TW201840740A - 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

 Colored material dispersion 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 the development of portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) has also increased, and the market for liquid crystal displays has been expanding. In addition, an organic light-emitting display device similar to an organic EL display having high visibility by self-luminescence has recently attracted attention as a next-generation image display device. In view of the performance of such image display devices, it is strongly desired to further improve the image quality or power consumption, such as improvement in contrast or color reproducibility.

Conventional display devices are mostly based on the international standard specification sRGB (IEC61966-2-1) of color space. However, in order to require closer to the performance of the object and to further improve the color reproducibility, DCI (Digital) corresponding to AdobeRGB with a wider color reproduction domain than sRGB, or a wider color reproduction domain in the red and green directions. Demand for display devices of Cinema Initiatives or BT (Broadcasting Service Television). 2020 is increasing.

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 containing a color pattern of three primary colors of red, green, and blue, and is formed in order to divide each coloring pattern. a light shielding portion on the transparent substrate.

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

On the other hand, as a problem specific to the liquid crystal display device, there is a problem in that the viewing angle dependence of the refractive index anisotropy of the liquid crystal cell or the polarizing plate is caused. This problem of the dependence of the viewing angle is a problem in which the hue or contrast of the image to be viewed changes when the liquid crystal display device is viewed from the front and when viewed from the oblique direction. The problem of such viewing angle characteristics is that the severity of this problem is further increased with the recent large screen of liquid crystal display devices.

In order to improve the problem of such viewing angle dependence, a method of assembling a retardation film into a liquid crystal display device has been widely used. However, since the color filter used in the liquid crystal display device has a different phase difference depending on the color pattern of each color of the colored layer, when the phase difference film is used, there is a phase difference in which the color pattern of each color cannot be compensated for. The problem of difference is difficult to completely solve the problem of viewing angle dependence.

In particular, since the red color material is easily crystallized due to its chemical structure, the red coloring layer has a problem that the phase difference in the thickness direction tends to be large compared to the color layer of the other color.

Further, in the case of using a red color material which is conventionally used, in order to expand the color reproduction domain, a red pixel which is yellow or blue in the redness region of the high color density is produced, since the pigment concentration is increased. There are problems such as contrast or decrease in brightness, or deterioration of plate making.

Patent Document 1 discloses a color filter which is used in combination as a red pigment: CI Pigment Red 177 (hereinafter sometimes abbreviated as PG177); and a 1:1 complex selected from azobarbituric acid and nickel, a pigment composed of at least one crystal of a group of crystals in which a tautomer and a compound of at least one of the compounds are inserted into a crystal lattice (CI Pigment Yellow 150 derivative (Ni complex)) ). However, if the pigment is used to express a dark red color, it is necessary to use a pigment having a very high concentration, which has a problem that the phase difference in the thickness direction becomes large, the contrast is lowered, and the plate making property is deteriorated.

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

 [Previous Technical Literature]    [Patent Literature]  

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

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

An object of the present invention is to provide a color material dispersion liquid for color filters which is excellent in dispersion stability of a color material and which can form a coloring layer which reduces the phase difference and simultaneously enhances the coloring layer; It is possible to form a colored resin composition for a color filter which reduces the phase difference value and at the same time compares the enhanced color reproducibility color layer; using the colored resin composition for the color filter, the phase difference value is reduced and simultaneously compared A color filter excellent in lifting and color reproducibility; and a display device which is improved in phase difference value and which is superior in contrast and 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, wherein the color material contains a red color material and a yellow color material; and the yellow color material contains: Selecting at least one anion of a group consisting of mono-, di-, tri-, and tetra-anions of an azo compound represented by the following general formula (A) and an azo compound of a tautomeric structure; selected from Cd, Co, An ion of at least two metals of a group consisting of Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a compound of the following general formula (B); the dispersant has the following general formula (I) A polymer of the constituent units shown.

Further, the colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent; and the color material includes a red color material and a yellow color material; and the yellow color material contains : at least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of an azo compound represented by the following general formula (A) and an azo compound of a tautomeric structure; selected from Cd, Co And ions of at least two kinds of metals composed of a group consisting of Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a compound represented by the following general formula (B); A polymer of the constituent units represented by the formula (I).

[Chemical 1] General formula (A)

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

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

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

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, wherein at least one of the colored layers belongs to the hardening of the colored resin composition for a color filter of the present invention. The color layer of the object.

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

According to the present invention, it is possible to provide a color material dispersion liquid for color filters which is excellent in dispersion stability of a color material and which can form a coloring layer which reduces the phase difference value and simultaneously contrasts the coloring layer; It is possible to form a colored resin composition for a color filter which reduces the phase difference value and at the same time compares the enhanced color reproducibility color layer; using the colored resin composition for the color filter, the phase difference value is reduced and simultaneously compared A color filter excellent in lifting and color reproducibility; and a display device which is improved in phase difference value and which is superior in contrast and color reproducibility by using the color filter.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

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

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

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

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

Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

In the present invention, the (meth)acrylic acid means acrylic acid and methacrylic acid, respectively, and the (meth)acrylic acid ester means acrylate and methacrylate, respectively.

Further, C.I. Pigment Red is simply referred to as "PR", C.I. Pigment Orange is simply referred to as "PO", and C.I. Pigment Yellow is simply referred to 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, wherein the color material contains a red color material and a yellow color material; and the yellow color material contains: selected from the following At least one anion of the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound represented by the formula (A) and the tautomeric structure of the tautomeric structure; selected from the group consisting of Cd, Co, Al, Cr, Sn And ions of at least two kinds of metals composed of Pb, Zn, Fe, Ni, Cu, and Mn; and a compound represented by the following general formula (B); wherein the dispersant has the following general formula (I) The polymer that makes up the unit.

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

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

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

The color material dispersion liquid of the present invention is a combination of the above-mentioned specific color material and a polymer having a structural unit represented by the general formula (I) as a dispersing agent, so that the dispersion stability of the color material is excellent, and the phase difference can be reduced and At the same time, compare the raised color layer.

Since the red color material is generally a planar structure having a ring shape, it is easy to crystallize when the coloring layer is formed as a color material dispersion liquid for a color filter, so that the phase difference in the thickness direction of the obtained colored layer is easy. Become bigger.

On the other hand, in the color material dispersion liquid of the present invention, it is estimated that a specific yellow color material containing two or more kinds of metal ions is used in combination with a red color material; and the polymerization which is specific to the structural unit represented by the general formula (I) The dispersant of the body; therefore, the interaction between the red color material and the specific yellow color material containing two or more kinds of metal ions can suppress the crystal growth and micronization of the red color material and the yellow color material, and In combination with the above dispersing agent, the red color material and the yellow color material are atomized and dispersed, so that a coloring layer which reduces the phase difference value and simultaneously enhances the contrast can be formed.

In the case where the metal containing the metal complex of the azo compound represented by the above general formula (A) is one color material, the crystallinity is high and it is difficult to atomize, and it is difficult to improve the contrast. Further, the phase difference value of the coloring layer obtained by combining the red color material tends to become higher. On the other hand, in the present invention, a specific yellow color material containing two or more kinds of metal ions with respect to the anion of the azo compound represented by the general formula (A) is used. By containing two or more kinds of metal ions, the yellow color material suppresses crystal growth of the yellow color material and suppresses crystal growth of the red color material, and is further combined with the specific dispersant to estimate the color material dispersion. Make it micronized.

Further, in the present invention, by combining the above-mentioned specific yellow color material with the red color material, it is possible to suppress the P/V ratio ((the color component quality in the composition) / (the solid content quality other than the color material component in the composition) ), the red pixel included in the redness region of the above high color density can still be produced.

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

Further, 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, and the plate-making property can be improved, and a coloring layer having 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 the range not impairing 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; and the yellow color material is characterized by containing: an azo compound selected from the following azo compounds of the general formula (A) and a tautomeric structure thereof; At least one anion of the group consisting of mono-, di-, tri-, and tetra-anions; at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn The ion; and the compound of the general formula (B) below.

In the present invention, since the specific yellow color material is used as the yellow color material, when the red color material is combined with the red color material, the decrease in luminance can be suppressed, and the crystallization can be suppressed to be atomized, and combined with a specific dispersant described later. When the dispersion is superior, the contrast can be improved, and the phase difference can be reduced.

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

The mercapto group in the mercaptoamine group in the general formula (A) may, for example, be an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group or a phenylsulfonyl group; or an alkyl group, a phenyl group or a naphthalene group. Alkyl-substituted mercapto group; an aminesulfonyl group which may be substituted with an alkyl group, a phenyl group or a naphthyl group; a formazan group which may be substituted with an alkyl group, a phenyl group or a naphthyl group. The alkyl group is preferably a carbon number of 1 or more and 6 or less. Further, the alkyl group may be substituted with a halogen such as F, Cl or Br, -OH, -CN, -NH ₂ and/or an alkoxy group having 1 or more and 6 or less carbon atoms. Further, the phenyl group and the naphthyl group may be, for example, a halogen such as F, Cl or Br, -OH, -CN, -NH ₂ or -NO ₂ , an alkyl group having 1 or more and 6 or less carbon atoms, and/or a carbon number. 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) is preferably a carbon number of 1 or more and 6 or less. The alkyl group may be substituted with a halogen such as F, Cl or Br, -OH, -CN, -NH ₂ and/or an alkoxy group having 1 or more and 6 or less carbon atoms.

The aryl group in the arylamine group in the general formula (A) may, for example, be a phenyl group or a naphthyl group. These aryl groups may also be, for example, a halogen such as F, Cl or Br, -OH, an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, -NH ₂ or -NO ₂ and -CN and so on.

In the azo compound represented by the above general formula (A) and the azo compound having a tautomeric structure, it is preferred that each of the azo compounds is ^a red hue hue, and each of them is independently -OH or -NH. ₂ , -NH-CN or alkylamino group. The two R ^a may be the same or different, respectively.

In the above general formula (A), from the viewpoint of hue, it is better that both R ^a are both -OH, both are -NH-CN, or one is -OH and one is -NH -CN, and even better, both are -OH.

Further, in the azo compound represented by the general formula (A) and the azo compound having a tautomeric structure, R ^b is preferably -OH from the viewpoint of a hue.

The metal is at least two selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and at least one of them is preferably a divalent or trivalent metal. The metal of the cation preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably contains at least Ni.

Further, it is preferable that Ni further contains at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and further preferably further contains Ni. At least one metal of the group consisting of Zn, Cu, Al, and Fe is preferable, and as the at least two metals, Ni and Zn, or Ni and Cu are preferable.

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

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 of the group is preferably contained in the molar ratio of Ni: other at least one metal of 97:3 to 10:90, and more preferably 90:10 to 10:90. The ear contains it.

Among them, from the viewpoint of the hue of the red hue, Ni and Zn are preferably contained in a molar ratio of Ni:Zn of 90:10 to 10:90, more preferably 80:20 to 20:80. More than it contains.

Alternatively, from the viewpoint of the hue of the red hue, Ni and Cu are preferably contained in a molar ratio of Ni:Cu of 97:3 to 10:90, more preferably 96:4 to 20:80. More than it contains.

In the case where the yellow color material is a hue of a red hue, even if the P/V ratio is suppressed, it is easy to produce a red pixel included in the redness region of the high color density described above.

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

The aspect in which the yellow color material contains at least two kinds of metal ions includes, for example, a case where at least two metal ions are contained in a common crystal lattice, and each of the individual crystal lattices contains one metal ion. The case where the crystals are agglomerated. Among them, in the case where the common crystal lattice contains at least two kinds of metal ions, it is preferable from the viewpoint of further improvement of the contrast. Further, it belongs to a state in which at least two metal ions are contained in a common crystal lattice, or a crystal in which each metal ion is contained in an individual crystal lattice is agglomerated, and for example, Japanese Patent Laid-Open No. 2014- Bulletin No. 12838 is appropriately judged by the X-ray diffraction method.

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 an anion of the azo compound represented by the above general formula (A) and an azo compound of a tautomeric structure and a specific metal ion, and the following general A complex molecule of a compound of formula (B). These intermolecular linkages can be formed by, for example, intermolecular interactions, or Lewis acid-base interactions, or coordination linkages. Further, it may be a structure in which a guest molecule is incorporated into an inclusion compound which constitutes a lattice of a main molecule. Alternatively, it is also possible to form a mixed crystal by forming a common crystal from two substances such that the atoms of the second component are located in a regular lattice position of the first component.

(In the general formula (B), R ^{c is} 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, more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group may also be substituted by an -OH group.

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

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

Further, the yellow color material used in the present invention may further contain: urea and substituted urea, such as phenyl urea, dodecyl urea, etc., and a polycondensate thereof with an aldehyde (particularly formaldehyde); For example, barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquine Porphyrin, 2,3-dihydroxyquine Porphyrin-6-sulfonic acid, oxazole, 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-three -2,4-diamine, cyanuric acid, and the like.

Further, the yellow color material used in the present invention may further contain: a water-soluble polymer such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid, such as carboxymethylcellulose, A modified cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl or ethyl hydroxyethyl cellulose.

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 is: P/V (red color material quality / solid content other than red color material) ratio = 0.2, and the spectroscopic penetration of the coating film having a film thickness of 2.5 μm is measured. In the case of the spectrum, the transmittance at a wavelength of 520 nm is 20% or less, and the transmittance at a wavelength of 640 nm is 70% or more. The red color material used in the present invention also includes a color material denoted as C.I. Pigment Orange as a red color material with a slight yellow hue (a redish orange material).

Further, in order to separately color the red color material for color measurement, a suitable dispersant, a binder component, and a solvent are prepared for the red color material to prepare a coating liquid, which is applied onto a transparent substrate and dried, as needed. Let it harden. As a binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin may be used under the premise that a clear coating film capable of color measurement can be formed. Things. Further, in the colored resin composition of the present invention to be described later, a coating film containing only a red color material as a color material is formed by using a composition containing only a red color material as a color material, and color measurement can be performed. Specifically, for example, the solid content used in the resin composition of Example 1 to be described later can be a solid content other than the red color material.

The transparent coating film containing a dispersing agent, a binder, and colorimetric measurement can be, for example, a film thickness of 2.0 μm or a transmittance of a spectral transmittance spectrum of 380 to 780 nm of 95% or more.

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

The red color material used in the present invention is not particularly limited, and examples thereof include a pyrrolopyrroledione pigment, a naphthol azo pigment, or other azo pigments, quinophthalone pigments, and A pigment, an anthraquinone pigment, a perinone pigment, an anthraquinone pigment, a thioindole pigment, and the like. The red color material used in the present invention preferably contains a pyrrolopyrroledione pigment, a naphthol azo pigment, an anthraquinone pigment, and an anthraquinone from the viewpoint of suppressing the P/V ratio. At least one of the group consisting of the pigments, and more preferably one selected from the group consisting of pyrrolopyrroledione pigments and anthraquinone pigments, from the viewpoint of easily forming a hue of a high color density and having a high luminance. Kind.

The pyrrolopyrrolodione-based pigment may, for example, be represented by the following general formula (1).

[Chemical 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 tert-butyl group, a phenyl group, an N,N-dimethylamino group, a trifluoromethyl group, or a cyanogen group. The bases, k and k' each independently represent an integer of 0 or more and 5 or less. When k and k' are each an integer of 2 or more, the plural A ³ and A ⁴ may be the same or different.

Specific examples of the pyrrolopyrroledione pigment 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 A pyrrolopyrroledione pigment (BrDPP) represented by the chemical formula (2).

Examples of the naphthol-based azo pigment 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, and 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, and the like.

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

Examples of the ruthenium-based pigment include C.I. Pigment Red 177, C.I. Pigment Red 168, C.I. Pigment Orange 51, and the like.

Examples of the ruthenium-based pigment 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.

From the viewpoint of easily obtaining the effect of the present invention, it is preferred to use a pyrrolopyrroledione pigment selected from the group consisting of CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 272, and the above chemical formula (2). One or more red color materials of the group consisting of (BrDPP), CI Pigment Red 242, CI Pigment Orange 38, CI Pigment Red 177, and CI Pigment Red 179; wherein, as the red color material, CI Pigment Red 254 is preferably used. The combination of the pyrrolopyrroledione pigment (BrDPP) represented by the above chemical formula (2) and CI Pigment Red 177.

The content ratio of the combination of the CI dye red 254 and the pyrrolopyrrolodione pigment (BrDPP) and the CI color red 177 represented by the above chemical formula (2) is appropriately adjusted depending on the desired color material, and is not particularly limited. The amount of the CI dye red 254 is preferably 10 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the total amount of the red color material, and the pyrrolopyrroledione pigment (BrDPP) represented by the above chemical formula (2) is 10 parts by mass. The above is 70 parts by mass or less, and the CI Pigment Red 177 is 10 parts by mass or more and 60 parts by mass or less. In the above range, the effect of the above combination is excellent. In addition, the ratio of the content of the red coloring material is preferably a ratio of the coloring resin composition to be described later, and the coloring material dispersion can be produced by appropriately mixing two or more kinds of the color material dispersion liquid to produce a colored resin composition. The content ratio which is the same as the colored resin composition described later is still suitable for use.

In the color material dispersion liquid of the present invention, the red color material and the specific yellow color material are used in combination as the color material, but other color materials exemplified as the colored resin composition described later may be used in combination. As the other color material, for example, another yellow color material, an orange color material not included in the red color material, and the like are preferably used. Among them, other yellow color materials exemplified as the colored resin composition described later are suitable from the viewpoint of the hue. .

In the color material dispersion liquid of the present invention, the content ratio of each of the red color material and the specific yellow color material and the content ratio when the color material is used is preferably the same as the content ratio of the colored resin composition to be described later. In addition, since the color material dispersion liquid can be used as a colored resin composition by mixing two or more types as appropriate, it is suitable to use even if it is not the same content ratio as the coloring resin composition mentioned later.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, and the color material used is not particularly limited. The type is preferably 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. When the average primary particle diameter of the color material is within the above range, a display device having a color filter manufactured using the color material dispersion of the present invention can be highly contrasted and of high quality.

Further, the average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material to be used, and is preferably in the range of 10 nm or more and 100 nm, more preferably 15 nm or more and 60 nm or less.

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

In the color material dispersion liquid of the present invention, the color material content is not particularly limited. The color material content is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion liquid, from the viewpoint of dispersibility and dispersion stability. More than 70 parts by mass or less.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, it is preferably 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion liquid. The above ratio is adjusted in a ratio of 75 parts by mass or less.

 <dispersant>  

In the present invention, a polymer having the structural unit represented by the above general formula (I) is used as a dispersant. The constituent unit represented by the above general formula (I) is alkaline and exhibits a function as a absorbing portion of the color material.

In the color material dispersion liquid of the present invention, by using the polymer having the structural unit represented by the above general formula (I), the absorbing property of the color material is improved, and the dispersibility and dispersion stability of the color material are improved.

In the general formula (I), A is a divalent bond group. Examples of the divalent linking group in A include an alkylene group having 1 or more and 10 or less carbon atoms, an extended aryl group, a -CONH- group, a -COO- group, and an ether having 1 or more and 10 or less carbon atoms. The 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 bond group containing a -COO- group.

R ² and R ³ may further contain a hydrocarbon group in a hydrocarbon group of a hetero atom, and examples thereof include an alkyl group, an aralkyl group, and an aryl group.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group or a cyclohexyl group; and the alkyl group preferably has a carbon number; It is 1 or more and 18 or less, and more preferably a methyl group or an ethyl group.

The aralkyl group may, for example, be a benzyl group, a phenethyl group, a naphthylmethyl group or a biphenylmethyl group. 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.

Further, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 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. Further, the above preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the above hydrocarbon group is substituted by a hetero atom. Examples of the hetero atom which may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a ruthenium atom.

Further, the hydrogen atom in the hydrocarbon group may be substituted by a halogen atom such as an alkyl group having 1 or more and 5 or less carbon atoms, a fluorine atom, a chlorine atom or a bromine atom.

R ² and R ³ may also 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 a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a pyridinium ring. A porphyrin ring or the like.

In the present invention, each of R ² and R ^{3 is} independently a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to each other to form a pyrrolidine ring or a piperidine ring. More preferably, at least one of R ² and R ^{3 is} an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to each other to form a pyrrolidine ring or a piperidine ring. A porphyrin ring.

The structural unit represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate or diethylaminoethyl. (meth) acrylate or the like containing an alkyl-substituted amino group such as (meth) acrylate or diethylamino propyl (meth) acrylate; dimethylaminoethyl (meth) acrylonitrile A (meth)acrylamide or the like containing an alkyl-substituted amine group such as an amine or dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl is preferably used from the viewpoint of improvement in dispersibility and dispersion stability. Aminopropyl (meth) acrylamide.

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

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

The polymer used in the present invention is preferably a block 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-luminance and high-contrast coloring layer. A copolymer or a graft copolymer, particularly preferably a block copolymer. The following is a detailed description of the preferred block copolymer.

 (block copolymer)  

When the block containing the structural unit represented by the above general formula (I) is an A block, the structural unit represented by the above general formula (I) in the A block is alkaline and exhibits absorption as a color material. The function of the part. On the other hand, the B block which 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 the respective blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The constituent unit constituting the B block may, for example, be a monomer having an unsaturated double bond which is copolymerizable with a monomer from which the structural unit represented by the general formula (I) is derived. Among them, the following general formula is preferred. The constituent unit shown in (II).

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

The above 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 bond group A' of 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) which is suitable 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, or an alkenyl group, an aralkyl group or an aryl group having 2 or more and 18 or less carbon atoms.

The alkyl group having 1 or more and 18 or less carbon atoms may be any of a linear chain, a branched chain, and a cyclic group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, Basis A group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a lower alkyl group-substituted adamantyl group or the like.

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

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

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

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

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

Further, the above preferred carbon number 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, further preferably an integer of 1 or more and 4 or less, and 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 1 or more and 2 or less.

The hydrocarbon group in the above R ⁸ may be the same as those shown in the above R ⁵ . In particular, the hydrocarbon group in the above 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 or more and 5 or less carbon atoms, and may be any of a linear chain, a branched chain or a cyclic chain.

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

Examples of R ^5, wherein, in accordance with the preferred system embodiment becomes the selected location by said compatibility between the solvent and the rear, specifically, for example, in the above-described solvent is used as a color filter colored resin composition of the solvent is generally used in the composition In the case of a solvent such as a glycol ether acetate type, an ether type or an ester type, a methyl group, an ethyl group, an isobutyl group, a n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.

Further, in the structural unit constituting the B block, the above-mentioned R ⁵ preferably contains -[CH(R ⁶ )-CH(R ⁷ )-O from the viewpoint of excellent developability and excellent development residue. ] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ .

Further, the R ⁵ may be substituted by a substituent such as an alkoxy group, a hydroxyl group, an epoxy group or an isocyanate group, without impeding the dispersion property of the block copolymer or the like. After the synthesis of the segment copolymer, it may be reacted with a compound having the above substituent to form the above substituent.

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

The glass transition temperature (Tg) of the block portion of the solvent affinity of the present invention can be calculated by the following formula. Further, the glass transition temperature of the color material affinity block portion and the block copolymer can be similarly calculated.

1/Tg=Σ(Xi/Tgi)

Here, the block portion of the solvent affinity is a copolymerization of 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 lanthanum adopts the sum of i=1 to n. Further, the value (Tgi) of the homopolymer glass transition temperature of each monomer can be a value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of constituent units of the block portion constituting the solvent affinity may be appropriately adjusted within the range in which the dispersibility of the color material is improved. In particular, the number of constituent units of the block portion constituting the solvent affinity is preferably 10 or more and 200 or less, from the viewpoint that the solvent affinity portion and the color material affinity portion effectively act to enhance the dispersibility of the color material. It is preferably 10 or more and 100 or less, more preferably 10 or more and 70 or less.

The block portion of the solvent affinity may be selected in such a manner as to function as a solvent affinity site, and the repeating unit constituting the block portion of the solvent affinity may be contained in one type or may contain two or more types of repeating units.

In addition, in the present invention, the dispersant is preferably composed of the above-described general formula (II) and having an amine value of 40 mgKOH from the viewpoint of good dispersibility, no precipitation of foreign matter during coating film formation, and improvement in brightness and contrast. a polymer of /g or more and 120 mgKOH/g or less.

When the amine value is within the above range, the viscosity stability or heat resistance is excellent, and alkali developability or solvent resolubility is also excellent. In the present invention, the amine valence of the dispersing agent is preferably from 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, from the viewpoints of dispersibility and dispersion stability. 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 is the number of mg of potassium hydroxide equivalent to perchloric acid required for neutralization of the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237. When the measurement is carried out by this method, even if the amine group which forms a salt with the organic acid compound in the dispersant is usually dissociated from the organic acid compound, the amine valence of the block copolymer itself which is a dispersant can be measured.

The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing the development residue. Among them, the acid value of the dispersing agent is more preferably 2 mgKOH/g or more from the viewpoint of further suppressing the effect of the development residue. On the other hand, the acid value of the dispersing agent is preferably 0 mgKOH/g from the viewpoint of dispersibility and dispersion stability. In addition, the acid value of the dispersing agent used in the present invention is preferably 18 mg KOH/g or less as the upper limit of the acid value of the dispersing agent from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. . In particular, the acid value of the dispersing agent is preferably 12 mgKOH/g or less, and more preferably 8 mgKOH/g or less, from the viewpoints of good development adhesiveness and solvent resolubility.

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 suppression effect of the development residue is enhanced. 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. Further, 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, still more preferably 8 mgKOH/g or less. This is because the development adhesiveness and the solvent resolubility become good.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or higher from the viewpoint of improving the development adhesiveness. That is, the dispersant preferably has a glass transition temperature of 30 ° C or higher, regardless of the block copolymer before salt formation or the salt block copolymer. If the glass transition temperature of the dispersant is low, especially when it is close to the developer temperature (usually about 23 ° C), there is a problem that the development adhesiveness is lowered. It is presumed that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, the development adhesiveness is deteriorated. When the glass transition temperature is 30 ° C or higher, it is estimated that the molecular motion of the dispersing agent during development is suppressed, so that the deterioration of the developing adhesiveness is suppressed.

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

The glass transition temperature of the dispersant of the present invention can be determined by measurement by differential scanning calorimetry (DSC) according to JIS K7121.

When the concentration of the color material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block having a constituent unit derived from a carboxyl group-containing monomer and has the above specific acid value and glass transition temperature, the development adhesiveness 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 is likely to occur during development.

As described above, in the present invention, the dispersion stability of the color material is superior and the contrast is improved, and the development residue is suppressed when the colored resin composition is formed, and the solvent resolubility is superior, and further, the development adhesiveness is high. The dispersant preferably contains a polymer having a structure represented by the above general formula (I) and having an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less, and an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less, glass transfer. The temperature is above 30 °C.

As the carboxyl group-containing monomer, a monomer which 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 a monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, isaconic acid, crotonic acid, and the like. Cinnamic acid, acrylic acid dimer, and the like. Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride group-containing monomer such as maleic anhydride, isaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

In the block copolymer before salt formation, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is appropriately set within the range in which the acid value of the block copolymer is in the specific acid value, and is not particularly limited. The total mass of the total constituent units of 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 unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is expressed. When the content is less than or equal to the above upper limit, deterioration of development adhesiveness or solvent redissolution can be prevented. Sexual deterioration.

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one or more kinds of constituent units, and may be contained in the above-mentioned specific acid value.

Further, from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or more and the development adhesiveness is improved, it is preferred that the value of the glass transition temperature (Tgi) of the monomer homopolymer is The monomer of 10 ° C or more is set to be 75 mass% or more, more preferably 8 mass% or more in total in the B block.

In the block copolymer, the ratio m/n of the number m of constituent units of the A block and the number n of constituent units of the B block is preferably 0.05 or more and 1.5 or less; From the viewpoint of dispersibility and dispersion stability of the color material, it is more preferably in 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, and from the viewpoint of satisfactory 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. More preferably 3,000 or more and 12,000 or less.

Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Further, the macromonomer, the salt block copolymer, and the graft block copolymer which are the raw materials of the block copolymer are also subjected to the above conditions.

The method for producing the above block copolymer is not particularly limited. The block copolymer can be produced by a known method, and it is preferably produced by a living polymerization method. Since the chain is not easily moved or deactivated, a polymer having a uniform molecular weight can be produced, and the dispersibility can be improved. The living polymerization method may, for example, be a living anionic polymerization method such as a living radical polymerization method or a base transfer polymerization method, or a living cationic polymerization method. By sequentially polymerizing the monomers by such methods, a copolymer can be produced. For example, an A block is first produced, and an A block is polymerized with a constituent unit constituting the B block to produce a block copolymer. Further, in the above production method, the polymerization order of the A block and the B block may be reversed. Further, the A block and the B block may be separately produced, and then the A block and the B block may be coupled.

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

In the present invention, from the viewpoint of dispersibility or dispersion stability of the color material, it is preferred 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 the halogenated hydrocarbon is used as a dispersing agent (hereinafter, such a polymer is referred to as a salt type polymer).

Among them, from the viewpoint of superior dispersibility and dispersion stability of the color material, it is preferred that the polymer having a repeating unit having a tertiary amine be a block copolymer, and the organic acid compound is a phenylphosphonic acid or a phenyl group. An acidic organophosphorus compound such as phosphinic acid. Specific examples of the organic acid compound to be used in the above-mentioned dispersing agent include an organic acid compound described in, for example, JP-A-2012-236882.

Further, as the halogenated hydrocarbon, at least one of a halogenated allyl group such as a brominated allyl group or a benzyl chloride group and a halogenated aralkyl group is preferred from the viewpoint of excellent dispersibility and dispersion stability of the color material. Kind.

In the color material dispersion liquid of the present invention, at least one type of polymer having the structural unit represented by the above general formula (I) is used as the dispersing agent, and the content thereof is blended with the type of the color material to be used, and further described later. The color filter is appropriately selected by the solid content concentration or the like in the colored resin composition.

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 based on 100 parts by mass of the total solid content in the color material dispersion liquid from the viewpoint of dispersibility and dispersion stability. More than 5 parts by weight and more than 35 parts by mass.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, the content of the dispersing agent is preferably 3 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the total solid content in the color material dispersion liquid. More preferably, it is blended in a ratio of 5 parts by mass or more and 20 parts by mass or less.

Further, in the present invention, the solid portion is all other than the above solvent, and includes a monomer dissolved in a solvent or the like.

 <solvent>  

The solvent to be used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the color material dispersion liquid and can be dissolved or dispersed. The solvent may be used alone or in combination of two or more.

Specific examples of the solvent include an alcohol solvent such as methanol, ethanol, isopropanol or methoxy alcohol; a carbitol solvent such as methoxyethoxyethanol or ethoxyethoxyethanol; and ethyl acetate B; Ester, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate An ester solvent such as isobutyl acetate, n-butyl butyrate or cyclohexanol acetate; a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone or 2-heptanone; methoxy B Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl ethyl a glycol ether acetate solvent such as an acid ester; a card such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, or butyl carbitol acetate (BCA) Alcohol acetate-based solvent; diacetate such as propylene glycol diacetate or 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether a glycol ether solvent such as diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; N,N-dimethylformamide, N,N - aprotic ether amine solvent such as dimethylacetamide or N-methylpyrrolidone; lactone solvent such as γ-butyrolactone; cyclic ether solvent such as tetrahydrofuran; benzene, toluene, and An unsaturated hydrocarbon solvent such as toluene or naphthalene; a saturated hydrocarbon solvent such as N-heptane, N-hexane or N-octane; or an organic solvent such as aromatic hydrocarbons such as toluene or xylene. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, and an ester solvent are preferably used from the viewpoint of 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 or coating suitability of other components. 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.

Further, from the viewpoints of developability, solvent resolubility, and the like, a mixed solvent containing two or more kinds of solvents is preferably used.

In the case of using a mixed solvent, the first solvent is preferably a glycol ether acetate-based solvent because of high safety, moderate volatility, and good dispersibility due to moderate solubility. Further, among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate which is more preferably a boiling point (refer to a boiling point at atmospheric pressure, the same applies hereinafter) of less than 150 ° C, particularly preferably a propylene glycol single Methyl ether acetate (PGMEA).

The second solvent (solvent other than the first solvent) is preferably a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150 ° C or higher. The second solvent may be used singly or in combination of two or more.

When a solvent having an alcoholic hydroxyl group is used as the second solvent, the dispersibility is improved and the solvent resolubility is likely to be good.

Examples of the solvent having an alcoholic hydroxyl group include the above-described alcohol solvent, the carbitol solvent, and the glycol ether solvent. Specific examples thereof include propylene glycol monomethyl ether (boiling point: 121 ° C), and 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 is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less based on the total solvent. Further, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 1% by mass or more.

When it is in the above range, the solubility of the dispersing agent is likely to be good, and the dispersing agent does not inhibit the dissolution of the first solvent, so that the dispersion stability is likely to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C, when a solvent having a boiling point of 150 ° C or higher is used as the second solvent, drying unevenness is less likely to occur, and foreign matter is less likely to occur, and solvent resolubility is also likely to be good.

Examples of the solvent having a boiling point of 150 ° C or higher include diethylene glycol ethyl methyl ether (boiling point: 179 ° C) and 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), and the like.

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

When it is in the above range, drying unevenness does not easily occur, or the drying time is not too long, and productivity is likely to be good.

The boiling point of the "solvent having a boiling point of 150 ° C or higher" is preferably 240 ° C or less, and particularly preferably 200 ° C or less from the viewpoint that the drying time is not too long.

The color material dispersion liquid of the present invention is preferably contained in an amount of 55 mass% or more and 95 mass% or less of the above solvent, and preferably 65 mass% or more, based on the total amount of the color material dispersion liquid containing the solvent. It is in the range of 90% by mass or less, more preferably 70% by mass or more and 88% by mass or less. When the amount of the solvent is too small, the viscosity increases and the dispersibility is liable to lower. Further, when the amount of the solvent is too large, the concentration of the color material is lowered, and it is difficult to achieve the target chromaticity coordinate.

 <Other ingredients>  

In the color material dispersion liquid of the present invention, the dispersion auxiliary resin and other components can be further prepared as needed without impairing the effects of the present invention.

The dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as a colored resin composition for a color filter to be described later. Since the steric hindrance of the alkali-soluble resin makes the color material particles hard to come into contact with each other, there is a case where the effect of the dispersing agent is reduced by dispersion stabilization or by a dispersion stabilizing effect.

Further, examples of the other component include a surfactant for improving wettability, a decane coupling agent for improving adhesion, an antifoaming agent, a shrinkage preventing agent, an antioxidant, an anti-aggregating agent, an ultraviolet absorber, and the like. .

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter to be described later. In other words, the color material dispersion liquid is prepared in a stage before the preparation of the colored resin composition for a color filter described later, and P/V (the mass of the color material component in the composition) / (in addition to the color material component in the composition) The solid content of the solid material dispersion is relatively high. Specifically, the ratio of (the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid and each component described later, it is possible to prepare a colored resin composition for a color filter excellent in dispersibility.

 [Manufacturing method of color material dispersion]  

In the present invention, the method for producing a color material dispersion liquid is not particularly limited as long as the color material is obtained by dispersing the color material to obtain a color material dispersion liquid dispersed in a solvent. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the color material, it is preferably one of the following two production methods.

That is, the first method for producing the color material dispersion of the present invention comprises the steps of: preparing the dispersant; and dispersing the color material in the presence of the dispersant in a solvent. In the solvent, two or more kinds of color materials may be co-dispersed in the presence of the dispersant, or one or more color materials may be dispersed or co-dispersed, and then two or more kinds of color material dispersions may be mixed. This also gives the color material dispersion of the present invention.

Further, in the second production method of the color material dispersion liquid of the present invention in the case of using a dispersant which is a salt type block copolymer, the solvent, the above block copolymer, the above organic acid compound or halogenated hydrocarbon and color are used. The material is mixed, and at least a part of the nitrogen portion at the terminal end of the structural unit represented by the above general formula (I) forms a salt with the organic acid compound or the halogenated hydrocarbon, and has a step of dispersing the color material. When the salt is formed on one side and the color material is dispersed, two or more color materials may be co-dispersed, or one or more color materials may be dispersed or co-dispersed, and then two or more color materials may be mixed and dispersed. The liquid material can also be used to obtain the color material dispersion of the present invention.

In the first manufacturing method and the second manufacturing method described above, the color material can be dispersed using a conventionally known disperser.

Specific examples of the dispersing machine include a roll mill such as a twin roll machine and a three roll machine, a ball mill such as a ball mill or a vibrating ball mill, a paint regulator, a continuous disc type bead mill, and a continuous ring type bead mill. Mill. The preferred dispersion conditions of the bead mill are 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 a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent; and the color material includes a red color material and a yellow color material; and the yellow color material contains: Selecting at least one anion of the group consisting of mono-, di-, tri-, and tetraanions of the azo compound represented by the above general formula (A) and the azo compound of the tautomeric structure thereof; selected from the group consisting of Cd, Co, and Al, An ion of at least two kinds of metals composed of Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a compound represented by the above general formula (B); wherein the dispersant has the general formula (I) The polymer that makes up the unit.

The coloring resin composition for a color filter of the present invention is excellent in dispersion property of color material similarly to the above-described color material dispersion liquid of the present invention, and can be formed as described in the item of the color material dispersion liquid of the present invention described above. A color layer with a reduced phase difference, high luminance and high contrast, and excellent color appearance.

The colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent, and may further contain other components within the range not impairing the effects of the present invention. Hereinafter, each component contained in the colored resin composition for a color filter of the present invention will be described. However, the red color material which is an essential component among the color materials, the specific yellow color material, the dispersant, and the solvent are the same as the above-described invention. Since the description of the color material dispersion liquid is the same, the description thereof is omitted.

 <color material>  

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

In the case of forming the colored layer of the color filter, the desired color development is not particularly limited, and various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination of two or more. Among them, organic pigments are suitable for use because of their high color developability and high heat resistance. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), and specifically has the following coloring index (C.I.).

Moreover, as the dispersible dye, for example, various substituents may be added to the dye, or a known disintegration (salting) method may be used to form a dispersible dye by insolubilizing a solvent, or a combination of low use. The solvent of solubility becomes a dispersible dye. By using such a dispersible dye in combination with the above dispersant, the dispersibility or dispersion stability of the dye can be improved.

As the dispersible dye, it can be suitably selected from known dyes. Examples of such a dye include an azo dye, a metal salt azo dye, an anthraquinone dye, and a triphenylmethane dye. Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, and the like.

Further, as a standard, when the amount of the dye dissolved is 10 mg or less based on 10 g of the solvent (or mixed solvent), it can be judged that the dye is dispersible in the solvent (or mixed solvent).

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

The other color material may, for example, be the following, but is not limited thereto.

As other yellow color materials, for example, 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, 185, and the like.

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 is appropriately adjusted depending on the desired chromaticity, and is not particularly limited.

In view of the fact that the phase difference is reduced and the color reproducibility is widened and the contrast is improved, it is preferable to contain the red color material in an amount of 35 mass% or more and 99 mass% or less, more preferably 40 mass, based on the total amount of the color material. % or more and 98% by mass or less, more preferably 45% by mass or more and 97% by mass or less.

In addition, the total content of the yellow color materials is preferably 1% by mass or more and 65% by mass or less, more preferably the total amount of the color materials, from the viewpoint of the reduction of the phase difference and the increase in the color reproducibility. 2% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 55% by mass or less.

In the colored resin composition for a color filter of the present invention, the single, the second, the third and the third of the yellow color material selected from the azo compounds represented by the above general formula (A) and the tautomeric structure thereof. At least one anion of the group consisting of tetraions and ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and the above general formula The total content of the compound (B), which is a specific yellow color material, is not particularly limited as long as it is appropriately adjusted in accordance with the desired chromaticity. In the above, the total content of the specific yellow color material is preferably 10% by mass or more and 100% by mass based on the total amount of the yellow color material, from the viewpoint of the reduction of the phase difference value and the increase in the color reproducibility. The following is 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.

Further, in the colored resin composition for a color filter of the present invention, the color material may further contain a red color material and a color material other than the yellow color material in a range that does not impair the effects of the present invention. The total content of the red color material and the yellow 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 based on the total amount of the color material. And 100% by mass or less.

 <Binder composition>  

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

As the curable binder component, for example, a photocurable binder component containing a photocurable resin which can be polymerized and cured by visible light rays, ultraviolet rays, electron beams or the like can be used, or can be heated by heating. A thermosetting binder component of a thermosetting resin which is polymer cured.

In the case where a photolithography step is used in forming the coloring layer, a photosensitive adhesive component having alkali developability is suitably used. Further, a thermosetting adhesive component may be further used in the photosensitive adhesive component.

Examples of the photosensitive adhesive component include a positive photosensitive adhesive component and a negative photosensitive adhesive component. The positive-type photosensitive adhesive component may, for example, contain an alkali-soluble resin and a system containing an ortho-quinonediazide-based compound as a photosensitive imparting component.

On the other hand, as the negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is suitably used.

In the colored resin composition for a color filter of the present invention, a negative photosensitive adhesive component is preferred from the viewpoint that a pattern can be easily formed by photolithography using an existing process.

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

 (alkali soluble resin)  

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

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

The alkali-soluble resin which is preferable in the present invention is a resin having an acidic group and usually a carboxyl group, and specific examples thereof include an acrylic resin having a carboxyl group and an acrylic resin having a carboxyl group and a styrene-acrylic copolymer. A carboxyl group-containing epoxy (meth) acrylate resin or the like. Among these, those having a carboxyl group in the side chain and further having an ethylenically unsaturated group in the side chain are preferred. The reason for this is that the film strength of the formed cured film can be enhanced by containing a photopolymerizable functional group. Further, two or more kinds of the acrylic resin and the epoxy acrylate resin such as the acryl-based copolymer and the styrene-acrylic copolymer may be used in combination.

An acrylic resin having a constitutive unit having a carboxyl group and an acryl-based resin having a carboxyl group such as a styrene-acrylic copolymer, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, copolymerizable The other monomer is a (co)polymer obtained by (co)polymerization by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, and itaconic acid. , butenoic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride group-containing monomer such as maleic anhydride, isaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring which is a large volume among the alkali-soluble resins, shrinkage during hardening, relaxation and peeling from the substrate, and adhesion of the substrate are improved. Further, the present inventors have found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer, can be suppressed. Although the effect has not yet been elucidated, it is presumed that the molecular action in the colored layer can be suppressed by the large-volume hydrocarbon ring in the colored layer, and as a result, the coating film strength is increased and the swelling due to the solvent is suppressed.

Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof, and the hydrocarbon ring may have an alkyl group, a carbonyl group, a carboxyl group, or an oxygen group. Substituents such as a carbonyl group, a decylamino group, a hydroxyl group, a nitro group, an amine group, a halogen atom or the like.

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

Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring such as alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) or adamantane; an aromatic hydrocarbon ring of benzene, naphthalene, anthracene, phenanthrene, anthracene or the like; biphenyl, A chain polycyclic ring such as terphenyl, diphenylmethane, triphenylmethane or hydrazine, or a fluorene structure (9,9-diarylfluorene).

The hydrocarbon ring preferably contains an aliphatic hydrocarbon ring from the viewpoint of improving the heat resistance or adhesion of the colored layer and improving the luminance of the obtained colored layer.

Moreover, from the viewpoint of improving the hardenability of the colored layer and improving the solvent resistance ((NMP swelling inhibition property), it is particularly preferable to contain the above-described ruthenium structure.

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

Specific examples of the crosslinked cyclic hydrocarbon ring include, for example, a lowering Alkane, different Alkane, adamantane, tricyclo[5.2.1.0(2,6)]decane, tricyclo[5.2.1.0(2,6)]nonene, tricyclopentene, tricyclopentane, tricyclopentadiene Dicyclopentadiene; a group in which one of these groups is substituted by a substituent.

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

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

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

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

In the case where the alkali-soluble resin has a maleic acid imide structure represented by the general formula (III), since the hydrocarbon ring has a nitrogen atom, the base belonging to the polymer having the structural unit represented by the above 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 enhanced.

In the R ^M of the general formula (III), specific examples of the hydrocarbon ring which may be substituted may, for example, be the same as the specific examples of the hydrocarbon ring described above.

For example, an aliphatic hydrocarbon ring such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, or a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group or a methoxybenzene group. An aromatic hydrocarbon ring such as a benzyl group, a hydroxyphenyl group or a naphthyl group, or a group in which one of these groups is substituted by a substituent.

In addition to the constituent unit having a carboxyl group, the alkali-soluble resin used in the present invention is easy to adjust the amount of each constituent unit and increase the amount of constituent units having the hydrocarbon ring, thereby facilitating the improvement of the function of the constituent unit. In other words, an acrylic copolymer having a constituent unit having the above hydrocarbon ring is preferably used.

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

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid. The ester, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development in the heat treatment. It is preferable to use at least one selected from the group consisting of cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in a side chain. In the case of having an ethylenic double bond, in the hardening step of the resin composition at the time of production of the color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond. The film strength of the cured film is further improved, the development resistance is improved, or the heat shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.

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 carboxyl group having an alkali-soluble resin is added to a compound having an epoxy group and an ethylenic double bond in the molecule, for example, glycidyl (meth)acrylate, and the like, and an ethylenic double is introduced into the side chain. A method of introducing a structural unit having a hydroxyl group into a copolymer, a compound having an isocyanate group and an ethylenic double bond in the molecule, and a method of introducing an ethylenic double bond into a side chain.

The alkali-soluble resin of the present invention may further contain other constituent units such as methyl (meth)acrylate or ethyl (meth)acrylate, and constituent units having an ester group. The constituent unit having an ester group has a function as a component which suppresses the alkali solubility of the coloring resin composition for a color filter, and also has a function as a component which improves the solubility in a solvent and further the solvent resolubility.

The alkali-soluble resin of the present invention preferably has an acrylic resin having a carboxyl group constituent unit, an acrylic copolymer having a hydrocarbon ring constituent unit, and a styrene-acrylic copolymer, and more preferably has a carboxyl group. An acrylic resin such as a unit, a constituent unit having a hydrocarbon ring, an acrylic copolymer having a constituent unit of an ethylenic double bond, and a styrene-acrylic copolymer.

The alkali-soluble resin can be made into an alkali-soluble resin having a desired property by appropriately adjusting the amount of each constituent unit to be filled.

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

When the ratio of the carboxyl group-containing ethylenically unsaturated monomer is at least the above lower limit value, the solubility of the obtained coating film to the alkali developing solution is sufficient; and, if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is the above upper limit When the value is below the value, there is a tendency that the formed pattern is less likely to fall off from the substrate or the film on the surface of the pattern is rough during development of the alkali developer.

Moreover, it is more preferable to use an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond as an alkali-soluble resin, and an acryl-based copolymer such as a styrene-acrylic copolymer, which is not compatible with the carboxyl group-containing ethylene. The amount of the saturated monomer to be added and the compound having an epoxy group and an ethylenic double bond are 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. In the case where the curing agent is hardened at a temperature of less than 1,000, the effect of the binder is remarkably lowered. If it exceeds 50,000, the pattern is difficult to form in the development of the alkali developer.

Further, the above weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be determined by using Shodex GPC System-21H (Shodex GPC System-21H) using THF as an eluent.

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

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones. The epoxy group-containing (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

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

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

When the ethylenic unsaturated bond equivalent of the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the effect of improving the film strength of the cured film and improving the development resistance and the adhesion to the substrate is improved. Good range of 100~2000, especially good range of 140~1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance or adhesion is excellent. In addition, when the ratio is 100 or more, the ratio of the constituent unit having a carboxyl group or the other constituent unit having a hydrocarbon ring is relatively increased, so that developability or heat resistance is excellent.

Here, the ethylenically unsaturated bond equivalent means the weight average molecular weight per 1 mole of the ethylenically unsaturated bond in the alkali-soluble resin, 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 molar number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).

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

The alkali-soluble resin to be used for the color filter resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and it is a coloring resin composition for a color filter. The total amount of the solid content, the alkali-soluble resin is preferably in the range of 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the alkali-soluble resin is at most the above lower limit value, sufficient alkali developability may not be obtained. When the content of the alkali-soluble resin is at least the above upper limit value, film roughness or pattern peeling may occur during development. situation.

 (multifunctional monomer)  

The polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited as long as it is polymerizable by the above photoinitiator, and usually has two or more ethylenic unsaturation. The compound having a double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl fluorenyl groups or methacryl fluorenyl groups.

Such a polyfunctional (meth) acrylate can be appropriately selected from known ones. Specific examples include those described in Japanese Laid-Open Patent Publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, when the colored resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds, and more preferably A poly(meth)acrylate of a trihydric or higher polyhydric alcohol or a modified dicarboxylic acid, specifically, preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol III ( Methyl) acrylate, succinic acid modification of pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, two A succinic acid modification of pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

The content of the above polyfunctional monomer used for the coloring resin composition for a color filter is not particularly limited, and the polyfunctional monomer is preferably 5 in terms of the total amount of the solid content of the colored resin composition for a color filter. It is in the range of % by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the polyfunctional monomer is at least the above-mentioned lower limit value, the photocuring is sufficiently performed, and the exposed portion is prevented from being eluted during development, and when the content of the polyfunctional monomer is at most the above upper limit value, the alkali developability is sufficient.

 (photoinitiator)  

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

The starting agent may, for example, be an aromatic ketone, a benzoin ether or a halomethyl group. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, 9-oxosulfur Wait. Specific examples of the initiator include aromatics such as diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl ketone. a ketone ketone, a benzoin ether such as benzoin methyl ether, a benzoin such as ethyl benzoin, or a 2-(o-chlorophenyl)-4,5-phenylimidazole dimer. Bis-imidazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethyl group such as oxadiazole Diazole compound, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Halomethyl-S-three Compound, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Polinylacetone, 1,2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzhydrylbenzoic acid, methyl benzhydrylbenzoate, 4-benzylidene-4' -methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino benzoate, p-amylamino benzoate, 2-n-butoxyethyl-4- Methylaminobenzoic acid ester, 2-chloro 9-oxo sulfur 2,4-diethyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur , 4-benzylidene-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-N- is preferably used. Polinyl propan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-N- Polinylphenyl)-1-butanone, 4,4'-bis(diethylamino)acetophenone, diethyl 9-oxosulfur . 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- Alkyl propan-1-one-like α-aminoacetophenone-based initiator and diethyl 9-oxosulfur 9-oxygen sulfur Is the initiator.

Using α-aminoacetophenone initiator and 9-oxosulfur In the case of the initiator, the total content of these is preferably 5% by mass or more and 15% by mass or less based on the total amount of the solid content of the colored resin composition. If the starting dose is 15% by mass or less, it is preferable because the sublimate in the manufacturing process is reduced. When the amount of the initiator is 5% by mass or more, development resistance such as water bleeding is improved.

In the present invention, the initiator is preferably an oxime ester-based photoinitiator from the viewpoint of enhancing sensitivity. By using an oxime ester-based photoinitiator, it is easy to suppress variations in line width in the plane when forming a fine line pattern. Further, by using an oxime ester-based photoinitiator, the developability is improved and the effect of suppressing water permeation tends to be high. In addition, the term "water permeation" refers to a phenomenon in which, after alkali development, after washing with pure water, a trace such as water infiltration occurs. Since such water permeation disappears after post-baking, there is no problem as a product. However, when the appearance of the pattern surface is examined after development, an abnormality is detected, and the problem that the normal product and the abnormal product cannot be distinguished is generated. . Therefore, if the inspection sensitivity of the inspection apparatus is lowered at the time of visual inspection, the result is that the yield of the final color filter product is lowered, which is a problem.

The oxime ester-based photoinitiator is preferably one having an aromatic ring or more preferably from the viewpoint of reducing contamination of the colored resin composition for a color filter or device contamination caused by the decomposition product. The condensed ring containing an aromatic ring is more preferably a condensed ring containing a benzene ring and a hetero ring.

As the oxime ester photoinitiator, 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzylidene fluorenyl)], ethyl ketone, 1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-ethylidene oxime), Japanese Patent Laid-Open No. 2000-80068, The oxime ester photoinitiators described in JP-A-2010- 527 842, JP-A-2010-527338, JP-A-2010- 041 153, and the like are appropriately selected. As a commercially available product, Irgacure OXE-02 (manufactured by BASF) having a carbazole skeleton, ADEKA ARKLS NCI-831 (manufactured by Adeka Co., Ltd.), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) having diphenyl can be used. ADEKA ARKLS NCI-930 (made by ADEKA), TR-PBG-345, TR-PBG-3057 (made by Changzhou Strong Electronic New Materials Co., Ltd.), Irgacure OXE-01 (made by BASF), and 茀Skeleton TR-PBG-365 (manufactured by Changzhou Power Electronic New Material Co., Ltd.). From the viewpoint of luminance, an oxime ester photoinitiator having a diphenyl sulfide skeleton or an anthracene skeleton is particularly preferably used. From the viewpoint of high sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used.

Further, from the viewpoint that the luminance and the development resistance are easily improved and the water permeation suppressing effect is high, it is preferred to use two or more kinds of oxime ester photoinitiators in combination. From the viewpoint of high luminance and high heat resistance, it is preferable to use two kinds of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or a combination of an oxime ester-based photopolymer having a diphenyl sulfide skeleton. The initiator and the oxime ester photoinitiator having an anthracene skeleton. Further, from the viewpoint of superior sensitivity and water permeation inhibition effect, it is preferred to use an oxime ester photoinitiator having a carbazole skeleton, an oxime ester photoinitiator having an anthracene skeleton, or a diphenyl group. An oxime ester of a thioether is a photoinitiator.

Further, from the viewpoint of suppressing water bleeding and improving sensitivity, it is preferred to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure having an oxygen quencher in the molecule, the radical generated by the initiator is not easily deactivated by oxygen, and the sensitivity can be improved. As a commercially available product of the above-mentioned photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-N- Androsolin-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-N- Polinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

Further, from the viewpoints of sensitivity adjustment, water permeation inhibition, and development resistance, it is preferred to use an oxime ester photoinitiator combination 9-oxygen sulfur. It is preferred to combine two or more kinds of oxime-based photoinitiators and 9 in terms of brightness, development resistance, easy adjustment sensitivity, high water permeation inhibition effect, and improvement of development resistance. - Oxygen sulfur Is the initiator.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass based on 100 parts by mass of the above polyfunctional monomer. More than or equal to 60 parts by mass. When the content is at least the above lower limit value, the photocuring is sufficiently performed, and the elution of the exposed portion at the time of development is suppressed. On the other hand, when the content is at most the above upper limit, the yellowing property of the obtained colored layer is weak, and the luminance can be suppressed. reduce.

In addition, the total content of two or more oxime-based photoinitiators of the photoinitiator used in the colored resin composition for a color filter of the present invention is such that the photoinitiator is sufficiently exhibited. From the viewpoint of the effect, the total amount of the solid content of the colored resin composition for a color filter 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.

In the coloring resin composition for a color filter of the present invention, the total amount of the binder component is preferably 35 mass% based on the total amount of the solid content of the coloring resin composition for a color filter. The ratio is more than 97% by mass or less, more preferably 40% by mass or more and 96% by mass or less. When it is more than the above lower limit value, a coloring layer excellent in hardness or adhesion to a substrate can be obtained. Moreover, when it is at most the above upper limit value, the developability is excellent, and the occurrence of minute wrinkles due to heat shrinkage is also suppressed.

 <arbitrarily added ingredients>  

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

As the additive, for example, an antimony compound, for example, a mercapto compound, a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, and a dense adhesion promotion are also mentioned. Agents, etc.

In the colored resin composition for a color filter of the present invention, it is preferable to further contain an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the color material, and improving the luminance. Moreover, it is preferable that the colored resin composition for color filters of the present invention further contains an antioxidant from the viewpoint of improving the adhesion of the SiN substrate.

The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and lanthanoid antioxidants, and are preferably blocked from the viewpoint of heat resistance. Phenolic antioxidants.

The hindered phenol-based antioxidant refers to an antioxidant having a structure in which at least one phenol structure is contained, and at least one of the two or six positions of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms. Construction.

Specific examples of the hindered phenol-based antioxidant include dibutylhydroxytoluene (BHT) and pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (products) Name: Irganox 1010, manufactured by BASF), 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-polyisocyanate (trade name: Irganox 3114, manufactured by BASF), 2, 4 , 6-gin (4-hydroxy-3,5-di-t-butylbenzyl)-symmetrical trimethylbenzene (trade name: Irganox 1330, manufactured by BASF), 6-(4-hydroxy-3,5-di-3rd Alkylamino)-2,4-bis(octylthio)-1,3,5-three (trade name: Irganox 565, manufactured by BASF), 2,2'-thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox) 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-t-butylphenyl)propanyl]anthracene (trade name: Irganox MD1024, manufactured by BASF), 3-( Octyl 4-hydroxy-3,5-diisopropylphenyl)propanoate (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-t-butyl-4-hydroxyphenyl)propanamine] (trade name: Irganox 1098, manufactured by BASF , 1,6-hexanediol bis[3-(3,5-di-t-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-tetraxoxaxo[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-gin[[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-tert-butyl-4-methylphenol) (trade name: SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 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-yl acrylate Tributyl-5-methylbenzyl)phenyl ester (trade name: SUMILIZER GM, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-tert-butyl-m-cresol) (trade name: SUMILIZER) WX-R, manufactured by Sumitomo Chemical Co., Ltd., 6,6'-di-t-butyl-4,4'-butylene m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA). Other compounds having an oligomeric type and a polymer type having a hindered phenol structure can also be used.

Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF) is preferred. Company system).

Further, from the viewpoint of forming a coloring layer which reduces the phase difference and simultaneously increases the luminance and contrast, a hindered phenol-based antioxidant having a molecular weight of 1,000 or less and a molecular weight of 280 equivalents or less per phenolic hydroxyl group is preferable. More preferably, it is a hindered phenol-based antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per one phenolic hydroxyl group. It is presumed that such an antioxidant has high fluidity and a large number of active points per weight unit, thereby suppressing color material agglomeration caused by rapid hardening shrinkage during exposure or post-baking by radical trapping, or inhibiting resin, etc. The yellowing is easy to obtain the above effects. As such an antioxidant, for example, 6,6'-di-t-butyl-4,4'-butylene-m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA) can be mentioned.

Further, in the present invention, it is preferable to use a latent antioxidant as an antioxidant from the viewpoint of forming a coloring layer which reduces the phase difference value and simultaneously contrasts the lift. When a latent antioxidant is used, it is estimated that the radical trapping effect is particularly high in post-baking, so that the coloring of the coloring material due to the rapid hardening shrinkage during post-baking is suppressed, and the above effects are easily obtained. The latent antioxidant in the present invention is a compound having a protective group which can be detached by heating, and exhibits an antioxidant function by being detached from the protective group. Among them, it is preferred that the protecting group is easily detached by heating at 150 ° C or higher. For example, a latent antioxidant as described in International Patent Publication No. 2014/021023 can be mentioned.

The latent antioxidant which is suitably used in the present invention is, for example, a latent hindered phenol-based antioxidant which protects the phenolic hydroxyl group of the hindered phenol-based antioxidant with a protective group which can be removed by heating. Examples of the latent hindered phenol-based antioxidant include a phenolic hydroxyl group of a hindered phenol-based antioxidant, an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a mercapto halogen compound, or an allyl ether compound. Etc. As a latent hindered phenol-based antioxidant, a structure in which a hydrogen of a phenol group of a hindered phenol-based antioxidant is substituted with a protective group such as a third butoxycarbonyl-based amine-based ester is suitably used. Specific examples are as follows: The chemical formulae (a) to (c) and the like are described, but are not limited thereto.

The method for producing the above-mentioned latent antioxidant is not particularly limited. For example, Japanese Patent Laid-Open No. Sho 57-111375, JP-A-3-173833, JP-A-6-128195, JP-A-7-20771, JP-A-7-252191 The phenolic compound produced by the method described in each of the publications of JP-A-2004-501128 is obtained by reacting with an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a mercapto chloride compound, an allyl ether compound, or the like. Further, a commercially available product can also be used.

When the colored resin composition for a color filter of the present invention contains the above-described oxime ester-based photoinitiator in combination with an antioxidant as a colored resin composition, it is preferable from the viewpoint of enhancing the luminance by the multiplication effect.

The content of 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 based on 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, if it is at most the above upper limit value, the colored resin composition of the present invention can be used as a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 100 parts by mass or more based on the total amount of the oxime ester-based photoinitiator, and the antioxidant is preferably 1 part by mass or more. Further, it is 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 excellent.

The colored resin composition for a color filter of the present invention preferably further contains a mercapto compound from the viewpoint of enhancing the effect of suppressing water permeation.

In addition, when the oxime ester-based photoinitiator and the mercapto compound are contained as a photosensitive colored resin composition in combination with the colored resin composition for a color filter of the present invention, the water osmosis is further enhanced from the viewpoint of improving development resistance. It is preferable from the viewpoint of the effect of suppressing the occurrence of dyeing, and the improvement in linearity when forming a fine line pattern, or the ability to form a fine line pattern as in the design of a mask line width. In addition, the term "linear improvement" means that the end portion of the coloring layer formed in the developing step after the application of the colored composition is less irregular, and is formed linearly or linearly.

The mercapto compound can function as a chain shifting agent, and has a property of receiving a radical by a radical having a slow reaction, thereby accelerating the reaction and improving the curability.

As the mercapto compound, for example, 2-mercaptobenzothiazole or 2-mercaptophenoxy Oxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, 3 - ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-gin (3-mercaptobutyloxyethyl)-1 , 3,5-three -2,4,6(1H,3H,5H)-trione, trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptopropyl acrylate) Acid ester), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The thiol compound may be used alone or in combination of two or more. From the viewpoint of increasing the crosslinking density and improving the water permeation inhibiting effect, it is preferably selected from the group consisting of two or more sulfhydryl groups in one molecule. One or more groups of the functional thiol compounds.

Further, from the viewpoint of easily maintaining a good water permeation inhibiting effect even in the case of long-term storage, it is preferred to have a secondary sulfhydryl group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom. The mercapto compound is more preferably a polyfunctional secondary mercapto compound having two or more such mercapto groups in one molecule.

The content of the mercapto compound used in the coloring resin composition for a color filter is not particularly limited, and the total amount of the solid content of the colored resin composition for a color filter is obtained from the viewpoint of sufficiently exerting the above effects. The mercapto compound is preferably in a 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.

Further, 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 coloring layer which reduces the phase difference and simultaneously enhances the contrast. The effect of improving these characteristics can be presumed to be caused by the agglomeration of the color material caused by the rapid hardening shrinkage in the exposure step. The ultraviolet absorber may be appropriately selected from conventionally known ones. Specific examples of the ultraviolet absorber include a benzotriazole-based compound, a diphenylketone-based compound, and three. A compound or the like. Among them, a benzotriazole-based compound is preferably used from the viewpoint that a coloring layer which reduces the phase difference value and simultaneously enhances the contrast can be formed.

The benzotriazole-based compound may, for example, be 2-(5-methyl-2-hydroxyphenyl)benzotriazole or 2-(2-hydroxy-5-t-butylphenyl)-2H-benzene. And triazole, octyl-3-[3-t-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-di-p-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-trioctylphenyl)benzene And triazole, 5% 2-methoxy-1-methylethyl acetate and 95% phenylpropionic acid, 3-(2H-benzotriazol-2-yl)-(1,1- a compound of dimethylethyl)-4-hydroxyl, C7-9 side chain and a linear alkyl ester, 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 or the like, but is not limited thereto.

Commercial products include, for example, "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 384-" manufactured by BASF. 2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", etc.

The benzotriazole-based compound is preferably a benzotriazole-based compound represented by the following general formula (IV) from the viewpoint of forming a coloring layer which reduces the phase difference value and simultaneously enhances the contrast.

(In the general formula (IV), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may be substituted by a phenyl group, and X represents a hydrogen atom or a chlorine atom.)

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

The content of the ultraviolet absorber to be used in the coloring resin composition for a color filter is not particularly limited, and the ultraviolet absorber is preferably 0.05 parts by mass or more and 10.00% by weight based on 100 parts by mass of the total solid content in the colored resin composition. It is below the mass part, more preferably 0.10 part by mass or more and 5.00 part by mass or less. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be used as a photosensitive resin composition having high sensitivity.

When the colored resin composition for a color filter of the present invention contains the above-described oxime ester-based photoinitiator in combination with the ultraviolet ray absorbing agent as a colored resin composition, it is preferable from the viewpoint of enhancing the luminance by the multiplication effect. good.

In the case where the ultraviolet absorber is used in combination with the above-mentioned oxime ester photoinitiator, the content of the ultraviolet absorber is preferably 1 in terms of 100 parts by mass of the total amount of the oxime ester photoinitiator. The mass part or more is 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.

Further, as a specific example of the surfactant and the plasticizer, for example, those described in JP-A-2013-029832 can be cited.

Examples of the decane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, and KBE-403. KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu SILICONE Co., Ltd.). Among them, from the viewpoint of the adhesion of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacrylic group and an acrylic group are preferable.

The content of the decane 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 or less based on 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit value and not more than the above upper limit value, the adhesion of SiN is excellent.

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

The total content of the color materials is 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 based on the total amount of the solid content of the colored resin composition for a color filter. . When the color filter resin composition is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less), the color layer has a sufficient concentration. Moreover, when it is at most the above upper limit value, the storage stability is excellent, and a coloring layer having sufficient hardness and adhesion to the substrate can be obtained. In particular, in the case of forming a color layer having a high color material concentration, the content of the color material is preferably 15% by mass or more and 65% by mass or less, more preferably the total amount of the solid content of the colored resin composition for a color filter. The ratio is 25 mass% or more and 60 mass% or less.

In addition, the content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed. For example, the content of the solid content of the colored resin composition for a color filter can be 1% by mass or more and 40% by mass or less. . In addition, the total amount of the solid content of the colored resin composition for a color filter is preferably 2% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 25% by mass or less. Provisioning. When it is more than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the coloring resin composition for a color filter is excellent in storage stability. Moreover, when it is below the said upper limit, the developability becomes favorable. In particular, in the case of forming a coloring layer having a high coloring material concentration, the content of the dispersing agent is preferably 2% by mass or more and 25% by mass or less, and more preferably the total amount of the solid content of the colored resin composition for a color filter. The ratio is 3% by mass or more and 20% by mass or less.

Further, the content of the solvent may be appropriately set depending on the range in which the coloring layer can be formed with high precision. The total amount of the colored resin composition for a color filter containing the solvent is usually preferably in the range of 55% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 88% by mass or less. . When the content of the solvent is within the above range, it is possible to obtain a coating property superior.

In the colored resin composition for a color filter of the present invention, the P/V ratio ((the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition)) 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 generation and ease of production, that is, solvent resolubility, development residue, and development adhesion. In view of superiority such as development resistance and water permeation inhibition effect, it is preferably 0.8 or less, more preferably 0.7 or less, and more preferably 0.6 or less from the viewpoint of development residue and development adhesion.

 <Cured film of colored resin composition for color filter>  

In the colored resin composition for a color filter, it is preferable that the chromaticity coordinates in the XYZ color system of JIS Z8701 which is measured using a C light source are in the range of x=0.550 to 0.700 and y=0.290 to 0.450. The hardened film inside.

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

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

The chromaticity coordinates in the XYZ color system of JIS Z8701 whose film thickness is 2.8 μm or less and the color measured by the C light source is a single pixel are used to represent x=0.570 to 0.693, y=0.300 to 0.426, and The ratio or combination of the color space in which the stimulation value Y is in the range of 9.0 ≦Y is preferably 45.0% by mass or more and 98.0% by mass or less based on the total amount of the color material, and the above-mentioned specific yellow color material 2.0% by mass or more and 55.0% by mass or less; more preferably, the red color material is 50.0% by mass or more and 95.0% by mass or less, and the specific yellow color material is 5.0% by mass or more and 50.0% by mass or less; 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.

 <Method for Producing Colored Resin Composition for Color Filter>  

The method for producing the colored resin composition for a color filter of the present invention is not particularly limited. For example, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator may be added to the color material dispersion of the present invention. Other components as needed are obtained by mixing them by a known mixing means. Alternatively, the coloring material dispersion liquid of each color material, various color material dispersion liquids, a binder component, and other components as necessary may be prepared by using a known dispersing agent, and mixing may be carried out by using a known mixing means.

 [Color Filter]  

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

The color filter of the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding portion 2, and a coloring layer 3.

 (colored layer)  

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

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

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

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

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

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

Next, using a hot plate or an oven, the wet coating film is dried, and then exposed to a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized to form a hard coating. membrane. Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the thickness of the light source or coating film to be used and the like.

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

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

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

 (lighting part)  

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

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light shielding portion may be a metal thin film such as chromium formed by a sputtering method, a vacuum 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 the resin binder. In the case of a resin layer containing light-shielding particles, there is a method of patterning by using a photosensitive resist by development, a method of patterning using an inkjet ink containing light-shielding particles, and heat-transfering a photosensitive resist. Printing method, etc.

The film thickness of the light-shielding portion is set to be 0.2 μm or more and 0.4 μm or less in the case of the metal thin film, and is set to be 0.5 μm or more and 2 μm or less in the case where the black pigment is dispersed or dissolved in the binder resin.

 (substrate)  

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

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

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

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

 [display device]  

The display device of the present invention is characterized by having the above-described color filter of the present invention. The configuration of the display device of the present invention is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device. Even in a liquid crystal display device of a horizontal electric field type, the present invention is suitable for various display defects such as a disorder of alignment of liquid crystals due to electrical characteristics of green pixels and a residual phenomenon caused by a threshold value of switching. Liquid crystal display device.

 <Liquid crystal display device>  

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

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

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.

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

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 and a liquid crystal dropping method.

 <Organic light-emitting display device>  

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

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

As a method of laminating the organic light-emitting body 80, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter is exemplified. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and the like in the organic light-emitting body 80 can be appropriately used. The organic light-emitting display device 100 thus produced can also be applied to, for example, an organic EL display of a passive driving type or an organic EL display of an active driving type.

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

 [Examples]  

The invention will be specifically described below by way of examples. The invention is not limited by the description.

Further, the acid value of the block copolymer before salt formation is determined by the method described in JIS K 0070.

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

The weight average molecular weight (Mw) of the block copolymer before salt formation is determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent value according to the above-described measurement method of the present invention.

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

 (Manufacturing Example 1 Modulation of Azo Derivative 1)  

In 550 g of distilled water, 23.1 g of azo barbituric acid and 19.2 g of barbituric acid were introduced. Subsequently, it was adjusted to azo barbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added by dropping. Thereafter, 38.7 g of melamine was introduced. Next, a 0.57 mol nickel chloride solution was mixed with a 0.03 mol copper chloride solution 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 by a mortar to obtain Azo derivative 1 (Ni: Cu = 95:5 (mole ratio) azo pigment).

 (Production Example 2 Modulation of Azo Derivative 2)  

In Production Example 1, except that 0.57 mole of nickel chloride solution and 0.03 mole of copper chloride solution were used, and 0.39 mole of nickel chloride solution and 0.21 mole of zinc chloride solution were used, Example 1 was carried out in the same manner to obtain Azo derivative 2 (azo pigment of Ni:Zn = 65:35 (mole ratio)).

 (Manufacturing Example 3 Modulation of Azo Derivative 3)  

In Production Example 1, except that 0.57 mole of nickel chloride solution and 0.03 mole of copper chloride solution were used, and 0.42 mole of nickel chloride solution and 0.18 mole of copper chloride solution were used, Example 1 was carried out in the same manner to obtain Azo derivative 3 (Ni: Cu = 70:30 (mole ratio) azo pigment).

 (Manufacturing Example 4 Modulation of Azo Derivative 4)  

In Production Example 1, except that 0.57 mole of nickel chloride solution and 0.03 mole of copper chloride solution were used, and 0.21 mole of nickel chloride solution and 0.39 mole of zinc chloride solution were used, Example 1 was carried out in the same manner to obtain Azo derivative 4 (azo pigment of Ni:Zn = 35:65 (mole ratio)).

 (Synthesis Example 1: Modulation of Dispersant a)  

In a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of the B block, 18.2 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-ethylhexyl methacrylate ( EHMA) 4.2 parts by mass, 7.0 parts by mass of n-butyl methacrylate (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of methyl methacrylate (MMA), using an addition funnel for 60 minutes dropping. After 30 minutes, the A block was dropped with a monomer of dimethylaminoethyl methacrylate (DMMA) in an amount of 30.8 parts by weight over 20 minutes. After allowing to react for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was purified by reprecipitation in hexane, filtration, and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the mixture was heated to 100 ° C and reacted for 7 hours to deprotect the structural unit derived from EEMA to form a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is purified by reprecipitation in hexane, filtration, and vacuum drying to obtain an A block containing a structural unit represented by the general formula (I) and a composition containing a carboxyl group-containing monomer. The unit is a solvent-soluble B block block copolymer A-1 (acid value: 12 mgKOH/g, Tg: 44 ° C). The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 8,100. Further, the amine value was 110 mgKOH/g.

Into a 100 mL round bottom flask, 29.35 parts by mass of PGMEA was dissolved in 29.35 parts by mass of the block copolymer A-1, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 1.59 parts by mass (relative to the DMMA of the block copolymer A-1). The unit 1 mol, phenylphosphonic acid was 0.1 mol, and 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 the formation of the salt is specifically calculated as follows.

1 g of a solution in which a salt-type block copolymer A-1 (solid matter after reprecipitation) was mixed with 91 parts by mass of chloroform-D1 NMR was added to the NMR sample tube, and a nuclear magnetic resonance apparatus (FTM, manufactured by JEOL Ltd.) was used. NMR, JNM-AL400) The ¹³ C-NMR spectrum was measured under the conditions of room temperature and cumulative number of times of 10,000 times. In the obtained spectral data, the nitrogen portion (amine group) at the terminal is calculated from the ratio of the peak of the carbon atom adjacent to the nitrogen atom in which the salt is not formed, and the integral value of the peak of the carbon atom adjacent to the nitrogen atom forming the salt. The ratio of the number of amine groups formed by salt to the total number of amine groups was confirmed to be the same as the theoretical salt formation ratio (the nitrogen of all the acidic groups of the phenylphosphonic acid and the terminal of the DMMA of the block copolymer A-1) The part forms a salt).

The amine value (22 mg KOH/g) of 0.20 mole parts of the DMMA unit was subtracted from the amine price of 110 mgKOH/g before salt formation, and 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 salt front block copolymer A-1. The acid value, amine value and Tg of the block copolymer A-1 before and after salt formation were shown in Table 1.

 (Synthesis Examples 2 to 4: Production of Dispersant b~d)  

In the synthesis example 1, except that the content shown in Table 1 was changed, the same as in Synthesis Example 1, and the salt pre-block copolymers A-2 to A-4 and the salt block copolymer A-2 were synthesized. (Dispersant b) ~ A-4 (dispersant d) solution. Further, 1-ethoxyethyl methacrylate (EEMA) was used in Synthesis Example 2 in an amount of 2.8 parts by mass, in Synthesis Example 3, 2.2 parts by mass, and in Synthesis Example 4, 1.1 parts by mass. The acid value, amine value and Tg of the obtained block copolymer before and after salt formation are shown in Table 1.

 (Synthesis Example 5: Modulation of Dispersant e)  

A 500 mL four-neck separation flask was dried under reduced pressure, and then Ar (argon) was replaced.

Under a flow of Ar, 0.1 g of dehydrated THF, 2.0 g of methyltrimethyldecyl dimethyl ketene acetal, and 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) were added. 3,5-trimethylbenzene 0.2 g. 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), benzyl by weight of benzyl methacrylate (BzMA), methacrylic acid, using a dropping funnel Methyl ester (MMA) 35.7 parts by mass was dropped over 45 minutes. Since the reaction was heated, the temperature was 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 give a block copolymer A-5. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 8,350, and the amine value was 95 mgKOH/g.

Into 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-5, and phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 3.17 parts by mass (relative to the block copolymer A-5). The DMMA unit was 1 mol, and the phenylphosphonic acid was 0.20 mol. The mixture was stirred at a reaction temperature of 30 ° C for 20 hours to obtain a salt-type block copolymer A-5 (dispersant e) solution. The amine valence after the formation of the salt was calculated in the same manner as in Synthesis Example 1. The acid value, amine value and Tg of the block copolymer before and after salt formation are shown in Table 1.

 (Synthesis Example 6: Modulation of Dispersant f)  

In addition to the phenylphosphonic acid, 3.80 parts by mass of chlorotoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) (1 mol of DMMA unit of the block copolymer A-5, and 0.3 mol of chlorotoluene) was used. The same procedure as in Synthesis Example 5 was carried out to synthesize a salt block copolymer A-6 (dispersant f) solution. The acid value, amine value and Tg of the obtained block copolymer before and after salt formation are shown in Table 1.

 (Synthesis Example 7: Modulation of Dispersant g)  

In Synthesis Example 5, in place of 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 Methyl methacrylate (MMA) 35.7 parts by mass, using 7.6 parts by mass of n-butyl methacrylate (BMA), 32.9 parts by mass of methyl methacrylate (MMA), and PME-1000 (methoxypolyethylene glycol) Monomethacrylate (polyethylene glycol chain repeat number n≒23), trade name BLEMMER PME-1000, manufactured by Nippon Oil Co., Ltd., 39.9 parts by mass, and substituted dimethylaminoethyl methacrylate (DMMA) 26.7 The same procedure as in Synthesis Example 5 was carried out, except that 19.6 parts by mass of the mass fraction was used, and a solution of the salt-forming block copolymer A-7 and the salt block copolymer A-7 (dispersant g) was obtained. The amine group after salt formation was calculated in the same manner as in Synthesis Example 1. The acid value, amine value and Tg of the obtained block copolymer before and after salt formation are shown in Table 1.

 (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 placed in a polymerization tank filled with 150 parts by mass of PGMEA, and dropped at 100 ° C for 3 hours under a nitrogen stream. After completion of the dropwise addition, the mixture was further heated at 100 ° C for 3 hours to obtain a polymer solution. The polymer solution had a weight average molecular weight of 7,000.

Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110 ° C for 10 hours in the reaction solution. The air is bubbled. The obtained alkali-soluble resin A is a resin obtained by introducing a side chain having an ethylenic double bond to a main chain formed by copolymerization of BzMA with MMA and MAA, and has a solid content of 42.6 mass% and an acid value of 74 mgKOH/g. The weight average molecular weight is 12,000. The weight average molecular weight was determined by using Shodex GPC System-21H (Shodex GPC System-21H) using polystyrene as a standard material and THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070.

 (Synthesis Example 9: Preparation of alkali-soluble resin B solution)  

In Synthesis Example 8, except for 40 parts by mass of BzMA which is a comonomer species in the polymerization, 20 parts by mass of styrene and N-phenyl maleimide (Tokyo Chemical Industry Co., Ltd.) 20 were used. The same procedure as in Synthesis Example 8 was carried out except for the mass portion, and an alkali-soluble resin B solution was obtained. The solid content was 42.6 mass%, the acid value was 74 mgKOH/g, and the weight average molecular weight was 12,000.

 (Synthesis Example 10: Synthesis of latent antioxidant (compound a))  

0.01 mol of the phenol compound represented by the following chemical formula (3), 0.05 mol of dibutyl butyl dicarbonate and 30 g of pyridine are mixed, and 0.025 mol of 4-dimethylaminopyridine is added at room temperature under a nitrogen atmosphere 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 thereto to carry out oil-water separation. After drying the organic layer 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 a latent antioxidant (compound a) represented by the above formula (a). Further, the structure of the obtained latent antioxidant was confirmed by IR and NMR.

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

6.23 parts by mass of a dispersing agent a solution of Synthesis Example 1 as a dispersing agent, pyrrolopyrroledione pigment (BrDPP, trade name Irgaphor RED S 3621CF, manufactured by BASF Corporation) of the following chemical formula (2) as a red color material 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 A49 derivative of the obtained Azo derivative 2, 14.59 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 having a particle diameter of 2.0 mm were placed in a melamine bottle to obtain a pigment. The oscillator (manufactured by Asada Iron Works Co., Ltd.) was shaken for 1 hour as a preliminary disintegration, and then zirconia beads having a particle diameter of 2.0 mm were replaced, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and dispersed by a pigment oscillator. 4 hours as a formal disintegration, a color material dispersion R1 was obtained.

 (2) Manufacture of colored resin composition R1 for color filter  

11.29 parts by mass of the color material dispersion liquid R1 obtained in the above (1), 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, and a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.60 mass. , 2-methyl-1-(4-methylthiophenyl)-2-N- Orolinylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1 (light initiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene) Mercapto)-9H-carbazol-3-yl]-,1-(o-ethylindenyl) (photoinitiator: trade name ADEKA ARCS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass, fluorine-based 0.07 parts by mass of a surfactant (trade name: MEGAFEC F559, manufactured by DIC Co., Ltd.), a decane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 parts by mass, a mercapto compound (pentaerythritol oxime (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, PGMEA 5.85 parts by mass, and 3-methoxy-3-methyl-1-butyl acetate 3.92 parts by mass to obtain a colored resin composition R1 for a color filter.

 (3) Formation of colored layer  

The colored resin composition R1 obtained in the above (2) was applied to a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") having a thickness of 0.7 mm and a thickness of 0.7 mm, and then coated with a spin coater. The heating plate was dried at 80 ° C for 3 minutes, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and further post-baked in a dust-free oven at 230 ° C for 30 minutes, thereby adjusting the film thickness after hardening to 2.10 μm. The color layer R1 is formed by the film thickness.

 (Examples 2 to 11 and Comparative Example 1)    (1) Manufacture of color material dispersions R2~R9, RC1  

In Examples 2 to 6 and Comparative Example 1, in the case of (1) of Example 1, the dispersant a solution was replaced as shown in Table 2, and the type and amount of the dispersant were changed to the same solid content. The color material dispersions R2 to R6 were obtained in the same manner as in the above (1) except that the amount of the PGMEA was adjusted in a total amount of 100 parts by mass.

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

Further, in Comparative Example 1, in the first embodiment, (1), the dispersant a solution was replaced as shown in Table 2, and the type and amount of the dispersant were changed to the same mass parts as the solid portion. In the same manner as (1) of Example 1, except that the amount of PGMEA was adjusted to 100 parts by mass in total, and the type and amount of the color material were changed, the color material dispersion liquid RC1 was obtained.

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

In each of Examples 2 to 9 and Comparative Example 1, except for the color material dispersion liquid R1 in (2) of Example 1, the color material dispersion liquids R2 to R9 and RC1 were used as shown in Table 2, respectively. The film thickness was 2.10 μm, and the amount of the alkali-soluble resin was adjusted so that the P/V ratio was the value shown in Table 2, and the same procedure as in (2) of Example 1 was carried out to obtain a coloring resin for a color filter. Objects R2~R9, RC1.

Further, in Example 10, in addition to the alkali-soluble resin A solution in the third embodiment, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used, and an antioxidant (trade name: IRGANOX 1010 (1010), manufactured by BASF) was further added 0.03. The coloring resin composition R10 for a color filter was obtained in the same manner as in the second embodiment (2) except for the mass portion.

Further, in Example 11, except that in Example 10, as shown in Table 2, the photoinitiator was used in place of 0.04 parts by mass of IRG369, and an oxime ester photoinitiator (trade name TR-PBG-365) was used. (PBG365), 0.04 parts by mass of Changzhou Strong Electronic New Material Co., Ltd., and used oxime-based photoinitiator (trade name: TR-PBG-3057 (PBG3057), manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) instead of 0.02 parts by mass of NCI831 In the same manner as in (2) of Example 10 except for 0.02 parts by mass, a colored resin composition R11 for a color filter was obtained.

 (3) Formation of colored layer  

In (3) of Example 1, except that the colored resin composition R1 was used instead of the colored resin compositions R2 to R11 and RC1, respectively, the same procedure as in (3) of Example 1 was carried out 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 (ethyl urethane 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 to 23)    (1) Manufacture of color material dispersion R12~R23  

In the examples (1) to (2), the types and the blending amounts of the color materials were changed as shown in Table 3, and the amount of PGMEA was adjusted so as to be 100 parts by mass in total. The color material dispersion liquids R12 to R23 were obtained in the same manner as in the above (1).

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

In place of the color material dispersion liquid R3 in (2) of Example 11, the color material dispersion liquids R12 to 23 were respectively used, and the film thickness was 2.50 μm, and the P/V ratios were respectively shown in Table 3. In the same manner as in (2) of Example 11, except that the amount of the alkali-soluble resin was adjusted, the colored resin compositions R12 to R23 for color filters were obtained.

 (3) Formation of colored layer  

In (3) of Example 11, except that the colored resin composition R11 was used instead of the above-described colored resin compositions R12 to R23, the colored layers R12 to R23 were obtained in the same manner as in the above (3) of Example 11.

 (Comparative examples 2 to 7)    (1) Manufacture of color material dispersion RC2~RC7  

In Comparative Examples 2 to 7, in (1) of Example 1, except that the dispersant a solution was replaced as shown in Table 3, and the type and amount of the dispersant were changed to the same mass parts as the solid content, The color material dispersions RC2 to RC7 were obtained in the same manner as in the first embodiment (1) except that the amount of the color material and the blending amount were changed as shown in Table 3, and the amount of PGMEA was adjusted to 100 parts by mass.

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

In place of the color material dispersion liquid R3 in (2) of Example 11, the color material dispersion liquids RC2 to RC7 were used, respectively, and the P/V ratio was changed to the value shown in Table 3 in order to make the film thickness 2.50 μm. In the same manner as in (2) of Example 11, except that the amount of the alkali-soluble resin was adjusted, the colored resin compositions RC2 to RC7 for color filters were obtained.

 (3) Formation of colored layer  

In (3) of the example 11, the colored layers RC2 to RC7 were obtained in the same manner as in the above (3) except that the colored resin composition R11 was used instead of the colored resin composition 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 quality / solid content other than red color material) ratio = 0.2 and measurement of 2.5 μm coating film In the split light transmittance spectrum, the transmittance at a wavelength of 520 nm is 20% or less, and the transmittance at a wavelength of 640 nm is 70% or more, which corresponds 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 (ethyl urethane dispersant, solid content 30% by mass, manufactured by BYK Chemie)

6919: trade name Disperbyk-LPN6919 (polymer having a structural unit represented by the general formula (I), an amine price of 120 mgKOH/g, a solid content of 60% by mass, manufactured by BYK Chemie)

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

In the examples (1), the types of the color materials and the blending amount were changed as shown in Table 4, and the amount of the PGMEA was adjusted so as to be 100 parts by mass in total. The rest was carried out in the same manner as in (1) of Example 3 to obtain a color material dispersion liquid R24 to R41.

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

In place of the color material dispersion liquid R3 in (2) of Example 11, the above-described color material dispersion liquids R24 to R41 were used, and the film thickness was 2.80 μm, and the P/V ratios were respectively shown in Table 4. In the same manner as in (2) of Example 11, except that the amount of the alkali-soluble resin was adjusted, the colored resin compositions R24 to R41 for color filters were obtained.

 (3) Formation of colored layer  

In (3) of Example 11, except that the colored resin composition R11 was used, and the colored resin compositions R24 to R41 were used, the colored layers R24 to R41 were obtained in the same manner as in the above (3).

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

6.23 parts by mass of a dispersant c solution of Synthesis Example 3 as a dispersing agent, pyrrolopyrroledione pigment (BrDPP, trade name Irgaphor RED S 3621CF, manufactured by BASF Corporation) of the above chemical formula (2) as a color material, 13.0 mass 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 having a particle diameter of 2.0 mm were placed in a cannabis bottle as a pigment shaker (Asada Iron Works Co., Ltd.) The system was shaken for 1 hour as a preliminary disintegration, and then zirconia beads having a particle diameter of 2.0 mm were replaced, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and dispersed by a pigment shaker for 4 hours as a formal disintegration to obtain a red color. Color material dispersion r1.

In the above-mentioned red color material dispersion r1, in place of 13.0 parts by mass of the pyrrolopyrroledione pigment (BrDPP) represented by the above chemical formula (2) as a color material, CI Pigment Red 254 (product name: The red color material dispersion r2 was obtained in the same manner as the red color material dispersion r1 except that 13.0 parts by mass of Hostaperm Red D2B-COF LV3781 (manufactured by CLARIANT).

In the above-mentioned red color material dispersion liquid r1, in place of 13.0 parts by mass of the pyrrolopyrroledione pigment (BrDPP) represented by the above chemical formula (2) as a color material, CI Pigment Red 177 (product name: The Pariogen Red L 4045 (manufactured by BASF) was used in the same manner as the red color material dispersion liquid r1 except for 13.0 parts by mass, to obtain a red color material dispersion liquid r3.

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

 (2) Manufacture of colored resin composition R42 for color filter  

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 liquid r2, 1.92 parts by mass of the red color material dispersion liquid r3, and 4.15 parts by mass of the yellow color material dispersion liquid y, and the alkali obtained in Synthesis Example 8. 1.90 parts by mass of a soluble resin A solution, a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.), 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)- 2-N- Orolinylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene) Mercapto)-9H-carbazol-3-yl]-,1-(o-ethylindenyl) (photoinitiator: trade name ADEKA ARCS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass, fluorine-based 0.07 parts by mass of a surfactant (trade name: MEGAFEC F559, manufactured by DIC Co., Ltd.), a decane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 parts by mass, a mercapto compound (pentaerythritol oxime (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, PGMEA 5.85 parts by mass, and 3-methoxy-3-methyl-1-butyl acetate 3.92 parts by mass to obtain a colored resin composition R42 for a color filter.

 (3) Formation of colored layer  

In (3) of Example 1, except that the colored resin composition R1 was used instead of the colored resin composition R41, the same procedure as in (3) of Example 1 was carried out to obtain a colored layer R42.

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

 (Examples 43 to 48)    (1) Manufacture of color material dispersion R47  

In Example 47, in (1) of Example 1, except that the dispersant a solution was replaced as shown in Table 5, the dispersant g solution was used, and the solid portion was changed to the same mass portion, and the total amount was The color material dispersion liquid R47 was obtained in the same manner as in the above (1) except that the amount of PGMEA was adjusted to 100 parts by mass.

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

In Example 43, except that the alkali-soluble resin B solution obtained in Synthesis Example 9 was used instead of the alkali-soluble resin A solution in Example 3, and further, for the photoinitiator, as shown in Table 5, 0.04 parts by mass of IRG369 was replaced. Further, 0.02 parts by mass of an oxime ester photoinitiator (trade name: Irgacure OXE 01 (OXE01), manufactured by BASF Corporation) was used, and 0.02 mass parts of NCI831 was used instead of the oxime ester photoinitiator (trade name Irgacure OXE 02 (OXE02). In the same manner as (2) of the third embodiment, a colored resin composition R43 for a color filter was obtained, except that it was 0.04 parts by mass.

Further, in Example 44, an antioxidant (trade name ADEKA STAB AO-40 (AO-40) was used instead of 0.03 parts by mass in place of the antioxidant (trade name: IRGANOX 1010 (1010), manufactured by BASF) in Example 11. In the same manner as (2) of Example 11, except that 0.03 parts by mass of ADEKA was used, a colored resin composition R44 for a color filter was obtained.

Further, in Example 45, in addition to 0.03 parts by mass of the antioxidant (product name IRGANOX 1010 (1010), manufactured by BASF Corporation) in Example 11, 0.04 mass of the latent antioxidant (compound a) of Synthesis Example 10 was used. In the same manner as in the above (2), the coloring resin composition R45 for a color filter was obtained.

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

In the same manner as in (2) of Example 3 except that the color material dispersion liquid R47 was used instead of the color material dispersion liquid R3 in Example 3, a colored resin composition for color filters R47 was obtained. .

In Example 48, a color material dispersion liquid R47 was used instead of the color material dispersion liquid R3 in Example 43, and an antioxidant (trade name: ADEKA STAB AO-40 (AO-40), manufactured by ADEKA) was added in an amount of 0.03 parts by mass. In the same manner as (2) of Example 43 except that the ultraviolet absorber (benzotriazole-based compound, trade name: TINUVIN 329, manufactured by BASF) was used in an amount of 0.03 parts by mass, a colored resin composition R48 for a color filter was obtained.

 (3) Formation of colored layer  

In (3) of the first embodiment, the colored layers R43 to R48 were obtained in the same manner as in the above (3) except that the colored resin composition R1 was used instead of the colored resin composition R1.

 [Evaluation method]    <Dispersibility evaluation of color material dispersion>  

The viscosity of the color material dispersion obtained in the examples and the comparative examples was measured immediately after preparation and after storage at 25 ° C for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. The viscosity was measured using a vibrating viscometer to measure a viscosity of 25.0 ± 0.5 °C. The results are shown in Tables 2 to 5.

 (Standard of viscosity stability evaluation)  

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

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

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

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

In addition, it is a value when the color material is 13 mass % with respect to the total mass of the solvent containing the color material dispersion liquid.

In the evaluation result, the color material dispersion liquid of C is practically used. However, when the evaluation result is B, the color material dispersion liquid is more excellent, and when the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

 <Optical performance evaluation, comparative evaluation>  

The contrast and chromaticity (x, y) and luminance (Y) of the coloring layers obtained in the examples and the comparative examples were measured using a large-spectrum electronic spectroscopic characteristic measuring device LCF-1500M and a pot-and-yellow comparative measuring device CT-1B.

 (Comparative evaluation benchmark)  

The value of x is set to 0.570~0.600 under C light source.

AA: More than 10,000

A: 8000~10000

B: 6000~7999

C: less than 6000

‧The value of x is set to 0.607~0.630 under C light source

AA: More than 9000

A: 7000~9000

B: 5000~6999

C: less than 5000

‧The value of x is set to 0.650~0.693 under C light source

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 retardation (Rth) in the thickness direction calculated by the following formula. The retardation (Rth) was measured using a phase difference measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS Co., Ltd.). The measurement wavelength of the red colored layer was measured at 620 nm and 665 nm.

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

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

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

Nz: refractive index in the thickness direction

d: film thickness (nm)

 <Evaluation of solvent resolubility>  

The front end of the 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 the comparative examples, and applied to the 1 cm long portion of the glass substrate. The glass substrate which was pulled up was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23 ° C and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film adhered was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually discriminated and evaluated.

 (Solvent resolubility evaluation standard)  

AA: Dry film is completely dissolved below 8 seconds

A: The dry coating film is completely dissolved

B: a thin film of a dried coating film is produced in a solvent, and the solution is colored.

C: no thin film of the dried coating film was produced in the solvent, and the solution was not colored.

When the evaluation criteria are AA, A or B, it is evaluated that the solvent resolubility is good, and it can be used practically without problems. When the evaluation result is A and further AA, the effect is further improved.

 <Development residue evaluation>  

The color filter composition for the color filter obtained in the examples and the comparative examples was applied to a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. After coating, it was dried at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. To the glass plate on which the colored layer was formed, a 0.05% by mass aqueous potassium hydroxide solution was used as an alkali developing solution for 60 seconds of shower development. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (manufactured by Toray Industries, Inc., trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the lens was visually observed. The degree of coloring of the cleaning cloth.

 (Development residue evaluation standard)  

AA: Even if the color layer of 3.5 μm thick was subjected to the same evaluation, the development residue was not visually observed, and the lens cleaning cloth was completely free from coloring.

A: The development residue was not visually confirmed, and the lens cleaning cloth was completely colorless.

B: The development residue was not visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

C: A slight development residue was visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

D: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

If the above evaluation criteria are AA, A, B or C, it can be used practically without problems. However, if the evaluation result is B, further A, or even AA, the effect is further superior.

 <Development resistance evaluation>  

The colored resin compositions for the color filters obtained in the examples and the comparative examples were coated on a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm, using a spin coater. After drying at 80 ° C for 3 minutes using a hot plate, ultraviolet rays of 40 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. The film thickness at this time was measured and set to T1 (μm). Thereafter, shower development was carried out using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution. The film thickness after development was measured and set to T2 (μm). Calculate T2/T2×100 (%).

 (Development resistance evaluation standard)  

AA: 98% or more

A: 95% or more and less than 98%

B: 90% or more and less than 95%

C: less than 90%

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

 <Water Infiltration Evaluation>  

The color filter composition of the color filter obtained in the examples and the comparative examples was baked on a glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.), and then baked to a thickness of 1.6 μm using a spin coater. After the film thickness of the color layer was applied, the film was dried at 60 ° C for 3 minutes using a hot plate, and then an ultraviolet ray of 60 mJ/cm ^{2 was} entirely irradiated with an ultrahigh pressure mercury lamp through a mask to form a coloring layer on the glass substrate. Subsequently, 0.05% by weight of potassium (KOH) was used as a developing solution for rotary development, and after contact with the developing solution for 60 seconds, it was washed with pure water to carry out development treatment, and the washed substrate was rotated for 10 seconds to be centrifuged to remove water. Water contact was evaluated by measuring the contact angle of pure water as follows.

The contact angle of pure water was measured by dropping the droplets of 1.0 μL of pure water on the surface of the colored layer immediately after centrifugation to remove water, and measuring the static contact angle after 10 seconds of dropping according to the θ/2 method. The measurement apparatus was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.

 (water infiltration evaluation benchmark)  

AA: contact angle of 80 degrees or more

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

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

C: contact angle of 50 degrees or more and less than 65 degrees

D: The contact angle is less than 50 degrees

If the water percolation evaluation standard is AA, A or B, it can be used practically without problems, but if the evaluation result is A or even AA, the effect is more excellent.

 <SiN adhesion evaluation>  

The colored resin compositions for the color filters obtained in the examples and the comparative examples were coated on a SiN substrate (manufactured by Foresight Co., Ltd.) using a spin coater, and then dried at 80 ° C for 3 minutes using a hot plate. Ultraviolet rays of 60 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp, and post-baking was performed for 30 minutes in a 230 ° C dust-free furnace, whereby the film thickness was adjusted so that the film thickness after hardening became 2.10 μm, and the coloring layer was formed.

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

 (SiN adhesion evaluation standard)  

AA: All plaids are not stripped

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

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

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

 [Results integration]  

As can be seen from the results of the table, Examples 1 to 41 in which the above-mentioned specific yellow color material is combined with a red color material, and a dispersant belonging to a polymer having a constituent monomer represented by the general formula (I) is further combined, and The color material dispersion of 47 has good viscosity stability. On the other hand, it was found that the color material dispersion liquid of Comparative Example 1 in which a conventional yellow color material or a urethane dispersant was combined with a red color material was found to have deteriorated viscosity stability. Moreover, it was clarified that the color material dispersion of Comparative Example 2 in which the urethane dispersant was combined was inferior in viscosity stability even when the above-mentioned specific yellow color material was combined with the red color material.

Further, in the color material dispersion liquid of Comparative Examples 3 to 7 in which the conventional yellow color material was combined with the red color material, the viscosity was stable even when a dispersant belonging to the polymer having the constituent monomer represented by the general formula (I) was used. Deterioration of sex.

Further, it is known that the above-described specific yellow color material is combined with the red color material, and the color filters of Examples 1 to 48 belonging to the polymer having the constituent monomer of the general formula (I) are further combined. The coloring resin composition for a sheet has a good dispersion stability of the coloring material, and the phase difference value of the coloring layer using the colored resin composition is lowered, and the contrast is excellent. Further, it was found that the coloring layers using the colored resin compositions of Examples 1 to 48 were excellent in adhesion to SiN, and the colored resins of Examples 11, 44, 45, 46, and 48 were used. The coloring layer of the composition is superior to SiN. Further, in Example 10, the adhesion to SiN was close to A of AA, which was good.

On the other hand, in Comparative Examples 1 and 3 to 7 in which the color materials different from the examples were combined, compared with the examples of the same chromaticity coordinates (x, y), the deterioration and the phase difference were large.

Further, even when the above-mentioned specific yellow color material was combined with the red color material, Comparative Example 2 in which the urethane dispersant was combined was compared with the example of the same chromaticity coordinate (x, y), and the contrast was deteriorated. The phase difference becomes larger.

Further, in Comparative Examples 1 and 3 to 7, the P/V ratio of the colored resin composition tends to be larger than that of the examples of the same chromaticity coordinates (x, y), and the adhesion to SiN is also deteriorated. .

Further, in Comparative Example 1, the examples of the same chromaticity coordinates (x, y) were also deteriorated in terms of solvent resolubility, suppression of development residue, development resistance, and water bleeding.

In the examples in which the alkali-soluble resin contains both the maleic acid imide structure having a hydrocarbon ring and the styrene structure and the antioxidant is added, the development residue is suppressed and the luminance is improved. Colored layer.

Further, it has been found that when two kinds of oxime ester-based photoinitiators are used in combination with an antioxidant, a coloring layer having improved development resistance and brightness is formed. Among them, from the viewpoint of superior luminance, it is preferred to use an oxime ester photoinitiator having an anthracene skeleton in combination with an oxime ester photoinitiator having diphenyl sulfide; the effect of inhibiting water permeation becomes high. From the viewpoint of the above, it is preferred to use an oxime ester photoinitiator having a carbazole skeleton in combination with an oxime ester photoinitiator having diphenyl sulfide.

Further, 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, and a coloring layer having a reduced retardation value and improved luminance was formed. Example 44 is a comparison of A close to AA to give a comparatively enhanced colored layer.

Further, in Example 45, in which a latent antioxidant was used, the phase difference was reduced, and the contrast was also A close to AA, and a coloring layer which was improved in comparison was obtained.

Further, in Example 46 using an ultraviolet absorber, the phase difference was reduced, and the contrast was also A close to AA, and a coloring layer which was improved in comparison was obtained.

Further, an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having diphenyl sulfide are used in combination, and a molecular weight of 500 or less and a molecular weight of 200 per phenolic hydroxyl group are used in combination. In Example 48, which is a hindered phenol-based antioxidant having an equivalent weight or less, and a UV absorber, a coloring layer having a reduced phase difference and improved luminance and improved water bleeding effect was formed. Example 48 is also a close to AA A, giving a comparatively enhanced coloring layer.

Claims (14)

A color material dispersion liquid for a color filter, which is a color material dispersion liquid containing a color material, a dispersant, and a solvent, wherein the color material comprises a red color material and a yellow color material; and the yellow color material contains: At least one anion of the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound and the tautomeric structure of the tautomeric structure represented by the following general formula (A); selected from the group consisting of Cd, Co, and Al, An ion of at least two metals of a group consisting of Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a compound represented by the following general formula (B); the above dispersant has the following general formula (I) ) an aggregate of the constituent units shown; (In general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, decylamino, alkylamino or arylamine, and R ^{b is} independently -OH or -NH ₂ ;) (In the general formula (B), R ^{c is} independently a hydrogen atom or an alkyl group;) (In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure).  The color material dispersion liquid for a color filter according to claim 1, wherein the red color material comprises a pyrrolepyrrole-based pigment, a naphthol-based azo pigment, an anthraquinone pigment, and an anthraquinone pigment. At least one of the groups.    The color material dispersion liquid for a color filter according to claim 1 or 2, wherein at least two of the yellow color materials contain Ni and are further selected from the group consisting of Cd, Co, Al, Cr, Sn, and Pb. At least one metal of the group consisting of Zn, Fe, Cu, and Mn.    The color material dispersion liquid for a color filter according to claim 1 or 2, wherein at least two of the yellow color materials are Ni and Zn, or Ni and Cu.   A colored resin composition for a color filter, comprising a color material, a dispersant, a binder component, and a solvent; wherein the color material comprises a red color material and a yellow color material; and the yellow color material comprises: At least one anion of the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound and the tautomeric structure of the tautomeric structure represented by the following general formula (A); selected from the group consisting of Cd, Co, and Al, An ion of at least two metals of a group consisting of Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a compound represented by the following general formula (B); the above dispersant has the following general formula (I) ) an aggregate of the constituent units shown; (In general formula (A), R ^{a is} independently -OH, -NH ₂ , -NH-CN, decylamino, alkylamino or arylamine, and R ^{b is} independently -OH or -NH ₂ ;) (In the general formula (B), R ^{c is} independently a hydrogen atom or an alkyl group;) (In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure).  The colored resin composition for a color filter according to claim 5, wherein the red color material comprises a pyrrolopyrrolidone pigment, a naphthol azo pigment, an anthraquinone pigment, and an anthraquinone pigment. At least one of the groups.    The colored resin composition for a color filter according to claim 5, wherein at least two of the yellow color materials contain Ni and are further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, and Zn. At least one metal of the group consisting of Fe, Cu, and Mn.    The colored resin composition for a color filter according to claim 5, wherein at least two of the yellow color materials are Ni and Zn, or Ni and Cu.    The coloring resin composition for a color filter according to claim 5, wherein the binder component contains an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and the photoinitiator is a hydrazine initiator.    A colored resin composition for a color filter according to claim 5, which further contains an antioxidant.    A colored resin composition for a color filter according to claim 9, which further contains an antioxidant.    The colored filter composition for a color filter according to claim 5, wherein the chromaticity coordinates in the XYZ color system of JIS Z8701 which can be formed using the C light source are x=0.550~0.700, y=0.290~ A cured film in the range of 0.450.    A color filter comprising at least one of a substrate and a coloring layer provided on the substrate, wherein at least one of the colored layers is a colored resin for a color filter according to any one of claims 5 to 12. A hardened substance of the composition.    A display device characterized by having a color filter of claim 13.