TWI748029B - Color material dispersion liquid for color filter, color resin composition for color filter, color filter, and display device - Google Patents

Abstract

Provided is a color resin composition for a color filter, which is configured to be excellent in color material dispersion stability and able to form a color layer with a low retardation value and high contrast. Disclosed is a color resin composition for a color filter, comprising color materials, a dispersant and a binder component, wherein the color materials include a red color material and a yellow color material; wherein the yellow color material includes at least one kind of anion selected from the group consisting of mono-, di-, tri- and tetra-anions of a specific azo compound and tautomers thereof, ions of at least two kinds of metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a melamine derivative; and the dispersant is a polymer having a specific constitutional unit.

Description

Color material dispersion liquid for color filter, colored resin composition for color filter, color filter, and display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light-emitting display devices, such as organic EL displays with high visibility through self-luminescence, are also attracting attention as next-generation image display devices. Regarding the performance of these image display devices, there is a strong desire for further enhancement of image quality or reduction of power consumption, such as improvement of contrast and color reproducibility.

Most of the conventional display devices are based on the international standard sRGB (IEC61966-2-1) of the color space. However, in order to be closer to the actual performance and to improve the color reproducibility, AdobeRGB, which has a wider color reproduction gamut than sRGB, or DCI (Digital Cinema Initiatives) or BT (Broadcasting Service Television). The demand for display devices in 2020 has increased.

Here, the color filter used in the liquid crystal display device generally has a transparent substrate, a coloring layer formed on the transparent substrate and including coloring patterns of the three primary colors of red, green, and blue, and a coloring layer formed in order to divide the coloring patterns. The shading part on the transparent substrate.

As a method of forming such a colored layer, a pigment dispersion method, a dyeing method, an electrical adhesion method, a printing method, etc. are known. Among them, from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy, the pigment dispersion method with average superior characteristics is most widely used.

On the other hand, as a problem peculiar to the liquid crystal display device, there is a problem of viewing angle dependence caused by the refractive index anisotropy of the liquid crystal cell or the polarizing plate. The problem of the viewing angle dependence is the problem of changes in the color tone or contrast of the viewed image when the liquid crystal display device is viewed from the front and when viewed from an oblique direction. The problem of the viewing angle characteristic is that the severity of this problem has become more serious with the larger 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 has been widely used. However, 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. Therefore, when the above retardation film is used, there is a phase difference that cannot be compensated for the color pattern of each color. The problem of difference, and it is difficult to completely solve the problem of viewing angle dependence.

In particular, the red color material is easy to crystallize due to its chemical structure, so compared to the coloring layers of other colors, the red coloring layer has the problem that the retardation value in the thickness direction tends to become larger.

In addition, when using the conventionally used red color material, in order to expand the color reproduction gamut, red pixels that are included in the high-density red region with a yellow or blue hue are produced because of the increase in pigment concentration. , And there are problems such as reduced contrast or brightness, or deterioration of plate making performance.

Patent Document 1 discloses a color filter used as a combination of a red pigment series: CI Pigment Red 177 (hereinafter sometimes referred to as PG177); and a 1:1 complex selected from azobarbituric acid and nickel, and A pigment composed of at least one of the group of tautomers and at least one of these compounds inserted into the crystal lattice of the crystal lattice of other compounds (CI Pigment Yellow 150 Derivative (Ni Complex) ). However, if you want to express a deep red color using this pigment, you must use a very high concentration of pigment, which has the problems of increased retardation in the thickness direction, decreased contrast, and deterioration of plate-making properties.

On the other hand, Patent Document 2 describes a metal azo pigment containing a metal azo compound composed of a dianion of a specific azo compound and at least two metal ions of ^{Zn 2+} and Ni ^{2+ and melamine or its} The adduct of the derivative has a specific signal and no specific signal in the X-ray diffraction pattern.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2010-144057

Patent Document 2: Japanese Patent Laid-Open No. 2014-12838

The object of the present invention is to provide a color material dispersion liquid for a color filter that has excellent dispersion stability of color materials and can form a coloring layer that reduces the retardation value and improves the contrast at the same time; using the color material dispersion liquid for color filters, A colored resin composition for color filters that can form a colored layer with excellent color reproducibility that reduces the retardation value and improves the contrast; using the colored resin composition for color filters reduces the retardation value and simultaneously contrasts Improved color filter with superior color reproducibility; and a display device with improved phase difference and improved contrast and superior color reproducibility by using the color filter.

The color material dispersion liquid for color filters of the present invention is a color material dispersion liquid containing a color material, a dispersant and a solvent, and is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains: At least one anion selected from the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound represented by the following general formula (A) and its tautomeric structure; Ions of at least two metals in the group consisting of Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and the compound represented by the following general formula (B); the above-mentioned dispersant system has the following general formula (I) A polymer of the structural unit shown.

In addition, the colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent; it is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains : At least one anion selected from the group consisting of the mono-, di-, tri- and tetra-anions of the azo compound represented by the following general formula (A) and its tautomeric structure; selected from Cd, Co Ions of at least two metals in the group consisting of, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; and the compound represented by the following general formula (B); the above-mentioned dispersant system has the following general A polymer of structural units represented by formula (I).

[化1] General formula (A)

(In the general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^{b is} independently -OH or -NH _2. )

(In general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group.)

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure.)

The color filter of the present invention has at least a substrate and a coloring layer provided on the substrate, and is characterized in that at least one of the coloring layers is the curing of the coloring resin composition for the color filter of the present invention The coloring layer of the object.

The present invention provides a display device characterized by having the above-mentioned color filter of the present invention.

According to the present invention, it is possible to provide a color material dispersion liquid for a color filter that has excellent dispersion stability of color materials and can form a coloring layer that reduces the retardation value while increasing the contrast; using the color material dispersion liquid for color filters, A colored resin composition for color filters that can form a colored layer with excellent color reproducibility that reduces the retardation value and improves the contrast; using the colored resin composition for color filters reduces the retardation value and simultaneously contrasts Improved color filter with superior color reproducibility; and a display device with improved phase difference and improved contrast and superior color reproducibility by using the color filter.

1‧‧‧Substrate

2‧‧‧Shading part

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧Opposite substrate

30‧‧‧Liquid crystal layer

40‧‧‧Liquid crystal display 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 diagram showing an example of the color filter of the present invention.

Fig. 2 is a schematic diagram showing an example of the display device of the present invention.

Fig. 3 is a schematic diagram showing another example of the display device of the present invention.

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

Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further includes radiation, which includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less.

In the present invention, the term “(meth)acrylic type” means acrylic acid and methacrylic acid, respectively, and the term “(meth)acrylate type” refers to acrylate and methacrylate, respectively.

In addition, C.I. Pigment Red is abbreviated as "PR", C.I. Pigment Orange is abbreviated as "PO", and C.I. Pigment Yellow is abbreviated as "PY".

[Color material dispersion]

The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, and is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains: selected from the following general At least one anion of the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound represented by formula (A) and its tautomeric structure; selected from Cd, Co, Al, Cr, Sn Ions of at least two metals in the group consisting of, Pb, Zn, Fe, Ni, Cu and Mn; and the compound represented by the following general formula (B); the above-mentioned dispersant system has the following general formula (I) The polymer of the building blocks.

(In the general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^{b is} independently -OH or -NH _2. )

(In general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group.)

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure.)

The color material dispersion liquid of the present invention combines the above-mentioned specific color materials, and the polymer having the structural unit represented by the general formula (I) is used in combination as a dispersant, so the color material dispersion stability is excellent, and the retardation value can be reduced and At the same time, contrast the enhanced coloring layer.

Since the red color material generally has a ring-shaped planar structure, it is easy to crystallize when forming a colored layer as a color material dispersion liquid for color filters, so the thickness direction retardation value in the obtained colored layer is easy Get bigger.

In contrast, in the color material dispersion of the present invention, it is estimated that the red color material is used in combination: a specific yellow color material containing two or more metal ions; The dispersant of the body; therefore, the interaction between the red color material and the specific yellow color material containing more than two metal ions can be used to inhibit the growth of the crystals of the red color material and the yellow color material and make it microparticulate. In combination with the above-mentioned dispersant, the red color material and the yellow color material are micronized and dispersed, so that a colored layer can be formed that reduces the retardation value and improves the contrast at the same time.

Conventionally, when the metal forming the metal complex containing the azo compound represented by the above general formula (A) is one type of color material, the crystallinity is high, making it difficult to micronize, and it is difficult to improve the contrast. In addition, the retardation value of the colored layer obtained by combining with the red color material tends to increase. In contrast, in the present invention, a specific yellow color material containing two or more kinds of metal ions relative to the anion of the azo compound represented by the general formula (A) is used. The yellow color material contains two or more kinds of metal ions, which not only inhibits the crystal growth of the yellow color material, but also inhibits the crystal growth of the red color material. By further combining with the above-mentioned specific dispersant, it is estimated that it can be used in the color material dispersion liquid. Make it micronized.

Furthermore, in the present invention, by combining the above-mentioned specific yellow color material with the red color material, even if the P/V ratio ((color material component mass in the composition)/(solid content other than the color material component in the composition) is suppressed ) Than), it is still possible to produce red pixels included in the above-mentioned high-density red areas.

By reducing the P/V ratio in the colored layer and suppressing the crystal growth of the red color material, it is estimated that the retardation value in the thickness direction of the colored layer is reduced.

In addition, since the total content of the color material components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, the plate-making performance can be improved, and the coloring layer with improved adhesion to the substrate can be formed.

The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order.

[Color material]

In the present invention, the color material contains a red color material and a yellow color material; the yellow color material is characterized by containing: selected from the group consisting of azo compounds represented by the following general formula (A) and their tautomeric structures At least one anion from the group consisting of mono, di, tri and tetra anions; at least 2 metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn The ion; and the compound represented by the following general formula (B).

In the present invention, since the above-mentioned specific yellow color material is used as the yellow color material, the reduction in brightness can be suppressed when combined with the red color material, and crystallization can be suppressed to make it microparticulate, and it can be combined with a specific dispersant described later The time dispersion is superior, so the contrast can be improved, and the phase difference can be reduced.

(In the general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^{b is} independently -OH or -NH _2. )

As the acyl group in the acylamino group in the general formula (A), for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, and a phenylsulfonyl group can be used; Aminoformyl substituted by a group; amidinoyl substituted by an alkyl group, a phenyl group or a naphthyl group; a carboxamidino group substituted by an alkyl group, a phenyl group or a naphthyl group, etc. The above-mentioned alkyl group preferably has 1 or more and 6 or less carbon atoms. In addition, the above-mentioned alkyl group may be substituted with halogen such as F, Cl, and Br, -OH, -CN, -NH ₂ , and/or an alkoxy group having 1 to 6 carbon atoms. In addition, the above-mentioned phenyl and naphthyl groups may also be treated with halogens such as F, Cl, Br, -OH, -CN, -NH ₂ , -NO ₂ , alkyl groups with 1 to 6 carbon atoms, and/or carbon atoms It is substituted by an alkoxy group of 1 or more and 6 or less.

The alkyl group in the alkylamino group in the general formula (A) preferably has a carbon number of 1 or more and 6 or less. The above-mentioned alkyl group may be substituted with halogen such as F, Cl, Br, -OH, -CN, -NH ₂ , and/or an alkoxy group having 1 to 6 carbon atoms.

Examples of the aryl group in the arylamino group in the general formula (A) include a phenyl group and a naphthyl group. These aryl groups can also be treated with halogens such as F, Cl, Br, -OH, alkyl groups with carbon numbers from 1 to 6 and alkoxy groups with carbon numbers from 1 to 6, -NH ₂ , -NO ₂ and Replaced by -CN etc.

Among the azo compounds represented by the above general formula (A) and their tautomeric structures ^{, from the viewpoint that Ra is a} hue of a red hue, it is preferable to independently be -OH and -NH _2. -NH-CN or alkylamino group. The two ^Ras may be the same or different.

In the general formula (A), from the viewpoint of the hue, the better both the two R ^a are -OH lines, both of which are -NH-CN, or a person who is -OH and one is -NH -CN, even better, both are -OH.

In addition, in the azo compound represented by general formula (A) and its tautomeric structure, as R ^b , from the viewpoint of hue, it is preferable that both are -OH.

As at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, among them, it is preferable to contain at least one of which is divalent or trivalent The cationic metal more preferably contains at least one selected from the group consisting of Ni, Cu and Zn, and more preferably contains at least Ni.

Furthermore, the preferred system and Ni further contain at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and the more preferred system and Ni further contain selected At least one metal selected from the group consisting of Zn, Cu, Al, and Fe. Among them, the at least two metals are preferably Ni and Zn, or Ni and Cu.

In the yellow color material used in the present invention, the content ratio of at least two metals may be appropriately adjusted.

Among them, from the point of view of the hue of red tones, in the yellow color material used in the present invention, Ni is further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn. The content ratio of at least one metal in the group is preferably based on Ni: the other at least one metal is contained in a molar ratio of 97:3-10:90, and more preferably is contained in a molar ratio of 90:10-10:90 Contains more than ears.

Among them, from the viewpoint of the hue of the red hue, it is better to contain Ni and Zn according to the molar ratio of Ni:Zn of 90:10 to 10:90, and more preferably to the molar ratio of 80:20 to 20:80. Than containing.

Or, from the viewpoint of the hue of the red hue, it is better to contain Ni and Cu based on the molar ratio of Ni:Cu of 97:3 to 10:90, and more preferably based on the molar ratio of 96:4 to 20:80 Than containing.

When the yellow color material has a red hue, even if the above-mentioned P/V ratio is suppressed, it is easy to produce red pixels included in the above-mentioned high-density redness region.

The yellow color material used in the present invention may further contain metal ions different from the above-mentioned specific metal ions. The yellow color material used in the present invention may also contain, for example, at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.

Examples of the aspect in which at least two metal ions are contained in the yellow color material include: a case where at least two metal ions are contained in a common crystal lattice; and a case where each of the individual crystal lattices contains one metal ion. The condition of agglomeration of crystals. Among them, the case where at least two kinds of metal ions are contained in the common crystal lattice is preferable from the viewpoint of enhancing the contrast. In addition, for a state in which at least two metal ions are contained in a common crystal lattice, or a state in which crystals each containing one metal ion in individual crystal lattices are aggregated, refer to, for example, Japanese Patent Laid-Open No. 2014- Bulletin 12838 uses the X-ray diffraction method for proper judgment.

The yellow color material used in the present invention further contains a compound represented by the following general formula (B). The yellow color material used in the present invention contains a metal complex composed of the anion of the azo compound represented by the above general formula (A) and its tautomeric structure of the azo compound and a specific metal ion, and the following general A compound molecule of the compound represented by formula (B). These intermolecular bonds can be formed by, for example, intermolecular interactions, or Lewis acid-base interactions, or coordination bonds. In addition, it may also have a structure like an inclusion compound in which guest molecules are incorporated into the lattice constituting the host molecule. Or, it can also be formed: a common crystal is formed from two substances, and the atoms of the second component are located in the regular lattice position of the first component.

(In general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group.)

The alkyl group in R ^c is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group may also be substituted by -OH group.

Among them, R ^{c is} preferably a hydrogen atom.

The content of the compound represented by the above general formula (B) is based on 1 mol of the azo compound represented by the above general formula (A) and its tautomeric structure, and is generally 5 mol or more and 300 Molar or less, preferably 10 mol or more and 250 mol or less, and more preferably 100 mol or more and 200 mol or less.

啉、2,3-二羥基喹

啉-6-磺酸、咔唑、咔唑-3,6-二磺酸、2-羥基喹啉、2,4-二羥基喹啉、己內酯、三聚氰胺、6-苯基-1,3,5-三

-2,4-二胺、6-甲基-1,3,5-三

-2,4-二胺、三聚氰酸等。 In addition, the yellow color material used in the present invention may further contain: urea and substituted urea, such as phenylurea, dodecylurea, etc., and polycondensates with aldehydes (especially formaldehyde); heterocycles, Such as barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquine

Phylloline, 2,3-dihydroxyquine

Lin-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactone, melamine, 6-phenyl-1,3 ,5-three

-2,4-diamine, 6-methyl-1,3,5-tri

-2,4-Diamine, cyanuric acid, etc.

In addition, the yellow color material used in the present invention may further contain: water-soluble polymers, such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid, such as carboxymethyl cellulose, Modified cellulose like hydroxyethyl cellulose, hydroxypropyl cellulose, methyl and ethyl hydroxyethyl cellulose, etc.

The yellow color material used in the present invention can be prepared by referring to, for example, Japanese Patent Laid-Open No. 2014-12838.

On the other hand, the red color material used in the present invention uses: P/V (mass of red color material/mass of solid content other than red color material) ratio = 0.2 to measure the spectral transmittance of the coating film with a thickness of 2.5 μm In the light spectrum, the transmittance of the wavelength of 520nm is 20% or less, and the transmittance of the wavelength of 640nm is more than 70%. The red color material used in the present invention also includes a color material marked as C.I. Pigment Orange as a red color material with a slightly yellowish tint (an orange material with a stronger red color).

Furthermore, in order to coat the red color material separately for color measurement, a suitable dispersant, binder component, and solvent are prepared for the red color material to prepare a coating liquid, which is coated on a transparent substrate and dried, if necessary Just harden it. As a binder component, a non-curable thermoplastic resin composition or a photocurable (photosensitive) or thermosetting resin composition can also be used on the premise that a transparent coating film can be formed for color measurement. Things. In addition, in the coloring resin composition of the present invention described below, by using a composition containing only a red color material as a color material, a coating film containing only a red color material as a color material is formed, and color measurement can also be performed. Specifically, for example, the solid content used in the resin composition of Example 1 described later may be a solid content other than the red color material.

As a clear coating that contains a dispersant, a binder, and can perform color measurement, for example, a film thickness of 2.0 μm and a transmittance of 95% or more of the spectral transmittance spectrum at 380 to 780 nm can be used as the standard.

Furthermore, the spectral transmittance spectrum can be measured using a spectroscopic measuring device (for example, a microscope OSP-SP200 manufactured by Olympus). The measurement condition is C light source.

系顏料、蒽醌系顏料、芘酮(perinone)系顏料、苝系顏料、硫靛系顏料等。本發明所使用之紅色色材中，由抑制P/V比之觀點而言，較佳係含有選自由吡咯并吡咯二酮系顏料、萘酚系偶氮顏料、蒽醌系顏料、及苝系顏料所構成群之至少1種；進而由容易形成高色濃度之色相且輝度高的觀點而言，更佳為選自由吡咯并吡咯二酮系顏料、及蒽醌系顏料所構成群之至少1種。 The red color material used in the present invention is not particularly limited. Examples include diketopyrrolopyrrole pigments, naphthol azo pigments or other azo pigments, quinacridone pigments, and diketopyrrolopyrrole pigments.

Pigments, anthraquinone pigments, perinone pigments, perylene pigments, thioindigo pigments, etc. From the viewpoint of suppressing the P/V ratio, the red color material used in the present invention preferably contains a diketopyrrolopyrrole-based pigment, a naphthol-based azo pigment, an anthraquinone-based pigment, and a perylene-based At least one of the group consisting of pigments; furthermore, from the viewpoint of easy formation of high color density hue and high brightness, more preferably at least one selected from the group consisting of diketopyrrolopyrrole pigments and anthraquinone pigments kind.

Examples of the diketopyrrolopyrrole pigments include those represented by the following general formula (1).

[化9] General formula (1)

(In the general formula (1), A ³ and A ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a tertiary butyl group, a phenyl group, a N,N-dimethylamino group, a trifluoromethyl group, or a cyano group The base, k and k'each independently represent an integer of 0 or more and 5 or less. When k and k'are an integer of 2 or more, the plural A ³ and A ⁴ may be the same or different.)

Specific examples of the diketopyrrolopyrrole pigments include CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Orange 71, CI Pigment Orange 73 and the following The diketopyrrolopyrrole pigment (BrDPP) and the like represented by the chemical formula (2) are described.

Examples of the naphthol-based azo pigments include CI Pigment Red 144, CI Pigment Red 166, CI Pigment Red 214, CI Pigment Red 242, CI Pigment Red 21, CI Pigment Red 2, CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 5, CI Pigment Red 146, CI Pigment Red 170, CI Pigment Orange 38, CI Pigment Red 187, CI Pigment Red 150, CI Pigment Red 185, etc.

Examples of other azo pigments include C.I. Pigment Red 38, C.I. Pigment Red 41, and the like.

As said anthraquinone pigment, C.I. Pigment Red 177, C.I. Pigment Red 168, C.I. Pigment Orange 51, etc. are mentioned, for example.

Examples of the perylene-based pigments include C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 190, C.I. Pigment Red 224, and the like.

As the red color material, from the viewpoint of easily obtaining the effects of the present invention, it is preferable to use a diketopyrrolopyrrole pigment selected from the group consisting of CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 272, and the above-mentioned chemical formula (2) (BrDPP), CI Pigment Red 242, CI Pigment Orange 38, CI Pigment Red 177, and CI Pigment Red 179 are composed of one or more red color materials; among them, CI Pigment Red 254 and CI Pigment Red 254 are suitable as red color materials. The combination of diketopyrrolopyrrole pigment (BrDPP) and CI Pigment Red 177 represented by the above chemical formula (2).

When combining CI Pigment Red 254 with the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) and CI Pigment Red 177, the content ratio can be adjusted appropriately according to the required color materials, and is not particularly limited. With respect to 100 parts by mass of the total amount of the red color material, preferably CI Pigment Red 254 is 10 parts by mass or more and 80 parts by mass or less, and the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) is 10 parts by mass More than and 70 parts by mass or less, and CI Pigment Red 177 is 10 parts by mass or more and 60 parts by mass or less. If it is within the above range, the effect of the above combination is superior. In addition, the content ratio of the red color material is a preferable ratio when making the color resin composition described later. Since two or more types of color material dispersion liquids can be appropriately mixed and used to produce a color resin composition, even if the color material dispersion liquid itself is not set It is suitable for use because the content ratio is the same as that of the colored resin composition described later.

In the color material dispersion of the present invention, a red color material and the above-mentioned specific yellow color material are used in combination as a color material, but other color materials exemplified in the color resin composition described below may also be used in combination. As other color materials, for example, other yellow color materials, orange color materials not included in the above red color materials, etc. are suitably used; among them, from the viewpoint of hue, it is suitable to use other yellow color materials as exemplified in the colored resin composition described later .

In the color material dispersion of the present invention, the respective content ratios of the red color material and the above-mentioned specific yellow color material, and further the content ratio when the color material is used, are preferably set to the same content ratio as the color resin composition described later. Among them, the color material dispersion liquid can be suitably used by mixing two or more kinds to produce a colored resin composition, so it is suitable for use even if it is not set to the same content ratio as the colored resin composition described later.

As the average primary particle size of the color material used in the present invention, in the case of the coloring layer of the color filter, it is not particularly limited as long as it can perform the desired color development. It depends on the color material used. It varies depending on the type, but it is preferably within a range of 10 nm or more and 100 nm or less, and more preferably 15 nm or more and 60 nm or less. Since the average primary particle size of the color material is in the above range, a display device equipped with a color filter manufactured using the color material dispersion liquid of the present invention can be a high-contrast and high-quality display device.

In addition, the average dispersed particle diameter of the color material in the color material dispersion depends on the type of color material used, and 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.

The average dispersed particle diameter of the color material in the color material dispersion is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, as measured by a laser light scattering particle size distribution meter. As the particle size measurement performed by the laser light scattering particle size distribution meter, the color material dispersion liquid is appropriately diluted by the solvent used in the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 Times, etc.), using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.), and the measurement was carried out at 23°C by the dynamic light scattering method. The average distribution particle size here is the volume average particle size.

The content of the color material in the color material dispersion of the present invention is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of color material is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. It is blended in a ratio of above and 70 parts by mass or less.

Especially in the case of forming a coating film or colored layer with a high color material concentration, relative to 100 parts by mass of the total solid content in the color material dispersion, preferably 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass It is blended in a ratio of above and 75 parts by mass or less.

<Dispersant>

In the present invention, a polymer having a structural unit represented by the above general formula (I) is used as the dispersant system. The structural unit represented by the above general formula (I) is alkaline and functions as an adsorption site for the color material.

The color material dispersion of the present invention uses a polymer having the structural unit represented by the above general formula (I), so that the absorption performance of the color material, the dispersibility and the dispersion stability of the color material are improved.

In general formula (I), A is a divalent bonding group. The divalent bonding group in A includes, for example, alkylene groups having 1 to 10 carbon atoms, arylene groups, -CONH- groups, -COO- groups, and ethers having 1 to 10 carbon atoms. Group (-R'-OR"-: R'and R" are each independently an alkylene group) and combinations thereof.

Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a -CONH- group or a divalent bonding group containing a -COO- group.

In R ² and R ³ , the hydrocarbon group in the hydrocarbon group which may contain a hetero atom, for example, an alkyl group, an aralkyl group, an aryl group, etc. can be mentioned.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc.; the number of carbon atoms in the alkyl group is preferred It is 1 or more and 18 or less, and among them, a methyl group or an ethyl group is more preferable.

As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.

Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group etc. are mentioned, for example. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less. In addition, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

The so-called heteroatom-containing hydrocarbyl group has a structure in which the carbon atoms in the hydrocarbyl group are replaced by heteroatoms. Examples of the hetero atom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.

In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom.

啉環等。 The term R ² and R ³ may be bonded to each other to form a ring structure, which means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ³ may also contain heteroatoms. The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

啉環，其中更佳係R²與R³至少一者為碳原子數1以上且5以下之烷基、苯基、或R²與R³鍵結形成吡咯啶環、哌啶環、

啉環。 In the present invention, wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, or a phenyl group, or R ² and R ^{3 are} bonded to form a pyrrolidine ring, a piperidine ring,

It is more preferred that ^{at least one of R 2} and R ^{3 is} an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to form a pyrrolidine ring, a piperidine ring,

Morpholino ring.

As the structural unit represented by the above general formula (I), for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (Meth)acrylates, such as (meth)acrylates, diethylaminopropyl (meth)acrylates, etc., containing alkyl-substituted amino groups, etc.; dimethylaminoethyl (meth)acrylic acid (Meth)acrylamide containing alkyl substituted amino groups such as amine, dimethylaminopropyl (meth)acrylamide, etc. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate are preferably used. Aminopropyl (meth)acrylamide.

The structural unit represented by general formula (I) may contain one type or two or more types of structural units.

As a polymer having a structural unit represented by the general formula (I), from the viewpoint of improving dispersibility, it is preferable to further contain a portion having solvent affinity. As the solvent affinity site, it is preferably a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer that derives the structural unit represented by the general formula (I), and is compounded in a solvent affinity manner. The solvent is appropriately selected and used. As a standard, with respect to the solvent used in combination, the solubility of the polymer at 23°C is 50 (g/100g solvent) or more, and the solvent affinity site is introduced.

As the polymer used in the present invention, from the viewpoint of improving the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, and forming a high-brightness and high-contrast colored layer, among them, the block is preferred. Copolymer or graft copolymer, particularly preferably block copolymer. The following is a detailed description of particularly good block copolymers.

(Block copolymer)

When the block containing the structural unit represented by the above general formula (I) is referred to as the A block, the A block is the structural unit represented by the above general formula (I) having basicity and serves as an absorption for color materials. The function of the location. On the other hand, the B block that does not contain the structural unit represented by the above general formula (I) has a function as a block having solvent affinity. 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 superior dispersibility, AB block copolymers or ABA block copolymers are preferred.

As the structural unit constituting the B block, for example, a monomer having an unsaturated double bond that can be copolymerized with the monomer from which the structural unit represented by the general formula (I) is derived, and among them, the following general formula is preferred (II) The structural unit shown.

(In general formula (II), A'is a direct bond or a divalent bond group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O ] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ^8. R ⁶ or R ^{7 is} each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, a hydrocarbon group,- In the monovalent group represented by CHO, -CH ₂ CHO or -CH ₂ COOR ^{9 , R 9} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

The above-mentioned hydrocarbon group may have a substituent.

x represents an integer of 1 or more and 30 or less, y represents an integer of 1 or more and 5 or less, and z represents an integer of 1 or more and 18 or less.

The divalent bonding group A'in the general formula (II) can be the same as A in the general formula (I). Among them, A'is preferably a direct bond, a -CONH- group, or a divalent bond group containing a -COO- group from the viewpoint of solubility in an organic solvent. From the viewpoint of the heat resistance of the obtained polymer or the solubility of propylene glycol monomethyl ether acetate (PGMEA) suitable for use as a solvent, or a relatively inexpensive material, A'is preferably a -COO- group.

The hydrocarbon group in R ⁵ is preferably an alkyl group having 1 or more and 18 or less carbon atoms, an alkenyl group having 2 or more and 18 or less carbon atoms, an aralkyl group or an aryl group.

基、異

基、二環戊烷基、二環戊烯基、金剛烷基、低級烷基取代金剛烷基等。 The above-mentioned alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc.

The above-mentioned alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched, or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. 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 of aliphatic hydrocarbons such as an alkyl group or an aralkyl group include a nitro group and a halogen atom.

As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.

Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or more, more preferably 7 or more and 14 or less.

Examples of the substituent of the aromatic ring such as an aryl group or an aralkyl group include, for example, an alkenyl group, a nitro group, a halogen atom, etc., in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 26 or less, more preferably an integer of 1 or more and 18 or less, still more preferably an integer of 1 or more and 4 or less, particularly preferably 1 or more And an integer of 2 or less; y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group in the above R ⁸ can be the same as that shown in the ^{above R 5.} Among them, ^{the hydrocarbon group in R 8} is preferably an alkyl group having 1 or more and 18 or less carbon atoms from the viewpoint of excellent developability.

R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be linear, branched, or cyclic.

^{In addition, R 5} in the structural unit represented by the above general formula (II) may be the same or different from each other.

Among them, R ^{5 is} preferably selected so as to have excellent compatibility with the solvent described later. Specifically, for example, the solvent is generally used as a solvent for a colored resin composition for a color filter In the case of glycol ether acetate-based, ether-based, ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.

In addition, in the structural unit constituting the B block, as the above-mentioned R ^{5 , it is preferable to contain -[CH(R 6} )-CH(R ⁷ )-O from the viewpoint of excellent developability and excellent suppression of development residue. ] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ .

Furthermore, within the range that does not interfere with the dispersibility of the block copolymer, the R ⁵ may be substituted by a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group. After the synthesis of the segmented copolymer, it can also be reacted with the compound having the above-mentioned substituent to add the above-mentioned substituent.

In the present invention, the glass transition temperature (Tg) of the solvent affinity block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block portion is preferably 80°C or higher, more preferably 100°C or higher.

The glass transition temperature (Tg) of the solvent affinity block part of the present invention can be calculated according to the following formula. In addition, the glass transition temperature of the color material affinity block portion and the block copolymer can also be calculated in the same manner.

1/Tg=Σ(Xi/Tgi)

Here, the solvent-affinity block part is set to be copolymerized by n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the Σ system uses the sum from i=1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of the Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of structural units constituting the block portion of solvent affinity may be appropriately adjusted within the range in which the dispersibility of the color material is improved. Among them, from the viewpoint that the solvent affinity site and the color material affinity site effectively act to improve the dispersibility of the color material, the number of structural units constituting the solvent affinity block portion is preferably 10 or more and 200 or less, and more Preferably it is 10 or more and 100 or less, more preferably 10 or more and 70 or less.

The solvent-affinity block portion may be selected in a manner that functions as a solvent-affinity portion, and the repeating unit constituting the solvent-affinity block portion may contain one type or two or more types of repeating units.

In addition, in the present invention, the dispersant system has good dispersibility and does not precipitate foreign matter during coating film formation, and from the viewpoints of enhancing brightness and contrast, it is preferable to contain the composition represented by the above general formula (II) and have an amine value of 40 mgKOH. /g or more and 120mgKOH/g or less polymer.

When the amine value is within the above range, the viscosity with time stability or heat resistance is superior, and the alkali developability or solvent resolubility is also superior. In the present invention, the amine valence of the dispersant is from the viewpoint of dispersibility and dispersion stability. Among them, the amine valence is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less.

The amine value refers to the mg number of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the measurement by this method, even if the amine group in the dispersant forms a salt with the organic acid compound, since the organic acid compound is usually dissociated, the amine value of the block copolymer itself used as the dispersant can be measured.

The lower limit of the acid value of the dispersant used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more from the viewpoint that the effect of suppressing the development residue is more superior. On the other hand, the acid value of the dispersant is preferably 0 mgKOH/g from the viewpoint of dispersibility and dispersion stability. In addition, the acid value of the dispersant used in the present invention is from the viewpoint of preventing the deterioration of developing adhesion or solvent resolubility. The upper limit of the acid value of the dispersant is preferably 18 mgKOH/g or less . Among them, the acid value of the dispersant is more preferably 12 mgKOH/g or less, and still more preferably 8 mgKOH/g or less, from the viewpoint that the developing adhesiveness and solvent resolubility become better.

In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. This is because the effect of suppressing development residue is improved. On the other hand, the acid value of the block copolymer before salt formation is preferably 0 mgKOH/g from the viewpoint of dispersibility and dispersion stability. In addition, the upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, and still more preferably 8 mgKOH/g or less. This is due to the good developing adhesion and solvent re-solubility.

Furthermore, in the present invention, the glass transition temperature of the dispersant is preferably 30°C or higher from the viewpoint of improvement in developing adhesion. That is, whether the dispersant is a block copolymer before salt formation or a salt-type block copolymer, its glass transition temperature is preferably 30°C or higher. If the glass transition temperature of the dispersant is low, especially when it is close to the temperature of the developer (usually around 23°C), there is a risk that the developing adhesion will decrease. This is presumed that if the glass transition temperature is close to the temperature of the developer, the movement of the dispersant during development will increase, and as a result, the development adhesion will deteriorate. Since the glass transition temperature is above 30°C, it is presumed that the molecular motion of the dispersant during development is suppressed, thereby suppressing the decrease in development adhesion.

The glass transition temperature of the dispersant is from the viewpoint of developing adhesion, and is preferably 32°C or higher, more preferably 35°C or higher. On the other hand, from the viewpoint of operability during use, such as ease of accurate weighing, the temperature is preferably 200°C or lower.

The glass transition temperature of the dispersant of the present invention can be obtained by measuring with differential scanning calorimetry (DSC) in accordance with JIS K7121.

If the color material concentration is increased and the dispersant content is increased, since the amount of binder is relatively reduced, the colored resin layer is likely to peel off from the base substrate during development. When the dispersant contains a B block having a structural unit derived from a carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, the development adhesion is improved. It is presumed that if the acid value is too high, although the developability is excellent, the polarity is too high and peeling easily occurs during development.

From the above, the present invention has excellent color material dispersion stability and improved contrast, and suppresses the occurrence of development residues when the coloring resin composition is made, at the same time, it has excellent solvent resolubility and high development adhesion. The above-mentioned dispersing agent preferably contains a polymer with the structure shown in the above general formula (I) and an amine value of 40mgKOH/g or more and 120mgKOH/g or less, and an acid value of 1mgKOH/g or more and 18mgKOH/g or less, glass transition The temperature is above 30°C.

As the above-mentioned carboxyl group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, Cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as a carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerization, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxyl group-containing monomer can be appropriately set so that the acid value of the block copolymer becomes the above-mentioned specific acid value, and is not particularly limited. The total mass of the total constituent units in the block copolymer is preferably 0.05% by mass or more and 4.5% by mass or less, more preferably 0.07% by mass or more and 3.7% by mass or less.

When the content ratio of the constituent units derived from the carboxyl group-containing monomer is above the above lower limit, the effect of suppressing development residues is exhibited; by below the above upper limit, the deterioration of development adhesion or solvent re-dissolution can be prevented Sexual deterioration.

In addition, the structural unit derived from the carboxyl group-containing monomer should just have the above-mentioned specific acid value, and it may contain one type or two or more types of structural units.

In addition, from the viewpoint of making the glass transition temperature of the dispersant used in the present invention higher than a specific value and improving the development adhesion, it is preferable to set the value of the glass transition temperature (Tgi) of the homopolymer of the monomer to The monomers at 10°C or higher are 75% by mass or more, more preferably 85% by mass or more in the B block in total.

In the block copolymer, the ratio m/n of the unit number m of the constituent unit of the A block to the unit number n of the constituent unit of the B block is preferably in the range of 0.05 or more and 1.5 or less; From the viewpoint of the dispersibility and dispersion stability of the color material, it is more preferably within the range of 0.1 or more and 1.0 or less.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited. From the viewpoint of good color material dispersibility and dispersion stability, it is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, and more More preferably 3,000 or more and 12,000 or less.

Here, the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC) in terms of standard polystyrene conversion value. In addition, the macromonomers, salt-type block copolymers, and graft block copolymers used as raw materials for the block copolymers are also carried out under the above-mentioned conditions.

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. This is due to the fact that it is not easy to cause chain movement or deactivation, can produce a copolymer with a uniform molecular weight, and can improve the dispersibility. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and radical transfer polymerization methods, living cationic polymerization methods, and the like. By sequentially polymerizing monomers by these methods, copolymers can be produced. For example, the A block is first produced, and the A block is polymerized with the constituent units constituting the B block to produce a block copolymer. Moreover, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and then the A block and the B block may be coupled.

Specific examples of such a block copolymer having a block portion containing a structural unit represented by the general formula (I) and a block portion having solvent affinity include, for example, the block copolymer described in Japanese Patent No. 4911253 Fit as appropriate.

In the present invention, from the viewpoint of the dispersibility or dispersion stability of the color material, it is preferable to use at least a part of the amine group in the polymer containing the structural unit represented by the above general formula (I), and an organic acid The salt formed by the compound or halogenated hydrocarbon is used as a dispersant (hereinafter, such a polymer is referred to as a salt polymer).

Among them, from the viewpoint of superior dispersibility and dispersion stability of the color material, it is preferable that the polymer containing the repeating unit with tertiary amine is a block copolymer, and the above-mentioned organic acid compound is phenylphosphonic acid or phenyl Acidic organic phosphorus compounds such as phosphinic acid. As a specific example of the organic acid compound used for such a dispersing agent, the organic acid compound described in Unexamined-Japanese-Patent No. 2012-236882 etc. is preferable, for example.

In addition, as the above-mentioned halogenated hydrocarbon, from the viewpoint of superior dispersibility and dispersion stability of the color material, at least 1 of halogenated allyl groups such as brominated allyl groups and chlorinated benzyl groups and halogenated aralkyl groups is preferred. kind.

In the color material dispersion liquid of the present invention, as a dispersant, at least one polymer having a structural unit represented by the above general formula (I) is used, and its content is based on the type of color material used, and further as described later The solid content concentration in the colored resin composition for color filters is appropriately selected.

From the viewpoint of dispersibility and dispersion stability, the content of the dispersant is preferably 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. It is blended in a ratio of not less than 1 part and not more than 35 parts by mass.

Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is relative to 100 parts by mass of the total solid content in the color material dispersion, preferably 3 parts by mass or more and 25 parts by mass or less , It is better to mix at a ratio of 5 parts by mass or more and 20 parts by mass or less.

Furthermore, in the present invention, the solid content is all other than the above-mentioned solvents, and also includes monomers dissolved in the solvents and the like.

<Solvent>

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse these. The solvent can be used alone or in combination of two or more kinds.

Specific examples of solvents include alcohol-based solvents such as methanol, ethanol, isopropanol, and methoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate Ester, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate , Isobutyl acetate, n-butyl butyrate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxy ethyl Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl ethyl Glycol ether acetate solvents such as acid esters; methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, butyl carbitol acetate (BCA), etc. Alcohol acetate solvent; propylene glycol diacetate, 1,3-butanediol diacetate and other diacetate esters; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether Glycol ethers such as ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc. Solvent; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic ether amine solvents; γ-butyrolactone and other lactones Solvent; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; toluene, An organic solvent such as xylene and other aromatic hydrocarbons. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used from the viewpoint of the solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 2-methyl from the viewpoint of solubility of other components or coating suitability. Oxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl One or more of the group consisting of acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate.

In addition, from the viewpoints of developability, solvent resolubility, etc., it is preferable to also use a mixed solvent containing two or more kinds of solvents.

In the case of using a mixed solvent, as the first solvent, it is preferable to use the aforementioned glycol ether acetate solvent for reasons such as high safety, moderate volatility, and good dispersibility due to moderate solubility. Furthermore, among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate with a boiling point (referring to the boiling point under atmospheric pressure, the same applies hereinafter) less than 150°C is more preferred, and propylene glycol monomethyl ether acetate is particularly preferred. Methyl ether acetate (PGMEA).

As the second solvent (a solvent other than the first solvent), a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150°C or higher is preferable. The second solvent may be used singly or as a mixture of two or more kinds.

If a solvent having an alcoholic hydroxyl group is used as the second solvent, the dispersibility becomes good and the solvent re-solubility easily becomes good.

Examples of solvents having alcoholic hydroxyl groups include the above-mentioned alcohol-based solvents, the above-mentioned carbitol-based solvents, and the above-mentioned glycol ether-based solvents. Specific examples include propylene glycol monomethyl ether (boiling point 121°C), 3- Methoxy-3-methyl-1-butanol (boiling point 174°C) and the like.

In the case of using a mixed solvent, the content of the solvent having an alcoholic hydroxyl group in the total solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less. Furthermore, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 1% by mass or more.

If it is within the above range, the solubility of the dispersing agent is likely to be good, and the dissolution of the dispersing agent to the first solvent is not hindered, so the dispersion stability is likely to be good.

When the first solvent is a solvent with a boiling point of less than 150°C, if a solvent with a boiling point of 150°C or higher is used as the second solvent, uneven drying is less likely to occur, foreign matter is less likely to be generated, and the solvent re-solubility is likely to be good.

Examples of solvents with a boiling point of 150°C or higher include diethylene glycol ethyl methyl ether (boiling point 179°C), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188°C) ), diethylene glycol ethyl methyl ether (boiling point 179°C), 3-methoxybutyl acetate (boiling point 172°C), etc.

In the case of using a mixed solvent, the content of the solvent with a boiling point of 150°C or higher is preferably 40% by mass or less, more preferably 30% by mass or less in the total solvent. Furthermore, it is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.

If it is in the above range, uneven drying is unlikely to occur, or the drying time is not too long, and productivity is likely to become good.

The boiling point of the above-mentioned "solvent with a boiling point of 150°C or higher" is preferably 240°C or lower, particularly preferably 200°C or lower, from the viewpoint that the drying time is not too long.

The color material dispersion of the present invention, relative to the total amount of the color material dispersion containing the solvent, usually preferably contains the above solvent in the range of 55% by mass to 95% by mass, and preferably 65% by mass or more And within the range of 90% by mass or less, more preferably within the range of 70% by mass or more and 88% by mass or less. If the solvent is too small, the viscosity will increase and the dispersibility will tend to decrease. In addition, if the solvent is too much, the concentration of the colored material will decrease, making it difficult to achieve the target chromaticity coordinates.

<Other ingredients>

In the color material dispersion of the present invention, without impairing the effect of the present invention, a dispersion auxiliary resin and other components can be further formulated as needed.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the colored resin composition for color filters described below. Due to the steric obstacle of the alkali-soluble resin, the color material particles are not easily contacted with each other, and there are cases where the dispersion stabilization is performed or the effect of the dispersant is reduced by the dispersion stabilization effect.

In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, shrinkage inhibitors, antioxidants, anti-aggregating agents, ultraviolet absorbers, etc. .

The color material dispersion liquid of this invention is used as a preliminary preparation for preparing the coloring resin composition for color filters mentioned later. In other words, the so-called color material dispersion is prepared at the stage before preparing the colored resin composition for color filters described later, P/V (mass of color material in the composition)/(other than color material in the composition) The solid content mass) is relatively high color material dispersion. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid content other than the color material components in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the components described below, a colored resin composition for color filters with excellent dispersibility can be prepared.

[Manufacturing Method of Color Material Dispersion Liquid]

In the present invention, the method for producing the color material dispersion is not particularly limited as long as it is a method of obtaining the color material dispersion liquid dispersed in a solvent by using the color material with the dispersant. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the color material, it is preferable to use any one of the following two production methods.

That is, the first manufacturing method of the color material dispersion of the present invention includes the step of preparing the above-mentioned dispersant and the step of dispersing the color material in the presence of the above-mentioned dispersant in a solvent. In the solvent, in the presence of the above dispersant, two or more color materials can be co-dispersed, or more than one color material can be dispersed or co-dispersed, and then two or more color material dispersions can be mixed. In this way, the color material dispersion of the present invention can also be obtained.

In addition, in the case of using a dispersant belonging to a salt-type block copolymer, the second method for producing a color material dispersion of the present invention includes: combining a solvent, the block copolymer, the organic acid compound or the halogenated hydrocarbon with the color When at least a part of the terminal nitrogen site of the structural unit represented by the above general formula (I) forms a salt with the above organic acid compound or halogenated hydrocarbon, there is a step of dispersing the color material at the same time. In the case of forming salt while dispersing color materials, two or more color materials can be co-dispersed, or more than one color material can be dispersed or co-dispersed, and then two or more color materials can be mixed to disperse In this way, the color material dispersion liquid of the present invention can also be obtained.

In the above-mentioned first manufacturing method and the above-mentioned second manufacturing method, the color material can be dispersed using a conventionally known dispersing machine.

Specific examples of the dispersing machine include roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, etc. Mill. As for the preferable dispersion conditions of the bead mill, the diameter of the grinding beads used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 or more and 2.0 mm or less.

[Colored resin composition for color filter]

The colored resin composition for color filters of the present invention contains a color material, a dispersant, a binder component, and a solvent; it is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains: At least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound represented by the above general formula (A) and its tautomeric structure; selected from the group consisting of Cd, Co, Al, Ions of at least two metals in the group consisting of Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; and the compound represented by the above general formula (B); the above dispersant system has the above general formula (I) The polymer of the building blocks.

The colored resin composition for a color filter of the present invention has superior color material dispersion and concealment as the above-mentioned color material dispersion of the present invention, and can be formed as described in the item of the above-mentioned color material dispersion of the present invention. A colored layer with reduced retardation, high brightness and high contrast, and excellent color reproducibility.

If the colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent, it may further contain other components within a range that does not impair the effects of the present invention. The following describes the components contained in the colored resin composition for color filters of the present invention, but the red color material, the above-mentioned specific yellow color material, dispersant and solvent, which are essential components in the color material, are in line with the above-mentioned present invention The description of the color material dispersion is the same, so the description is omitted here.

<color material>

The color material in the colored resin composition for a color filter of the present invention contains a red color material and the above-mentioned specific yellow color material as essential components, but in order to adjust the color tone, other color materials may be further used in combination.

It is not particularly limited as long as it can develop the desired color when forming the coloring layer of the color filter, and various organic pigments, inorganic pigments, and dispersible dyes can be used alone or in combination of two or more. Among them, organic pigments are suitable for use due to their high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), and specific examples include those with the following color index (C.I.).

In addition, as the above-mentioned dispersible dyes, for example, various substituents can be given to the dyes, or the well-known lakeing (salting) technique can be used to insolubilize the solvent to become a dispersible dye, or a combination of low dyes can be used. Solubility of the solvent becomes a dispersible dye. By using this dispersible dye in combination with the above-mentioned dispersant, the dispersibility or dispersion stability of the dye can be improved.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 As the dispersible dye, it can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

Furthermore, as a standard, if the dissolved amount of the dye is 10 mg or less with respect to 10 g of the solvent (or mixed solvent), it can be determined that the dye is dispersible in the solvent (or mixed solvent).

As other color materials, it is preferable to use other yellow color materials and orange color materials not included in the above-mentioned red color materials.

Examples of other color materials include the following, but they are not limited to these.

Examples of other yellow color materials include CI Pigment Yellow 1, 3, 11, 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, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 and 185 etc.

In the colored resin composition for a color filter of the present invention, the content ratio of the red color material to the entire color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited.

Among them, from the viewpoint of reducing the retardation value and increasing the color reproducibility and improving the contrast, relative to the total amount of color materials, it is preferable to contain the red color material at 35% by mass to 99% by mass, and more preferably 40% by mass. % Or more and 98% by mass or less, more preferably 45% by mass or more and 97% by mass or less.

In addition, from the viewpoint that the retardation value is reduced while the color reproducibility is widened and the contrast is improved, the total content of the yellow color material relative to the total color material is preferably 1% by mass or more and 65% by mass or less, and more preferably 2% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 55% by mass or less.

In the colored resin composition for color filters of the present invention, the yellow color material is selected from single, two, three, and three azo compounds represented by the general formula (A) and their tautomeric structures. At least one anion from the group consisting of four anions, and at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and the above general formula (B) The total content of the compound (the above-mentioned specific yellow color material) can be adjusted appropriately according to the required chromaticity, and is not particularly limited. Among them, from the viewpoint of reducing the retardation value and increasing the color reproducibility and improving the contrast, the total content of the above-mentioned specific yellow color material is preferably 10% by mass or more and 100% by mass relative to the total amount of the yellow color material. Below, more preferably 15% by mass or more and 100% by mass or less, still more preferably 20% by mass or more and 100% by mass or less, still more preferably 25% by mass or more and 100% by mass or less.

In addition, in the colored resin composition for a color filter of the present invention, the color material may further contain a red color material and other color materials other than the yellow color material within a range that does not impair the effects of the present invention, and The total content of the red color material and the yellow color material relative to the total amount of the color material is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and still more preferably 80% by mass or more And 100% by mass or less.

<Binder Ingredients>

The colored resin composition for a color filter of the present invention contains a binder component in order to form a film or impart adhesiveness to a coated surface. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable adhesive component. The curable adhesive component is not particularly limited, and conventionally known curable adhesive components for forming the colored layer of a color filter can be suitably used.

As the curable adhesive component, for example, a photocurable adhesive component containing a photocurable resin that can be polymerized and hardened by visible light, ultraviolet rays, electron beams, etc. can be used; or The thermosetting binder component of polymerized and hardened thermosetting resin.

In the case of using a photolithography step when forming the coloring layer, it is suitable to use a photosensitive binder component having alkali developability. In addition, a thermosetting adhesive component may be further used in the photosensitive adhesive component.

Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. As the positive photosensitive binder component, for example, a system containing an alkali-soluble resin, and a system containing an o-quinonediazide group-containing compound as a photosensitive imparting component, and the like can be mentioned.

On the other hand, as a negative photosensitive binder component, it is suitable to use a system containing at least an alkali-soluble resin, a multifunctional monomer, and a photoinitiator.

The colored resin composition for color filters of the present invention is preferably a negative photosensitive adhesive component from the viewpoint that patterns can be easily formed by photolithography using an existing process.

Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive adhesive component will be specifically described.

(Alkali-soluble resin)

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

In the present invention, the alkali-soluble resin system can target an acid value of 40 mg KOH/g or more.

The preferred alkali-soluble resin in the present invention has an acidic group, usually a carboxyl group. Specific examples include acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups. Epoxy (meth)acrylate resin of carboxyl group, etc. Among these, particularly preferable ones are those having a carboxyl group in the side chain, and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that by containing a photopolymerizable functional group, the film strength of the formed cured film can be improved. In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins can also be used in combination of two or more types.

Acrylic resins such as acrylic copolymers having structural units with carboxyl groups and styrene-acrylic copolymers with carboxyl groups, for example, are copolymers of ethylenically unsaturated monomers containing carboxyl groups and optionally copolymers. Other monomers are (co)polymers obtained by (co)polymerization by a known method.

Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. , Crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as a carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerization, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of superior adhesion of the colored layer. Since the alkali-soluble resin has a large-volume hydrocarbon ring, the shrinkage during curing is suppressed, the peeling from the substrate is eased, and the adhesion of the substrate is improved. In addition, the inventors of the present invention have discovered that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the resulting colored layer, especially the swelling of the colored layer, can be suppressed. The effect has not been elucidated, but it is speculated that the coloring layer contains large-volume hydrocarbon rings, which can inhibit the molecular action in the coloring layer. As a result, the strength of the coating film becomes higher and the swelling caused by the solvent is suppressed.

Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may also have a substituent, an aromatic hydrocarbon ring which may also have a substituent, and combinations thereof. The hydrocarbon ring may also have an alkyl group, a carbonyl group, a carboxyl group, and an oxygen group. Substituents such as carbonyl group, amide group, hydroxyl group, nitro group, amine group, halogen atom, etc.

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、茀等之芳香族烴環；聯苯、聯三苯、二苯基甲烷、三苯基甲烷、茋等之鏈狀多環，或咔哚構造(9,9-二芳基茀)等。 As specific examples of the hydrocarbon ring, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane,

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

As the hydrocarbon ring, from the viewpoint of improving the heat resistance or adhesion of the colored layer and at the same time improving the brightness of the resulting colored layer, it is preferable to contain an aliphatic hydrocarbon ring.

In addition, from the viewpoint of improving the curability of the colored layer and improving the solvent resistance ((NMP swelling inhibitory property)), it is particularly preferable to include the above-mentioned carbodole structure.

The alkali-soluble resin is preferably one that belongs to an aliphatic hydrocarbon ring having a structure in which two or more rings share two or more atoms, and has a crosslinked cyclic hydrocarbon ring.

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；此等基之一部分被取代基所取代的基。 As a specific example of the cross-linked cyclic hydrocarbon ring, for example,

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 part of these groups is substituted by substituents.

As said substituent, an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom etc. are mentioned, for example.

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

In addition, the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).

[In general formula (III), R ^M is a hydrocarbon ring which may also be substituted. ]

When the alkali-soluble resin has a maleimide structure represented by the general formula (III), since it has a nitrogen atom in the hydrocarbon ring, it is compatible with the base of the polymer having the structural unit represented by the general formula (I). The compatibility between the dispersants is very good, the development speed is fast, and the suppression effect of the development residue is improved.

^{In R M} of the general formula (III), specific examples of the hydrocarbon ring that may be substituted include, for example, the same as the specific examples of the above-mentioned hydrocarbon ring.

Examples include aliphatic hydrocarbon rings such as cyclopentyl, cyclohexyl, and cyclooctyl, or phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, methoxybenzene Aromatic hydrocarbon rings such as benzyl, benzyl, hydroxyphenyl, naphthyl, etc., and a group in which a part of these groups is substituted with a substituent.

In the alkali-soluble resin used in the present invention, in addition to the structural unit having a carboxyl group, it is easy to adjust the amount of each structural unit, increase the amount of the structural unit having a hydrocarbon ring, and easily improve the function of the structural unit. In other words, it is preferable to use an acrylic copolymer having a structural unit having the above-mentioned hydrocarbon ring.

An acrylic copolymer having a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be produced by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".

酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等，由顯影後之著色層之剖面形狀於加熱處理中仍維持之效果較大的觀點而言，較佳係使用選自(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸苄酯、及苯乙烯之至少1種。 Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, isopropyl (meth)acrylate

Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., from the viewpoint that the cross-sectional shape of the colored layer after development is maintained during the heat treatment, it is more effective than Preferably, at least one selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene is used.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer, etc. can form a cross-linked bond in the curing step of the resin composition when the color filter is manufactured. The film strength of the hardened film is improved, and the development resistance is improved, or the heat shrinkage of the hardened film is suppressed, and the adhesion between the hardened film and the substrate becomes superior.

The method of introducing an ethylenic double bond into the alkali-soluble resin can be appropriately selected by a conventionally known method. For example, a compound having an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of an alkali-soluble resin, and an ethylenic double bond is introduced into the side chain. A method of bonding; or a method of introducing a structural unit having a hydroxyl group into the copolymer in advance, adding a compound with an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain, etc.

The alkali-soluble resin of the present invention may further contain other structural units such as methyl (meth)acrylate, ethyl (meth)acrylate, etc., structural units having an ester group. The structural unit having an ester group not only functions as a component that inhibits the alkali solubility of the colored resin composition for color filters, but also functions as a component that improves solubility in solvents and further solvent resolubility.

The alkali-soluble resin of the present invention is preferably an acrylic resin having a structural unit having a carboxyl group, an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a hydrocarbon ring, and more preferably a structure having a carboxyl group Acrylic resins such as units, structural units having a hydrocarbon ring, and structural units having an ethylenic double bond, and acrylic resins such as styrene-acrylic copolymers.

Alkali-soluble resins can be made into alkali-soluble resins with required properties by appropriately adjusting the filling amount of each constituent unit.

The filling amount of the carboxyl group-containing ethylenically unsaturated monomer is, from the viewpoint of obtaining a good pattern, with respect to the total amount of monomers, it is preferably 5 mass% or more, more preferably 10 mass% or more. On the other hand, from the viewpoint of suppressing film roughness on the surface of the pattern after development, the filling amount of the carboxyl-containing ethylenically unsaturated monomer is preferably 50% by mass or less, more preferably, relative to the total amount of monomers. 40% by mass or less.

If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is above the above lower limit, the resulting coating film will have sufficient solubility in alkaline developing solutions; and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is the above upper limit If the value is less than the value, during the development of the alkaline developer, the formed pattern will not easily fall off the substrate or the film on the surface of the pattern will tend to be rough.

In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units with ethylenic double bonds, which are alkali-soluble resins, can be used more preferably. The filling amount of the saturated monomer, the compound having both an epoxy group and an ethylenic double bond, is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass 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. When it is less than 1,000, the adhesive function after curing may be significantly reduced. If it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer.

Furthermore, the above-mentioned weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured with polystyrene as a standard substance and THF as the eluent by Shodex GPC System-21H (Shodex GPC System-21H).

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. A more suitable one is an epoxy obtained by reacting an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Base (meth)acrylate compound.

Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known materials for use. The epoxy (meth)acrylate resin having a carboxyl group may be used individually by one type, or two or more types may be used in combination.

From the viewpoint of the developability (solubility) of the alkaline aqueous solution used in the developer, the alkali-soluble resin preferably has an acid value of 50 mgKOH/g or more. From the viewpoint of the developability (solubility) of the alkaline aqueous solution used in the developer and the viewpoint of the adhesion to the substrate, the acid value of the alkali-soluble resin is preferably 70 mgKOH/g or more and 300 mgKOH/g or less , More preferably 80mgKOH/g or more and 280mgKOH/g or less.

Furthermore, in the present invention, the acid value can be measured in accordance with JIS K 0070.

The ethylenic unsaturated bond equivalent when the side chain of the alkali-soluble resin has ethylenic unsaturated groups is more effective in terms of improving the film strength of the cured film, improving the development resistance, and having superior adhesion to the substrate. It is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2,000 or less, the development resistance and the close adhesion are excellent. Moreover, if it is 100 or more, since the ratio of other structural units, such as the structural unit having a carboxyl group or the structural unit having a hydrocarbon ring, can be relatively increased, it is excellent in developability and heat resistance.

Here, the equivalent of ethylenic unsaturated bond refers to the weight average molecular weight of the ethylenic unsaturated bond in the alkali-soluble resin per 1 mol, and is represented by the following formula (1).

Formula (1) Ethylene unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The above-mentioned ethylenically unsaturated bond equivalent can be calculated by measuring the number of ethylenic double bonds per 1 g of the alkali-soluble resin in accordance with the test method for iodine value as described in JIS K 0070: 1992, for example.

The alkali-soluble resin used in the colored resin composition for color filters can be used singly or in combination of two or more. The content is not particularly limited, and is relative to the colored resin composition for color filters. As for the total solid content, the alkali-soluble resin is preferably within a range of 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 40 mass% or less. 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 is more than the above upper limit, film roughness or pattern peeling may occur during development. situation.

(Multifunctional monomer)

The polyfunctional monomer used in the colored resin composition for color filters is not particularly limited as long as it is polymerizable using the above-mentioned photoinitiator. Generally, two or more ethylenic unsaturations can be used. The compound with a double bond is particularly preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups.

As such a polyfunctional (meth)acrylate, it can select suitably from a conventionally well-known thing, and can use it. Specific examples include those described in JP 2013-029832 A, etc.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the colored resin composition for color filters of the present invention is required to have excellent photocurability (high sensitivity), the multifunctional monomer preferably has three (trifunctional) or more polymerizable double bonds, more preferably Poly(meth)acrylates of trivalent or higher polyols, or these dicarboxylic acid modifiers, specifically, preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol tri( Meth) acrylate, pentaerythritol tri(meth)acrylate modified by succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate Succinic acid modification product of pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The content of the above-mentioned polyfunctional monomer used in the colored resin composition for color filters is not particularly limited. The polyfunctional monomer is preferably 5 relative to the total solid content of the colored resin composition for color filters. In the range of mass% or more and 60 mass% or less, more preferably 10 mass% or more and 40 mass% or less. If the content of the polyfunctional monomer is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion can be prevented from eluting during development, and if the content of the polyfunctional monomer is below the above upper limit, the alkali developability will be sufficient.

(Photoinitiator)

The initiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and it can be used alone or in combination of two or more from various conventional initiators.

二唑化合物、α-胺基酮、雙咪唑類、N,N-二甲基胺基二苯基酮、鹵甲基-S-三

系化合物、9-氧硫

等。起始劑之具體例可舉例如二苯基酮、4,4’-雙二乙基胺基二苯基酮、4-甲氧-4’-二甲基胺基二苯基酮等之芳香族酮類，苯偶姻甲基醚等之苯偶姻醚類，乙基苯偶姻等之苯偶姻，2-(鄰氯苯基)-4,5-苯基咪唑二聚物等之雙咪唑類，2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑等之鹵甲基

二唑化合物，2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三

等之鹵甲基-S-三

系化合物，2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲基硫基)苯基]-2-N-

啉基丙酮、1,2-苄基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、苄基、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、4-苯甲醯基-4’-甲基二苯基硫醚、苄基甲基縮酮、二甲基胺基苯甲酸酯、對二甲基胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲基胺基苯甲酸酯、2-氯9-氧硫

、2,4-二乙基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、4-苯甲醯基-甲基二苯基硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲基胺基)-1-[4-(4-

啉基)苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯 基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲基硫基)苯基]-2-(4-

啉基)-1-丙酮等。 As the initiator, for example, aromatic ketones, benzoin ethers, halomethyl

Diazole compounds, α-amino ketones, bisimidazoles, N,N-dimethylamino diphenyl ketone, halomethyl-S-tri

Series compounds, 9-oxysulfur

Wait. Specific examples of the initiator include aromatics such as benzophenone, 4,4'-bisdiethylamino benzophenone, 4-methoxy-4'-dimethylamino benzophenone, etc. Group ketones, benzoin ethers such as benzoin methyl ether, benzoin such as ethyl benzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, etc. Bisimidazoles, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-

Halomethyl

Diazole compound, 2-(4-butoxy-naphthalene-1-yl)-4,6-bis-trichloromethyl-S-tri

Halomethyl-S-three

Series compound, 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Alkylacetone, 1,2-benzyl-2-dimethylamino-1-(4-N-

(Hydroxyphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl-4' -Methyl diphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-di Methyl amino benzoate, 2-chloro-9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-

(Alkolinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4-

(Alpinyl)-1-acetone and the like.

啉基丙-1-酮、2-苄基-2-(二甲基胺基)-1-(4-N-

啉基苯基)-1-丁酮、4,4’-雙(二乙基胺基)苯乙酮、二乙基9-氧硫

。由感度調整、抑制水滲染、提升顯影耐性的觀點而言，更佳係組合2-甲基-1-[4-(甲基硫基)苯基]-2-N-

啉基丙-1-酮般之α-胺基苯乙酮系起始劑與二乙基9-氧硫

般之9-氧硫

系起始劑。 Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Linylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-N-

(Hydroxyphenyl)-1-butanone, 4,4'-bis(diethylamino)acetophenone, diethyl 9-oxysulfur

. From the viewpoints of sensitivity adjustment, suppression of water bleeding, and improvement of development resistance, it is more preferable to combine 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Alpha-aminoacetophenone-like starter and diethyl 9-oxysulfur

General 9-oxysulfur

Department of initiator.

系起始劑時，此等之合計含量係相對於著色樹脂組成物之固形份總量，較佳為5質量%以上且15質量%以下。若起始劑量為15質量%以下，由於減低製造製程中之昇華物，故較佳。若起始劑為5質量%以上，則水滲染等顯影耐性提升。 For the use of α-aminoacetophenone initiators and 9-oxysulfur

In the case of an initiator, the total content of these is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the colored resin composition. If the starting dose is 15% by mass or less, it is better because it reduces the sublimate in the manufacturing process. If the initiator content is 5% by mass or more, development resistance such as water bleeding and staining is improved.

In the present invention, from the viewpoint of improving sensitivity, the initiator preferably contains an oxime ester-based photoinitiator. By using the oxime ester-based photoinitiator, it is easy to suppress the deviation of the in-plane line width when forming a fine line pattern. Furthermore, by using an oxime ester-based photoinitiator, the developability is improved and the effect of suppressing the occurrence of water bleeding tends to be higher. In addition, the term "water bleeding" refers to a phenomenon in which if a component that improves alkali developability is used, after alkali development and washing with pure water, marks like water bleeding will occur. This kind of water bleeding disappears after post-baking, so there is no problem as a product. However, during the appearance inspection of the pattern surface after development, it will be detected as uneven and abnormal, causing the problem that normal products and abnormal products cannot be distinguished. . Therefore, if the inspection sensitivity of the inspection device is reduced during the appearance inspection, it will result in a decrease in the yield of the final color filter product, which becomes a problem.

As the oxime ester-based photoinitiator, from the viewpoint of reducing contamination of the colored resin composition for color filters or device contamination caused by decomposition products, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred. Those having a condensed ring containing an aromatic ring are more preferably those having a condensed ring containing a benzene ring and a heterocyclic ring.

As the oxime ester-based photoinitiator, 1,2-octanedione-1-[4-(phenylthio)-, 2-(orthobenzyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, JP The oxime ester-based photoinitiators described in Bulletin 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc. are appropriately selected. As commercially available products, Irgacure OXE-02 (manufactured by BASF) with a carbazole skeleton, ADEKA ARKLS NCI-831 (manufactured by ADEKA Corporation), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) can be used. ADEKA ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (the above are manufactured by Changzhou Qiangli Electronic New Materials Co.), Irgacure OXE-01 (manufactured by BASF), Frame TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Material Co.), etc. From the viewpoint of brightness, it is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. From the viewpoint of higher sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton.

In addition, from the viewpoints that the brightness and development resistance are easily improved, and the effect of suppressing the occurrence of water bleeding is relatively high, it is preferable to use two or more oxime ester-based photoinitiators in combination. From the viewpoint of high brightness and high heat resistance, it is particularly preferable to use two types of oxime ester photoinitiators with a diphenyl sulfide skeleton in combination, or use an oxime ester photoinitiator with a diphenyl sulfide skeleton in combination. Starter and oxime ester-based photoinitiator with citron skeleton. In addition, from the viewpoint of superior sensitivity and water bleeding prevention effect, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton, an oxime ester-based photoinitiator having a pyruvate skeleton, or a diphenylene-based photoinitiator in combination. The oxime ester of sulfide is a photoinitiator.

啉基丙-1-酮(例如Irgacure 907、BASF公司製)、2-苄基-2-(二甲基胺基)-1-(4-N-

啉基苯基)-1-丁酮(例如Irgacure 369，BASF公司製)、4,4’-雙(二乙基胺基)二苯基酮(例如Hicure ABP，川口藥品製)等。 In addition, from the viewpoint of suppressing water bleeding and improving sensitivity, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator. The photoinitiator with a tertiary amine structure has a tertiary amine structure of an oxygen quencher in the molecule, so the free radicals generated by the initiator are not easily deactivated by oxygen, which can increase the sensitivity. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-N-

Alkylpropan-1-one (e.g. Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-N-

(Alolinylphenyl)-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.

系起始劑；由輝度、顯影耐性提升、容易調整感度、水滲染發生抑制效果高、提升顯影耐性的觀點而言，較佳係組合2種以上之肟酯系光起始劑、與9-氧硫

系起始劑。 In addition, from the viewpoints of sensitivity adjustment, suppression of water bleeding, and improvement of development resistance, it is preferable to use the oxime ester-based photoinitiator combination 9-oxysulfur

It is an initiator; from the viewpoints of brightness, development resistance improvement, easy adjustment of sensitivity, high water bleeding suppression effect, and improvement of development resistance, it is better to combine two or more oxime ester-based photoinitiators, and 9 -Oxysulfur

Department of initiator.

The content of the photoinitiator used in the colored resin composition for color filters of the present invention is generally 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass relative to 100 parts by mass of the above-mentioned polyfunctional monomer. Parts by mass or more and 60 parts by mass or less. If the content is more than the above lower limit, the photohardening progresses sufficiently and the elution of the exposed part during development is suppressed; on the other hand, if the content is less than the above upper limit, the yellowing property of the resulting colored layer becomes weak and the brightness can be suppressed reduce.

In addition, the total content of two or more oxime ester-based photoinitiators as the photoinitiator used in the colored resin composition for color filters of the present invention is determined by fully exerting these photoinitiators. From the viewpoint of the combined effect, relative to the total solid content of the colored resin composition for color filters, the range is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less Inside.

The total content of the binder components used in the colored resin composition for color filters of the present invention is relative to the total solid content of the colored resin composition for color filters, preferably 35% by mass It is blended in a proportion of above and 97% by mass or less, and more preferably 40% by mass or more and 96% by mass or less. If it is more than the above lower limit, a colored layer with excellent hardness or adhesion to the substrate can be obtained. In addition, if it is less than the above upper limit value, the developability is excellent and the occurrence of fine wrinkles due to thermal shrinkage is also suppressed.

<Optional ingredients>

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

Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization stoppers, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters.剂 etc.

In the colored resin composition for a color filter of the present invention, it is preferable to further contain an antioxidant from the viewpoints of improving heat resistance, suppressing color fading, and improving brightness. In addition, from the viewpoint of improving the adhesion of the SiN substrate, it is also preferable that the colored resin composition for a color filter of the present invention 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.

The so-called hindered phenol-based antioxidant refers to an antioxidant having the following structure: containing at least one phenol structure, and at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure is substituted with a substituent with 4 or more carbon atoms的结构。 The structure.

(商品名：Irganox 565，BASF製)、2,2’-硫二乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名：Irganox 1035，BASF製)、1,2-雙[3-(4-羥基-3,5-二第三丁基苯基)丙醯基]肼(商品名：Irganox MD1024，BASF製)、3-(4-羥基-3,5-二異丙基苯基)丙酸辛酯(商品名：Irganox 1135，BASF製)、4,6-雙(辛基硫基甲基)-鄰甲酚(商品名：Irganox 1520L，BASF製)、N,N’-六亞甲基雙[3-(3,5-二第三丁基-4-羥基苯基)丙醯胺](商品名：Irganox 1098，BASF製)、1,6-己二醇雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名：Irganox 259，BASF製)、1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯基氧基]乙基]2,4,8,10-四側氧螺[5.5]十二烷(商品名：ADK STAB AO-80，ADEKA製)、雙(3-第三丁基-4-羥基-5-甲基苯丙酸)乙烯雙(氧基乙基)(商品名：Irganox 245，BASF製)、1,3,5-參[[4-(1,1-二甲基乙基)-3-羥基-2,6-二甲基苯基]甲基]-1,3,5-三

-2,4,6(1H,3H,5H)-三酮(商品名：Irganox 1790，BASF製)、2,2’-亞甲基雙(6-第三丁基-4-甲基酚)(商品名：SUMILIZER MDP-S，住友化學製)、6,6’-硫基雙(2-第三丁基-4-甲基酚)(商品名：Irganox 1081，BASF製)、3,5-二第三丁基-4-羥基苄基磺酸二酯(商品名：Irgamod 195，BASF製)、丙烯酸2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯酯(商品 名：SUMILIZER GM，住友化學製)、4,4’-硫基雙(6-第三丁基-間甲酚)(商品名：SUMILIZER WX-R，住友化學製)、6,6’-二第三丁基-4,4’-亞丁基二間甲酚(商品名：ADEKASTAB AO-40，ADEKA製)等。其他亦可使用具有受阻酚構造之寡聚物型及聚合物型的化合物等。 As specific examples of hindered phenol antioxidants, for example, dibutylhydroxytoluene (BHT), pentaerythritol 4 [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (commercial Name: Irganox 1010, manufactured by BASF), 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) trimeric isocyanate (trade name: Irganox 3114, manufactured by BASF), 2,4 , 6-Ginseng (4-hydroxy-3,5-di-tert-butylbenzyl) symmetric trimethylbenzene (trade name: Irganox 1330, manufactured by BASF), 6-(4-hydroxy-3,5-di-tert-butyl Anilino)-2,4-bis(octylthio)-1,3,5-tri

(Trade name: Irganox 565, manufactured by BASF), 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-tert-butylphenyl)propanyl]hydrazine (trade name: Irganox MD1024, manufactured by BASF), 3-( 4-hydroxy-3,5-diisopropylphenyl) octyl propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: Irganox 1520L, manufactured by BASF), N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (trade name: Irganox 1098, manufactured by BASF) ), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl -2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy]ethyl]2,4,8,10-tetra-side oxyspiro[5.5]dodecane (Trade name: ADK STAB AO-80, manufactured by ADEKA), bis(3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid) ethylene bis(oxyethyl) (trade name: Irganox 245, BASF), 1,3,5-ginseng [[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5 -three

-2,4,6(1H,3H,5H)-trione (trade name: Irganox 1790, manufactured by BASF), 2,2'-methylenebis(6-tertiarybutyl-4-methylphenol) (Trade name: SUMILIZER MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5 -Di-tert-butyl-4-hydroxybenzylsulfonic acid diester (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3- Tributyl-5-methylbenzyl)phenyl ester (trade name: SUMILIZER GM, manufactured by Sumitomo Chemical), 4,4'-thiobis(6-tertiarybutyl-m-cresol) (trade name: SUMILIZER WX-R, manufactured by Sumitomo Chemical), 6,6'-di-tert-butyl-4,4'-butylene xylenol (trade name: ADEKASTAB AO-40, manufactured by ADEKA), etc. Other oligomer type and polymer type compounds with hindered phenol structure can also be used.

Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 4 [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, BASF Company system).

In addition, from the viewpoint of forming a colored layer that reduces the retardation value while simultaneously increasing the brightness and contrast, a hindered phenol antioxidant having a molecular weight of 1,000 or less and a molecular weight of 280 equivalents or less per phenolic hydroxyl group is preferred. More preferably, it is a hindered phenolic antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per phenolic hydroxyl group. It is presumed that this antioxidant has high fluidity and many active points per weight unit, so it suppresses the aggregation of color materials caused by rapid hardening and shrinkage during exposure or post-baking by capturing free radicals, or inhibits resins, etc. The yellowing can easily obtain the above-mentioned effects. Examples of such antioxidants include 6,6'-di-tert-butyl-4,4'-butylene-m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA).

Furthermore, in the present invention, it is preferable to use a latent antioxidant as an antioxidant from the viewpoint of forming a colored layer that can reduce the retardation value and increase the contrast at the same time. If a latent antioxidant is used, it is presumed that the effect of capturing radicals is increased especially during post-baking, so that the aggregation of color materials caused by rapid hardening and shrinkage during post-baking is suppressed, and the above-mentioned effect is easily obtained. The so-called latent antioxidant in the present invention is a compound having a protective group that can be detached by heating, and a compound that exhibits an antioxidant function when the protective group is detached. Among them, it is preferable that the protective group is easily removed by heating at 150°C or higher. Examples include latent antioxidants as described in International Patent Publication No. 2014/021023.

As the latent antioxidant suitable for use in the present invention, for example, a latent hindered phenol antioxidant in which the phenolic hydroxyl group of the hindered phenol antioxidant is protected with a protective group that can be removed by heating. Examples of latent hindered phenol antioxidants include phenolic hydroxyl groups of hindered phenol antioxidants, acid anhydrides, acid chlorides, Boc chemical reagents, alkyl halide compounds, silyl halide compounds, or allyl ether compounds. And other reactants. As the latent hindered phenol antioxidant, it is suitable to use a structure in which the hydrogen of the phenol group of the hindered phenol antioxidant is replaced with a urethane-based protective group such as a tertiary butoxycarbonyl group. Specific examples are as follows The chemical formulae (a) to (c) are described, but are not limited to these.

The method for producing the above-mentioned latent antioxidant is not particularly limited. For example, Japanese Patent Laid-Open No. 57-111375, Japanese Patent Laid-Open Hei 3-173343, Japanese Patent Laid-Open Hei 6-128195, Japanese Patent Laid-Open Hei 7-206771, JP Hei 7-252191, and Japanese Patent Application No. 7-252191 The phenolic compound produced by the method described in the publications of 2004-501128 is obtained by reacting with acid anhydride, acid chloride, Boc chemical reagent, alkyl halide compound, silyl chloride compound, allyl ether compound, etc. In addition, commercially available products can also be used.

If the colored resin composition for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator in combination with an antioxidant as the colored resin composition, it is preferable from the viewpoint of enhancing the brightness due to the synergistic effect.

As the content of the antioxidant, relative to 100 parts by mass of the total solid content in the colored resin composition, the antioxidant is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5.00 parts by mass or less. If it is more than the above 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 relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator, and the antioxidant is preferably 1 part by mass or more And 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is within the above range, the effect of the above combination is superior.

The colored resin composition for color filters of the present invention preferably further contains a mercapto compound from the viewpoint of enhancing the effect of inhibiting the occurrence of water bleeding.

In addition, in the colored resin composition for color filters of the present invention, if the above-mentioned oxime ester-based photoinitiator and a mercapto compound are combined as a photosensitive colored resin composition, the water penetration is further improved from the viewpoint of improving the development resistance. It is preferable from the viewpoint of the effect of suppressing the occurrence of dyeing and the viewpoint that the linearity is improved when the thin line pattern is formed, or the ability to form the thin line pattern like the design of the mask line width is improved. In addition, the term "improvement of linearity" means that the end portion of the colored layer formed in the development step after the application of the colored composition has less unevenness and is formed in a linear or slightly linear shape.

The mercapto compound can function as a chain transfer agent, and has the property of accelerating the reaction by receiving free radicals from the slow-reacting free radicals and enhancing the hardening property.

唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑、3-巰基丙酸、3-巰基丙酸甲酯、3-巰基丙酸乙酯、3-巰基丙酸辛酯、1,4-雙(3-巰基丁醯基氧基)丁烷、1,3,5-參(3-巰基丁基氧基乙基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷參(3-巰基丙酸酯)、季戊四醇肆(3-巰基丁酸酯)、季戊四醇肆(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、及四乙二醇雙(3-巰基丙酸酯)等。 As the mercapto compound, for example, 2-mercaptobenzothiazole, 2-mercaptophenoxy

Azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3 -Ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,3,5-ginseng(3-mercaptobutyloxyethyl)-1 ,3,5-three

-2,4,6(1H,3H,5H)-triketone, trimethylolpropane (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate), pentaerythritol 4 (3-mercaptopropane) Acid ester), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The mercapto compound may be used alone or in combination of two or more. Among them, from the viewpoint of increasing the crosslinking density and enhancing the effect of inhibiting water bleeding, it is preferably selected from as many as having two or more mercapto groups in one molecule. One or more of the group consisting of functional mercapto compounds.

In addition, from the viewpoint that it is easy to maintain a good water bleeding inhibition effect even after long-term storage, it is preferable to have a secondary mercapto group with a secondary sulfhydryl group in which the carbon atom to which the sulfhydryl group is bonded is a secondary carbon atom. The sulfhydryl compound is more preferably a multifunctional secondary sulfhydryl compound having two or more secondary sulfhydryl groups in one molecule.

The content of the mercapto compound used in the colored resin composition for color filters is not particularly limited. From the viewpoint of fully exerting the above effects, relative to the total solid content of the colored resin composition for color filters, The mercapto compound is preferably in the range of 0.2% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less.

系化合物等。其中，由可形成使相位差值減低且同時對比提升之著色層的觀點而言，較佳為使用苯并三唑系化合物。 In addition, in the colored resin composition for a color filter of the present invention, it is preferable to further contain an ultraviolet absorber from the viewpoint of forming a colored layer that can reduce the retardation value and increase the contrast at the same time. The effect of improving these characteristics can be presumed to be due to the suppression of color material aggregation caused by the rapid hardening shrinkage in the exposure step. What is necessary is just to select an ultraviolet absorber suitably from a conventionally well-known thing. Specific examples of ultraviolet absorbers include, for example, benzotriazole-based compounds, diphenyl ketone-based compounds, three

Department of compounds and so on. Among them, it is preferable to use a benzotriazole compound from the viewpoint of forming a colored layer that can reduce the retardation value and increase the contrast at the same time.

Examples of benzotriazole-based compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole and 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzene Triazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethyl A mixture of hexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy- 3,5-bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5 -Chlorobenzotriazole, 2-(3,5-ditertiarypentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzene Triazole, 5% of 2-methoxy-1-methylethyl acetate and 95% of phenylpropionic acid, 3-(2H-benzotriazol-2-yl)-(1,1- Dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl -1-Phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3, 3-trimethylbutyl)phenol and the like, but are not limited to these.

Examples of commercially available products include "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", and "TINUVIN 384-" manufactured by BASF. 2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", etc.

As the benzotriazole-based compound, a benzotriazole-based compound represented by the following general formula (IV) is preferred from the viewpoint of forming a colored layer that can reduce the retardation value and increase the contrast at the same time.

(In general formula (IV), R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group with 1 to 20 carbons which may be substituted with a phenyl group, and X represents a hydrogen atom or a chlorine atom.)

In general formula (IV), R ^{12 is} preferably methyl, tertiary butyl, tertiary pentyl, tertiary octyl, or α,α-dimethylbenzyl, and R ^{11 is} preferably a hydrogen atom, Tributyl, tertiary amyl, or α,α-dimethylbenzyl.

The content of the ultraviolet absorber used in the colored resin composition for color filters is not particularly limited. With respect to 100 parts by mass of the total solid content in the colored resin composition, the ultraviolet absorber is preferably 0.05 parts by mass or more and 10.00 Parts by mass or less, more preferably 0.10 parts by mass or more and 5.00 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.

If the colored resin composition for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator in combination with an ultraviolet absorber as the colored resin composition, it is better from the viewpoint of enhancing the brightness by synergistic effects. good.

When the ultraviolet absorber is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the ultraviolet absorber is preferably 1 with respect to 100 parts by mass of the total amount of the above-mentioned oxime ester-based photoinitiator. Parts by mass or more and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, still more 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.

Moreover, as a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

As the silane coupling agent, for example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBM-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu SILICONE), etc. Among them, from the viewpoint of the adhesiveness of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacrylic group and an acrylic group are preferable.

As the content of the silane coupling agent, the silane coupling agent is 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass, relative to 100 parts by mass of the total solid content in the colored resin composition. If it is more than the above lower limit and below the above upper limit, SiN is excellent in dense viscosity.

<The mixing ratio of the components in the colored resin composition for color filters>

The total content of the color materials is relative to the total solid content of the colored resin composition for color filters, preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less . If it is more than the above lower limit, the colored resin composition for a color filter has a sufficient concentration when the colored resin composition is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less). In addition, if it is less than the above upper limit value, the storage stability is excellent, and at the same time, a colored layer having sufficient hardness and adhesion to the substrate can be obtained. Especially in the case of forming a colored layer with a high color material concentration, the content of the color material is relative to the total solid content of the colored resin composition for color filters, preferably 15% by mass or more and 65% by mass or less, more preferably It is blended in a proportion of 25% by mass or more and 60% by mass or less.

In addition, the content of the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, relative to the total solid content of the colored resin composition for color filters, it can be used from 1% by mass to 40% by mass. . Furthermore, relative to the total solid content of the colored resin composition for color filters, it is preferably formulated in a ratio of 2% by mass or more and 30% by mass or less, and particularly preferably in a ratio of 3% by mass or more and 25% by mass or less Deployment. If it is more than the above lower limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the colored resin composition for color filters is excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a colored layer with a high color material concentration, the content of the dispersant is relative to the total solid content of the colored resin composition for color filters, preferably 2% by mass or more and 25% by mass or less, more preferably Blending in a ratio of 3% by mass or more and 20% by mass or less.

In addition, the content of the solvent may be appropriately set according to the range in which the colored layer can be formed accurately. Relative to the total amount of the colored resin composition for color filters containing the solvent, it is usually preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass . When the content of the above-mentioned solvent is within the above-mentioned range, it can be made to have excellent coating properties.

In the colored resin composition for color filters of the present invention, the P/V ratio ((the mass of the color material in the composition)/(the mass of the solid content other than the color material in the composition) ratio) is determined by From the viewpoint of gas or heat shrinkage, it is preferably 0.1 or more, more preferably 0.2 or more; on the other hand, it is excellent in suppression of phase difference and manufacturing convenience, that is, solvent resolubility, development residue, and development adhesion From the viewpoint of superior development resistance and water bleeding prevention effect, it is preferably 0.8 or less, more preferably 0.7 or less; from the viewpoint of development residue and development adhesion, it is more preferably 0.6 or less.

<Cured film of colored resin composition for color filter>

In the colored resin composition for color filters, it is preferable to form the chromaticity coordinates in the range of x=0.550~0.700 and y=0.290~0.450 in the XYZ color system of JIS Z8701, which is measured using a C light source. Those within the hardened film.

Among them, from the viewpoint of improving color reproducibility, it is preferable to form the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source as x=0.570~0.693, y=0.300~0.426 The cured film within the range is more preferably the cured film within the range of x=0.600~0.690 and y=0.300~0.348, and the cured film within the range of x=0.630~0.690 and y=0.300~0.329 is more preferred.

In the cured film of the colored resin composition for color filters, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured by a single pixel using a C light source with a film thickness of 2.8 μm or less are preferable The color space can be expressed as x=0.570~0.693, y=0.300~0.426, and the stimulus value Y is within the range of 9.0≦Y. More preferably, the system can be expressed as x=0.600~0.690, y=0.300~0.348 and the stimulus value Y The color space is within the range of 9.5≦Y. In addition, the thickness of the cured film here is that after the colored resin composition for color filters is coated, dried, exposed to light and the polyfunctional monomer is cured, it is post-baked in a dust-free oven at 230°C Film thickness after 30 minutes.

In the chromaticity coordinates in the XYZ color system of JIS Z8701 measured by a single pixel using a C light source with a film thickness of 2.8μm or less, it is used to indicate x=0.570~0.693, y=0.300~0.426 and A good blending ratio or combination of the color space with the stimulus value Y in the range of 9.0≦Y is relative to the total amount of color materials, preferably the red color material is 45.0% by mass or more and 98.0% by mass or less, the above-mentioned specific yellow color material 2.0% by mass or more and 55.0% by mass or less; more preferably red color material is 50.0% by mass or more and 95.0% by mass or less, the specific yellow color material is 5.0% by mass or more and 50.0% by mass or less; particularly preferred red color The material is 55.0% by mass or more and 90.0% by mass or less, and the specific yellow color material is 10.0% by mass or more and 45.0% by mass or less.

<Manufacturing Method of Colored Resin Composition for Color Filter>

The manufacturing method of the colored resin composition for color filters of the present invention is not particularly limited. For example, it can be achieved by adding an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator to the color material dispersion of the present invention described above. If necessary, other ingredients are mixed and obtained by using a well-known mixing method. Or using the above-mentioned dispersing agent, the color material dispersion liquid of each color material, various color material dispersion liquids, binder components, and other components as needed are prepared separately, and they can be obtained by mixing them with a known mixing means.

[Color filter]

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

The color filter of this invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has 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 a color filter of the present invention, or a colored layer formed 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 it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width, area, etc. of the colored layer can be arbitrarily set.

The thickness of the colored layer is appropriately controlled by the coating method, adjustment of the solid content concentration or viscosity of the colored resin composition for color filters, etc., and is generally preferably in the range of 1 μm or more and 5 μm or less.

This colored layer can be formed by the following method, for example.

First, the above-mentioned colored resin composition for a color filter of the present invention is applied to a substrate described later using coating means such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating. On top, a wet coating film is formed. Among them, the spin coating method and the die coating method are preferably used.

Next, use a hot plate or oven to dry the wet coating film, and then expose it through a mask with a predetermined pattern to cause the alkali-soluble resin and polyfunctional monomers to undergo photopolymerization to form a hardened coating. membrane. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, are mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film.

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 the components in the colored resin composition for color filters used, the thickness of the coating film, and the like.

Secondly, a developing solution is used to perform a development process, and by dissolving and removing the unexposed part, a coating film is formed according to the desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is generally used. In this alkaline solution, an appropriate amount of surfactant, etc. can also be added. In addition, general methods can be adopted for the development method.

After the development process, washing with a developing solution is usually performed, and the cured coating film of the colored resin composition for color filters is dried to form a colored layer. In addition, after the development treatment, heat treatment may be performed in order to sufficiently 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 in 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 used as a light-shielding portion on a general color filter.

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 such as chromium formed by a sputtering method, a vacuum vapor deposition method, 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. In the case of a resin layer containing light-shielding particles, there are methods such as a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and a thermal transfer of the photosensitive resist. Printing method, etc.

The film thickness of the light-shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and is set to about 0.5 μm or more and 2 μm or less in the case of dispersing or dissolving the black pigment in the binder resin.

(Substrate)

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

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

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

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

[Display device]

The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. The configuration of the display device in the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device, or an organic light-emitting display device. Even in a liquid crystal display device of the horizontal electric field method, various display defects such as disturbance of the alignment of the liquid crystal caused by the electrical characteristics of the green pixels and the residual phenomenon caused by the threshold deviation of the switching are suppressed, the present invention is suitable for selection as Liquid crystal display device.

<Liquid crystal display device>

The liquid crystal display device of the present invention is characterized by having 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. 2 is a schematic diagram showing an example of the display device of the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a counter substrate 20 formed between the color filter 10 and the counter substrate 20. Liquid crystal layer 30.

Furthermore, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2 and can be a known structure 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. As such a driving method, for example, a TN method, an IPS method, an OCB method, and an MVA method can be cited. In the present invention, any of these methods can be suitably used.

In addition, as the counter substrate, it can be appropriately selected according to the driving method of the liquid crystal display device of the present invention and the like.

As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method or a liquid crystal dropping method.

<Organic Light Emitting Display Device>

The organic light-emitting display device of the present invention is characterized by having the above-mentioned color filter and organic light-emitting body of the present invention.

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

As a layering method of the organic light-emitting body 80, 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. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the 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 75, the cathode 76 and other components in the organic light-emitting body 80 can be appropriately used known materials. The organic light emitting display device 100 fabricated in this way can also be applied to, for example, an organic EL display in a passive driving mode or an organic EL display in an active driving mode.

Furthermore, 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]

The following examples illustrate the present invention in detail. The present invention is not limited to these descriptions.

In addition, the acid value of the block copolymer before forming the salt is obtained by the method described in JIS K 0070.

The amine valence of the block copolymer before salt formation is obtained by the method described in JIS K 7237.

The weight-average molecular weight (Mw) of the block copolymer before salt formation is obtained by GPC (Gel Permeation Chromatography) as a standard polystyrene conversion value in accordance with the above-mentioned measuring method of the present invention.

The glass transition temperature (Tg) of the block copolymer before and after the salt formation is determined by the method described in JIS K 7121, using differential scanning calorimetry (DSC) (manufactured by SII NANO TECHNOLOGY, EXSTAR DSC 7020) Determination.

(Manufacturing Example 1 Preparation of Azo Derivative 1)

In 550g of distilled water, introduce 23.1g of azobarbituric acid and 19.2g of barbituric acid. Next, it was adjusted to azobarbituric acid (0.3 mol) using a potassium hydroxide aqueous solution, and mixed with 750 g of distilled water. Add 5g of 30% hydrochloric acid by dropping. After that, 38.7 g of melamine was introduced. Next, 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution were mixed and added, and stirred at a temperature of 80°C for 8 hours. The pigment was separated by filtration, washed, dried at 120°C, and ground in a mortar to obtain Azo derivative 1 (Ni:Cu=95:5 (mole ratio) azo pigment).

(Manufacturing Example 2 Preparation of Azo Derivative 2)

In Manufacturing Example 1, except for replacing 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution, and using 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution, the rest is the same as the manufacturing Example 1 was carried out in the same way, and Azo derivative 2 (Ni:Zn=65:35 (mole ratio) azo pigment) was obtained.

(Manufacturing Example 3 Preparation of Azo Derivative 3)

In manufacturing example 1, except for replacing 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution, and using 0.42 mol of nickel chloride solution and 0.18 mol of copper chloride solution, the rest is the same as the manufacturing Example 1 was carried out in the same way, and Azo derivative 3 (Ni:Cu=70:30 (mole ratio) azo pigment) was obtained.

(Manufacturing Example 4 Preparation of Azo Derivative 4)

In manufacturing example 1, except for replacing 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution, and using 0.21 mol of nickel chloride solution and 0.39 mol of zinc chloride solution, the rest is the same as the manufacturing Example 1 was carried out in the same way, and Azo derivative 4 (Ni:Zn=35:65 (mole ratio) azo pigment) was obtained.

(Synthesis example 1: Preparation of dispersant a)

In a 500 mL round-bottom four-necked separation flask equipped with a cooling tube, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to fully perform nitrogen substitution. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyl lithium (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. The monomers for the B block were 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.2 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 2-ethylhexyl methacrylate ( EHMA) 4.2 parts by mass, n-butyl methacrylate (BMA) 7.0 parts by mass, benzyl methacrylate (BzMA) 24.7 parts by mass, methyl methacrylate (MMA) 13.3 parts by mass, using the addition funnel for 60 minutes dropping. After 30 minutes, 30.8 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is the monomer for the A block, was dropped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was refined by reprecipitation in hexane, filtered, and vacuum dried, and diluted with PGMEA to prepare a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to make the structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is purified by reprecipitation in hexane, filtration, and vacuum drying to obtain a structure containing an A block containing a structural unit represented by the general formula (I) and a carboxyl-containing monomer Block copolymer A-1 (acid value 12mgKOH/g, Tg44°C) of unit and solvent-philic B block. The block copolymer A-1 thus obtained was confirmed by GPC (Gel Permeation Chromatography). As a result, the weight average molecular weight Mw was 8,100. In addition, the amine value is 110 mgKOH/g.

In a 100 mL round bottom flask, 29.35 parts by mass of PGMEA was dissolved in 29.35 parts by mass of block copolymer A-1, and 1.59 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry) was added (relative to the DMMA of block copolymer A-1) The unit is 1 mol, and the phenylphosphonic acid is 0.1 mol), and the mixture is stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining a salt-type block copolymer A-1 (dispersant a) solution. The amine value after salt formation is specifically calculated as follows.

Add 1 g of a solution of 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1NMR in the NMR test tube, and use a nuclear magnetic resonance device (manufactured by JEOL, FT ^{NMR, JNM-AL400) The 13} C-NMR spectrum was measured under the conditions of room temperature and 10,000 cumulative times. In the obtained spectrum data, the nitrogen portion (amine group) at the end is calculated from the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that does not form a salt and the peak of the carbon atom adjacent to the nitrogen atom that forms the salt The ratio of the number of salt-formed amine groups to the total number of amine groups is confirmed to be the same as the theoretical salt-forming ratio (the two acidic groups of all phenylphosphonic acid and the nitrogen at the end of the DMMA of the block copolymer A-1 Site formation of salt).

From the amine value before salt formation 110 mgKOH/g minus the 0.20 mole part of the amine value (22 mgKOH/g) of the DMMA unit, the amine value after salt formation was calculated to be 88 mgKOH/g. The acid value of the block copolymer A-1 after salt formation is the same as that of the block copolymer A-1 before salt formation. Table 1 shows the acid value, amine value and Tg of the block copolymer A-1 before and after salt formation.

(Synthesis example 2~4: manufacture of dispersant b~d)

In Synthesis Example 1, except for changing the content shown in Table 1, the rest was carried out in the same manner as Synthesis Example 1, and synthesized to form salt pre-block copolymers A-2 to A-4, and salt-type block copolymers A-2 (Dispersant b)~A-4 (Dispersant d) solution. In addition, 1-ethoxyethyl methacrylate (EEMA) used 2.8 parts by mass in Synthesis Example 2, 2.2 parts by mass in Synthesis Example 3, and 1.1 parts by mass in Synthesis Example 4. Table 1 shows the acid value, amine value and Tg of the block copolymers obtained before and after salt formation.

(Synthesis Example 5: Preparation of Dispersant e)

After drying a 500 mL four-necked separating flask under reduced pressure, Ar (argon) substitution was performed.

Under Ar air flow, add 100g dehydrated THF, 2.0g methyltrimethylsilyldimethylketene acetal, 0.15ml 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), 1, 3,5-Trimethylbenzene 0.2g. A dropping funnel was used to mix 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), and methacrylic acid. 35.7 parts by mass of methyl ester (MMA) was dropped over 45 minutes. Since heat is generated during the reaction, the temperature is kept below 40°C by ice cooling. After 1 hour, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer A-5. The weight average molecular weight calculated by GPC measurement (NMP LiBr10mM) was 8,350, and the amine value was 95mgKOH/g.

In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-5 was dissolved in 29.35 parts by mass of PGMEA, and 3.17 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) was added (relative to block copolymer A-5). The DMMA unit is 1 mol, and the phenylphosphonic acid is 0.20 mol), stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining a salt-type block copolymer A-5 (dispersant e) solution. The amine valence system after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value and Tg of the block copolymer before and after salt formation.

(Synthesis example 6: Preparation of dispersant f)

In Synthesis Example 5, in place of phenylphosphonic acid, 3.80 parts by mass of chlorotoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) (with respect to 1 mol of DMMA unit of block copolymer A-5 and 0.3 mol of chlorotoluene) were used. The rest was the same as Synthesis Example 5, and a solution of salt type block copolymer A-6 (dispersant f) was synthesized. Table 1 shows the acid value, amine value and Tg of the block copolymers obtained before and after salt formation.

(Synthesis Example 7: Preparation of Dispersant g)

In Synthesis Example 5, except for 13.4 parts by mass of substituted 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), and 35.7 parts by mass of methyl methacrylate (MMA), and 7.6 parts by mass of n-butyl methacrylate (BMA), 32.9 parts by mass of methyl methacrylate (MMA), and PME-1000 (methoxy polyethylene glycol) Monomethacrylate (polyethylene glycol chain repeating number n≒23), trade name BLEMMER PME-1000, manufactured by NOF Corporation) 39.9 parts by mass, and substituted for dimethylaminoethyl methacrylate (DMMA) 26.7 Except for 19.6 parts by mass, the rest was carried out in the same manner as in Synthesis Example 5 to obtain a solution of pre-salt block copolymer A-7 and salt type block copolymer A-7 (dispersant g). The amine group after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value and Tg of the block copolymers obtained before and after salt formation.

(Synthesis example 8: Preparation of alkali-soluble resin A solution)

A mixture of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was charged into a polymerization tank containing 150 parts by mass of PGMEA, and dropped under a nitrogen stream at 100° C. for 3 hours. After the dripping, it was further heated at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution is 7000.

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 resulting polymer solution, and heat it at 110°C for 10 hours. Blow the air in the middle. The obtained alkali-soluble resin A is a resin in which side chains with ethylenic double bonds have been introduced into the main chain formed by the copolymerization of BzMA, MMA and MAA using GMA. The solid content is 42.6% by mass and the acid value is 74 mgKOH/g. The weight average molecular weight is 12,000. The weight average molecular weight was determined by Shodex GPC System-21H (Shodex GPC System-21H) with polystyrene as the standard substance and THF as the eluent. In addition, the method for measuring the acid value is based on JIS K 0070.

(Synthesis Example 9: Preparation of Alkali-soluble Resin B Solution)

In Synthesis Example 8, in addition to substituting 40 parts by mass of BzMA as a comonomer species during polymerization, 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (Tokyo Chemical Industry Co., Ltd.) were used. Except for parts by mass, the rest was performed in the same manner as in Synthesis Example 8 to obtain an alkali-soluble resin B solution. The solid content is 42.6% by mass, the acid value is 74 mgKOH/g, and the weight average molecular weight is 12,000.

(Synthesis Example 10: Synthesis of Latent Antioxidant (Compound a))

Mix 0.01 mol of the phenol compound represented by the following chemical formula (3), 0.05 mol of di-tertiary butyl dicarbonate, and 30 g of pyridine, and add 0.025 mol of 4-dimethylaminopyridine at room temperature under a nitrogen environment at 60°C Stir for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to separate oil and water. After the organic layer was dried with anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60°C for 3 hours to obtain the latent antioxidant (compound a) represented by the above chemical formula (a). In addition, the structure of the obtained latent antioxidant was confirmed by IR and NMR.

(Example 1) (1) Manufacturing of color material dispersion R1

The dispersant a solution of Synthesis Example 1 as a dispersant was 6.23 parts by mass, and the diketopyrrolopyrrole pigment represented by the following chemical formula (2) as a red color material (BrDPP, trade name Irgaphor RED S 3621CF, manufactured by BASF Corporation) 2.57 parts by mass, CI Pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT) 3.86 parts by mass, CI Pigment Red 177 (trade name Cromophtal Red A2B, manufactured by BASF) 2.08 parts by mass, as a production example of yellow color material 2 The obtained Azo derivative 2 4.49 parts by mass, 14.59 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, 66.12 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were put into the mayonnaise bottle, and the pigment Shaker (manufactured by Asada Iron Works Co., Ltd.) was shaken for 1 hour as a preliminary disintegration. Then, instead of zirconia beads with a diameter of 2.0 mm, 200 parts by mass of zirconia beads with a diameter of 0.1 mm were added, and the same was dispersed with a pigment oscillator. Four hours were used as the main disintegration to obtain the color material dispersion liquid R1.

(2) Manufacturing of colored resin composition R1 for color filters

啉基丙烷-1-酮(光起始劑：商品名Irgacure907(IRG907)，BASF製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-N-

啉基苯基)- 丁酮-1(光起始劑：商品名Irgacure369(IRG369)，BASF製)0.04質量份、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARCS NCI-831(NCI831)，ADEKA製)0.02質量份、氟系界面活性劑(商品名MEGAFEC F559，DIC(股)製)0.07質量份、矽烷偶合劑(商品名KBM-503，信越聚矽氧製)0.07質量份、巰基化合物(季戊四醇肆(3-巰基丁酸酯))0.05質量份、PGMEA5.85質量份、3-甲氧基-3-甲基-1-丁基乙酸酯3.92質量份，得到彩色濾光片用著色樹脂組成物R1。 Add 11.29 parts by mass of the color material dispersion R1 obtained in (1) above, 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, and a multifunctional monomer (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.60 mass Parts, 2-methyl-1-(4-methylthiophenyl)-2-N-

Linylpropan-1-one (photoinitiator: trade name Irgacure907 (IRG907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N-

Alolinophenyl)-butanone-1 (photoinitiator: trade name Irgacure369 (IRG369), manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) (Acetyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARCS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass, fluorine-based Surfactant (trade name MEGAFEC F559, manufactured by DIC Corporation) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Polysiloxane) 0.07 parts by mass, mercapto compound (pentaerythritol 4 (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, 5.85 parts by mass of PGMEA, and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate to obtain a colored resin composition R1 for a color filter.

(3) Formation of colored layer

Apply the colored resin composition R1 obtained in (2) above on a 0.7mm thick 100mm×100mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"), and then apply it using a spin coater The heating plate was dried at 80°C for 3 minutes, and an ultra-high pressure mercury lamp was used to irradiate 60mJ/cm ² of ultraviolet rays, and then post-baked in a dust-free oven at 230°C for 30 minutes to adjust the cured film thickness to 2.10μm. The film is thick and the colored layer R1 is formed.

(Examples 2-11, Comparative Example 1) (1) Manufacturing of color material dispersion R2~R9, RC1

In Examples 2 to 6 and Comparative Example 1, in (1) of Example 1, except that the solution of dispersant a was replaced as shown in Table 2, the type and amount of dispersant were changed to the same solid content Except that the amount of PGMEA was adjusted so that the total was 100 parts by mass, the same procedure as in Example 1 (1) was carried out to obtain color material dispersion liquids R2 to R6.

In addition, in Examples 7 to 9, in (1) of Example 3, except that the type and amount of color materials used were changed as shown in Table 2, the same procedure as in (1) of Example 3 was carried out to obtain Color material dispersion R7~R9.

In addition, in Comparative Example 1, in (1) of Example 1, except that the dispersant a solution was replaced as shown in Table 2, the type and usage amount of the dispersant were changed to the same mass parts as the solid content. The amount of PGMEA was adjusted so that the total amount was 100 parts by mass, and the type and usage amount of the color material were changed. The rest was the same as (1) of Example 1 to obtain a color material dispersion liquid RC1.

(2) Manufacturing of colored resin composition R2~R11, RC1 for color filters

In Examples 2-9 and Comparative Example 1, in addition to replacing the color material dispersion liquid R1 in (2) of Example 1, the above color material dispersion liquids R2 to R9 and RC1 were used as shown in Table 2, respectively, for Except for adjusting the film thickness to 2.10 μm and adjusting the amount of alkali-soluble resin so that the above P/V ratio becomes the value shown in Table 2, the same procedure as in Example 1 (2) was carried out to obtain a colored resin composition for a color filter物R2~R9, RC1.

In addition, in Example 10, in addition to replacing the alkali-soluble resin A solution in Example 3, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used, and an antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) 0.03 was added. Except for parts by mass, the same procedure as in (2) of Example 3 was carried out to obtain a colored resin composition R10 for a color filter.

In addition, in Example 11, except for Example 10, for the photoinitiator system as shown in Table 2, instead of 0.04 parts by mass of IRG369, an oxime ester-based photoinitiator (trade name TR-PBG-365 (PBG365), manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) 0.04 parts by mass, and used oxime ester-based photoinitiator (trade name TR-PBG-3057 (PBG3057), manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) instead of 0.02 parts by mass of NCI831 ) Except for 0.02 part by mass, the same procedure as in (2) of Example 10 was carried out to obtain a colored resin composition R11 for a color filter.

(3) Formation of colored layer

In Example 1 (3), except that instead of the colored resin composition R1, the above colored resin compositions R2 to R11 and RC1 were used, respectively, the same procedure as in Example 1 (3) was performed to obtain colored layers R2 to R11 , RC1.

Here, the abbreviations in the table are as follows.

Y150 derivative: C.I. Pigment Yellow 150 derivative (Ni complex) (trade name: LEVASCREEN YELLOW G01, manufactured by LANXESS Co., Ltd.)

Byk-161: Trade name Disperbyk-161 (urethane-based dispersant, solid content 30% by mass, manufactured by BYK Chemie)

Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)

Solvent B: 3-methoxy-3-methyl-1-butyl acetate

(Examples 12~23) (1) Manufacturing of color material dispersion R12~R23

In Examples 12 to 23, in (1) of Example 3, except that the types and blending amounts of color materials were changed as shown in Table 3, and the amount of PGMEA was adjusted so that the total amount became 100 parts by mass, the rest The same procedure as in Example 3 (1) was carried out to obtain color material dispersion liquids R12 to R23.

(2) Manufacture of colored resin composition R12~R23 for color filters

Except for replacing the color material dispersion liquid R3 in (2) of Example 11, the above color material dispersion liquids R12 to 23 were used. In order to make the film thickness 2.50 μm, the above P/V ratio was set to the values shown in Table 3 Except for adjusting the amount of alkali-soluble resin in this manner, the same procedure as in Example 11 (2) was carried out to obtain colored resin compositions R12 to R23 for color filters.

(3) Formation of colored layer

In Example 11 (3), except that the colored resin composition R11 was replaced with the above colored resin compositions R12 to R23, the same procedure was performed as in Example 11 (3) to obtain colored layers R12 to R23.

(Comparative example 2~7) (1) Manufacturing of color material dispersion RC2~RC7

In Comparative Examples 2-7, in (1) of Example 1, except that the dispersant a solution was replaced as shown in Table 3, the type and usage amount of the dispersant were changed to the same mass parts as the solid content, and then As shown in Table 3, the type and blending amount of color materials were changed, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, and the rest was performed in the same manner as in Example 1 (1) to obtain color material dispersion liquids RC2 to RC7.

(2) Manufacture of colored resin composition RC2~RC7 for color filters

Except for replacing the color material dispersion liquid R3 in (2) of Example 11, the above color material dispersion liquids RC2 to RC7 were used, respectively, and the above P/V ratio was set to the values shown in Table 3 in order to make the film thickness 2.50μm Except for adjusting the amount of alkali-soluble resin in this manner, the same procedure was performed as in (2) of Example 11 to obtain colored resin compositions RC2 to RC7 for color filters.

(3) Formation of colored layer

In Example 11 (3), except that the colored resin composition R11 was replaced with the above colored resin compositions RC2 to RC7, the same procedure was performed as in Example 11 (3) to obtain colored layers RC2 to RC7.

R264: C.I. Pigment Red 264 (trade name: Irgazin Red L 4010 HD, manufactured by BASF)

R242: C.I. Pigment Red 242 (trade name: Novoperm Scarlet 4RF, manufactured by CLARIANT)

O38: CI Pigment Orange 38 (trade name: Novoperm Red HF, manufactured by CLARIANT); CI Pigment Orange 38 series P/V (red color material mass/solid content mass other than red color material) ratio = 0.2 and measured 2.5μm coating film In the spectral transmittance spectrum, the transmittance of the wavelength of 520nm is less than 20%, and the transmittance of the wavelength of 640nm is more than 70%, which is equivalent to the red color material of the present invention.

R177: C.I. Pigment Red 177 (trade name: Cromophtal Red A2B, manufactured by BASF)

R179: C.I. Pigment Red 179 (trade name: Paliogen Maroon L 3980, manufactured by BASF Dispersions & Pigments Asia Pacific)

R272: C.I. Pigment Red 272 (trade name: Irgazin Flame Red K 3800, manufactured by BASF)

Y150 derivative: C.I. Pigment Yellow 150 derivative (Ni complex) (trade name: LEVASCREEN YELLOW G01, manufactured by LANXESS Co., Ltd.)

Byk-161: Trade name Disperbyk-161 (urethane-based dispersant, solid content 30% by mass, manufactured by BYK Chemie)

6919: Trade name Disperbyk-LPN6919 (polymer with structural units represented by general formula (I), amine value 120mgKOH/g, solid content 60% by mass, manufactured by BYK Chemie)

(Manufacturing of Examples 24-41) (1) Manufacturing of color material dispersion R24~R41

In Examples 24 to 41, in (1) of Example 3, except that the types and blending amounts of color materials were changed as shown in Table 4, and the amount of PGMEA was adjusted so that the total was 100 parts by mass, The rest was the same as (1) of Example 3 to obtain color material dispersion liquids R24 to R41.

(2) Manufacture of colored resin composition R24~R41 for color filters

Except for replacing the color material dispersion liquid R3 in (2) of Example 11, the above color material dispersion liquids R24 to R41 were used, respectively, to make the film thickness 2.80μm, and the above P/V ratios were set to the values shown in Table 4 Except for adjusting the amount of alkali-soluble resin in this way, the same procedure as in (2) of Example 11 was carried out to obtain colored resin compositions R24 to R41 for color filters.

(3) Formation of colored layer

In (3) of Example 11, except that the colored resin compositions R24 to R41 were used instead of the colored resin composition R11, the same procedure as in (3) of Example 11 was carried out to obtain colored layers R24 to R41.

(Example 42) (1) Manufacturing of color material dispersion

6.23 parts by mass of the dispersant c solution of Synthesis Example 3 as a dispersant, and 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP, trade name Irgaphor RED S 3621CF, manufactured by BASF) represented by the above chemical formula (2) as the color material Parts, 14.59 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm were put into a mayonnaise bottle, and a pigment shaker (Asada Iron Works Co., Ltd.) Preparation) Shake for 1 hour as a preliminary disintegration, then replace the zirconia beads with a diameter of 2.0 mm, add 200 parts by mass of zirconia beads with a diameter of 0.1 mm, and disperse with a pigment shaker for 4 hours as the formal disintegration to obtain a red color Color material dispersion liquid r1.

In the red color material dispersion liquid r1, in addition to substituting 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as the color material, CI Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781 (manufactured by CLARIANT) except 13.0 parts by mass, and the rest was carried out in the same manner as the above-mentioned red color material dispersion liquid r1 to obtain a red color material dispersion liquid r2.

In the red color material dispersion liquid r1, in addition to substituting 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as the color material, CI Pigment Red 177 (trade name: Except for Paliogen Red L 4045 (manufactured by BASF) 13.0 parts by mass, the rest was performed in the same manner as the above-mentioned red color material dispersion liquid r1 to obtain a red color material dispersion liquid r3.

In the red color material dispersion liquid r1, in addition to substituting 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) as the color material, 13.0 parts by mass of the Azo derivative 2 as the color material was used. , And the rest is the same as the above-mentioned red color material dispersion liquid r1 to obtain a yellow color material dispersion liquid y.

(2) Manufacturing of colored resin composition R42 for color filters

啉基丙烷-1-酮(光起始劑：商品名Irgacure907(IRG907)，BASF製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁酮-1(光起始劑：商品名Irgacure369(IRG369)，BASF製)0.04質量份、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARCS NCI-831(NCI831)，ADEKA製)0.02質量份、氟系界面活性劑(商品名MEGAFEC F559，DIC(股)製)0.07質量份、矽烷偶合劑(商品名KBM-503，信越聚矽氧製)0.07質量份、巰基化合物(季戊四醇肆(3-巰基丁酸酯))0.05質量份、PGMEA5.85質量份、3-甲氧基-3-甲基-1-丁基乙酸酯3.92質量份，得到彩色濾光片用著色樹脂組成物R42。 Add 1.65 parts by mass of the color material dispersion r1 obtained in the above (1), 3.57 parts by mass of the red color material dispersion r2, 1.92 parts by mass of the red color material dispersion r3, 4.15 parts by mass of the yellow color material dispersion y, and the alkali obtained in Synthesis Example 8. Soluble resin A solution 1.90 parts by mass, polyfunctional monomer (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)- 2-N-

Linylpropan-1-one (photoinitiator: trade name Irgacure907 (IRG907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N-

Alolinophenyl)-butanone-1 (photoinitiator: trade name Irgacure369 (IRG369), manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) (Acetyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARCS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass, fluorine-based Surfactant (trade name MEGAFEC F559, manufactured by DIC Corporation) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Polysiloxane) 0.07 parts by mass, mercapto compound (pentaerythritol 4 (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, 5.85 parts by mass of PGMEA, and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate to obtain colored resin composition R42 for color filters.

(3) Formation of colored layer

In Example 1 (3), except that the colored resin composition R1 was replaced with the above colored resin composition R41, the same procedure was performed as in Example 1 (3) to obtain a colored layer R42.

The obtained colored resin composition R42 for color filters has the same composition as the colored resin composition R3 for color filters of Example 3. The evaluation results of the colored resin composition R42 for color filters and the colored layer R42 are the same The evaluation results of the colored resin composition R3 for color filters and the colored layer R3 were the same.

(Examples 43~48) (1) Manufacturing of color material dispersion R47

In Example 47, it was in (1) of Example 1, except that the dispersant a solution was replaced, the dispersant g solution was used as shown in Table 5, and the solid content was changed to the same parts by mass, and the total Except that the amount of PGMEA was adjusted so as to be 100 parts by mass, the same procedure as in (1) of Example 1 was carried out to obtain a color material dispersion liquid R47.

(2) Manufacture of colored resin composition R43~R48 for color filters

In Example 43, in addition to replacing the alkali-soluble resin A solution in Example 3, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used, and for the photoinitiator, as shown in Table 5, 0.04 parts by mass of IRG369 was replaced An oxime ester-based photoinitiator (trade name Irgacure OXE 01 (OXE01), manufactured by BASF Corporation) was used instead of 0.02 parts by mass of NCI831, and an oxime ester-based photoinitiator (trade name Irgacure OXE 02 (OXE02) was used instead of 0.02 parts by mass. ), BASF Corporation) except for 0.04 parts by mass, the rest was carried out in the same manner as in (2) of Example 3 to obtain a colored resin composition R43 for a color filter.

In addition, in Example 44, in addition to replacing 0.03 parts by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 11, an antioxidant (trade name ADEKA STAB AO-40 (AO-40) , Manufactured by ADEKA) except for 0.03 parts by mass, the rest was carried out in the same manner as in (2) of Example 11 to obtain a colored resin composition R44 for color filters.

In addition, in Example 45, in addition to substituting 0.03 parts by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF Corporation) in Example 11, 0.03 parts by mass of the latent antioxidant (compound a) of Synthesis Example 10 was used. Except for the parts, the same procedures as in (2) of Example 11 were carried out to obtain colored resin composition R45 for color filters.

In addition, in Example 46, in addition to substituting 0.03 parts by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF Corporation) in Example 11, an ultraviolet absorber (benzotriazole compound, trade name TINUVIN) was added. 329, manufactured by BASF), except for 0.03 parts by mass, and otherwise in the same manner as in (2) of Example 11, a colored resin composition R46 for color filters was obtained.

In Example 47, except that the color material dispersion liquid R47 was used in place of the color material dispersion liquid R3 in Example 3, the rest was performed in the same manner as in Example 3 (2) to obtain a colored resin composition for color filters R47 .

In Example 48, the color material dispersion liquid R47 was used instead of the color material dispersion liquid R3 in Example 43, and 0.03 parts by mass of antioxidant (trade name ADEKA STAB AO-40 (AO-40), manufactured by ADEKA) was added. , Except for 0.03 parts by mass of the ultraviolet absorber (benzotriazole compound, trade name TINUVIN 329, manufactured by BASF), the rest was carried out in the same manner as (2) of Example 43 to obtain a colored resin composition R48 for color filters.

(3) Formation of colored layer

In Example 1 (3), except that the colored resin composition R1 was replaced with the above colored resin composition R43 to R48, the same procedure was performed as in Example 1 (3) to obtain colored layers R43 to R48.

[Evaluation method] <Evaluation of Dispersibility of Color Material Dispersion Liquid>

For the color material dispersions obtained in the Examples and Comparative Examples, the viscosity immediately after preparation and after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. In the viscosity measurement system, a vibrating viscometer was used to measure the viscosity at 25.0±0.5°C. The results are shown in Tables 2 to 5.

(Viscosity stability evaluation standard)

A: The viscosity change rate before and after storage is less than 10%

B: The viscosity change rate before and after storage is more than 10% and less than 15%

C: The viscosity change rate before and after storage is more than 15% and less than 25%

D: The viscosity change rate before and after storage is more than 25%

Here, it is a value when the color material is 13% by mass relative to the total mass of the solvent containing the color material dispersion liquid.

Although the color material dispersion liquid whose evaluation result is C can be used for practical use, if the evaluation result is B, the color material dispersion liquid is more favorable, and if the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

<Optical performance evaluation, comparative evaluation>

Using a spectroscopic characteristic measuring device LCF-1500M manufactured by Otsuka Electronics and a contrast measuring device CT-1B manufactured by Kosaka Electric, the contrast, chromaticity (x, y), and brightness (Y) of the colored layers obtained in the Examples and Comparative Examples were measured.

(Comparative evaluation criteria)

Under C light source x is set to the value of 0.570~0.600

AA: more than 10,000

A: 8000~10000

B: 6000~7999

C: less than 6000

‧Under C light source x is set to the value of 0.607~0.630

AA: more than 9000

A: 7000~9000

B: 5000~6999

C: less than 5000

‧Under C light source x is set to the value of 0.650~0.693

AA: more than 8000

A: 6000~8000

B: 4000~5999

C: less than 4000

<Evaluation of phase difference>

The phase difference of the colored layer is based on the thickness direction retardation (Rth) calculated by the following formula as an index. The delay (Rth) was measured using a phase difference measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS). The measurement wavelength of the red colored layer is measured at 620nm and 665nm.

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

Nx: Refractive index in the direction of the slow axis in the plane

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

Nz: Refractive index in thickness direction

d: Film thickness (nm)

<Evaluation of Solvent Resolubility>

The front end of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored resin composition for color filters obtained in the Examples and Comparative Examples, and coated on the portion of the glass substrate with a length of 1 cm. The pulled up glass substrate is placed in a constant temperature and humidity machine so that the glass surface is horizontal, and it is dried under the conditions of a temperature of 23° C., a humidity of 80% RH and 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. The re-dissolution state of the dried coating film at this time was visually judged and evaluated.

(Evaluation criteria for solvent resolubility)

AA: The coating film is completely dissolved after drying in less than 8 seconds

A: The dried coating film is completely dissolved

B: Thin slices of dry coating film produced in the solvent, the solution is colored

C: No dry film is produced in the solvent, and the solution is not colored

If the above evaluation criteria are AA, A, or B, it is evaluated that the solvent re-solubility is good and can be used without any problems in practical use; if the evaluation result is A and then AA, the effect is more excellent.

<Evaluation of developing residue>

The colored resin compositions for color filters obtained in the Examples and Comparative Examples were respectively applied to a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm, using a spin coater After coating, it was dried at 60°C for 3 minutes using a hot plate, thereby forming a 2.5 μm thick colored layer. The glass plate on which the colored layer was formed was subjected to 60-second shower development using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. After visually observing the unexposed part (50mm×50mm) of the glass substrate after the colored layer has been formed, wipe it with a lens cleaning cloth containing ethanol (TORAYSEE MK cleaning cloth, manufactured by Toray), and observe the lens visually The degree of coloration of the cleaning cloth.

(Evaluation criteria for developing residue)

AA: Even if the same evaluation is performed on the coloring layer with a thickness of 3.5μm, no development residue is visually confirmed, and the lens cleaning cloth is completely uncolored

A: No developing residue is confirmed visually, and the lens cleaning cloth is completely uncolored

B: No development residue was confirmed visually, but slight coloration of the lens cleaning cloth was confirmed

C: A slight development residue is visually confirmed, and a slight coloration of the lens cleaning cloth is confirmed

D: A slight development residue is visually confirmed, and the coloring of the lens cleaning cloth is confirmed

If the above evaluation criterion is AA, A, B, or C, it can be used without any problem in practical use, but if the evaluation result is B, further A, or even AA, the effect is more excellent.

<Evaluation of development tolerance>

The colored resin compositions for color filters obtained in the Examples and Comparative Examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater. After drying on a hot plate at 80°C for 3 minutes, use an ultra-high pressure mercury lamp to irradiate 40mJ/cm ² of ultraviolet rays. The film thickness at this point was measured and set as T1 (μm). After that, shower development was performed using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. The film thickness after development was measured and set as T2 (μm). Calculate T2/T2×100(%).

(Evaluation Criteria for Development Resistance)

AA: more than 98%

A: More than 95% and less than 98%

B: More than 90% and less than 95%

C: Less than 90%

If the evaluation criteria are AA, A, and B, it can be used practically without any problems, but if the above evaluation result is A or even AA, the effect is more excellent.

<Evaluation of Water Penetration>

The colored resin composition for color filters obtained in the Examples and Comparative Examples was baked on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater to form a thickness of 1.6μm After the film thickness of the coloring layer is coated, it is dried at 60°C for 3 minutes using a hot plate, and 60mJ/cm ² of ultraviolet rays are irradiated on the glass substrate using an ultra-high pressure mercury lamp without going through the mask, thereby forming a coloring layer on the glass substrate. Next, use 0.05wt% potassium (KOH) as a developer for rotational development. After contacting the developer for 60 seconds, it is washed with pure water for development. The washed substrate is rotated for 10 seconds and centrifuged to remove the water. The contact angle of pure water was measured as follows to evaluate water bleeding.

The contact angle of pure water is measured by dropping a drop of 1.0 μL of pure water on the surface of the colored layer just after the water has been removed by centrifugation, and measuring the static contact angle after 10 seconds of dropping according to the θ/2 method. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.

(Evaluation Criteria for Water Penetration)

AA: The contact angle is above 80 degrees

A: The contact angle is more than 75 degrees and less than 80 degrees

B: The contact angle is more than 65 degrees and less than 75 degrees

C: The contact angle is more than 50 degrees and less than 65 degrees

D: The contact angle is less than 50 degrees

If the water bleeding evaluation criterion is AA, A, or B, it can be used without any problem in practice, but if the evaluation result is A or even AA, the effect is even more superior.

<SiN Adhesiveness Evaluation>

The colored resin compositions for color filters obtained in the Examples and Comparative Examples were applied to SiN substrates (manufactured by Foresight Co., Ltd.) using a spin coater, and dried using a hot plate at 80°C for 3 minutes, and then An ultra-high pressure mercury lamp was used to irradiate 60mJ/cm ² of ultraviolet rays, and then post-baked in a dust-free oven at 230°C for 30 minutes to adjust the film thickness so that the cured film thickness became 2.10μm to form a colored layer.

The obtained colored layer was subjected to a cross test in accordance with JIS K 5600-5-6, and after repeating the tape peeling operation 5 times, the presence or absence of peeling of the coating film was observed, and the evaluation was performed according to the following evaluation criteria.

(SiN Adhesiveness Evaluation Criteria)

AA: All grids are not peeled off

A: Although there is a small peeling of the coating film at the intersection of cutting, the specific area of peeling is less than 5%.

B: The coating film peeled off at the intersection along the cutting line. The specific area of peeling is more than 5% and less than 15%.

C: The coating film was partially and completely peeled off along the cutting line. The specific area of peeling is 15% or more and less than 35%.

[Result integration]

It can be seen from the results in the table that the red color material was combined with the above-mentioned specific yellow color material, and then combined with the dispersant belonging to the polymer of the constituent monomer represented by the general formula (I) in Examples 1 to 41, and The color material dispersion of 47 has good viscosity stability. On the other hand, it is clear that the color material dispersion liquid of Comparative Example 1 in which a conventional yellow color material and a urethane-based dispersant are combined with a red color material has deteriorated viscosity stability. Furthermore, it was clarified that even if the above-mentioned specific yellow color material was combined with the red color material, the color material dispersion of Comparative Example 2 in which the urethane-based dispersant was combined had poor viscosity stability.

In addition, the color material dispersion liquids of Comparative Examples 3 to 7 in which the conventional yellow color material was combined with the red color material, even if a dispersant belonging to a polymer having the constituent monomer represented by the general formula (I) is used, the viscosity is stable The deterioration of sex.

In addition, it can be seen that the above-mentioned specific yellow color material is combined with the red color material, and the color filter of Examples 1 to 48 is further combined with the dispersant belonging to the polymer of the monomer having the general formula (I). The colored resin composition for a sheet has good dispersion stability of the color material, and the colored layer using the colored resin composition has a reduced retardation value and excellent contrast. In addition, it can be seen that the coloring layers using the coloring resin compositions of Examples 1 to 48 are respectively superior in adhesion to SiN. Among them, the coloring resins of Examples 11, 44, 45, 46, and 48 are used. The colored layer of the composition is superior in adhesion to SiN. In addition, the adhesion to SiN of Example 10 is close to A of AA, which is good.

On the other hand, in Comparative Examples 1, 3 to 7 which combined color materials different from the Examples, compared with the Examples with the same chromaticity coordinates (x, y), the contrast deteriorated and the phase difference became larger.

In addition, even if the above-mentioned specific yellow color material is combined with the red color material, the comparative example 2 in which the urethane-based dispersant is combined is inferior to the example with the same chromaticity coordinates (x, y). , The phase difference value becomes larger.

In addition, in Comparative Examples 1, 3 to 7, compared with the examples with the same chromaticity coordinates (x, y), the P/V ratio of the colored resin composition tends to become larger, and the adhesion to SiN also deteriorates. .

Furthermore, in Comparative Example 1, compared with the examples with the same chromaticity coordinates (x, y), the solvent resolubility, the suppression of development residue, the development resistance, and the water bleeding are also deteriorated.

It can be seen that in the examples, the alkali-soluble resin contains both a maleimide structure with a hydrocarbon ring and a styrene structure, and in the examples where antioxidants are added, the formation of development residue is suppressed and the brightness is improved. Colored layer.

In addition, it can be seen that when two types of oxime ester-based photoinitiators and antioxidants are used in combination, a colored layer with improved development resistance and brightness is formed. Among them, from the viewpoint of superior brightness, it is preferable to use an oxime ester-based photoinitiator having a stilbene skeleton and an oxime ester-based photoinitiator having a diphenyl sulfide together; the effect of inhibiting bleeding from water becomes higher From a viewpoint, it is preferable to use together an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a diphenyl sulfide.

In addition, in Example 44, a hindered phenol-based antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per phenolic hydroxyl group was used to form a colored layer with reduced retardation and improved brightness. In Example 44, the contrast was close to AA, and the coloring layer with improved contrast was obtained.

In addition, in Example 45 using latent antioxidants, the retardation value was reduced, the contrast was also close to AA, and the coloring layer with improved contrast was obtained.

In addition, in Example 46 using the ultraviolet absorber, the retardation value was reduced, the contrast was also close to AA, and the coloring layer with improved contrast was obtained.

In addition, an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having a diphenyl sulfide are used in combination, and the molecular weight is 500 or less and the molecular weight per phenolic hydroxyl group is 200 in combination. In Example 48, where the hindered phenol antioxidant and the ultraviolet absorber are less than equivalent, a colored layer with reduced retardation value, increased brightness, and improved water bleeding effect is formed. In Example 48, the contrast is also close to AA, and a colored layer with improved contrast is obtained.

Claims (17)

A color material dispersion liquid for color filters, which is a color material dispersion liquid containing a color material, a dispersant, and a solvent, and is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains: At least one anion of the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound represented by the following general formula (A) and its tautomeric structure of the azo compound; selected from Cd, Co, Al, Ions of at least two metals of the group consisting of Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; and the compound represented by the following general formula (B); the above-mentioned dispersant system has the following general formula (I ) The polymer of the structural unit shown;

(In the general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^{b is} independently -OH or -NH ₂ ;)

(In general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group;)

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure). For the color material dispersion liquid for color filters of claim 1, wherein the total content of the red color material and the yellow color material is 80% by mass or more and 100% by mass or less with respect to the total amount of the color material. The color material dispersion liquid for color filters according to claim 1, wherein the red color material is composed of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment At least one of the group. According to claim 1 or 2, the color material dispersion liquid for color filters, wherein at least two metals in the yellow color material contain Ni and further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, At least one metal from the group consisting of Zn, Fe, Cu, and Mn. According to claim 1 or 2, the color material dispersion liquid for color filters, wherein at least two of the yellow color materials are Ni and Zn, or Ni and Cu. A colored resin composition for color filters, which contains a color material, a dispersant, a binder component, and a solvent; it is characterized in that the color material contains a red color material and a yellow color material; the yellow color material contains: At least one anion of the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound represented by the following general formula (A) and its tautomeric structure of the azo compound; selected from Cd, Co, Al, Ions of at least two metals of the group consisting of Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; and the compound represented by the following general formula (B); the above-mentioned dispersant system has the following general formula (I ) The polymer of the structural unit shown;

(In the general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^{b is} independently -OH or -NH ₂ ;)

(In general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group;)

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure). The colored resin composition for color filters according to claim 6, wherein the total content of the red color material and the yellow color material is 80% by mass or more and 100% by mass or less with respect to the total amount of color materials. The colored resin composition for a color filter according to claim 6, wherein the red color material is composed of a diketopyrrolopyrrole-based pigment, a naphthol-based azo pigment, an anthraquinone-based pigment, and a perylene-based pigment At least one of the group. According to claim 6, the colored resin composition for color filters, wherein at least two metals in the yellow color material contain Ni and further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, At least one metal of the group consisting of Fe, Cu, and Mn. According to claim 6, the colored resin composition for a color filter, wherein at least two metals in the yellow color material are Ni and Zn, or Ni and Cu. According to claim 6, the colored resin composition for a color filter, wherein the binder component contains an alkali-soluble resin, a multifunctional monomer, and a photoinitiator, and the photoinitiator is an oxime initiator. The colored resin composition for color filters according to claim 6, which further contains an antioxidant. The colored resin composition for color filters of claim 11, which further contains an antioxidant. The colored resin composition for a color filter according to claim 12 or 13, wherein the antioxidant contains at least one of the following: the phenolic hydroxyl group of the hindered phenol antioxidant is protected by a urethane-based protecting group Latent hindered phenolic antioxidants; and hindered those with a molecular weight of 1000 or less and the molecular weight of each phenolic hydroxyl group is 280 equivalents or less Phenolic antioxidants. For example, the colored resin composition for color filters of claim 6, wherein a cured film can be formed, and the chromaticity coordinates of the cured film in the XYZ color system of JIS Z8701 measured with a C light source are x=0.550~ 0.700, y=0.290~0.450. A color filter having at least a substrate and a coloring layer provided on the substrate, characterized in that at least one of the coloring layers is the coloring resin for color filters of any one of claims 6 to 15 The hardened substance of the composition. A display device characterized by the color filter of claim 16.

Images