atoms, that is, C (carbon atom) in general formula (3) and R ²² are not bonded by other atoms. The divalent linking group system may be the same as Q in general formula (2). Among them, Q'is a divalent linking group including a -CONH- group or a -COO- group that is directly bonded from the viewpoint of solubility in organic solvents.

In 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 above-mentioned alkyl groups with 1 to 18 carbon atoms can be linear, branched, or cyclic Either.

The alkenyl group having 2 to 18 carbon atoms may be any of linear, branched, and cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited. From the viewpoint of the reactivity of the obtained polymer, it is preferable to have a double bond at the end of the alkenyl group.

Examples of the substituent systems of aliphatic hydrocarbons such as alkyl groups and alkenyl groups include nitro groups and halogen atoms.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl and the like, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6-24, more preferably 6-12.

In addition, the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc., and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7-20, more preferably 7-14.

Examples of the substituent systems of aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, and examples thereof include alkenyl groups, nitro groups, and halogen atoms.

In addition, the aforementioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

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

The hydrocarbon group of R ²⁵ may be the same as that represented by R ²² .

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

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

The above-mentioned R ^{22 is} preferably selected so as to have excellent compatibility with the solvent described below. Specifically, when the above-mentioned solvent is used, for example, a glycol ether acetate-based solvent for a color resin composition for general color filters is used. In the case of solvents such as ether, ether, and ester, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.

In addition, the above-mentioned R ²² may be substituted with substituents such as alkoxy, hydroxyl, epoxy, isocyanate, etc. within the range that does not interfere with the dispersibility of the above-mentioned block copolymer, and may also be substituted in the above-mentioned block copolymer. After the complex is synthesized, it is reacted with the compound having the above-mentioned substituent to add the above-mentioned substituent.

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

The number of structural units constituting the B block is not particularly limited. From the viewpoint of the solvent affinity site and the pigment adsorption site effectively functioning to improve the dispersibility of the pigment, it is preferably 10 to 300, more preferably 10 to 100 One, 10~70 special series.

In the B block of the block copolymer, the content ratio of the structural unit represented by the above general formula (3) is relative to the total mass of the total structural unit of the B block from the viewpoint of improving the solubility and pigment dispersibility. Preferably it is 50-100% by mass, more preferably 70-100% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass when the B block is synthesized.

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

As long as the B block system functions as a solvophilic part, the structural unit can be appropriately selected. The structural unit system represented by the above general formula (3) may be composed of a single type or two or more types. The building blocks of. Two or more types of structural units contained in the B block may be randomly arranged in the block.

The weight average molecular weight Mw of the copolymer is not particularly limited. From the viewpoint of improving pigment dispersibility and dispersion stability, it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 3,000 to 12,000.

Here, the weight average molecular weight (Mw) is obtained by using a gel permeation chromatography (GPC) to obtain a standard polystyrene conversion value.

In addition, in the present invention, the weight average molecular weight Mw of the block copolymer is obtained by GPC (Gel Permeation Chromatography Analyzer) based on a standard polystyrene conversion value. Tosoh Corporation’s HLC-8120GPC was used for the measurement, and the elution solvent was N-methylpyrrolidone with 0.01 mol/liter lithium bromide added, and the polystyrene standards for the calibration curve were set to Mw377400, 210500 , 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (all of the above are Easi PS-2 series manufactured by Polymer Laboratories), and Mw1090000 (manufactured by Tosoh Co., Ltd.), and the measurement column system uses 2 Implementation of TSK-GEL ALPHA-MX (Tosoh Corporation).

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and can be, for example, AB block copolymer, ABA block copolymer, BAB block copolymer, and the like. Among them, from the viewpoint of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.

The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method.

Furthermore, the preparation method of the salt block copolymer may include, for example, dissolving or dispersing the polymer having the structural unit represented by the above general formula (2) in a solvent, and then adding it from the above general formula (I) to (III) A method of selecting one or more compounds from the group constituted by stirring, and heating as necessary.

In addition, in the polymer having the structural unit represented by the above general formula (I), the terminal nitrogen portion of the structural unit represented by the general formula (2) is different from the terminal nitrogen portion of the general formula (I) to (III). The selection of one or more compounds 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 suitably selected for use from the function of a binder resin and soluble in the developer used in pattern formation, especially the alkali developer.

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

In addition, the acid value of the present invention means the mass (mg) of KOH required for neutralizing 1 g of solid content, and is a value obtained by potentiometric titration in accordance with JIS K 0070:1992.

The preferred alkali-soluble resin of the present invention is a resin having a carboxyl group as an acidic group, and specific examples of such resins include acrylic copolymers having carboxyl groups, epoxy (meth)acrylate resins having carboxyl groups, and poly(meth)acrylate resins having carboxyl groups. Amide resin etc.

Among these, a particularly preferable one has a carboxyl group in the side chain, and further has a photopolymerizable functional group such as an ethylenically unsaturated bond group in the side chain. The reason is the use of photopolymerizable functional groups It is caused by increasing the film strength of the formed cured film. To the resin having a carboxyl group, for example, an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group and a hydroxyl group is added to obtain an alkali-soluble resin in which an ethylenically unsaturated bond group is introduced into the side chain.

Furthermore, alkali-soluble resins selected from the group consisting of acrylic copolymers having carboxyl groups, epoxy acrylate resins having carboxyl groups, and polyamide imide resins having carboxyl groups can also be used in combination More than 2 kinds.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers.

Specific examples of acrylic copolymers having a carboxyl group include those described in Japanese Patent Laid-Open No. 2013-029832, and specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, Ethylene unsaturated monomers not having a carboxyl group such as styrene, and copolymers composed of one or more selected from (meth)acrylic acid and its anhydrides. In addition, in the above-mentioned copolymers, for example, an ethylenically unsaturated compound having reactive functional groups such as glycidyl group and a hydroxyl group is added, and an ethylenically unsaturated bond is introduced. Not limited to these.

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

Such hydrocarbon ring systems may include, for example, an aliphatic hydrocarbon ring that may also have a substituent, an aromatic hydrocarbon ring that may also have a substituent, and combinations of these. The hydrocarbon ring may also have, for example, an alkyl group, a carbonyl group, and a carboxyl group. , Oxycarbonyl, amide, hydroxyl, nitro, amino, halogen atom and other substituents.

The hydrocarbon ring may be contained as a monovalent group, or may be contained as a group having a valence of two or more.

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

Alkane, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, pyrene and other aromatic hydrocarbon rings; biphenyl, Triphenyl, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic rings; cardo structure (9,9-diaryl stilbene) etc.

From the viewpoint of improving the heat resistance and adhesion of the colored layer, and improving the brightness of the obtained colored layer, it is preferable to contain an aliphatic hydrocarbon ring as the hydrocarbon ring.

The alkali-soluble resin is preferably a crosslinked cyclic hydrocarbon ring belonging to 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 cross-linked cyclic hydrocarbon ring include:

Alkane, iso

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

Examples of the above-mentioned substituent system include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

The carbon number of the crosslinked cyclic hydrocarbon ring is preferably 5 or more, more preferably 7 or more in terms of compatibility with other materials and solubility in 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 5-50% by mass, preferably 10-40% by mass. In this case, if 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 developer is reduced, which makes pattern formation difficult. In addition, if the copolymerization ratio exceeds 50% by mass, when developing with an alkali developer, the formed pattern tends to fall off from the substrate or the pattern 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, Especially preferred are 60mgKOH/g or more and 120mgmgKOH/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 3,000 to 20,000. If it is less than 1,000, the function of the hardened adhesive may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern when developing with an alkali developer.

In addition, the weight average molecular weight (Mw) of the alkali-soluble resin can be measured using polystyrene as a standard substance and THF as an eluent, using Shodex GPC System 21H (Shodex GPC System-21H).

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

The acid value of the carboxyl 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, particularly preferably 60 mgKOH/g or more and 120mgmgKOH/g or less.

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride for preparing the epoxy (meth)acrylate resin having a carboxyl group can be appropriately selected and used from known ones.

Furthermore, the polyimide resin having a carboxyl group is not particularly limited. From the viewpoint of developability, it is preferably 90 mgKOH/g or more, more preferably 110 mgKOH/g or more, particularly preferably 130 mgKOH/g or more . On the other hand, the acid value of the polyimide resin having a carboxyl group is preferably 300KOHmg/g or less, and more preferably 250KOHmg/g from the standpoints of inhibiting water penetration and excellent stability of the colored resin composition the following.

The polyamide imine resin with carboxyl group can be obtained from the brightness and contrast From the viewpoint of an improved coloring layer and easy to become a colored resin composition for color filters that has good developability and prevents water penetration after development, it is preferable to have a repeating unit represented by the following general formula (A) The polyamide imide resin.

(In the general formula (A), Ra is the residue of an independent divalent aliphatic diisocyanate; Rb is the structural unit shown in the following general formula (B1), (B2) or (B3); Rc is the following The general formula (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10) shows the structural unit. The plural Ra, Rb and Rc present in the amine imine resin may be the same or different. 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. n represents the number of repeating units, and 1 or more.)

[化35]

(General formula (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) In and (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue with 6 to 20 carbon atoms that may be substituted. Re is independently from an alcohol compound Removed the residue of the hydroxyl group.)

The aliphatic diisocyanate residue of the repeating unit represented by the above general formula (A), the aromatic or aliphatic tricarboxylic acid residue or the tetracarboxylic acid residue which may have a substituent with 6 to 20 carbon atoms, etc., It is sufficient to appropriately select an aromatic or aliphatic tricarboxylic acid or tetracarboxylic acid, which may be substituted with an aliphatic diisocyanate, and a carbon number of 6 to 20. 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 series include, for example, linear aliphatic diisocyanates, cycloaliphatic diisocyanates, such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (HTMDI) ), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate (HTDI), hydrogenated xylene diisocyanate (HXDI), reduced

Alkyl diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate, etc. From the viewpoint of increasing the brightness of the colored layer and suppressing the occurrence of water penetration, Ra is preferably a residue of a divalent cyclic aliphatic diisocyanate independently of each other. From the viewpoint of increasing the brightness of the colored layer and suppressing the occurrence of water penetration, the Ra type is preferably a residue of isophorone diisocyanate.

The aromatic tricarboxylic acid anhydride having 6 to 20 carbon atoms which may have a substituent includes, for example, trimellitic anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride and the like. In addition, examples of the aliphatic tricarboxylic acid anhydrides having 6 to 20 carbon atoms and optionally having substituents include linear aliphatic tricarboxylic acid anhydrides and cycloaliphatic tricarboxylic acid anhydrides, such as propane tricarboxylic acid anhydride and cyclohexane. Alkyl tricarboxylic acid anhydride, methyl cyclohexane tricarboxylic acid anhydride, cyclohexene tricarboxylic acid anhydride, methyl cyclohexene tricarboxylic acid anhydride, etc.

In addition, the aromatic or aliphatic tetracarboxylic anhydride system having 6 to 20 carbon atoms which may have a substituent includes, for example, pyromellitic dianhydride, and diphenyl ketone-3,3',4,4'- Tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, etc.

The polyamide imide resin having the repeating unit represented by the above general formula (A) can be prepared, for example, by referring to International Publication No. 2015/008744.

The above-mentioned polyimide resin preferably contains an unsaturated double bond group from the viewpoint of forming a colored layer with improved brightness and contrast and increasing the residual film rate of the colored layer. To the carboxyl group of the polyamideimide resin, an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group and 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 polyamide imide resin containing a carboxyl group. Among them, from the viewpoint of easily reducing the absolute value of the retardation, it is preferable to contain a polyamide having a repeating unit represented by the general formula (A). Amide imine resin.

Furthermore, the alkali-soluble resin used in the present invention can form a colored layer with improved brightness and contrast while reducing the absolute value of the retardation, and improve the stability and solvent resolubility of the colored resin composition over time From the viewpoint of, it is preferable to contain an acrylic copolymer having an acid value of 50 KOHmg/g or more and the polyamide resin having a carboxyl group.

The alkali-soluble resin used in the colored resin composition for color filters can be used singly or in combination of two or more. There is no particular restriction on its content, compared to the colored resin composition for color filters The total solid content of the substance is preferably in the range of 5-60% by mass, more preferably 10-40% by mass of the alkali-soluble resin. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained; and if the content of the alkali-soluble resin exceeds the above upper limit, film roughness and pattern defects may occur during development. Case. In addition, the solid content of the present invention is all substances other than the above-mentioned solvents, and includes liquid polyfunctional monomers and the like.

<Single>

The monomers used in the colored resin composition for color filters are not particularly limited as long as they can be polymerized with a photoinitiator described later. Generally, compounds having ethylenically unsaturated double bonds are used, preferably It has an acrylic or methacrylic group. Moreover, it is preferable to contain the polyfunctional group (meth)acrylate which has 2 or more ethylenically unsaturated double bonds.

Such a polyfunctional (meth)acrylate system may be appropriately selected from conventionally known materials and used. Specific examples include things described in JP 2013-029832 A, etc.

These (meth)acrylates can be used alone or in combination Use more than two kinds. In addition, when the colored resin composition for the color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds, Preferably, poly(meth)acrylates of trivalent or higher polyols and these dicarboxylic acid modifiers are preferred. Specifically, preferred examples include trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Esters, succinic acid modification products of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Among them, more preferred are succinic acid modified products of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

The content of the above-mentioned monomers used in the colored resin composition for color filters is not particularly limited. Relative to the total solid content of the colored resin composition for color filters, the monomer is preferably 5-60 mass. %, more preferably within the range of 10-40% by mass. If the monomer content is less than the above lower limit, the photocuring cannot be carried out sufficiently, resulting in the elution of the exposed part during development; and if the monomer content is more than the above upper limit, the alkali developability may decrease Possibility.

Furthermore, especially when the pigment concentration is high, in order to improve the development solubility, it is better to further contain an alkylene oxide modifying monomer. Specific examples include: trimethylolpropane PO modified triacrylate, trimethylolpropane Hydroxymethylpropane EO modified triacrylate, isocyanuric acid EO modified triacrylate, diglycerol EO modified acrylate, etc. Among them, particularly good series are diglycerol EO modified acrylate and trimethylolpropane EO modified triacrylate.

In addition, the so-called "EO modification" refers to a block structure having ethylene oxide units (-CH ₂ -CH ₂ -O-); the so-called "PO modification" refers to having propylene oxide units (-CH _2- CH(CH ₃ )-O-) block structure.

The addition amount of the above-mentioned alkylene oxide-modifying monomer can be appropriately adjusted, and it is preferably added in the range of 5-100% by mass relative to the total amount of monomers from the viewpoint of the balance of developing solubility and curability.

<Initiator>

The photoinitiator used in the colored resin composition for color filters is not particularly limited, and can be used singly or in combination of two or more from various known photoinitiators. Specific examples include things described in JP 2013-029832 A, etc.

The photoinitiator system may use only 1 type, and may use 2 or more types of compounds together. The photoinitiator system preferably contains an oxime ester-based photoinitiator from the viewpoints that the effect of suppressing pattern defects and the effect of suppressing water penetration are high. If a dispersant having an acid value is used, water penetration tends to occur particularly, but if an oxime ester-based photoinitiator is combined, the occurrence of water penetration can be suppressed and it is suitable for use. In addition, the so-called "water penetration" refers to the occurrence of water stains like water penetration after washing with pure water after alkali development. Because this kind of "water penetration" disappears after post-baking, it does not pose a problem as a product. However, when the appearance of the pattern surface is inspected after development, abnormal spots will be detected, making it impossible to distinguish normal products. Problems with abnormal products. Therefore, if the inspection sensitivity of the inspection device is reduced during the appearance inspection, the yield of the final color filter product will be reduced as a result, which constitutes a problem.

The oxime ester-based photoinitiator is preferably one having an aromatic ring, and more preferably one having an aromatic ring from the viewpoint of reducing contamination of the colored resin composition for color filters due to decomposition products or contamination of the device The condensed ring, especially the best system has the condensation of benzene ring and heterocyclic ring 合环.

The oxime ester-based photoinitiator can be selected from 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzyl oxime)], ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(o-acetoxime), Japanese Patent Laid-Open No. 2000-80068, JP 2001 -233842, JP 2010-527339, JP 2010-527338, JP 2013-041153 and other oxime ester-based photoinitiators are appropriately selected. Commercial products can also be used, for example: IRGACURE OXE-01, IRGACURE OXE-02, IRGACURE OXE-03 (all made by BASF) with a carbazole skeleton; ADEKA ARKLSN-1919, ADEKA ARKLS NCI-831 (all of the above are made by BASF); ADEKA Corporation); TR-PBG-304, TR-PBG-326 (all of the above are manufactured by Changzhou Qiangli Electronic New Materials Co.); ADEKA ARKLS NCI-930 (made by ADEKA Corporation) with a diphenyl sulfide skeleton; TR-PBG -345, TR-PBG-3057 (all of the above are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.); TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc.

In particular, from the viewpoint of brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. Moreover, from the viewpoint of sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton.

Furthermore, from the viewpoint of easily improving the development resistance and enhancing the effect of suppressing the occurrence of water penetration, it is preferable to use two or more kinds of oxime ester-based photoinitiators in combination. In particular, from the viewpoint of easy brightness enhancement and high heat resistance, it is preferable to use two kinds of oxime ester photoinitiators with a diphenyl sulfide skeleton or an oxime ester with a diphenyl sulfide skeleton in combination. Photoinitiator, and oxime ester photoinitiator with citron skeleton. In addition, from the viewpoint of superior sensitivity and brightness, it is preferable to combine an oxime ester photoinitiator with a carbazole skeleton, an oxime ester photoinitiator with a fluorine skeleton, or an oxime with 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。 Furthermore, from the viewpoint of improving sensitivity, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator. The reason is that the photoinitiator with a tertiary amine structure has a tertiary amine structure that is an oxygen delustering agent in the molecule, so the free radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. Examples of commercially available photoinitiators with tertiary amine structure include: 2-methyl-1-(4-methylthiophenyl)-2-

Linyl propane-1-one (e.g. IRGACURE 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-

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

The content of the photoinitiator used in the colored resin composition for color filters is not particularly limited. With respect to the total solid content of the colored resin composition for color filters, the photoinitiator is preferably 0.1~ 12% by mass, more preferably within the range of 0.6-8% by mass. If the content is less than the above-mentioned lower limit, the photohardening is not sufficiently performed, and the exposed part may be eluted during development; on the other hand, if the content is more than the above-mentioned upper limit, the yellowing of the obtained colored layer Enhancement may lead to a decrease in brightness.

<Solvent>

The solvent used in the present invention does not react with the components in the coloring resin composition, and can dissolve or disperse the organic solvent, and the rest is not particularly limited. A solvent can be used individually or in combination of 2 or more types.

Specific examples of solvents include, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol Carbitol solvents such as 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, Ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxy ethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate and other glycol ether acetate solvents; methoxy acetate Carbitol acetate solvents such as ethyl ethoxyethyl acetate, ethoxyethoxy ethyl acetate, butyl carbitol acetate (BCA), etc.; propylene glycol diacetate, 1,3-butanediol diacetic acid Diacetate esters such as esters; 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 Glycol ether solvents such as monomethyl ether and dipropylene glycol dimethyl ether; non-protonic alcohols such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone Amine solvents; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; N-heptane, N-hexane, N-octane Saturated hydrocarbon solvents such as alkanes; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, from the viewpoint of solubility with other components, it is preferable to use glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents. Among them, the solvent used in the present invention is preferably selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, and butyl carbitol acetic acid from the viewpoint of solubility with other components and coating suitability. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate Choose one or more from the group.

In the present invention, it is preferable to use ethyl 3-ethoxypropionate, 3-methoxy-3-methyl butyl acetate, etc., which have a boiling point of 150°C~200°C and a high boiling point solvent, when the pigment concentration reaches 30% In the above, the high boiling point solvent preferably contains 0-40% by mass in the entire solvent, and more preferably contains 0-30% by mass. If the content of the high-boiling point solvent is within the above range, by improving the re-solubility, even if the pigment is at a high concentration, it still has good developability and re-solubility. Effect.

<Optional ingredients>

The colored resin composition for color filters may contain various additives as necessary.

In addition to antioxidants, the additives include, for example, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters.

Furthermore, within a range that does not impair the effects of the present invention, color materials such as dyes may be contained.

From the viewpoint of heat resistance, the colored resin composition for a color filter of the present invention preferably further contains an antioxidant. The antioxidant system may be appropriately selected from conventionally known materials. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. From the viewpoint of heat resistance, it is preferable to use hindered antioxidants. Phenolic antioxidants. It is also possible to use, for example, the potential antioxidant described in International Publication No. 2014/021023.

Examples of hindered phenol antioxidants include: neopentylerythritol [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation) , 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-ginseng ( 4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl Phenol) (trade name: SUMIRAIZA-MDP-S, manufactured by Sumitomo Chemical), 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, neopentylerythritol [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, BASF company system).

In the colored resin composition for color filters of the present invention, if the photosensitive colored resin composition contains the above-mentioned oxime ester-based photoinitiator and an antioxidant in combination, it can have a synergistic effect and is less likely to cause damage during development. Stripping, damage and fall off during development caused by this, when viewing the colored layer from an oblique direction, it is not easy to cause color spots due to diffuse reflection of light, so it is preferable. Since the colored resin composition for a color filter of the present invention contains the above-mentioned red pigment, the pigment concentration tends to increase, and it is preferable to contain it in combination from the viewpoint that the above-mentioned problems are unlikely to occur.

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

When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is based on 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator, and the antioxidant is preferably at least 1 part by mass and 250 parts by mass. Parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, 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 surfactants and plasticizers include those described in JP 2013-029832 A.

染料、酞菁染料、 靛藍染料等。 Furthermore, the dye system can be appropriately selected and used from known dyes. Specific examples include azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, phthalocyanine dyes, indigo dyes, etc.

<Blend Ratio of Components in Colored Resin Composition for Color Filter>

The total content of the pigment is blended at a ratio of 3 to 65% by mass, and more preferably 4 to 60% by mass relative to the total solid content of the colored resin composition for color filters.

If it exceeds the above lower limit, when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm), the colored layer has a sufficient color density. Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability, sufficient hardness, and has adhesiveness with a board|substrate can be obtained. Especially when forming a high pigment concentration colored layer, the pigment content is relative to the total solid content of the colored resin composition for color filters, preferably 15-65% by mass, more preferably 25-60% by mass Proportion blending.

Furthermore, the content of the dispersant is on the premise that the pigment can be dispersed uniformly, and the rest is not particularly limited. For example, relative to the total solid content of the colored resin composition for color filters, 1-40 mass can be used %. In addition, it is preferably blended at a ratio of 2-30% by mass, more preferably blended at a ratio of 3-25% by mass relative to the total solid content of the colored resin composition for color filters. If it is more than the above lower limit, both the dispersibility and dispersion stability of the pigment are excellent, and the storage stability of the colored resin composition for color filters is more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a high pigment concentration colored layer, the dispersant content is relative to the total solid content of the colored resin composition for color filters, preferably 2-25% by mass, more preferably 3-20% by mass The proportion of blending. In addition, the quality of the dispersant is based on the salt block copolymer, the block copolymer before salt formation, and one or more selected from the group consisting of the general formulas (I) to (III). The total mass of the compound.

In addition, the solvent content may be appropriately set within a range where the colored layer can be formed accurately. With respect to the total amount of the colored resin composition for color filters containing the solvent, it is usually preferably in the range of 55 to 95% by mass, more preferably in the range of 65 to 88% by mass. When the content of the solvent is within the above range, the coating property can be excellent.

<Coloring layer of colored resin composition for color filter>

The colored resin composition for the first color filter of the present invention uses C light source for color measurement when forming the colored layer of the colored resin composition. In the XYZ chromaticity system of JIS Z8701: 1999, the chromaticity coordinate system is x =0.630~0.665, y=0.326~0.335, and the phase difference (Rth) of light with a wavelength of 620nm in the thickness direction of the colored layer is -30nm or more and 120nm 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 even more preferable system can form x=0.650~0.665, y=0.326~ Hardened film within 0.335.

Among them, the phase difference (Rth) of light with 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, particularly preferably -10 nm or more and 20 nm or less.

Furthermore, the contrast of the colored layer is preferably above 4000, more preferably above 5000, particularly preferably above 6000. By using the red pigment represented by the above chemical formula (1-1), the phase difference within the range of chromaticity (x, y) of 0.630≦x≦0.665 and 0.326≦y≦0.335 is less increased, and the brightness and contrast can be improved.

The second colored resin composition for color filters of the present invention is the above-mentioned pigment and further contains one selected from among red pigments, orange pigments, and yellow pigments that are different from the red pigment represented by the above general formula (1) Above the pigment, and when forming the When coloring the colored layer of the colored resin composition, use C light source for color measurement. In the XYZ colorimetric system of JIS Z8701: 1999, the chromaticity coordinate system x=0.630~0.665, y=0.295~0.360 range, and the thickness direction of the colored layer The phase difference (Rth) of light with a wavelength of 620nm is -30nm or more and 120nm 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 even more preferable system can form x=0.640~0.665, y=0.315~ Hardened film within 0.335.

Among them, the phase difference (Rth) of light with 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, particularly preferably 0 nm or more and 10 nm or less.

Furthermore, the contrast of the colored layer is preferably above 4000, more preferably above 5000, particularly preferably above 6000. By using the red pigment represented by the above chemical formula (1-1), the phase difference within the range of chromaticity (x, y) of 0.630≦x≦0.665 and 0.295≦y≦0.360 is less increased, and the brightness and contrast can be improved.

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

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

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

Nx: In-plane refractive index in the slow axis direction

Ny: In-plane refractive index in the fast axis direction

Nz: Refractive index in thickness direction

d: Film thickness (nm)

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

<Manufacturing Method of Colored Resin Composition for Color Filter>

The manufacturing method of the colored resin composition for the color filter of the present invention is not particularly limited. For example, it contains a pigment containing a red pigment represented by the above general formula (1), and a component having a structural unit represented by the above general formula (2). It can be obtained by adding an alkali-soluble resin, a monomer, a photoinitiator, and other components as necessary to the dispersant of the copolymer and the pigment dispersion of the solvent, and mixing by a known mixing means. Alternatively, use the above dispersant to prepare a dispersion of the red pigment represented by the general formula (1) and a pigment dispersion of other pigments as necessary, and then combine the dispersions, alkali-soluble resins, monomers, and photoinitiators , And other ingredients as needed, can be obtained by mixing using known mixing means.

The method for preparing the pigment dispersion is not particularly limited as long as it is a method of dispersing the pigment in a solvent using the dispersant to obtain a pigment dispersion.

When preparing the dispersion, the pigment system can be dispersed using a conventionally known dispersing machine.

Specific examples of the dispersing machine include: roller crushers such as two-roll mills and three-roll mills; ball mills such as ball mills and vibrating ball mills; bead mills such as paint conditioners, continuous disc type bead mills, and continuous ring type bead mills. machine. For the better dispersion conditions of the bead mill, the diameter of the balls used is preferably 0.03~3.0mm, more preferably 0.05~2.0mm.

A specific system can be, for example, pre-dispersion using 2.0 mm zirconia beads with a larger diameter, and then formal dispersion using 0.1 mm zirconia beads with a smaller diameter. Also, after dispersion, it is best to filter with a 0.5-2μm filter.

[Color filter]

The color filter of the present invention includes at least a substrate and a colored layer provided on the substrate; wherein at least one of the colored layers is a cured product belonging to the colored resin composition for the color filter of the present invention The coloring layer.

The color filter of the present invention will be described with reference to the drawings. Fig. 1 shows a schematic cross-sectional view of an example of the 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-shielding portion 2, and a coloring layer 3.

(Colored layer)

At least one of the colored layers used in the color filter of the present invention is a cured product of the colored resin composition for the color filter of the present invention, even if the colored resin composition is cured.

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

In addition, the arrangement of the colored layers is not particularly limited, and can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. In addition, the width and area 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, viscosity, etc. of the colored resin composition for color filters, and is generally preferably in the range of 1 to 5 μm.

This colored layer can be formed in accordance with the following method, for example.

First, the aforementioned colored resin composition for color filters of the present invention is applied to the coating method using spray coating, dip coating, bar coating, roll coating, spin coating, and die coating methods. A wet coating film is formed on the substrate described later. Among them, the spin coating method and the die coating method are preferably used.

Next, after drying the wet coating film using a hot plate, an oven, etc., it is exposed via a mask of a predetermined pattern to cause the alkali-soluble resin and monomers to undergo photopolymerization to form a cured coating film. Examples of the light source system used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and other ultraviolet light, electron beams, and the like. The amount of exposure is appropriately adjusted according to the light source used, the thickness of the coating film, etc.

Furthermore, in order to promote the polymerization reaction after 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 color filters used, the thickness of the coating film, and the like.

Next, a developing solution is used to perform a development process, and the unexposed part is dissolved and removed to form a coating film in a desired pattern. The developer usually uses a solution in which an alkali is dissolved in water or a water-soluble solvent. Surfactant etc. can also be added suitably to this alkali solution. In addition, a general method can be used for the development method.

After the development process, washing with a developing solution is usually performed, and the cured coating film of the photosensitive colored resin composition for color filters is dried to form a colored layer. In addition, after the development treatment, heat treatment may be applied to fully harden the coating film. The heating conditions are not particularly limited, and can be appropriately selected according to the application of the coating film.

(Shading part)

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

The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may be a metal thin film in which chromium or the like is applied by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. With For the resin layer of light-shielding particles, for example, a method of using a photosensitive photoresist and patterning by development, a method of using inkjet ink containing light-shielding particles for patterning, and a thermal transfer of the photosensitive resist Method and so on.

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

(Substrate)

As the substrate, a transparent substrate or a silicon substrate described later is used, and aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrate. On these substrates, other color filter layers, resin layers, transistors such as TFTs, and circuits can also be formed.

The transparent substrate of the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and transparent substrates used in general color filters can be used. Specific examples include non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates; or, for example, transparent resin films, optical resin plates, flexible glass, and other flexible transparent materials. material.

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

In addition, the color filter of the present invention can also be formed with, for example, protective layers, transparent electrode layers, alignment films, alignment protrusions, columnar spacers, etc., in addition to the above-mentioned substrate, light-shielding portion, and coloring layer.

[Display device]

The display device of the present invention is characterized in that it is provided with the above-mentioned color filter of the present invention. The structure of the display device of the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices, organic light emitting display devices, and the like. The invention is a horizontal electric field type liquid crystal display device, it can still suppress various display defects such as disordered liquid crystal alignment caused by the electrical characteristics of the green pixels, and burn-in caused by the threshold shift of the switch, so it is quite suitable for liquid crystal Display device.

<Liquid crystal display device>

The liquid crystal display device of the present invention is characterized in that it is provided with the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 shows a schematic diagram of an example of the display device of the present invention, and a schematic diagram of an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 of the present invention is provided with: a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and between the color filter 10 and the counter substrate 20 The formed liquid crystal layer 30.

In addition, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may be a well-known configuration of a liquid crystal display device that generally uses color filters.

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

Furthermore, the counter substrate can be appropriately selected according to the driving method of the liquid crystal display device of the present invention.

Furthermore, the liquid crystal system constituting the liquid crystal layer can cooperate with the driving of the liquid crystal display device of the present invention Methods, etc., use various liquid crystals with different dielectric anisotropies, and mixtures of these.

The method of forming the liquid crystal layer can be the method used in the production method of general liquid crystal cells, such as: vacuum injection method, liquid crystal dropping method, etc.

<Organic Light Emitting Display Device>

The organic light emitting display device of the present invention is characterized by being provided with the aforementioned 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 shows a schematic diagram of another example of the display device of the present invention, and a schematic diagram of an example of an organic light emitting display device. As shown 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 also be provided between the color filter 10 and the organic light-emitting body 80.

The layering method of the organic light-emitting body 80 includes, for example, a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the color filter. ; A method of attaching an organic light-emitting body 80 that has been formed on another substrate to an inorganic oxide film 60, etc. 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 structural systems can use known materials as appropriate. The organic light emitting display device 100 fabricated in this way can also be applied to, for example, passively driven organic EL displays, and can also be applied to actively driven organic EL displays.

In addition, the organic light-emitting display device of the present invention is not limited to the structure shown in FIG. 3, and can be a well-known structure of an organic light-emitting display device that generally uses color filters.

[Example]

Hereinafter, a specific description will be given of exemplary embodiments of the present invention. However, the present invention is not limited by these descriptions.

(Production Example 1: Production of Dispersant I)

(1) Synthesis of block copolymer I

In a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, addition funnel, nitrogen inlet pipe, mechanical stirrer, and digital thermometer, add THF: 250 parts by mass, 0.6 parts by mass of lithium chloride, and Fully implement nitrogen substitution. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Then, the monomers for the B block were 2.22 parts by mass of 1-ethoxyethyl 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). The funnel dripped over 60 minutes. After 30 minutes, 26.6 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was dropped over 20 minutes. After 30 minutes of reaction, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was re-precipitated in hexane, filtered, vacuum-dried for purification, and then diluted with PGMEA to become a 30% solid solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C., and the reaction was performed for 7 hours, and the EEMA-derived structural unit was deprotected to become a methacrylic acid (MAA)-derived structural unit. The obtained block copolymer PGMEA solution was re-precipitated in hexane, filtered and vacuum-dried for purification to obtain the A block containing the structural unit represented by the general formula (2) and the carboxyl-containing monomer Structural unit and solvent-philic The block copolymer I of the functional B block. The block copolymer I thus obtained was confirmed by GPC (Gel Permeation Chromatography Analyzer), 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: 10.0 parts by mass was dissolved in 42.12 parts by mass of PGMEA, and 0.53 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) belonging to the compound represented by the above general formula (III) was added ( The compound represented by the above general formula (III) is 0.20 mol based on 1 mol of DMMA unit of block copolymer I), and stirred at a reaction temperature of 30°C for 20 hours to obtain a salt block copolymer with a solid content of 20% by mass I (dispersant I) solution.

(Production Example 2: Production of Dispersant II)

Except that in Production Example 1, the amount of monomers was changed in Table 1 below, in the same manner as in Production Example 1, salt block copolymer II (dispersant II) was obtained.

(Production Example 3: Production of Dispersant III)

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

(Production Example 4: Production of Dispersant IV)

In (I) of Production Example 1, in addition to changing the type and amount of monomers in Table 1 below, For the rest, the block copolymer IV was obtained in the same manner as in (1) of Production Example 1. Next, in a 100 mL round bottom flask, the block copolymer IV: 10.0 parts by mass was dissolved in 42.56 parts by mass of PGMEA, and 0.64 parts by mass of benzyl chloride (manufactured by Kanto Chemical Co., Ltd.), which is a salt forming component, was added ( (0.3 equivalent of the block copolymer relative to the DMMA unit system) was stirred at a reaction temperature of 80°C for 12 hours to prepare a salt block copolymer solution IV with 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 BzMA: 40 parts by mass, MMA: 15 parts by mass, MAA: 25 parts by mass, and 3 parts by mass of azoisobutyronitrile (AIBN) was dropped onto the PGMEA150 under a nitrogen stream at 100°C for 3 hours Parts by mass in the polymerization tank. After the dripping is finished, it is heated at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution is 7,000.

Next, add 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol to the obtained polymer solution, and heat it at 110°C for 10 hours. , And the reaction between the carboxylic acid group of the main chain methacrylic acid and the epoxy group of glycidyl methacrylate is performed to obtain an alkali-soluble resin A solution. During the reaction, in order to prevent the polymerization of glycidyl methacrylate, air was bubbled in the reaction solution. In addition, the reaction is tracked by measuring the acid value of the solution. The obtained alkali-soluble resin A solution is based on the main chain formed by the copolymerization of BzMA, MMA, and MAA, and GMA is used to introduce the resin with the side chain of the ethylenic double bond. The solid content is 40% by mass and the acid value is 74mgKOH/g. , The weight average molecular weight is 12,000.

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

A mixed solution of 15 parts by mass of styrene (St), 5 parts by mass of cyclohexyl methacrylate (CHMA), MMA: 23.9 parts by mass, MAA: 26.9 parts by mass, and 3 parts by mass of azoisobutyronitrile (AIBN) , Under a nitrogen stream, it was dropped into a polymerization tank filled with 150 parts by mass of PGMEA at 100°C for 3 hours. After the dropping is finished, heating is performed at 100°C for 3 hours to obtain a polymer solution.

Next, to the obtained polymer solution, 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, and heated at 110°C for 10 hours. , And implement the carboxylic acid group of the main chain methacrylic acid, The reaction with the epoxy group of glycidyl methacrylate obtains an alkali-soluble resin B solution. During the reaction, in order to prevent the polymerization of glycidyl methacrylate, air was bubbled in the reaction solution. In addition, the reaction is tracked by measuring the acid value of the solution. The obtained alkali-soluble resin B solution is based on the main chain formed by the copolymerization of St, CHMA, MMA, and MAA, and GMA is used to introduce the resin with the side chain of the ethylenic double bond. The solid content is 40% by mass and the acid value is 77mgKOH. /g, weight average molecular weight 17,600.

(Production example 7: Production of alkali-soluble resin C (polyamide imide resin))

Add 1086 parts by mass of PGMEA, IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 587.3 parts by mass (0.80) to a flask equipped with a stirring device, thermometer, and condenser. Parts by mole), and 499.1 parts by mass (2.52 parts by mole) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and the temperature was increased to 140°C. The reaction is carried out under foaming. The reaction was carried out for 8 hours at this temperature. The system is a pale yellow liquid. After measuring the characteristic absorption by infrared spectroscopy, it is confirmed that the 2270cm ^-1 which is the characteristic absorption of isocyanate groups has completely disappeared, and the absorption of the imine group is found at 1780cm ^-1 and 1720cm ^-1 .

After cooling down to 110°C, add 1.2 parts by mass of p-methoxyphenol, 153.5 parts by mass (1.08 mole parts) of glycidyl methacrylate (GMA), and 9.6 parts by mass of triethylamine, and carry out at 110°C for 15 hours Addition reaction. After measuring the characteristic absorption by infrared spectroscopy, it was confirmed that the absorption at 1860 cm ^{-1 which is} the characteristic absorption of acid anhydride groups has completely disappeared. The acid value is calculated as 148KOHmg/g in terms of solid content, and the molecular weight is calculated as the coefficient average molecular weight of 5000 in terms of polystyrene. In addition, the concentration of the resin component is 51.3% by mass. Let this be an alkali-soluble resin C solution. The obtained alkali-soluble resin C solution is a polyamide imide resin having a carboxyl group, and a resin having a side chain having an ethylenic double bond is introduced using GMA.

(Examples 1-16: Preparation of pigment dispersion)

According to the composition shown in Table 2 below, 100 parts by mass of pigment, dispersant, pigment derivative, alkali-soluble resin, pigment dispersant, solvent, and zirconium dioxide beads with a particle size of 2.0 mm were charged into Mayonnaise. In the squeezing bottle, the pre-crushing system uses a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) to perform 1 hour shaking, then take out the zirconia beads with a diameter of 2.0mm, and add 200 masses of zirconia beads with a diameter of 0.1mm In the same manner, the main crushing system was dispersed for 6 hours using a paint stirrer to obtain the pigment dispersions of Examples 1 to 16.

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

A pigment, a dispersant, a solvent, etc. were mixed so as to have the composition shown in Table 2 below to obtain a comparative pigment dispersion.

The chemical formula numbers in Table 2 correspond to the chemical formulas described in the item of pigments and pigment derivatives. In addition, in Table 2, the R177 series means C.I. Pigment Red 177, and the Y150 series means C.I. Pigment Yellow 150.

(Example 17: Preparation of colored resin composition)

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

‧The pigment dispersion of Example 1 (solid content 21.5 mass%): 48.3 mass parts

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

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

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

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

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

‧Surfactant (made by DIC (stock), MEGAFAC R-08MH): 0.9 parts by mass

‧PGMEA: 36.5 parts by mass

(Examples 18~39: 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 amount of each component was changed as shown in Table 3 and Table 4 below.

In addition, among the ingredients listed in Tables 3 and 4 below, the first occurrence is as follows:

‧Photocurable multifunctional monomer (EO modified) (Toagosei, Aronix M-350)

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

(Comparative example 3)

In the above-mentioned Example 18, except that the pigment dispersion of Example 1 was replaced with the pigment dispersion of Comparative Example 2, and the blending amount of each component was changed as shown in Table 3 below, the rest were all in accordance with the example 18 In the same manner, the colored resin composition of Comparative Example 3 was prepared.

In addition, since the results of the stability evaluation with time described later of Comparative Example 1 showed gelation, the preparation of the colored resin composition could not be performed.

[Evaluation]

<Evaluation of dispersion stability of pigment dispersion>

The pigment dispersions of the Examples and Comparative Examples were stored at room temperature (25°C), and the viscosity was measured after storage for 1 day and 1 month after preparation. The viscosity was measured at 25.0±1.0°C using a vibrating viscometer (VM-200T2 manufactured by SEKONIC), and the value 30 seconds after the start of the measurement was used.

The viscosity after 1 day of dispersion is compared with the viscosity after 1 month of storage, and the viscosity change within 2% is rated as "AA", the viscosity change within 5% is rated as "A", viscosity Those with a change of more than 5% and less than 10% are rated as "B", and those with more than 10% are rated as "C". The results are shown in Table 2. If the viscosity change is within 10%, it is rated as excellent in dispersion stability and belongs to the practical range.

<Evaluation of Optical Properties>

The colored resin composition obtained in each embodiment and each comparative example was applied to the glass substrate using a spin coater and then baked into the desired color (red colored layer: x=0.630 under C light source) (NH TECHNO GLASS (share) system, "NA35"). After heating and drying on an 80°C hot plate for 3 minutes, an ultra-high pressure mercury lamp was used to irradiate 60 mJ/cm ² ultraviolet rays. Then, post-baking was performed in a 230°C dust-free oven for 25 minutes, and the contrast, chromaticity (x, y), and brightness (Y) of the obtained colored film were measured. The contrast is measured using the Kosaka Electric Co., Ltd. "contrast measuring device CT-1B"; the color and brightness are measured using the Olympus Co., Ltd. "microscopic light measuring device OSP-SP200".

<Evaluation of Phase Difference (Rth)>

The phase difference of the colored layer uses the thickness direction retardation (Rth) calculated according to the following formula as an index. The delay (Rth) was measured using a retardation layer measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS). The measurement wavelength of the red colored layer was measured at 620 nm.

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

Nx: In-plane refractive index in the slow axis direction

Ny: In-plane refractive index in the fast axis direction

Nz: Refractive index in thickness direction

d: Film thickness (nm)

<Developability evaluation (development time)>

The colored resin compositions obtained in the Examples and Comparative Examples were coated on a 100mm×100mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7mm using a spin coater, and then heated The board was dried at 80°C for 3 minutes to form a colored layer with a thickness of 2.5 μm. This colored layer was irradiated with 60 mJ/cm ² ultraviolet rays using an ultra-high pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The above-mentioned glass plate on which the colored layer has been formed is shower-developed using a 0.05% by mass potassium hydroxide aqueous solution of an alkali developer. The development completion time at this time was used as an index of developability.

A: Development time ~ 20 seconds

B: Development time 20~40 seconds

C: Development time is more than 1 minute

<Spots>

The colored resin compositions obtained in the Examples and Comparative Examples were coated on a 100mm×100mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7mm using a spin coater, and then heated The board was dried at 60°C for 3 minutes, and the number of revolutions was adjusted so that the film thickness described in the table after post-baking was used to form a colored layer. The colored layer was irradiated with 60 mJ/cm ² ultraviolet rays using an ultra-high pressure mercury lamp through a mask having a mask opening width of 80 μm and a mask width of 160 μm. The glass plate with the colored layer formed above was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution of an alkali developer. Next, for the colored substrate that was baked in a 230°C dust-free oven for 30 minutes, the stain of the colored layer was visually observed under a projector, and then the edge of the colored layer in the range of 50mm×50mm was measured with an optical microscope. The number of gaps.

(Evaluation criteria for stains)

AA: No stains, no marginal gaps

A: No stains, less than 20 gaps at the edge

B: Spots are observed in some of them

C: Spots are observed in all

If the stain evaluation criterion is AA, A, or B, it is practical, but if the evaluation result is A or even AA, the effect is even better.

(Examples 40~43: Preparation of pigment dispersion)

The pigments, dispersants, pigment derivatives, alkali-soluble resins, pigment dispersants, and solvents were mixed so as to have 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 chemical formulas described in the item of pigments and pigment derivatives. In addition, in Table 5, the R177 series means C.I. Pigment Red 177, the Y150 series means C.I. Pigment Yellow 150, and the Y185 series means C.I. Pigment Yellow 185.

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

In the preparation of the colored resin composition, the coloring 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 ingredients listed in Table 6 below, the first occurrence is as follows:

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

‧Oxime-based photopolymerization initiator (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., TR-PBG-3057)

‧Antioxidant (made by BASF, IRGANOX1010)

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

In the same way as in Example 2, the pigment, dispersant, pigment derivative, alkali-soluble resin, pigment dispersant, and solvent were mixed separately, and the formal crushing system of Example 59 was performed with a paint mixer for 24 hours For dispersion, the main crushing system of Example 60 was dispersed for 3 hours using a paint stirrer, and the rest was the same as in Example 2 to obtain each pigment dispersion.

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

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

In the same way as in Example 1, the pigment, dispersant, pigment derivative, alkali-soluble resin, pigment dispersant, and solvent were mixed separately, and the formal crushing system of Example 61 was performed with a paint mixer for 24 hours For dispersion, the main crushing system of Example 62 was dispersed for 3 hours using a paint stirrer, and the rest was the same as in Example 1 to obtain each pigment dispersion.

The coloring 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 phase difference and contrast were evaluated in the same manner as in Example 17.

Furthermore, the coloring resin composition of each example was diluted 1000 times with PGMEA, and a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution by Nikkiso Co., Ltd.) was used. The measuring device UPA-EX150) uses the dynamic light scattering method to measure the average dispersed particle size at 23°C.

The results of each evaluation are shown in Table 7.

[Results finishing]

From the results of Table 3 and Table 4, it is known that the combination of 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 dispersant containing a pyrrolo The pigment dispersions of Examples 1 to 16 in which one or more pigment derivatives are selected from the pigment derivative of the diketopyrrole skeleton and the pigment derivative of the azo lake skeleton are excellent in stability over time. The pigment dispersions of Examples 10 and 11 in which the sulfonated diketopyrrolopyrrole derivative and the sulfonated quinacridone derivative are used in combination are particularly excellent in stability over time.

The combination of 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 diketopyrrolopyrrole skeleton, and The coloring resin compositions of Examples 17 to 28 and Examples 32 to 39 in which one or more pigment derivatives are selected from the pigment derivatives of the azo lake skeleton, the coloring layer chromaticity (x, y) formed is satisfied 0.630≦x≦0.665, 0.326≦y≦0.335, and achieve a light retardation (Rth) of -30nm or more with a wavelength of 620nm in the thickness direction of the colored layer Below 120nm.

Furthermore, a pigment containing a red pigment represented by the general formula (1), and one or more pigments selected from red pigments, orange pigments, and yellow pigments that are different from the red pigment represented by the general formula (1) For the colored resin compositions of Examples 27 to 31, the chromaticity (x, y) of the formed colored layer satisfies 0.630≦x≦0.665, 0.295≦y≦0.360, and achieves light with a wavelength of 620nm in the thickness direction of the colored layer The phase difference (Rth) is -30nm or more and 120nm or less.

From the results of Table 6, it is found that when Y185 is used for the yellow pigment system, the absolute value of the retardation tends to be small. Because Y185 has an asymmetric molecular structure, it is estimated that the phase difference is unlikely to increase.

Furthermore, comparing Example 54 and Example 55, Example 32 and Example 57, Example 33 and Example 58 respectively, it can be seen that if polyamideimide resin is contained as an alkali-soluble resin, it can reduce The absolute value of the phase difference.

Furthermore, if Example 32 is compared with Example 57, and Example 33 with Example 58, it is known that if polyamide imide resin is contained as an alkali-soluble resin, and at least two kinds of diphenyl sulfide skeletons are contained The oxime-based starter has a tendency to increase brightness.

Furthermore, it is found that when at least two oxime-based initiators are contained and an antioxidant is further contained, even if the pigment concentration is increased, the occurrence of stains at the edge can be easily suppressed.

From the results in Table 7, it can be seen that 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 absolute value of the retardation tends to increase. On the other hand, with regard to the red pigment represented by the general formula (1-1), it is known that even if the particle size is excessively reduced, the absolute value of the retardation still tends to increase. Especially from the viewpoint of reducing the absolute value of the retardation, the average The primary particle size is preferably 40 nm to 60 nm.

Claims (12)

A colored resin composition for color filters, containing: a pigment containing a red pigment represented by the following general formula (1), a dispersant containing a copolymer having a structural unit represented by the following general formula (2), and a pigment Derivatives, alkali-soluble resins, monomers, initiators, and solvents; the above-mentioned pigment derivatives contain diketopyrrolopyrrole derivatives alkylated from the imine shown in the following chemical formula 1, and the following general formula B Among the aminated diketopyrrolopyrrole derivatives, the sulfonated diketopyrrolopyrrole derivatives represented by the following general formula C, and the derivatives with the azo lake pigment skeleton represented by the following general formula D Choose one or more types; when forming the colored layer of the colored resin composition, the chromaticity (x, y) of the colored layer measured by light source C satisfies 0.630≦x≦0.665, 0.326≦y≦0.335, and the light The optical retardation (Rth) of wavelength 620nm in the thickness direction of the colored layer is -30nm or more and 120nm or less;

(In general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl); [化2] general formula (2)

(In general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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; x is Represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18);

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

(In general formula C, X is derived from sulfonic acid group, -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 sulfonate, R'and R" each independently represent a hydrogen atom, saturated or unsaturated, which can be substituted with 1 to 20 carbon atoms Alkyl or aryl, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; plural R ⁶ are each independently a hydrogen atom and the number of carbon atoms 1-4 alkyl groups, 6-12 aryl groups, halogen atoms, or substituents X; n is an integer of 1 to 6, and m is an integer of 1 to 4);

(In general formula D, X is derived from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One selected from the group consisting of _n -SO ₃ H and sulfonate, R'and R" each independently represent a hydrogen atom, saturated or unsaturated alkane with 1 to 20 carbon atoms that can be substituted Group or aryl group, or R'and R" are bonded together with the adjacent nitrogen atom to form a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms; n is an integer from 1 to 6, and m is from 1 to 4 Integer). 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 a block part having the following general formula (3) The block part of the structural unit; the structural 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 units;

(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 is} 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, and -CHO , -CH ₂ CHO, or -CH ₂ COOR ^{26 is} a monovalent group; R ²⁶ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents an integer of 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18). The colored resin composition for color filters according to claim 1, wherein the red pigment system represented by the above general formula (1) contains the red pigment represented by the following chemical formula (1-1) and the following chemical formula (1-2) The red pigment shown;

The colored resin composition for color filters according to claim 1, wherein the alkali-soluble resin contains a polyamide resin having a carboxyl group. The colored resin composition for color filters of claim 1, wherein the starter system contains at least two oxime-based starters, and further contains an antioxidant. A colored resin composition for color filters, containing: a pigment containing a red pigment represented by the following general formula (1), a dispersant containing a copolymer having a structural unit represented by the following general formula (2), and a pigment Derivatives, alkali-soluble resins, monomers, initiators, and solvents; the above-mentioned pigment derivatives contain diketopyrrolopyrrole derivatives alkylated from the imine shown in the following chemical formula 1, and the following general formula B Among the aminated diketopyrrolopyrrole derivatives, the sulfonated diketopyrrolopyrrole derivatives represented by the following general formula C, and the derivatives with the azo lake pigment skeleton represented by the following general formula D One or more selected; the pigment system further contains one or more pigments selected from the red pigment, orange pigment, and yellow pigment that are different from the red pigment represented by the general formula (1); in forming the colored resin In the case of the colored layer of the 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 light phase is 620nm in the thickness direction of the colored layer The difference (Rth) is above -30nm and below 120nm;

(In general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl);

(In general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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; x is Represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18);

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

(In general formula C, X is derived from sulfonic acid group, -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 sulfonate, R'and R" are each independently a hydrogen atom, saturated or unsaturated with 1 to 20 carbon atoms and can be substituted Alkyl or aryl, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; plural R ⁶ are each independently a hydrogen atom and the number of carbon atoms 1-4 alkyl groups, 6-12 aryl groups, halogen atoms, or substituents X; n is an integer of 1 to 6, and m is an integer of 1 to 4);

(In general formula D, X is derived from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One selected from the group consisting of _n -SO ₃ H and sulfonate, and R'and R" are each independently a hydrogen atom, saturated or unsaturated with 1 to 20 carbon atoms and can be substituted Alkyl group or aryl group, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; n is an integer of 1 to 6, and m is 1 to 4 Integer). The colored resin composition for color filters according to claim 6, wherein the above-mentioned pigment It contains C.I. Pigment Yellow 185. The colored resin composition for color filters according to claim 6, wherein the alkali-soluble resin contains a polyamideimide resin having a carboxyl group. The colored resin composition for color filters of claim 6, wherein the starter system contains at least two oxime-based starters and further contains an antioxidant. A pigment dispersion liquid, which is a pigment dispersion liquid for preparing the colored resin composition for a color filter according to any one of claims 1 to 9; it contains: 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 above-mentioned pigment derivative contains an alkylated pyrrolopyrrole from an imine represented by the following chemical formula 1. Ketone derivatives, aminated diketopyrrolopyrrole derivatives represented by the following general formula B, sulfonated diketopyrrolopyrrole derivatives represented by the following general formula C, and azo compounds represented by the following general formula D Choose one or more of the derivatives of the pigment skeleton of the lake;

(In general formula (1), R ¹ and R ² are each independently 4-chlorophenyl or 4-bromophenyl); [化9] general formula (2)

(In general formula (2), R ¹¹ represents a hydrogen atom or a methyl group; Q represents a divalent linking group; R ¹² represents an alkylene group with 1 to 8 carbon atoms, according to -[CH(R ¹⁵ )-CH (R ¹⁶ )-O] _x -CH(R ¹⁵ )-CH(R ¹⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ¹³ And R ¹⁴ are each independently a chain or cyclic hydrocarbon group that 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; x is Represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18);

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

(In general formula C, X is derived from sulfonic acid group, -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 sulfonate, R'and R" each independently represent a hydrogen atom, saturated or unsaturated, which can be substituted with 1 to 20 carbon atoms Alkyl or aryl, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; plural R ⁶ are each independently a hydrogen atom and the number of carbon atoms 1-4 alkyl groups, 6-12 aryl groups, halogen atoms, or substituents X; n is an integer of 1 to 6, and m is an integer of 1 to 4);

(In general formula D, X is derived from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _n -NR'R", -SO ₂ NH-(CH ₂ ) _n -COOH, -SO ₂ NH-(CH ₂ ) One selected from the group consisting of _n -SO ₃ H and sulfonate, and R'and R" each independently represent a hydrogen atom, saturated or unsaturated, which can be substituted with 1 to 20 carbon atoms Alkyl group or aryl group, or R'and R" are bonded together with adjacent nitrogen atoms to form a heterocyclic ring which may further contain nitrogen, oxygen, or sulfur atoms; n is an integer of 1 to 6, and m is 1 to 4 Integer). A color filter comprising at least a substrate and a coloring layer provided on the substrate; characterized in that at least one of the coloring layers is used for the color filter of any one of claims 1 to 9 Cured material of colored resin composition. A display device characterized by having the color filter of claim 11.

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