JP6768302B2 - Colored resin compositions for color filters, color filters, and display devices - Google Patents

Description

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

Many thin image display devices such as displays, so-called flat panel displays, have been put on the market because they are thinner than CRT displays and do not take up space in the depth direction. The market price is becoming more affordable year by year with the evolution of production technology, the demand is expanding further, and the production volume is also increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TVs. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emission display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and the light passes through a color filter to express colors. Therefore, color filters are indispensable for the color expression of LCD TVs, and they also play a major role in affecting the performance of displays. Further, in the organic light emitting display device, there are cases where the color adjustment of the pixels is performed by using a color filter, and there are cases where a color filter is used for the organic light emitting element of white light emission to form a color image in the same manner as the liquid crystal display device.

As a trend in recent years, there is a demand for power saving of image display devices, and in particular, there is a demand for higher brightness of color filters in order to improve the utilization efficiency of backlights. This is a major issue especially for mobile displays (mobile phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of electricity stored in mobile devices is still finite, while the power consumption tends to increase as the screen size increases. An image display device including a color filter influences the design and performance of the mobile terminal because it is directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.
In the method for forming such a colored layer, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a coloring material has been widely used. However, it has become difficult for conventional color filters using pigments to meet the current demand for higher brightness.

As one means for achieving high brightness, a photosensitive resin composition for a color filter using a dye having a high transmittance is generally studied, and further, in order to improve the heat resistance and light resistance of the dye. It is being considered to use a rake colorant in which the dye is insolubilized.
Dyes generally have higher transmittance than pigments and can produce high-brightness color filters, but they have poor heat resistance and light resistance, and the chromaticity is likely to change during high-temperature heating in the color filter manufacturing process. There was a problem. Further, the colored resin composition used by dissolving the dye has many problems in being used as a color filter application, for example, foreign matter is easily deposited on the surface of the cured coating film in the drying step and the contrast is remarkably lowered.

For example, Patent Document 1 discloses a blue pigment for a color filter, which comprises a basic triarylmethane dye, one or more elements selected from tungsten, silicon, and phosphorus, and an anion containing oxygen as an essential element. It is said that by using the pigment, it is possible to provide a liquid crystal display device which has less color change at the time of high-temperature firing and can display a liquid crystal having excellent brightness for a long period of time. In the photocurable composition of Patent Document 1, a polyester acrylate resin and a polyfunctional acrylate compound, which are photocurable compounds, are used as binder components.

Patent Document 2 describes a specific coloring resin composition for a color filter, which comprises a specific coloring material containing a divalent or higher cation in which a plurality of dye skeletons are crosslinked by a cross-linking group and a divalent or higher anion. Color filters and the like using color materials are disclosed. According to Patent Document 2, by using a colored resin composition for a color filter containing the above-mentioned coloring material, it is possible to form a colored layer having high contrast, excellent solvent resistance and electrical reliability. In the colored resin composition for a color filter of Patent Document 2, an acrylic copolymer having a carboxyl group corresponding to an alkali-soluble resin and a polyfunctional acrylate compound are used as a binder component.

Further, Patent Document 3 includes a colorant composed of a copper phthalocyanine blue pigment and a metal lake pigment of a xanthene dye as a blue coloring composition of a color filter capable of high brightness, a wide color reproduction region, and a high contrast ratio. A blue coloring composition for a color filter is disclosed. In the blue coloring composition for a color filter of Patent Document 3, an acrylic resin solution corresponding to an alkali-soluble resin and a polyfunctional acrylate compound are used as binder components.

On the other hand, Patent Document 4 contains a polyamide-imide resin soluble in a general-purpose solvent, and can produce a cured product having excellent transparency and storage stability and long pot life even when blended with a curable resin. For the purpose of providing a curable resin composition and a cured product thereof, an isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure is reacted with a tricarboxylic acid anhydride to produce a polyamide-imide resin. A curable resin composition containing an alcohol-modified polyamide-imide resin obtained by reacting an alcohol compound, an alcohol-modified polyamide-imide resin, and a curable resin and / or a reactive diluent is described. However, Patent Document 4 does not describe any colored resin composition for a color filter containing a coloring material and a dispersant.

Japanese Unexamined Patent Publication No. 2011-186043 International Publication No. 2012/144521 JP-A-2010-026334 International Publication No. 2015/008744

When a conventionally used pigment is used as the coloring material, there is a problem that the brightness is lowered due to the low transmittance of the pigment, and when a dye or a rake coloring material is used, a color filter is manufactured. There is a problem that the brightness decreases after the post-baking process in the process. However, as described above, it is particularly required to increase the brightness of the color filter, and at the same time, it is required to further improve the contrast.
Further, in recent color filters, it is necessary to solve various problems in mass production of color filters with the technology for improving the dispersibility of color materials in order to realize the demand for high brightness and high contrast. There is. That is, in order to increase the concentration of the coloring material in the resin composition, it is inevitably necessary to increase the amount of the dispersant, which causes problems such as delay in development time. However, if a component that enhances alkaline developability is used, traces of water stains are likely to occur after alkaline development and rinsing with pure water (hereinafter, this phenomenon is referred to as "water stain"). There is. Since such water stains disappear after post-baking, there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the appearance inspection of the patterning surface after development, and it is not possible to distinguish between a normal product and an abnormal product. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, as a result, the yield of the final color filter product is lowered, which becomes a problem. Therefore, with the aim of increasing the brightness and contrast of the image, reducing the cost, and improving the manufacturing stability, the developability in the development process of the photolithography method is improved, and the occurrence of water stains after development is suppressed. Is required to do. As described in Patent Documents 2 and 3, acrylic resins are often used as conventional alkali-soluble resins because their performance can be easily adjusted by the monomer type and composition, and they are easy to synthesize and inexpensive. I came. However, there is a further demand for the use of an alkali-soluble resin that has good developability and can suppress the occurrence of water stains after development while improving brightness and contrast.

The present invention has been made in view of the above circumstances, and is capable of forming a colored layer with improved brightness and contrast, has good developability, and is colored for a color filter in which water stain generation after development is suppressed. Provided are a resin composition, a color filter having a colored layer formed by using the colored resin composition for a color filter, improved brightness and contrast, and improved productivity, and a display device using the color filter. The purpose is.

The coloring resin composition for a color filter according to the present invention contains a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent for coloring for a color filter. It is characterized by being a resin composition.

(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)

(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) , And (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue that may independently have a substituent having 6 to 20 carbon atoms. Re is an independent substance. Represents a residue obtained by removing the hydroxyl group from the alcohol compound.)

In the colored resin composition for a color filter of the present invention, the polyamide-imide resin has the Rc of the general formula (A) and at least one of the resin terminals of the general formulas (C4), (C5) and (C6). By including the structural unit represented by (C9) or (C10), it is possible to form a colored layer having improved brightness and contrast, the colored resin composition is excellent in solvent resolubility, and the development time is longer. It is preferable because it is shortened.

In the colored resin composition for a color filter of the present invention, the polyamide-imide resin containing an unsaturated double bond group can form a colored layer with improved brightness and contrast, and further, a residual film of the colored layer. It is preferable because the rate is improved.

In the colored resin composition for a color filter of the present invention, further containing an acrylic resin having an acid value of 50 KOH mg / g or more can form a colored layer with improved brightness and contrast, and further, the colored resin composition. It is preferable from the viewpoint of improving the stability over time and the solvent resolubility.

In the colored resin composition for a color filter of the present invention, it is preferable that the coloring material is a rake coloring material from the viewpoint of further improving the brightness of the color filter.

In the colored resin composition for a color filter of the present invention, the color material is a rake color material represented by the following general formula (I), which is excellent in heat resistance and light resistance, and provides a high-brightness color filter. It is preferable because it can be formed.

(In the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. ^Bc− contains at least tungsten. Represents a c-valent polyacid anion. R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱ . R ⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ^{i to} R ^v and Ar ¹ may be the same or different, respectively. A and c represent two or more integers, b and d represent one or more integers. E is 0 or 1, and when e is 0, the coupling is It does not exist. Multiple e may be the same or different.)

In the colored resin composition for a color filter of the present invention, the color is that the dispersant is a polymer having a structure represented by the following general formula (1) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. It is preferable from the viewpoint of improving the contrast and brightness of the filter.

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁵ )). -CH (R ⁶ ) -O] _x- CH (R ⁵ ) -CH (R ⁶ )-or-[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- divalent organic group , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R ⁶ is an independent hydrogen atom or methyl group, respectively.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the colored resin composition for a color filter of the present invention, the solvent contains propylene glycol monomethyl ether acetate, and further, 3-methoxy-3-methyl-1-butanol and 3-methoxy-3-methyl-1-butyl. It is preferable that at least one solvent selected from acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol monomethyl ether may be contained from the viewpoint of improving the contrast and brightness of the color filter.

The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It is characterized by having a colored layer made of a cured product of the product.

The display device according to the present invention is characterized by having the color filter according to the present invention.

The present invention has been made in view of the above circumstances, and is a colored resin for a color filter capable of forming a colored layer having improved brightness and contrast, having good developability, and suppressing the occurrence of water stains after development. To provide a composition, a color filter having a colored layer formed by using the colored resin composition for the color filter, improved brightness and contrast, and improved productivity, and a display device using the color filter. Can be done.

FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the display device of the present invention. FIG. 3 is a schematic cross-sectional view showing another example of the display device of the present invention. FIG. 4 is a schematic diagram showing the molecular association state of the coloring material represented by the general formula (I).

Hereinafter, the colored resin composition for a color filter, the color filter, and the display device according to the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, the organic group means a group having one or more carbon atoms.
Further, in the present invention, the solid content means all components other than the solvent constituting the colored resin composition, and even a liquid monomer is contained in the solid content.

1. 1. Colored Resin Composition for Color Filters The colored resin composition for color filters according to the present invention comprises a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent. It is characterized by containing.

(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)

(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) , And (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.)

The colored resin composition for a color filter of the present invention is good because a colored layer having improved brightness and contrast can be formed by using the polyamide-imide resin having the specific repeating unit as a binder resin or an alkali-soluble resin. It is a colored resin composition for a color filter that has developability and suppresses the occurrence of water stains after development, and can form a color filter having improved brightness and contrast with excellent productivity.

The action of exerting the above-mentioned effect by the above-mentioned specific combination is presumed as follows, although there is an unclear part.
Since the specific polyamide-imide resin contains an isocyanurate structure derived from an aliphatic diisocyanate contained in the repeating unit represented by the general formula (A), it can be used as a suitable solvent for producing a color filter as described later. It is presumed that it has solubility, has a higher glass transition temperature than conventional acrylic resins, is rigid, has good packing between resins, and becomes a dense film when formed into a film. Therefore, when the colored layer is formed by using the specific polyamide-imide resin as a binder component, the movement of the colored material in the colored layer is suppressed and oxygen is also difficult to penetrate, so that the decomposition or oxidation of the colored material is further suppressed. It is presumed that the brightness is improved as compared with the conventional case because the fading of the coloring material is suppressed even after the color filter manufacturing process.
Further, it is estimated that the specific polyamide-imide resin has good contrast with the coloring material in addition to suppressing aggregation of the coloring materials due to the above-mentioned effect, so that the contrast is also improved as compared with the conventional one. Will be done.
Further, since the specific polyamide-imide resin contains an isocyanurate structure derived from an aliphatic diisocyanate, it tends to contain an acidic group at the terminal, and has high solubility in an alkaline developer and is excellent in developability, as described above. It is presumed that the formation of water stains after development is suppressed because the film is dense and highly hydrophobic due to its structural features.

The colored resin composition for a color filter of the present invention contains at least a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the general formula (A), and a solvent. If necessary, other components may be further contained as long as the effects of the invention are not impaired. Examples of other components include other alkali-soluble resins different from the specific polyamide-imide resin, polyfunctional monomers, initiators, and other optional additive components.
Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail in order from the polyamide-imide resin having the repeating unit represented by the general formula (A), which is characteristic of the present invention.

[Polyamide-imide resin]
The polyamide-imide resin used in the present invention is a polyamide-imide resin having a repeating unit represented by the general formula (A). The polyamide-imide resin functions as a binder resin and also functions as an alkali-soluble resin because it contains an acidic group in the molecule.
The specific polyamide-imide resin may be used alone or in combination of two or more.

In the general formula (A), Ra independently represents a residue of a divalent aliphatic diisocyanate, contains an isocyanurate-type polyisocyanate structural unit synthesized from an isocyanate having an aliphatic structure, and Rb is each. It independently comprises a residue of tricarboxylic acid anhydride or tetracarboxylic acid anhydride, and at least one of Rb contains a residue of tricarboxylic acid anhydride. Since the polyamide-imide resin used in the present invention has such a structure in the general formula (A), it is also soluble in a general-purpose solvent useful for a color filter as described later.

Ra independently represents a residue of divalent aliphatic diisocyanates, that is, a partial structure obtained by removing two isocinate groups from divalent aliphatic diisocyanates. Examples of the divalent aliphatic diisocyanates include linear aliphatic diisocyanates and cyclic aliphatic diisocyanes, for example, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (HTMDI), isophorone diisocyanate (IPDI), and the like. Examples thereof include 4,4'-dicyclohexamethylene diisocyanate, hydrogenated tolylene diisocyanate (HTDI), hydrogenated xylene diisocyanate (HXDI), norbornan diisocyanate (NBDI), and hydrogenated diphenylmethane diisocyanate.

In the general formula (A), the isocyanurate-type polyisocyanate structural unit synthesized from the divalent aliphatic diisocyanates is contained, and the isocyanurate-type polyisocyanate synthesized from the diisocyanates includes, for example, hexamethylene diisocyanate. Isocyanurate-type triisocyanate (HDI3N) synthesized from, isocyanurate-type triisocyanate (HTMDI3N) synthesized from trimethylhexamethylene diisocyanate, isocyanurate-type triisocyanate (IPDI3N) synthesized from isophorone diisocyanate, hydrogenated tolylene diisocyanate. From isocyanurate-type triisocyanate (HTDI3N) synthesized from, isocyanurate-type triisocyanate (HXDI3N) synthesized from hydrogenated xylene diisocyanate, isocyanurate-type triisocyanate (NBDI3N) synthesized from norbornan diisocyanate, hydrogenated diphenylmethane diisocyanate. Examples thereof include the synthesized isocyanurate type triisocyanate (HMDI3N). These may be used together or alone.

In the general formula (A), Ra is a residue of divalent cyclic aliphatic diisocyanates independently of each other, which further improves the brightness of the colored layer and suppresses the occurrence of water stains. preferable. Among them, Ra is preferably a residue of isophorone diisocyanate from the viewpoint of further improving the brightness of the colored layer and suppressing the occurrence of water stains.
The content of residues of divalent cyclic aliphatic diisocyanates in all Ra is based on the mass of the divalent aliphatic diisocyanate that induces Ra, that is, (the divalent cyclic fat that induces Ra). The total amount of group diisocyanates / the total amount of divalent aliphatic diisocyanates that induce Ra) is 50% by mass to 80% by mass from the viewpoint of further improving the brightness of the colored layer and suppressing the occurrence of water stains. Preferably, 80% by mass to 100% by mass is more preferable, and 100% by mass is most preferable.

In the general formula (A), Rb is a structural unit represented by the general formula (B1), (B2) or (B3), and Rd independently contains substituents having 6 to 20 carbon atoms. Aromatic or aliphatic tricarboxylic acid residue or tetracarboxylic acid residue which may have, that is, carboxyl of aromatic or aliphatic tricarboxylic acid or tetracarboxylic acid which may have a substituent having 6 to 20 carbon atoms. Represents a partial structure excluding groups.
The aromatic or aliphatic tricarboxylic acid residue or tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms may have a substituent having 6 to 20 carbon atoms, respectively. It is introduced by the reaction of an aliphatic tricarboxylic acid anhydride or a tetracarboxylic acid anhydride with an isocyanate group.

Examples of the aromatic tricarboxylic acid anhydride which may have a substituent having 6 to 20 carbon atoms include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride and the like. Further, examples of the aliphatic tricarboxylic acid anhydride having a substituent having 6 to 20 carbon atoms include linear aliphatic tricarboxylic acid anhydride and cyclic aliphatic tricarboxylic acid anhydride, and examples thereof include propanetricarboxylic acid. Examples thereof include anhydrides, cyclohexanetricarboxylic acid anhydrides, methylcyclohexanetricarboxylic acid anhydrides, cyclohexcentricarboxylic acid anhydrides, and methylcyclohexcentricarboxylic acid anhydrides. As the tricarboxylic acid anhydride, one kind or a mixture of two or more kinds can be used.
Examples of the cyclohexane tricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and cyclohexane-1. , 2,3-Tricarboxylic acid-2,3-anhydride and the like. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride from the viewpoint of forming a polyamide-imide resin having excellent solvent solubility, further improving the brightness of the colored layer, and suppressing the occurrence of water stains. Is preferable.

Examples of aromatic or aliphatic tetracarboxylic dianhydrides that may have a substituent having 6 to 20 carbon atoms include pyromellitic dianhydride and benzophenone-3,3', 4,4'-tetracarboxylic dianhydride. An anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, Bensen-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3'4,4'- Tetetracarboxylic dianhydride, biphenyl-2,2'3,3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4 5-Tetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl -1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Dichloride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Ethylene, Fetentene-1,3,9,10-Tetracarboxylic dianhydride, Belylene-3,4,9,10-Tetracarboxylic dianhydride, Bis (2,3-dicarboxyphenyl) methanedianhydride Mono, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,11 bis (3,4-dicarboxyphenyl) Etan dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) An anhydride of a tetracarboxylic acid having an aromatic group in the molecule, such as carboxyphenyl) sulfone dianhydride and bis (3,4-dicarboxyphenyl) ether dianhydride, or cyclohexane-1,2,4,5- Examples thereof include tetracarboxylic dianhydride and cyclohexane-1,2,3,4-tetracarboxylic dianhydride, and one or more of these can be used.

Rb is a structural unit represented by the general formula (B1), (B2) or (B3), and at least one is a structural unit represented by the general formula (B1) or (B2). The polyamide-imide resin having the repeating unit represented by the general formula (A) used in the present invention may be synthesized by mixing tricarboxylic acid anhydride and tetracarboxylic acid anhydride, but it is always tricarboxylic acid anhydride. Is synthesized using.
The blending ratio (molar ratio) ((B3) / (B1 + B2)) of the tetracarboxylic acid anhydride (B3) and the tricarboxylic acid anhydride (B1 + B2) is preferably 0 to 2, and further 0 to 1. It is preferably a ratio. If the blending ratio of the tetracarboxylic dianhydride (B3) exceeds this range, the concentration of the imide bond may increase and the solvent solubility may not always be sufficient.

In the general formula (A), Rc is the general formula (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or It is a structural unit represented by (C10), and Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may independently have a substituent having 6 to 20 carbon atoms. is there. The aromatic or aliphatic tricarboxylic acid residue or tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms may be the same as described above, and thus the description thereof is omitted here.
The polyamide-imide resin used in the present invention is Rc because no isocyanate group remains on the terminal side of the isocyanurate-type polyisocyanate that binds to Ra, and the stability of the obtained polyamide-imide resin is good. Is preferable.
The polyamide-imide resin used in the present invention has an acidic group in the molecule and functions as an alkali-soluble resin. Therefore, the polyamide-imide resin contains an acidic group at least one of Rc and the resin terminal.

In the structural unit represented by the general formula (C4), (C5), (C6), (C9), or (C10), Re independently represents a residue obtained by removing a hydroxyl group from an alcohol compound. The polyamide-imide resin is represented by the general formula (C4), (C5), (C6), (C9), or (C10) at least one of the Rc and the resin terminal of the general formula (A). It contains a structural unit, that is, it contains a residue obtained by removing a hydroxyl group from an alcohol compound (hereinafter, a polyamide-imide resin containing a residue obtained by removing a hydroxyl group from an alcohol compound may be referred to as an "alcohol-modified polyamide-imide resin". ) Is preferable because the colored resin composition has excellent solvent resolubility and the development time is shorter.
Here, the solvent resolubility means the property that the solid content of the colored resin composition once dried dissolves in the solvent again, and a person having such a property is required in the manufacturing process of the color filter. .. For example, if the colored resin composition adheres to the tip of the die lip during coating with a die coater, a solidified product is generated by drying, but the solidified product must be easily dissolved in the colored resin composition when the coating is resumed. , The solidified substance on the die lip is partially peeled off and easily adheres to the colored layer of the color filter, which causes foreign matter defects. In particular, when the concentration of the coloring material of the colored resin composition is increased in order to increase the brightness, the solvent resolubility tends to be insufficient, and the decrease in yield due to the generation of the above-mentioned foreign matter in the manufacturing process of the color filter becomes a problem. Was there.

The alcohol-modified polyamide-imide resin is obtained by producing a polyamide-imide resin described later and then subjecting an alcohol compound to an esterification reaction with an acid anhydride group of the polyamide-imide resin.
Examples of the alcohol compound for introducing a residue obtained by removing the hydroxyl group from the alcohol compound include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, and ethylene glycol. , Propylene glycol, trimethylolpropane, benzyl alcohol and other alcohols with 10 or less carbon atoms; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, Alcohols with 10 or less carbon atoms containing ether bonds such as 3-methoxy-1-butyl alcohol and 2-isopropoxyethyl alcohol; alcohols having 10 or less carbon atoms containing ketone groups such as 3-hydroxy-2-butanone; Examples thereof include alcohols containing an ester group such as methyl hydroxyisobutyrate and having 10 or less carbon atoms. In the present invention, it is preferable to use a monohydric alcohol having 10 or less carbon atoms and 5 or less carbon atoms from the viewpoint of excellent solvent resolubility of the colored resin composition and shorter development time.

The polyamide-imide resin having the repeating unit represented by the general formula (A) used in the present invention includes at least an isocyanurate-type polyisocyanate synthesized from the divalent aliphatic diisocyanates and a tricarboxylic acid anhydride. Can be obtained by reacting.
When the isocyanate group in the polyisocyanate reacts with the carboxyl group of the tricarboxylic acid anhydride and the acid anhydride portion, amides and imides are formed, respectively, and the resin of the present invention becomes an amide imide resin. Further, when the polyisocyanate is reacted with the tricarboxylic acid anhydride, the polyisocyanate and the tricarboxylic acid anhydride are left in a proportion that leaves the carboxylic acid component (carboxyl group and acid anhydride portion) of the tricarboxylic acid anhydride. When reacted with an object, the resulting polyamideimide resin will contain an acidic group at least at Rc and at least one of the resin ends.

Polyamideimide having a repeating unit represented by the general formula (A) used in the present invention by reacting an isocyanurate-type polyisocyanate synthesized from the divalent aliphatic diisocyanates with a tricarboxylic acid anhydride. When obtaining the resin, it is preferable to react in a polar solvent containing neither a nitrogen atom nor a sulfur atom. The presence of a polar solvent containing a nitrogen atom or a sulfur atom tends to cause environmental problems, and the reaction of the isocyanurate-type polyisocyanate with a tricarboxylic acid anhydride tends to hinder the growth of molecules.
In the present invention, the polar solvent containing neither nitrogen atom nor sulfur atom is more preferably an aprotic solvent. Examples of the aprotonic solvent include ether solvents having no hydroxyl groups, ester solvents having no hydroxyl groups, and ketone solvents having no hydroxyl groups. Among them, ether solvents having no hydroxyl groups include ether solvents. It is particularly preferable because it has a weak polarity and provides an excellent reaction field in the reaction between the isocyanurate-type polyisocyanate synthesized from the divalent aliphatic diisocyanates and the tricarboxylic acid anhydride.
Such ether-based solvents having no hydroxyl group include ethylene glycol dialkyl ethers; polyethylene glycol dialkyl ethers; ethylene glycol monoalkyl ether acetates; polyethylene glycol monoalkyl ether acetates; propylene glycol dialkyl ethers; polypropylene glycol dialkyl. Ethers; propylene glycol monoalkyl ether acetates; polypropylene glycol monoalkyl ether acetates; monoacetate monoalkyl ethers; or copolymerized polyether glycol dialkyl ethers such as low molecular weight ethylene-propylene copolymers, and copolymerization Monoacetate monoalkyl ethers of polyether glycols; or alkyl esters of such polyether glycols; monoalkyl esters of polyether glycols Monoalkyl ethers and the like can be mentioned, and specific solvents thereof include International Publication No. 2015-008744. Reference can be made to paragraph 0029 of the publication.
Among them, isocyanurate-type polyisocyanates synthesized from the divalent aliphatic diisocyanates and tricarboxylic acids in propylene glycol monomethyl ether acetate from the viewpoint of boiling point, solubility, and stability when used as a colored resin composition. It is preferable to react with an anhydride.

The polyamide-imide resin having the repeating unit represented by the general formula (A) used in the present invention is further reacted with tetracarboxylic dianhydride as described above as long as the effect of the present invention is not impaired. May be obtained by.
Further, the polyamide-imide resin having the repeating unit represented by the general formula (A) used in the present invention is a bifunctional dicarboxylic acid compound such as adipic acid or sebacic acid, as long as the effect of the present invention is not impaired. It may be obtained by reacting with phthalic acid, fumaric acid, maleic acid and their acid anhydrides, and further, two or more isocyanate groups in the molecule, which does not correspond to the isocyanurate type polyisocyanate. It may be obtained by reacting with an isocyanate having.
Examples of isocyanates having two or more isocyanate groups in the molecule, which do not correspond to the isocyanurate-type polyisocyanates, include aromatic isocyanates such as phenylenedi isocyanate and xylene diisocyanate, and one or more aliphatic and aromatic isocyanates. Bullet, an adduct obtained by a urethanization reaction between one or more of aliphatic and aromatic isocyanates and various polyols, isocyanurates of aromatic isocyanates, and pentamers or more polymers of aliphatic and aromatic isocyanates. And so on.
In the preparation of the polyamide-imide resin having the repeating unit represented by the general formula (A) used in the present invention, an isocyanate having two or more isocyanate groups in the molecule, which does not correspond to the isocyanurate type polyisocyanate, is used. Even if it is used, it is adjusted so that it is used within a range in which the effect of the present invention is not impaired. The isocyanate having two or more isocyanate groups in the molecule, which does not correspond to the isocyanurate type polyisocyanate, is a total isocyanate compound used in the preparation of the polyamide-imide resin having the repeating unit represented by the general formula (A). It is preferably used in an amount of 30% by mass or less, further 20% by mass or less, and further more preferably 10% by mass or less.
Among them, isocyanurate-type polyisocyanate in which 100% by mass of the total isocyanate compound used in the preparation of the polyamide-imide resin having the repeating unit represented by the general formula (A) is synthesized from the divalent aliphatic diisocyanates. Is preferable from the viewpoint of further improving the brightness of the colored layer and the stability of the colored resin composition.

The polyamideimide resin having the repeating unit represented by the general formula (A) used in the present invention is the number of moles (N) of isocyanate groups of the total isocyanate compound and tricarboxylic acid anhydride and / or tetracarboxylic acid anhydride. The number of moles of the carboxyl group (M1) and the number of moles of the acid anhydride group (-CO-O-CO-group obtained by intramolecular dehydration condensation of two carboxylic acid molecules) (M2) satisfy the following formula. Is preferable. 3> ((M1) + (M2)) / (N))> 1.1. Particularly preferably, 2> ((M1) + (M2)) / (N))> 1.2. At this time, if the sum of the number of moles of the carboxyl group (M1) and the number of moles of the acid anhydride group (M2) is more than the number of moles of the isocyanate group (N), the polarity in the reaction system becomes high. Reasons such as the reaction proceeds smoothly, isocyanate groups do not remain, the stability of the obtained polyamideimide resin is good, the residual amount of tricarboxylic acid anhydride and the like is small, and separation problems such as recrystallization are unlikely to occur. More preferably, the obtained polyamideimide resin will contain an acidic group at least at Rc and at least one of the resin terminals.

The imidization reaction is preferably carried out by mixing one or more types of polyisocyanate compounds and one or more types of tricarboxylic acid anhydride in a solvent or no solvent, and raising the temperature while stirring. The reaction temperature is preferably in the range of 50 ° C. to 250 ° C., particularly preferably in the range of 70 ° C. to 180 ° C. By setting the reaction temperature to such a level, the reaction rate is increased, and side reactions and decomposition are unlikely to occur. In the reaction, a hydroxyl group and an isocyanate group form an imide group with decarboxylation. The progress of the reaction can be tracked by analytical means such as infrared vector, acid value, and quantification of isocyanate groups. The infrared spectrum, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was reduced as the reaction further acid anhydride group is reduced with a characteristic absorption at 1860 cm ^-1 and 850 cm ^-1. On the other hand, the absorption of imide groups increases at 1780 cm ^-1 and 1720 cm ^-1 . The reaction may be completed by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the isocyanate group disappears from the viewpoint of stability over time.

As the polyamide-imide resin used as a raw material when preparing the alcohol-modified polyamide-imide resin, the one produced by the above method can be used, but since the side reaction of urethanization can be suppressed during the reaction with the alcohol compound. , It is preferable to use one in which the isocyanate group is completely eliminated. The disappearance of the isocyanate group can be confirmed, for example, by the disappearance of 2270 cm ^-1, which is the characteristic absorption of the isocyanate group, in the infrared spectrum.

The reaction between the polyamide-imide resin used as a raw material and the alcohol compound is the ratio of the number of moles of acid anhydride groups (M3) in the polyamide-imide resin to the number of moles of hydroxyl groups (L) of the alcohol compound, L / M3 = 1 The range of 5 is preferable because the storage stability of the obtained polyamide-imide resin is high, and the range of L / M3 = 1 to 2 is more preferable from the viewpoint of reducing excess alcohol.
The number of moles (M3) of the acid anhydride group in the polyamide-imide resin is determined by the following method because the tricarboxylic acid anhydride and the tetracarboxylic acid anhydride are consumed in the reaction with the polyisocyanate. Can be done.
(1) The polyamide-imide resin used as a raw material is diluted with a solvent or the like, and the acid value (a) is determined by titration of an aqueous KOH solution.
(2) The polyamide-imide resin is diluted with a solvent or the like, an excess amount of n-butanol is reacted with the acid anhydride group, and then the acid value (b) is determined by titration of an aqueous KOH solution. In (2), the reaction between the acid anhydride group and n-butanol shall be carried out at 117 ° C. The disappearance of the acid anhydride is confirmed by the infrared spectrum by the complete disappearance of 1860 cm ^-1, which is the characteristic absorption of the acid anhydride group.
(3) From the difference between the acid value (a) and the acid value (b), the concentration of the acid anhydride group in the polyamide-imide resin (A1) of the present invention is calculated and converted into the number of moles (M3).

The dehydration esterification reaction is preferably carried out by mixing a polyamide-imide resin used as a raw material and one or more alcohol compounds in a solvent or no solvent, and raising the temperature while stirring. The reaction temperature is preferably in the range of 50 ° C. to 150 ° C., particularly preferably in the range of 70 ° C. to 130 ° C. By setting the reaction temperature to such a level, the reaction rate is increased, and side reactions and decomposition are unlikely to occur. The reaction forms an ester bond with a dehydration reaction. The progress of the reaction can be tracked by analytical means such as infrared vector, acid value, and quantification of ester bonds. The infrared spectrum, 1860 cm ^-1 and 850 cm ^-1 which is the characteristic absorption of an acid anhydride group decreases with the reaction. The reaction may be completed by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the acid anhydride group disappears from the viewpoint of stability over time.

The polyamide-imide resin used in the present invention thus obtained is obtained with no isocyanate group remaining on the terminal side bonded to Ra of isocyanurate-type polyisocyanate and residues of other polyisocyanate compounds. Rc is preferable from the viewpoint of good stability of the imide resin.

The polyamide-imide resin used in the present invention thus obtained is represented by, for example, the following general formula (A-1).

(In the general formula (A-1), Ra, Rb and Rc are independently the same as in the general formula (A). N represents the number of repeating units and is 1 or more.)

The polyamide-imide resin used in the present invention has at least a repeating unit represented by the general formula (A), but Rb does not correspond to the isocyanurate-type polyisocyanate, and two or more isocyanates in the molecule. Repeating units introduced when prepared with group-bearing isocyanates may be further bonded.

Further, the polyamide-imide resin used in the present invention has at least a repeating unit represented by the general formula (A), and further, a repeating unit containing a branched structure as represented by the following general formula (A'). May have. The repeating unit of the general formula (A) may be independently combined with the two Rbs of the following general formula (A'), or the repeating unit represented by the following general formula (A') may be combined. It may be bonded, or even if a repeating unit introduced when prepared using an isocyanate having two or more isocyanate groups in the molecule, which does not correspond to the isocyanurate-type polyisocyanate, is bonded. Alternatively, the terminal structures combined by the following general formula (A ") may be bonded.

(In the general formula (A'), Ra and Rb are independently the same as in the general formula (A). N'represents the number of repeating units and is 1 or more.)

(In the general formula (A "), Ra and Rc are independently the same as those in the general formula (A).)

The acid value of the polyamide-imide resin used in the present invention is preferably 90 KOH mg / g or more, more preferably 110 KOH mg / g or more, and even more preferably 130 KOH mg / g or more. When the acid value is 90 KOH mg / g or more, the developability is improved in combination with the structure of the polyamide-imide resin, and the effect of shortening the developing time can be obtained.
On the other hand, the acid value of the polyamide-imide resin used in the present invention is preferably 300 KOH mg / g or less, and more preferably 250 KOH mg / g or less. When the acid value is 300 KOH mg / g or less, the points of suppressing water stain and the stability of the colored resin composition are excellent.
In the present invention, the acid value represents the mass (mg) of KOH required to neutralize 1 g of solid content, and refers to a value determined by a potentiometric titration method according to JIS K 0070.

The number average molecular weight of the polyamide-imide resin used in the present invention is preferably 1000 or more, and more preferably 2000 or more. When the number average molecular weight is 1000 or more, the film forming property as a colored layer is excellent, and the solvent resistance of the film is also good.
On the other hand, the number average molecular weight of the polyamide-imide resin used in the present invention is preferably 20000 or less, and more preferably 8000 or less. When the number average molecular weight is 20000 or less, the solubility in a solvent is good and the workability is excellent.
In the present invention, the number average molecular weight of the polyamide-imide resin was determined as a standard polystyrene conversion value using gel permeation chromatography (GPC). The measurement was carried out using HLC-8120GPC manufactured by Tosoh Corporation, the column was TFKguardcolumnhxl-L and TFKgel (G1000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation, and the elution solvent was THF. is there.

Since the polyamide-imide resin used in the present invention contains an isocyanurate-type polyisocyanate structural unit synthesized from the divalent aliphatic diisocyanates, it has solubility in a general-purpose solvent. Among them, propylene. A polyamide-imide resin that dissolves in any part of 3 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of glycol monomethyl ether acetate (PGMEA) is preferable.
A polyamide-imide resin having the above-mentioned solubility is used for a color filter having excellent solvent solubility in a solvent preferable for a colored resin composition for a color filter as described later and having excellent coating suitability. A colored resin composition can be obtained.

<Color material>
In the present invention, the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, and dispersible dyes are used. Can be done. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) Examples include those with numbers.

C. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,55,60,61,65,71,73,74,81,83,93,95,97,98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and C.I. I. Pigment Yellow 150 derivative pigment;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment Green 7, 36, 58, 59;
C. I. Pigment Brown 23, 25;
C. I. Pigment Black 1, 7.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when a pattern of a light-shielding layer is formed on a substrate of a color filter by using the colored resin composition for a color filter according to the present invention, a black pigment having a high light-shielding property is blended in the ink. As the black pigment having a high light-shielding property, for example, an inorganic pigment such as carbon black or iron tetraoxide, or an organic pigment such as cyanine black can be used.

The dispersible dyes include dyes that can be dispersed by adding various substituents to the dyes and insolubilizing them in a solvent, dyes that can be dispersed by using them in combination with a solvent having low solubility, and solvents. Examples thereof include a rake coloring material in which a soluble dye is salt-formed with counter ions to insolubilize (lake). By using such a dispersible dye in combination with a dispersant, the dispersibility and dispersion stability of the dye can be improved.
As a guide, if the amount of the dye dissolved in 10 g of the solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

In the present invention, it is particularly preferable to use the rake coloring material from the viewpoint of improving brightness and contrast. The rake coloring material can usually be obtained by mixing a dye soluble in a solvent and a rake agent described later in a solvent. As the dye soluble in the solvent, it is preferable to use a dye having high transmittance from the viewpoint of increasing the brightness of the color filter. The dye may be appropriately selected according to a desired color tone, and may be an azo dye, a metal complex salt azo dye, anthraquinone dye, triarylmethane dye, xanthene dye, cyanine dye, indigo dye, naphthoquinone dye, etc. It may be a dye having any basic skeleton (coloring site) such as a quinoneimine dye, a methine dye, and a phthalocyanine dye. Further, the dye may be a dye classified into any of the following types, such as an acid dye having an anionic substituent and a basic dye having a cationic substituent.
When forming a blue colored layer, at least one of a triarylmethane dye, a xanthene dye, and a cyanine dye is preferable, and a triarylmethane dye is more preferable, from the viewpoint of increasing the brightness. preferable.

Examples of acid dyes include C.I. I. Acid Violet 29,31,33,34,36,36: 1,39,41,42,43,47,51,63,76,103,118,126, C.I. I. Acid Blue 2,8,14,25,27,35,37,40,41,41: 1,41: 2,43,45,46,47,49,50,51,51,53,54,55, 56, 57, 58, 62, 62: 1,63,64,65,68,69,70,78,79,80,81,96,111,124,127,127: 1,129,137,138, 143,145,150,175,176,183,198,203,204,205,208,215,220,221,225,226,227,230,231,232,233,235,239,245,247, 253,257,258,260,261,264,266,270,271,272,273,274,277,277: 1,278,280,281,228,286,287,288,289,290,291 292,293,294,295,298,301,302,304,305,306,307,313,316,318,322,324,327,331,333,336,339,340,343,344,350, C. I. Anthraquinones such as acid green 10,17,25,25: 1,27,36,37,38,40,41,42,44,54,59,69,71,81,84,95,101,110,117 Acid dyes; C.I. I. Acid Violet 15,16,17,19,21,23,24,25,38,49,72, C.I. I. Acid Blue 1,3,5,7,9,19,22,83,90,93,100,103,104,109, C.I. I. Acid greens 3,5,6,7,8,9,11,13,14,15,16,18,22,50,50: 1 etc. Triarylmethane acid dyes; I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Examples thereof include xanthene-based acid dyes such as Acid Violet 9, 30, 102, Sulforhodamine G, Sulforhodamine B, Sulforhodamine 101, and Sulforhodamine 640. Xanthene-based acid dyes include, among others, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. It is preferably a rhodamine-based acid dye such as Acid Blue 19.
Further, as a commercially available basic dye, for example, C.I. I. Basic Violet 1, 3, 14, C.I. I. Basic Blue 1,5,7,8,11,26, C.I. I. Triarylmethane basic dyes such as Basic Greens 1 and 4; C.I. I. Basic Yellow 13, C.I. I. Cyanine-based basic dyes such as Basic Red 14; C.I. I. Azo-based basic dyes such as Basic Red 29; C.I. I. Examples thereof include xanthene-based basic dyes such as Basic Violet 11. Triarylmethane-based basic dyes include C.I. I. Basic blue 1,5,7,8,11,26 is preferable. Further, as the triarylmethane-based basic dye in the present invention, a dye having a cation of a coloring material represented by the general formula (I') described later is also preferable.
These dyes can be used alone or in combination of two or more.

In the rake coloring material, the counter ion differs depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the rake agent is appropriately selected and used according to the dye. That is, when the acid dye is insolubilized, a compound that produces a counter cation of the dye is used as a rake agent, and when the basic dye is insolubilized, a counter anion of the dye is generated as a rake agent. Compounds are used.

Examples of the counter cation of the acid dye include ammonium cation, metal cation, inorganic polymer and the like.
Examples of the rake agent that generates ammonium ions include primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like. Among them, secondary amine compounds are excellent in heat resistance and light resistance. It is preferable to use an amine compound or a tertiary amine compound.
Further, the rake agent that generates a metal cation may be appropriately selected from metal salts having a desired metal ion.
The counter cations of acid dyes can be used alone or in combination of two or more.

As the rake color material containing an acid dye, a rake color material containing a xanthene dye is preferable from the viewpoint of achieving high brightness.
As the xanthene-based acid dye in the rake coloring material, it is preferable to have a compound represented by the following general formula (II), that is, a rhodamine-based acid dye.

In (formula ^{(II), R} I ~R ^IV are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, ^{R I} and R ^III, by bonding R ^II and ^{R IV} good .R ^V to form a ring structure, an acidic group, X is, .m represents a halogen atom is an integer of 0 to 5. general formula (II) are those having at least one acidic group , N is an integer greater than or equal to 0.)

The alkyl group in R ^I to R ^IV is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. , It is more preferable that it is a linear or branched alkyl group having 1 to 5 carbon atoms. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like, and further, a substituent. It may have a halogen atom or an acidic group.
Aryl group in R ^I to R ^IV is not particularly limited. For example, an aryl group which may have a substituent having 6 to 20 carbon atoms can be mentioned, and among them, a group having a phenyl group, a naphthyl group and the like is preferable. Heteroaryl groups in R ^I to R ^IV are include heteroaryl group which may have a substituent group having 5 to 20 carbon atoms, as a hetero atom, a nitrogen atom, an oxygen atom, those containing a sulfur atom is preferable ..
Examples of the substituent which the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, a carboxylic acid ester group and the like. ..
R ^{I to} R ^IV may be the same or different.

Specific examples of the acidic group or a salt thereof, a carboxyl group (-COOH), a carboxylato group (-COO ^-), carboxylate (. -COOM, where M is a metal atom), a sulfonato group (-SO ₃ ⁻ ), sulfo group (-SO ₃ H), sulfonic acid base (-SO ₃ M, where M represents a metal atom) and the like, among which sulfonate group (-SO ₃ ⁻ ) and sulfo group It is preferable to have at least one of (-SO ₃ H) or a sulfonic acid base (-SO ₃ M). Examples of the metal atom M include a sodium atom and a potassium atom.

As the compound represented by the general formula (II), acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, acid blue 19 and the like are preferable from the viewpoint of increasing the brightness.
From the viewpoint of heat resistance, a compound having a betaine structure having m = 1 and n = 0 in the general formula (II) is preferable.
Further, among them, m = 1, and a n = 0, R ^I and R ^II are each independently an alkyl group or an aryl group, R ^III and R ^IV is selected each are independently an aryl group or a heteroaryl group This is preferable from the viewpoint that a colored layer having excellent brightness and light resistance can be formed.
The method for producing the compound represented by the general formula (II) is not particularly limited, and can be obtained by referring to, for example, Japanese Patent Application Laid-Open No. 2010-21198.

As the metal lake coloring material of the xanthene acid dye, one containing a metal atom is used as a lake agent. By using a rake agent containing a metal atom, the heat resistance of the coloring material is increased. As such a rake agent, a rake agent containing a metal atom that becomes a divalent or higher metal cation is preferable.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent.

Moreover, you may use a known acid dye as an organic anion. In this case, the rake coloring material contains an acid dye and a basic dye as an ion pair.
Examples of the rake agent for generating these organic anions include the above-mentioned alkali metal salts of organic anions and alkaline earth metal salts.

On the other hand, the inorganic anion, for example, anions of oxo acids (phosphoric acid ion, chromate ion, tungstate ion _(WO ^{4 2-),} molybdate ions _(MoO ^{4 2-),} etc.) and a plurality of Examples thereof include inorganic anions such as polyacid anions condensed with oxometalates and mixtures thereof.
Examples of the polyacid, isopoly acid anion _{(M m} O ^{n) c-} and a even heteropoly acid anion _{(X l} M _m O ⁿ⁾ may be a ^c-. In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, and n represents a composition ratio of an oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co.
Among them, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

Examples of the rake agent that generates an inorganic anion include an alkali salt and an alkali metal salt of the inorganic anion.
The counter anion of the basic dye in the rake coloring material can be used alone or in combination of two or more.
In the present invention, the rake color material is preferably a rake color material composed of a basic dye and an inorganic anion, and more preferably a basic dye and a polyacid anion, from the viewpoint of heat resistance and light resistance. .. In the case of a rake coloring material containing a polyacid anion, the silane coupling agent is susceptible to change with time, but in the present invention, the content ratio of the silane coupling agent is the total solid content in the colored resin composition. On the other hand, since it is 1% by mass or less, the influence of the change with time is small, while the heat resistance and light resistance are high, so that it is particularly preferably used as the rake coloring material of the present application.

In the present invention, the rake coloring material preferably contains a rake coloring material having a triarylmethane dye from the viewpoint of improving the brightness of the color filter, and among them, a triarylmethane basic dye and a polyacid. It preferably contains an anion.

In the present invention, the rake coloring material is excellent in heat resistance and light resistance, and from the viewpoint of achieving high brightness of the color filter, it is a molecule that the rake coloring material is represented by the following general formula (I). It is preferable because it forms an assembled state and exhibits better heat resistance.

(In the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. ^Bc− contains at least tungsten. Represents a c-valent polyacid anion. R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱ . R ⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

As shown in FIG. 4, the coloring material represented by the general formula (I) contains a divalent or higher anion 202 and a divalent or higher cation 201. Therefore, in the aggregate of the coloring material, the anion It is presumed that the anion and the cation are not simply ionic bonded one molecule to one molecule, but form a molecular aggregate 210 in which a plurality of molecules are associated via the ionic bond 203. Therefore, the apparent molecular weight of the coloring material represented by the general formula (I) is significantly increased as compared with the molecular weight of the conventional rake coloring material. It is presumed that the formation of such molecular aggregates further enhances the cohesive force in the solid state, reduces the thermal motion, suppresses the dissociation of ion pairs and the decomposition of the cation portion, and improves the heat resistance.

A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is at least a saturated fat at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a group hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) are contained in the carbon chain. It may be. Since the carbon atom that directly bonds with N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color-developing site are not affected by the linking group A or other color-developing sites, and are not affected by the monomer. Similar colors can be retained. From the viewpoint of heat resistance, it is preferable that A does not have a siloxane bond, and more preferably it does not have Si (silicon atom).
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is linear, branched or cyclic unless the carbon atom at the terminal directly bonded to N has a π bond. Any of these may be used, carbon atoms other than the terminal may have an unsaturated bond, or may have a substituent, and O, S, and N are contained in the carbon chain. May be good. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
Further, in A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at a terminal that is directly bonded to at least N. It may be mentioned and may have a substituent, and may be a heterocycle containing O, S and N.
Among them, from the viewpoint of skeletal robustness, A preferably contains a cyclic aliphatic hydrocarbon group or aromatic group.
As the cyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group Aribashi is particularly preferable from the viewpoint of skeletal robustness. The bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a bridging structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the alicyclic hydrocarbon groups with bridges, norbornane is preferable. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferable. For example, when A is a divalent organic group, an aromatic group in which two linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms or alkylene groups having 1 to 20 carbon atoms such as a xylylene group are substituted. And so on.

The valence a in the general formula (I) is the number of color-developing cation sites constituting the cation, and a is an integer of 2 or more. In the coloring material of the present invention, since the valence a of the cation is 2 or more, it is excellent in heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, and more preferably 3 or less.

The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms can be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a direct group having 1 to 5 carbon atoms is used. A chain or branched alkyl group is more preferable from the viewpoint of brightness and heat resistance. Of these, it is particularly preferable that the alkyl group in R ^{i to} R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.
Among them The chemical stability ^R i to R ^v in terms of, independently, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, ^{or, R ii} and ^{R iii, R iv} and ^{R v} are bound It is preferable that a pyrrolidine ring, a piperidine ring, and a morpholine ring are formed.

Each of R ^{i to} R ^v can have the above-mentioned structure independently, but among them, it is preferable that R ⁱ is a hydrogen atom from the viewpoint of color purity, and further, from the viewpoint of ease of production and raw material procurement, R ^{i i} to R ^v . It is more preferable that all ^Rvs are the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as that listed in the aromatic group in A.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group consisting of a condensed polycyclic carbon ring having 10 to 14 carbon atoms. Of these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{i to} R ^v and Ar ¹ in one molecule may be the same or different. The desired color can be adjusted by combining R ^{i to} R ^v and Ar ¹ .

In the coloring material represented by the general formula (I), the anion portion (B ^c− ) represents a c-valent polyacid anion containing at least tungsten and may contain molybdenum.

As the polyacid anion in the coloring material represented by the general formula (I), the above anions can be used alone or in combination of two or more, and when two or more are used in combination, the polyacid anion can be used. It is preferable that the ratio of tungsten to molybdenum as a whole is 90: 10 to 100: 0 from the viewpoint of heat resistance and light resistance.

In the general formula (I), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations in the molecular assembly may be used alone or in combination of two or more. Further, when d is 2 or more, a plurality of anions in the molecular assembly may be used alone or in combination of two or more, and organic anions and inorganic anions may be used in combination. ..

E in the general formula (I) is an integer of 0 or 1. e = 0 represents the triarylmethane skeleton and e = 1 represents the xanthene skeleton. A plurality of e may be the same or different. That is, for example, it may be a cation portion having only a triarylmethane skeleton or a plurality of xanthene skeletons, or a cation portion containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, it is preferable that the anion portion has only the same skeleton. On the other hand, the color material represented by the general formula (I) can be adjusted to a desired color by forming a cation portion containing both a triarylmethane skeleton and a xanthene skeleton.

In the present invention, it is easy to adjust to a desired color by using a color material represented by the following general formula (I') in which e in the color material represented by the general formula (I) is 0. More preferred.

(Each reference numeral in the general formula (I') is the same as the general formula (I).)

When the color material represented by the general formula (I) has a xanthene skeleton, it may be contained in the xanthene dye, but as long as it corresponds to the color material represented by the general formula (I), in the present invention. , It shall be treated as corresponding to the coloring material represented by the general formula (I).

The method for producing the coloring material represented by the general formula (I) is not particularly limited. For example, it can be obtained by the manufacturing method described in Pamphlet No. 2012/144520.

In the present invention, the coloring material may be used alone or in combination of two or more.
In the present invention, as the coloring material, a rake coloring material is preferably used as described above from the viewpoint of improving brightness and contrast, and a rake coloring material represented by the general formula (I) and a rake containing the xanthene dye. Coloring materials and combinations thereof are particularly preferably used.
In addition, C.I. I. Zinc phthalocyanine pigments such as Pigment Green 58 and 59 are pigments that tend to form a thick film and are difficult to develop. However, when combined with the specific polyamide-imide resin, brightness and contrast can be improved. It is suitably used as the coloring material of the present invention.

The average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can develop a desired color when the coloring layer of the color filter is used, and varies depending on the type of coloring material used. Is preferably in the range of 10 nm to 100 nm, and more preferably 15 nm to 60 nm. When the average primary particle size of the coloring material is within the above range, the display device provided with the color filter manufactured by using the coloring material dispersion liquid according to the present invention can be made to have high contrast and high quality. it can.

The coloring material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available coloring material may be miniaturized and used.

[Dispersant]
In the colored resin composition for a color filter of the present invention, the coloring material is used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. The dispersant may be used alone or in combination of two or more. As the dispersant, for example, a cationic, anionic, nonionic, amphoteric, silicone-based, or fluorine-based surfactant can be used. Among the surfactants, the polymer dispersant is preferable because it can be dispersed uniformly and finely.

Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; and (partial) amine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modifications; polyurethanes; unsaturated polyamides; polysiloxane Classes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly (lower alkyleneimine) with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxyls) Examples thereof include a reaction product obtained by reacting one or more compounds selected from three kinds of compounds of a group-bearing polyester, polyamide or a copolymer of an ester and an amide (polyester amide)).

As the polymer dispersant, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable from the viewpoint that the coloring material can be preferably dispersed and the dispersion stability is good. Among them, the polymer dispersant made of a polymer containing a repeating unit having a tertiary amine has good dispersibility in combination with the specific polyamideimide resin and does not precipitate foreign substances during coating film formation. It is preferable from the viewpoint of improving brightness and contrast.
By using a polymer containing a repeating unit having a tertiary amine as a dispersant, the dispersibility and dispersion stability of the coloring material are improved by the combination with the specific polyamide-imide resin. The repeating unit having a tertiary amine is a site having an affinity for the coloring material. A polymer dispersant consisting of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that serves as a site having an affinity for a solvent. As a polymer containing a repeating unit having a tertiary amine, a block copolymer having a block portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity is particularly heat resistant. It is preferable in that it is possible to form a coating film having excellent and high brightness.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may form a main chain.
Above all, it is preferable that it is a repeating unit having a tertiary amine in the side chain, and above all, it has a structure represented by the following general formula (1) because the main chain skeleton is hard to be thermally decomposed and has high heat resistance. However, it is more preferable.

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁵ ) -CH ( R ⁶ ) -O] _x- CH (R ⁵ ) -CH (R ⁶ )-or-[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- , a divalent organic group represented by R ³ and R ⁴ each independently represent an optionally substituted linear or cyclic hydrocarbon group, .R ⁵ and R ⁶ R ³ and R ⁴ form a ring structure by bonding with each other is, Each is independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

Examples of the divalent linking group Q of the general formula (1) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, an -COO- group, and an ether group having 1 to 10 carbon atoms (-. R'-OR "-: R'and R" are independently alkylene groups) and combinations thereof. Among them, Q is a -COO- group or -CONH- because of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA) preferably used as a solvent, and the relatively inexpensive material. It is preferably a group.

The divalent organic group R ² of the above general formula (1) is an alkylene group having 1 to 8 carbon atoms, − [CH (R ⁵ ) -CH (R ⁶ ) −O] _{x −} CH (R ⁵ ) −CH. (R ⁶ )-or-[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- . The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups and various hexylene groups. Groups, various octylene groups, etc.
R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively.
The R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and more preferably R ² is a methylene group, an ethylene group, a propylene group or a butylene group, and the methylene group and ethylene. Groups are more preferred.

Examples of the cyclic structure formed by bonding R ³ and R ⁴ of the general formula (1) to each other include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. Be done. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring.

Examples of the repeating unit represented by the general formula (1) include alkyl group-substituted aminos such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

In the block portion composed of the repeating unit having the tertiary amine, it is preferable that three or more structural units represented by the general formula (1) are contained. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100 pieces, more preferably 3 to 50 pieces, and further preferably 3 to 30 pieces.

A block having a block portion composed of a repeating unit having the tertiary amine (hereinafter, may be referred to as A block) and a block portion having solvent affinity (hereinafter, may be referred to as B block). The block portion having solvent affinity in the copolymer does not have the structural unit represented by the general formula (1) from the viewpoint of improving solvent affinity and improving dispersibility, and the general formula is used. It has a solvent-affinity block portion having a structural unit copolymerizable with (1). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like can be used. Of these, AB block copolymers or ABA block copolymers are preferable because they are excellent in dispersibility.
The structural unit that can be copolymerized with the general formula (1) is a configuration represented by the following general formula (2) from the viewpoint of improving the dispersibility and dispersion stability of the rake coloring material while also improving the heat resistance. It is preferably a unit.

(In the general formula (2), R ⁷ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ⁸ is an alkyl group having 1 to 18 carbon atoms, and an alkenyl having 2 to 18 carbon atoms. Group, aralkyl group, aryl group, monovalent group represented by-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _x- R ¹¹ or-[(CH ₂ ) _y- O] _z- R ^11. R ⁹ and R ¹⁰ are independent hydrogen atoms or methyl groups, respectively, and R ¹¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and the like. It is a monovalent group represented by an aryl group, -CHO, -CH ₂ CHO, or -CH ₂ COOR ¹² , where R ¹² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. The group is. X is an integer of 1 to 18, y is an integer of 1 to 5, z is an integer of 1 to 18. m is an integer of 3 to 200, and n is an integer of 10 to 200.)

The divalent linking group A of the general formula (2) can be the same as Q in the general formula (1), and the heat resistance of the obtained polymer and propylene glycol preferably used as a solvent can be used. A is preferably a -COO- group because of its solubility in monomethyl ether acetate (PGMEA) and its relatively inexpensive material.

In R ^8, the alkyl group having 1 to 18 carbon atoms, linear, branched, or cyclic, e.g., methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl Group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, Examples thereof include a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a lower alkyl group substituted adamantyl group and the like.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, and various octadecenyl groups. Cyclopentenyl group, cyclohexenyl group, cyclooctenyl group and the like can be mentioned.
Among them, dispersibility, substrate adhesiveness R ⁸ is a methyl group in terms of, various butyl groups, various hexyl group, a benzyl group, a cyclohexyl group, hydroxyethyl group is preferred.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include a linear and branched alkyl groups having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like.

Further, the above R ¹¹ may have a hydrogen atom or a substituent, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH2CHO, or It is a monovalent group represented by −CH2COOR ¹² , and R ¹² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms.
In the monovalent group represented by R ^11, a substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in R ¹¹ are as shown in R ⁸ .
In R ⁸ , x, y and z are the same as R ² in the general formula (1).

In the present invention, the glass transition temperature (Tg) of the solvent-friendly block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-friendly block portion is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the solvent-affinity block portion in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the color material-affinity block portion and the block copolymer can be calculated.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the solvent-friendly block portion. 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. However, Σ is the sum of i = 1 to n. As the value (Tgi) of the homopolymer glass transition temperature of each monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

The number of structural units constituting the solvent-affinitive block portion may be appropriately adjusted within the range in which the colorant dispersibility is improved. Above all, the number of the constituent units constituting the solvent-affinity block portion is 10 to 200 from the viewpoint that the solvent-affinity portion and the color material-affinity portion act effectively to improve the dispersibility of the color material. It is preferably 10 to 100, more preferably 10 to 70, and even more preferably 10 to 70.

The solvent-affinity block portion may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block portion may consist of one type or two or more types. May include repeating units of.
In the block copolymer used as the dispersant of the present invention, the ratio of the number of units m of the structural unit represented by the general formula (1) to the number n of the other structural units constituting the solvent-friendly block portion. The m / n is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 from the viewpoint of dispersibility and dispersion stability of the coloring material.

Further, among them, in the present invention, the dispersant contains a structure represented by the general formula (1), and a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less is combined with the specific polyamide-imide resin. Therefore, it is preferable from the viewpoint that the dispersibility is good, foreign matter is not deposited when the coating film is formed, and the brightness and contrast are improved.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and also in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, from the viewpoint 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, and more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of perchloric acid and equivalent potassium hydroxide required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group is salt-formed with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant itself. The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of exhibiting the effect of suppressing the development residue. Above all, the acid value of the dispersant is more preferably 2 mgKOH / g or more because the effect of suppressing the development residue is more excellent. Further, the acid value of the dispersant used in the present invention is preferably 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration of development adhesion. Above all, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving the development adhesion.
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, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. .. This is because the development adhesion is improved.
When the concentration of the coloring 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 underlying substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling is likely to occur during development.

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 adhesion. That is, regardless of whether the dispersant is a pre-salt block copolymer or a salt-type block copolymer, the glass transition temperature thereof is preferably 30 ° C. or higher. If the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and the development adhesion may be lowered. It is presumed that this is because when the glass transition temperature is close to the developer temperature, the movement of the dispersant becomes large during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, and it is presumed that the decrease in development adhesion 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 development adhesion. On the other hand, it is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) in accordance with JIS K7121.

Further, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (1) 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. When it is 18 mgKOH / g or less and the glass transition temperature is 30 ° C. or more, the colorant dispersion stability is excellent and the contrast is improved, and when the colored resin composition is prepared, the generation of development residue is suppressed. Further, it is preferable because it has high development adhesion.

As the carboxy group-containing monomer, a monomer copolymerizable with a monomer having a structural unit represented by the general formula (1) and containing an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxy group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used. Of these, (meth) acrylic acid is particularly preferable 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 structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the above specific acid value range, and in particular, Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all the constituent units of the block copolymer. Is more preferable.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the lower limit value, the effect of suppressing the development residue is exhibited, and when it is at least the upper limit value, deterioration of development adhesion can be prevented.
The structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may be composed of one type, or may contain two or more types of structural units.

Further, from the viewpoint of setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher and improving the development adhesion, the monomer having a glass transition temperature value (Tgi) of a homopolymer of the monomer of 10 ° C. or higher. Is preferably 75% by mass or more in the B block in total, and more preferably 85% by mass or more.

In the block copolymer, the ratio m / n of the number of units m of the constituent units of the A block and the number of units n of the constituent units of the B block shall be within the range of 0.05 to 1.5. Is preferable, and it is more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the coloring material.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, preferably 2000 to 15000, from the viewpoint of improving the dispersibility and dispersion stability of the coloring material. More preferably, it is more preferably 3000 to 12000.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene conversion value by gel permeation chromatography (GPC).

The method for producing the block copolymer is not particularly limited. The block copolymer can be produced by a known method, but it is particularly preferable to produce the block copolymer by the living polymerization method. This is because chain transfer and deactivation are unlikely to occur, copolymers having a uniform molecular weight can be produced, and dispersibility can be improved. Examples of the living polymerization method include a living anion polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cationic polymerization method. A copolymer can be produced by sequentially polymerizing the monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block with the A block. Further, in the above production method, the order of polymerization of the A block and the B block can be reversed. It is also possible to manufacture the A block and the B block separately, and then couple the A block and the B block.

As a specific example of a block copolymer having a block portion composed of a repeating unit having such a tertiary amine and a block portion having solvent affinity, for example, the block copolymer described in Japanese Patent No. 4911253 can be used. It can be mentioned as a suitable one.

When the coloring material is dispersed by using the polymer containing the repeating unit having the tertiary amine as a dispersant, the polymer containing the repeating unit having the tertiary amine is dispersed with respect to 100 parts by mass of the coloring material. The content of is preferably 15 parts by mass to 300 parts by mass, and more preferably 20 parts by mass to 250 parts by mass. If it is within the above range, the dispersibility and dispersion stability are excellent, and the effect of improving the contrast is enhanced.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino groups in the polymer containing the repeating unit having the tertiary amine and the organic acid compound form a salt. It is more preferable to use the above-mentioned compound as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
By using the salt-type polymer, in particular, the dispersibility and dispersion stability of the coloring material represented by the general formula (I) and the coloring material represented by the general formula (II) are improved. Among them, it is represented by the rake coloring material, particularly the general formula (I), that the polymer containing a repeating unit having a tertiary amine is a block copolymer and the organic acid compound is an acidic organic phosphorus compound. It is preferable from the viewpoint of excellent dispersibility and dispersion stability of the color material and the color material represented by the general formula (II).

In the present invention, the organic acid compound is not particularly limited as long as it is a compound having one or more carbon atoms and an acidic group. Examples of the acidic group contained in the organic acid compound include a carboxy group, a sulfo group, a phosphoric acid group, etc., and the organic acid compound should be a sulfo group or a phosphoric acid group from the viewpoint of dispersibility, dispersion stability, heat resistance and alkali developability. Is preferable. Moreover, it is preferable to have a phosphoric acid group from the viewpoint of alkali developability.
The number of acidic groups contained in one molecule of the organic acid compound is not particularly limited, but the number of acidic groups in one molecule may be 1 to 3 from the viewpoint of dispersibility and dispersion stability, heat resistance and alkali developability. It is preferably 1 or 2, and more preferably 1 or 2. The valence of the acidic group is not particularly limited, but from the viewpoint of dispersion stability, heat resistance and developability, it is preferably a 1 to 3 valent acid, and more preferably a 1 to 2 valent acid. preferable.
In the present invention, the organic acid compound preferably has a molecular weight of 5000 or less, more preferably 100 or more and 1000 or less, and further 150 or more and 500 or less, from the viewpoint of easily forming a salt with the amino group of the dispersant. More preferred.

In the present invention, the organic acid compound is one or more selected from the group consisting of the following general formula (3) and the following general formula (4), that is, dispersibility, dispersion stability, heat resistance and alkali developability. It is preferable because it is excellent in.

(Equation (3) and the formula (4), the ^{R a} and R ^{a 'are} each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl _{^{group, - [CH (R c)}} -CH (R d) -O] s -R e, - [(CH 2) t -O] 1 represented by u -R ^e, or -O-R ^{a ''} the valence of the group, ^'.R any of containing a carbon atom ^{a' R a} and R ^{a 'is} an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group ,-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e ,-[(CH ₂ ) _t- O] _u- R ^e is a monovalent group.
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, − [CH (R ^c ) -CH (R ^d ) −O] _s −R ^e , − [(CH ₂ ) _t- O] It is a monovalent group represented by _u- R ^e or -O-R ^b' . R ^{b 'is} an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e, or _- is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and ^Re is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, and the like. -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH _{2 A} monovalent group represented by COOR ^f , where R ^f is a hydrogen atom or carbon. Alkyl groups of numbers 1-5.
In R ^a , ^Ra' , and R ^b , the alkyl group, the alkenyl group, the aralkyl group, and the aryl group may each have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. )

In the general formula (3), if R ^a and R ^{a 'is} an aromatic ring, the aromatic ring suitable substituents on, for example, C1-4 linear, and branched alkyl groups You may have.
The alkyl group, aralkyl group, and aryl group having 1 to 18 carbon atoms can be the same as those of R ⁸ in the dispersant.

R ^a and / or R ^{a 'are,} in the case of ^{-O-R a ",} the acidic phosphoric acid ester.
When ^{Ra "} has an aromatic ring, it may have an appropriate substituent, for example, a linear or branched alkyl group having 1 to 4 carbon atoms on the aromatic ring.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms of the above R ^e is as shown by the above R ^8, alkenyl group having 2 to 18 carbon atoms is as indicated by the above R ^a and R ^{a '} ..
R ^a, at R ^{a 'and R a ",} s is 1 to 18 integer, t is an integer of from 1 to 5, u is 1 to 18 integer .s is preferably an integer of 1 to 4, more It is preferably an integer of 1 to 2, t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2. is there.

In the above general formula (4), when R ^b has an aromatic ring, even if it has an appropriate substituent, for example, a linear or branched alkyl group having 1 to 4 carbon atoms on the aromatic ring. Good.
When R ^b is −OR ^b ′, it becomes an acidic sulfate ester. The ^{R b} 'is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e , Or-[(CH ₂ ) _t- O] _u- R ^e is a monovalent group.
The alkyl group, aralkyl group, and aryl group having 1 to 18 carbon atoms are as shown in R ⁸ above, and the alkenyl group having 2 to 18 carbon atoms is as shown in ^Ra and ^Ra'. Is. In the case where R b ^'is an aromatic ring, the aromatic ring suitable substituents on, for example, C1-4 linear, may have such branched alkyl groups.
The R ^c , R ^d and ^Re are the same as those described above.
In R ^b and R ^b ', s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. Preferred s, t, u are the same as above ^{R a, R} a ^{'and R a ".}

The organic acid compound represented by the general formula (3), the general formula (3) R ^a and R ^{a 'in} each independently represent a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a substituent Yes It may be an aryl group or an aralkyl group, a vinyl group, an allyl group,-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e , or-[(CH ₂ ) _t- O] _u. -R ^e or, ^'is a monovalent group represented by, ^{R a} and R ^a' -O-R ^{a 'either} contains carbon atoms, and, the R ^a'', a methyl group, ethyl An aryl group or an aralkyl group which may have a group or a substituent, a vinyl group, an allyl group,-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e , or-[(CH _2). ) and ^{_{t -O] u -R e, R}} c and R ^d are, that are each independently hydrogen atom or a methyl group, to improve the dispersibility of the colorant, and the contrast of the resulting colored layer high and, preferably from the viewpoint of excellent heat resistance, R ^a is a hydroxyl group, and, more preferably R a ^'is an aryl group which may have a substituent.

Further, as the organic acid compound represented by the general formula (4), R ^b in the general formula (4) may have a methyl group, an ethyl group or a substituent, and an aryl group, an aralkyl group or a vinyl group. , Allyl group,-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e , or-[(CH ₂ ) _t- O] _u- R ^e , or -O-R ^b' It is a monovalent group shown, and R ^b'may have a methyl group, an ethyl group, a substituent, an aryl group or an aralkyl group, a vinyl group, an allyl group,-[CH (R ^c ) -CH. (R ^d ) -O] _s- R ^e or-[(CH ₂ ) _t- O] _u- R ^e , and R ^c and R ^d are independently hydrogen atoms or methyl groups, respectively. It is preferable because the dispersibility of the coloring material is improved, the contrast of the obtained colored layer is high, and the heat resistance is excellent, and it is more preferable that R ^b is an aryl group which may have a substituent. ..

Above all, the general formula (3) and an organic acid compound represented by the general formula (4) ^{is, R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' It is preferable to have an aromatic ring because the dispersibility of the coloring material is improved, the contrast of the obtained colored layer is high, and the heat resistance is excellent. At least one of R ^a , R ^{a'and Ra''} , or R ^b or R ^b' , may have a substituent, an aryl group or an aralkyl group, more specifically, a benzyl group. A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of colorant dispersibility. In the above general formula (3), R ^a and R ^{a 'when} one of an aromatic ring, R ^a and R ^a' the other is also preferably used are hydrogen atom or a hydroxyl group.

Further, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the above general formulas (3) and (4) include phosphorus (P), sulfur (S) and carbon. preferably atom is a compound bonded directly, R ^a and R ^{a 'are} each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl Group,-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e ,-[(CH ₂ ) _t- O] _u- R ^e , which is a monovalent group represented by ^Ra and one of R a ^'preferably contains carbon atoms. Further, R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, and-[CH (R ^c ) -CH (R ^d ) -O] _s- R ^e. , _- is preferably a monovalent group represented by _{[(CH 2) t -O]} u -R e.

In the present invention, the organic acid compound is preferably benzenesulfonic acid, p-toluenesulfonic acid, monobutylphosphate, dibutylphosphate, methylphosphate, dibenzylphosphate, diphenylphosphate, phenylphosphonic acid, etc. from the viewpoint of dispersibility and heat resistance. Of these, p-toluenesulfonic acid and phenylphosphonic acid are more preferable. As the organic acid compound, a hydrate such as p-toluenesulfonic acid monohydrate may be used.
In the present invention, the organic acid compound may be used alone or in combination of two or more.

As a method for preparing a salt-type block copolymer, a group consisting of the general formulas (3) and (4) in a solvent in which a polymer having a structural unit represented by the general formula (3) is dissolved or dispersed. Examples thereof include a method of adding one or more compounds selected from the above, stirring, and heating if necessary.
From the terminal nitrogen moiety of the structural unit represented by the general formula (1) of the polymer having the structural unit represented by the general formula (1) and the general formulas (3) and (4). The fact that one or more compounds selected from the above group form a salt and the ratio thereof can be confirmed by a known method such as NMR.

[solvent]
In the present invention, the solvent does not react with each component in the colored resin composition, and can be appropriately selected and used from the solvents capable of dissolving or dispersing them. The solvent may be used alone or in combination of two or more.
From the viewpoint of dispersibility of the coloring material, it is preferable to select a solvent having a solubility of the coloring material at 23 ° C. of 0.1 (g / 10 ml solvent) or less. By using such a solvent that is substantially insoluble in the coloring material or a solvent that is poorly soluble, the coloring material can be dispersed as fine particles and used, so that the colored resin composition has excellent heat resistance and light resistance. Can be obtained. Among them, the solvent used in the present invention is a solvent having a solubility of the coloring material at 23 ° C. of 0.05 (g / 10 ml solvent) or less because it has excellent dispersibility and heat resistance and a high-luminance coating film can be obtained. It is preferable to have.
In the present invention, the solvent having a solubility of the coloring material at 23 ° C. of 0.1 (g / 10 ml solvent) or less can be easily determined by the following evaluation method.
First, it can be determined by the following method whether or not the solvent is a solvent that does not substantially dissolve the coloring material.
In a 20 mL sample tube bottle, 0.1 g of a coloring material to be judged for solubility is added, solvent S is added using a 10 ml whole pipette, the lid is further closed, and then the treatment is performed with ultrasonic waves for 3 minutes. The obtained liquid is left to stand for 60 minutes in a water bath at 23 ° C. 5 ml of this supernatant is filtered through a PTFE 5 μm membrane filter, and further filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorption spectrum of the obtained filtrate is measured with an ultraviolet-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell. The absorbance (abs) at the maximum absorption wavelength of each color material is determined. At this time, if the absorbance (abs) is less than 40% of the upper limit of measurement (in the case of UV-2500PC manufactured by Shimadzu Corporation, the absorbance (abs) is less than 2), the solvent does not substantially dissolve the coloring material. It can be evaluated as a solvent. At this time, when the absorbance (abs) is 40% or more of the upper limit value of measurement, the solubility is further determined by the following evaluation method.
First, instead of the solvent S, a good solvent for the coloring material (for example, an alcohol such as methanol) for which the solubility is to be determined is used to obtain a filtrate in the same manner to prepare a coloring material solution, and then 10,000 times. Dilute appropriately to about 100,000 times, and similarly measure the absorbance of the coloring material at the maximum absorption wavelength. The solubility of the coloring material in the solvent S is calculated from the absorbance and the dilution ratio of the coloring material solution of the solvent S and the coloring material solution of a good solvent.
As a result, it is determined that the solvent having a solubility of 0.1 (g / 10 ml solvent) or less in the coloring material is a solvent in which the coloring material is poorly soluble, which can be used in the present invention.
The solvent having a solubility of 0.1 (g / 10 ml solvent) or less in the coloring material should be contained in the total solvent of the coloring material dispersion in an amount of 95% by mass or more from the viewpoint of improving the dispersion stability of the coloring material dispersion. Is preferable, 98% by mass or more is preferable, and 100% by mass is most preferable.

In the colored resin composition of the present invention, it is preferable to appropriately select and use the ester solvent from the viewpoint of dispersion stability.
The ester solvent refers to a solvent containing at least an ester group, for example, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3. -Methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate , 1,6-Hexanediol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.
In addition, glycol ether solvents such as 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether, and glycol diether solvents such as diethylene glycol ethyl methyl ether are also suitable from the viewpoint of adjusting solubility. Used for. These solvents are preferably used because they can easily improve the solubility and compatibility when two or more kinds of alkali-soluble resins are used or when an alkali-soluble resin having a high acid value is used.
The solvent used in the present invention includes propylene glycol monomethyl ether acetate (PGMEA), 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, propylene glycol monomethyl ether, and diethylene glycol ethyl methyl. At least one solvent selected from ether and diethylene glycol monomethyl ether is preferable from the viewpoint of improving the solubility and coating suitability of other components and improving the contrast and brightness of the color filter.
Of these, propylene glycol monomethyl ether acetate (PGMEA) is preferably used because it has a low risk to the human body and has low volatility near room temperature but good heat-drying property. In this case, there is an advantage that a special cleaning step is not required even when switching to the colored resin composition using the conventional PGMEA. Therefore, the solvent used in the present invention contains propylene glycol monomethyl ether acetate, and further includes 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, propylene glycol monomethyl ether, and the like. It is more preferable that at least one solvent selected from diethylene glycol ethyl methyl ether and diethylene glycol monomethyl ether may be contained.
The solvent used in the present invention preferably contains propylene glycol monomethyl ether acetate in an amount of 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more in the total solvent.

[Other alkali-soluble resins]
In the present invention, in addition to the specific polyamide-imide resin, other alkali-soluble resins may be further contained. The other alkali-soluble resin may be used alone or in combination of two or more.
The other alkali-soluble resin in the present invention is different from the specific polyamide-imide resin, has an acidic group and usually a carboxyl group, acts as a binder resin, and forms a pattern. As long as it is soluble in the developer to be used, particularly preferably an alkaline developer, it can be appropriately selected and used.
In the present invention, the alkali-soluble resin can be referred to as having an acid value of 40 mgKOH / g or more as a guide.

In the present invention, other alkali-soluble resins preferable to be used in combination with the specific polyamideimide resin are specifically an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include acrylic resins such as, and epoxy (meth) acrylate resins having a carboxyl group. Among these, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, two or more kinds of acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be mixed and used.

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxy group are, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Be done. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Moreover, you may use an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride as a precursor of a carboxyl group. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved. Further, the present inventors have found that the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer, is suppressed by using an alkali-soluble resin having a hydrocarbon ring. Although the action has not been clarified, the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in higher strength of the coating film and suppression of swelling due to the solvent. It is presumed to be.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof. May have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, or an amide group. Above all, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornan, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantan. Rings: Aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilben, and cardo structures represented by the following chemical formula (5). Be done.

When the hydrocarbon ring contains an aliphatic ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the cardo structure represented by the chemical formula (5) is contained, the curability of the colored layer is improved and the solvent resistance (suppression of NMP swelling) is improved, which is particularly preferable.

In the alkali-soluble resin used in the present invention, it is easier to adjust the amount of each structural unit by using an acrylic copolymer having the above-mentioned structural unit having a hydrocarbon ring in addition to the structural unit having a carboxyl group. It is preferable because it is easy to increase the amount of the structural unit having the hydrocarbon ring to improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxyl and the above-mentioned hydrocarbon ring shall be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". Can be done.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene. And so on.

Other alkali-soluble resins used in the present invention are also ethylene because the film strength of the cured film is improved to improve the development resistance, the heat shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent. It is preferable to have a sex double bond. When it has an ethylenic double bond, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer can form a cross-linking bond in the curing step of the resin composition at the time of producing the color filter. As a result, it is presumed that the film strength of the cured film of the colored layer is improved, the heat shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond, for example, glycidyl (meth) acrylate, is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Alternatively, a method in which a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and an ethylenic double bond is introduced into a side chain. And so on.

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

The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and a styrene-acrylic copolymer. An acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. Is more preferable.

The alkali-soluble resin can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charging amount of each structural unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer charged 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, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, preferably 40% by mass or less, based on the total amount of the monomers. More preferably.
If the proportion of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkaline developer is lowered, and the effect of the present invention may be impaired. Further, when the proportion of the carboxyl group-containing ethylenically unsaturated monomer exceeds 50% by mass, the formed pattern tends to fall off from the substrate and the film on the pattern surface tends to be roughened during development with an alkaline developer.

Further, in an acrylic resin such as an acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring and a styrene-acrylic copolymer, which are preferably used as an alkali-soluble resin, a carboxyl group is used. The amount of the ethylenically unsaturated monomer charged is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the monomers. Further, in the acrylic resin, the amount of the hydrocarbon ring group-containing ethylenically unsaturated monomer charged is preferably 30% by mass to 80% by mass, preferably 40% by mass to 75% by mass, based on the total amount of the monomers. Is more preferable.

Further, an acrylic copolymer and a styrene-acrylic type having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond, which are more preferably used as an alkali-soluble resin. In the case of introducing an ethylenic double bond by adding a compound having both an epoxy group and an ethylenic double bond in the molecule to a carboxyl group-containing ethylenically unsaturated monomer in an acrylic resin such as a copolymer. The amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the monomers. In the acrylic resin, the amount of the hydrocarbon ring group-containing ethylenically unsaturated monomer charged is preferably 30% by mass to 80% by mass, and preferably 40% by mass to 75% by mass, based on the total amount of the monomers. More preferred. Further, in the acrylic resin, the compound having both an epoxy group and an ethylenically double bond is preferably 10% by mass to 95% by mass, preferably 10% by mass to 95% by mass, based on the amount of the carboxyl group-containing ethylenically unsaturated monomer charged. More preferably, it is from% by mass to 90% by mass.
When the acrylic resin has a structural unit having a carboxyl group and a hydrocarbon ring, the structural unit shall be included in each of the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring.

It is preferable to select and use the other alkali-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) in the alkaline aqueous solution used for the developing solution. The other alkali-soluble resin preferably has an acid value of 80 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used for a developing solution and adhesion to a substrate. Above all, it is preferably 90 mgKOH / g or more and 280 mgKOH / g or less, and more preferably 100 mgKOH / g or more and 250 mgKOH / g or less. An alkali-soluble resin having an acid value of 100 mgKOH / g or more is preferable because it improves heat resistance and improves the brightness of the colored layer when combined with a rake coloring material. Further, when the metal lake color material is used in combination with the metal lake color material of an acid dye, it is preferable to use an alkali-soluble resin having an acid value of 90 mgKOH / g or more from the viewpoint of improving heat resistance.
The alkali-soluble resin having an acid value of the lower limit or more easily interacts with the basic group of the anion existing near the surface of the molecular assembly of the coloring material represented by the general formula (I), and as a result, , It is presumed that the alkali-soluble resin is easily adsorbed on the surface of the molecular aggregate. Since the alkali-soluble resin has a relatively high acid value, once adsorbed, it is difficult to dissociate even when heated at a high temperature, decomposition of the coloring material can be further suppressed, a decrease in brightness is suppressed, and heat resistance is significantly improved. It is presumed to be.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Further, if it is 100 or more, the ratio of the structural unit having a carboxyl group and other structural units such as the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. There is.
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical formula (1).

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

The ethylenically unsaturated bond equivalent is determined by, for example, measuring the number of ethylenically double bonds contained in 1 g of an alkali-soluble resin in accordance with a test method for raw materials as described in JIS K 0070: 1992. It may be calculated.

The weight average molecular weight of the alkali-soluble resin is not particularly limited. Of these, it is preferably in the range of 1,000 to 500,000, and more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably deteriorated, and if it exceeds 500,000, it may be difficult to form a pattern during development with an alkaline developer.

[Polyfunctional monomer]
The polyfunctional monomer used in the colored resin composition for a color filter of the present invention may be any as long as it can be polymerized by an initiator described later, and is not particularly limited, and usually has two or more ethylenically unsaturated double bonds. A compound having is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable, and a trifunctional or higher polyfunctional (meth) acrylate is more preferable.

Among the polyfunctional (meth) acrylates, the trifunctional or higher functional (meth) acrylate includes, for example, trimethylolpropanthritol (meth) acrylate, trimethylol ethanetri (meth) acrylate, glycerol tri (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, pentaerythritol anhydride-modified pentaerythritol tetra (meth) acrylate, phosphate tri (meth) acrylate, tris (acrythroxythritol) ) Pentaerythritol, tris (methroxythritol) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol Monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, carboxylic acid-modified dipentaerythritol penta (meth) acrylate, Examples thereof include pentaerythritol anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, and ester hexa (meth) acrylate.

In the present invention, from the viewpoint of improving photocurability (high sensitivity), the polyfunctional monomer preferably has three or more polymerizable double bonds (trifunctional), for example, trivalent or higher. Poly (meth) acrylates of polyhydric alcohols are preferably mentioned. Further, in the present invention, it is preferable that the polyfunctional monomer has a carboxyl group from the viewpoint of improving the alkali developability. Examples of the polyfunctional monomer having a carboxyl group include carboxylic acid-modified products of the poly (meth) acrylates of the polyhydric alcohol.
Specific examples of poly (meth) acrylates of polyhydric alcohols include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Examples of carboxylic acid-modified products of poly (meth) acrylates of polyhydric alcohols include succinic acid-modified products of pentaerythritol tri (meth) acrylate and succinic acid-modified products of dipentaerythritol penta (meth) acrylate. ..
One of these polyfunctional monomers may be used alone, or two or more thereof may be used in combination. For example, a polyfunctional monomer having a carboxyl group and a polyfunctional monomer having no carboxyl group may be used in combination. From the viewpoint of improving heat resistance and adhesion, a succinic acid-modified product of pentaerythritol tri (meth) acrylate having a carboxyl group and a succinic acid-modified product of dipentaerythritol penta (meth) acrylate are preferable.
As such a polyfunctional monomer, a commercially available product may be used as appropriate. For example, as a commercially available product containing a succinic acid-modified product of dipentaerythritol penta (meth) acrylate, trade names M-520D and TO-2371 (Toagosei) are used. Co., Ltd.) and the like.

[Initiator]
The initiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and one or a combination of two or more of various conventionally known initiators can be used.

Examples of the initiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone and the like. Can be done. Specific examples of the initiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and benzoin such as ethylbenzoin. , 2- (o-Chlorophenyl) -4,5-phenylimidazole dimer and other biimidazoles, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazol and other halos Methyloxaziazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid Isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl -Phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [ 4- (Methylthio) phenyl] -2- (4-morpholinyl) -1-propanone and the like can be mentioned.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxane-based initiator such as diethylthioxanthone. It is preferable because it suppresses adjustment and water stains and improves development resistance.
When the α-aminoacetophenone-based initiator and the thioxane-based initiator are used, the total content thereof is preferably 5% by mass to 15% by mass with respect to the total solid content of the colored resin composition. When the amount of the initiator is 15% by mass or less, the sublimated product in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the initiator preferably contains an oxime ester-based photoinitiator because it has a high effect of suppressing the occurrence of water stains.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored resin composition for a color filter by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Examples of the oxime ester-based photoinitiator include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF), ADEKA OPT-N-1919, ADEKA Arkuru's NCI-930, Adeka Arkuru's NCI-831 (above, ADEKA). , TR-PBG-304, TR-PBG-326, TR-PBG-345, TR-PBG-3057 (all manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.) and the like may be used.

As the oxime ester-based photoinitiator used in the present invention, it is preferable to use an oxime ester-based photoinitiator that generates an aryl radical, particularly a phenyl radical, and further an oxime ester-based photoinitiator that generates an alkyl radical, particularly a methyl radical. It is preferable to use a photoinitiator because it is excellent in solvent resistance, development resistance, and water stain generation suppressing effect. It is presumed that alkyl radicals are more likely to activate radical transfer than aryl radicals. Examples of the oxime ester-based photoinitiator that generates an alkyl radical include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime). (Product name: Irgacure OXE-02, manufactured by BASF), Metanon, [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11-( 2-Ethylhexyl) -11H-benzo [a] carbazole-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), etanone, 1- [9-ethyl -6- (1,3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA) ), Metanon, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime (trade name: Adecaarc) Luz NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyl) Oxime) (trade name TR-PBG-304, manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1- [2- (2-pyrimidinylthio) -9H-carbazole-3-yl]-, 1- (o-Acetyloxyme) (trade name TR-PBG-314, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazole-3-3 Il]-, 1- (o-acetyloxime) (trade name TR-PBG-326, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H- Carbazole-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-331, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), 1-octanone, 1- [4- [3- [1-[ (Acetyloxy) imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl) thio] -2-methylbenzoyl] -9H-carbazole-9-yl] phenyl]-, 1-( o-Acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical) and the like.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water stains and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. is there. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (eg, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) (Made by Kawaguchi Yakuhin), etc.

In the present invention, the initiator is preferably an oxime ester-based photoinitiator, and more preferably contains an alkyl radical-based oxime ester compound.
When the alkyl radical oxime ester compound and the α-aminoalkylphenone-based initiator are combined, a coating film having an excellent water stain suppressing effect can be obtained, and the sensitivity can be easily adjusted.
Further, when the alkyl radical oxime ester compound and the aryl radical oxime ester compound are used in combination, a coating film having particularly excellent solvent resistance and water stain suppression can be obtained with a small amount of the initiator, and the sensitivity is high. Adjustment is also easy.
When the alkyl radical oxime ester compound is used, the content is preferably 2% by mass to 7% by mass with respect to the total solid content of the colored resin composition. When the amount of the initiator is less than 7 mass, the pattern does not become too thick with respect to the mask opening, which is preferable. When the amount of the initiator is 2% by mass or more, the solvent resistance is good.

<Arbitrary additive component>
The colored resin composition of the present invention may contain various additives, if necessary, as long as the effects of the present invention are not impaired. Examples of the additive include an antioxidant, a polymerization inhibitor, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion accelerator and the like. .. Further, a resin having no alkali solubility may be further contained.

(Antioxidant)
The colored resin composition of the present invention preferably contains an antioxidant from the viewpoint of heat resistance and light resistance. 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, hydrazine-based antioxidants, and the like, and have heat resistance. From the viewpoint of light resistance, it is preferable to use a hindered phenolic antioxidant.

Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF). 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3) , 5-Di-tert-butylbenzyl) mecitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, 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-hydroxybenzylphosphone Benzyl acid acid (trade name: Irgamod 195, manufactured by BASF) and the like can be mentioned. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. ..

When an antioxidant is used, its content is not particularly limited as long as the effect of the present invention is not impaired. The content of the antioxidant is preferably 0.1 part by mass to 5.0 parts by mass, and 0.5 part by mass, based on 100 parts by mass of the total solid content in the colored resin composition. More preferably, it is from 10 parts by mass to 4.0 parts by mass. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

<Mixing ratio of each component in the colored resin composition>
The total content of the coloring material is preferably 3% by mass to 65% by mass, more preferably 4% by mass to 55% by mass, based on the total solid content of the colored resin composition. When it is at least the above lower limit value, the colored layer when the colored resin composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent dispersibility and dispersion stability, sufficient hardness, and adhesion to a substrate.
The content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. 40% by mass can be used. Further, 5% by mass to 35% by mass is preferable, and 5% by mass to 25% by mass is more preferable with respect to the total solid content of the colored resin composition. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, the contrast is improved, and the viscosity with time is excellent. Further, when it is not more than the above upper limit value, the brightness of the colored layer becomes good.

The content of the polyamide-imide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is within the range of 5% by mass to 60% by mass with respect to the total solid content of the colored resin composition. It is preferable that the content is in the range of 10% by mass to 40% by mass. If the content of the polyamide-imide resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the polyamide-imide resin is more than the above upper limit, the film may become rough during development. Pattern chipping may occur.
In the present invention, when another alkali-soluble resin different from the specific polyamide-imide resin is used, the total amount of the alkali-soluble resin (the specific polyamide-imide resin and the other alkali different from the specific polyamide-imide resin). The total amount of the soluble resin) is preferably in the range of 5% by mass to 60% by mass, and further in the range of 10% by mass to 40% by mass with respect to the total solid content of the colored resin composition. Is preferable.
In the present invention, when another alkali-soluble resin different from the specific polyamide-imide resin is used, the total amount of the alkali-soluble resin (the specific polyamide-imide resin and the specific polyamide) from the viewpoint of the effect of the present invention. The specific polyamide-imide resin is preferably 35% by mass or more, and more preferably 50% by mass or more, based on the total amount of other alkali-soluble resins different from the imide resin.

When the polyfunctional monomer is used in the colored resin composition for a color filter of the present invention, the content of the polyfunctional monomer is not particularly limited, but the content of the polyfunctional monomer with respect to the total solid content of the colored resin composition is 5, 60% by mass is preferable, and 10% by mass to 40% by mass is more preferable. If the content of the polyfunctional monomer is less than the above range, photocuring may not proceed sufficiently and the exposed portion may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability may decrease. There is.
When the initiator is used in the colored resin composition of the present invention, the content of the initiator is not particularly limited, but is preferably 1% by mass to 40% by mass with respect to the total solid content of the colored resin composition. 2, 2% by mass to 30% by mass is more preferable, and 3% by mass to 20% by mass is particularly preferable. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. On the other hand, if it is more than the above range, the colored resin composition The content of the coloring material or the like in the solid content becomes relatively small, and a sufficient coloring concentration may not be obtained.

The total content of the alkali-soluble resin, the polyfunctional monomer, and the initiator is 10% by mass to 92% by mass, preferably 15% by mass to 87% by mass, based on the total solid content of the colored resin composition. It is preferable to mix. When it is at least the above lower limit value, a colored layer having sufficient hardness and adhesion to the substrate can be obtained. Further, when it is not more than the above upper limit value, the developability is excellent and the generation of minute wrinkles due to heat shrinkage is suppressed.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55% by mass to 95% by mass, and more particularly preferably in the range of 65% by mass to 88% by mass, based on the total amount of the colored resin composition containing the solvent. preferable. When the content of the solvent is within the above range, the coating property can be made excellent.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes a liquid polyfunctional monomer and the like.

<Manufacturing method of colored resin composition for color filter>
The method for producing a colored resin composition for a color filter of the present invention contains a coloring material, a dispersant, the polyamide-imide resin, a solvent, a polyfunctional monomer, and various additive components used as desired such as an initiator. However, any method may be used as long as the coloring material can be uniformly dispersed in the solvent by the dispersant, and the colorant can be prepared by mixing using a known mixing means.
Examples of the method for preparing the resin composition include (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion liquid, and the polyamide imide resin and the polyamide imide resin are added to the dispersion liquid. A method of mixing a polyfunctional monomer and various additive components used as desired such as an initiator; (2) Desirability of a coloring material, a dispersant, the polyamideimide resin, a polyfunctional monomer, an initiator, etc. in a solvent. Method of simultaneously adding and mixing various additive components used in the above; (3) Add a dispersant, the polyamideimide resin, a polyfunctional monomer, various additive components used as desired, such as an initiator, to the solvent. Then, after mixing, a method of adding a coloring material and dispersing; (4) A coloring material, a dispersant, and another alkali-soluble resin are added to a solvent to prepare a coloring material dispersion liquid, and the dispersion thereof is performed. Examples thereof include a method of further adding and mixing the above-mentioned polyamideimide resin, a solvent, a polyfunctional monomer, and various additive components used as desired such as an initiator to the liquid.
Among these methods, the above methods (1) and (4) are preferable because they can effectively prevent agglomeration of the coloring material and disperse the color material uniformly. When another alkali-soluble resin such as an acrylic resin is added by the method (4) above, it is preferable because the effect of improving the stability over time and the solvent resolubility of the colored resin composition is enhanced.

As a method for preparing the color material dispersion liquid, a conventionally known dispersion method can be appropriately selected and used. For example, (1) a dispersant is mixed with a solvent and stirred in advance to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt of an amino group contained in the dispersant and the organic acid compound. Let me. A method of mixing this with a coloring material and other components as necessary and dispersing them using a known stirrer or disperser; (2) Mixing and stirring the dispersant with a solvent to prepare a dispersant solution, and then dispersing the dispersant. , Coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) Dispersant is mixed with a solvent and stirred. , Dispersant solution is prepared, then the coloring material and other components are mixed if necessary to prepare a dispersion using a known stirrer or disperser, and then an organic acid compound is added as necessary. The method etc. can be mentioned.
In the present invention, the method (1) described above is preferable from the viewpoint of dispersion stability of the coloring material.

Examples of the disperser for performing the dispersion treatment include a roll mill such as a two-roll and three-roll mill, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

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

2. Color filter The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is for the color filter according to the present invention. It has a colored layer made of a cured product of the colored resin composition.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer made of a cured product of the colored resin composition for a color filter according to the present invention.
The colored layer is usually formed in the opening of a light-shielding portion on a transparent substrate described later, and is usually composed of a colored pattern of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-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 adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but is usually preferably in the range of 1 μm to 5 μm.

When the colored resin composition is a photosensitive resin composition, for example, the colored layer can be formed by the following method.
First, the above-mentioned colored resin composition for a color filter of the present invention is applied onto a transparent substrate described later by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. Is applied to form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized. Use a photosensitive coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developing solution is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected according to the application of the coating film.

The chromaticity of the colored layer of the color filter may be appropriately adjusted according to the light source and the like, and is not particularly limited. For example, in the case of the blue colored layer, x is 0 in the chromaticity (x, y) of the C light source. It is preferable that 12 to 0.27 and y are in the range of 0.04 to 0.18.

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a striped shape and a matrix shape. Examples of the light-shielding portion include a black pigment dispersed or dissolved in a binder resin, a metal thin film such as chromium and chromium oxide, and the like. This metal thin film may be a CrO _x film (x is an arbitrary number) and a Cr film in which two layers are laminated, or a CrO _x film having a further reduced reflectance (x is an arbitrary number). , CrN _y film (y is an arbitrary number) and Cr film may be laminated in three layers.
When the light-shielding portion is a black color material dispersed or dissolved in a binder resin, the method for forming the light-shielding portion is not particularly limited as long as the light-shielding portion can be patterned. For example, a photolithography method, a printing method, an inkjet method, etc. using a colored resin composition for a light-shielding portion can be mentioned.
The patterned light-shielding portion can be formed, for example, by the same method as the formation of the colored layer.

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

(Transparent board)
The transparent substrate in the color filter of the present invention may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used in a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or a flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but for example, one having about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition to the transparent substrate, light-shielding portion, and colored layer, the color filter of the present invention has, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. You may.

3. 3. Display device The display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited and can be appropriately selected from conventionally known display devices. Examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]
The liquid crystal display device is characterized by having the above-mentioned color filter according to the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 comprises a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. Have.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive system of the liquid crystal display device of the present invention is not particularly limited, and a drive system generally used for a liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be preferably used.
Further, as the facing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

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

[Organic light emission display device]
The organic light emitting display device is characterized by having the above-mentioned color filter according to the present invention and an organic light emitting body.
Such an organic light emitting display device will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional 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 includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which the organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations of the organic light emitter 80, known ones can be appropriately used. The organic light emitting display device 100 produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of Resin A)
PGMEA (propylene glycol monomethyl ether acetate) 1086 parts by mass, IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate: NCO% = 17.2) 587.3 parts by mass in a flask equipped with a stirrer, a thermometer, and a condenser. (0.80 mol parts) and 499.1 parts by mass (2.52 mol parts) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added, and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption by infrared spectrum, the characteristic absorption of isocyanate groups of 2270 cm ^-1 disappeared completely, and the absorption of imide groups was absorbed in 1780 cm ^-1 and 1720 cm ^-1. confirmed. The acid value was 212 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 4700 in terms of polystyrene. The concentration of acid anhydride was 1.14 mmol / g in terms of solid content. The concentration of the resin content was 47.4% by mass. This was used as a resin A solution.

(Synthesis Example 2: Synthesis of Resin B)
96.3 parts by mass (1.3 mol parts) of n-butanol was added to the resin A solution obtained in Synthesis Example 1 and reacted at 120 ° C. for 5 hours. As a result of measuring the characteristic absorption by the infrared spectrum, the characteristic absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, completely disappeared. The acid value was 148 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 4800 in terms of polystyrene. The resin content was 49.2% by mass. This was used as a resin B solution.

(Synthesis Example 3: Synthesis of Resin C)
Add 1569 parts by mass of PGMEA, 959 parts by mass (1.31 mol) of IPDI3N and 791 parts by mass (4.12 mol) of trimellitic anhydride to a flask equipped with a stirrer, a thermometer and a condenser, and raise the temperature to 140 ° C. It was warm. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption by infrared spectrum, the characteristic absorption of isocyanate groups of 2270 cm ^-1 disappeared completely, and the absorption of imide groups was absorbed in 1780 cm ^-1 and 1720 cm ^-1. confirmed. The acid value was 185 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 5700 in terms of polystyrene. The concentration of acid anhydride was 0.57 mmol / g in terms of solid content. The concentration of the resin content was 50.2% by mass. This was used as a resin C solution.

(Synthesis Example 4: Synthesis of Resin D)
79.9 parts by mass (1.08 mol parts) of n-butanol was added to the resin C solution obtained in Synthesis Example 3, and the mixture was reacted at 120 ° C. for 5 hours. As a result of measuring the characteristic absorption by the infrared spectrum, the absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, completely disappeared. The acid value was 153 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 5800 in terms of polystyrene. The resin content was 51.1% by mass. This was used as a resin D solution.

(Synthesis Example 5: Synthesis of Resin E)
A flask equipped with a stirrer, a thermometer, and a condenser contains 1086 parts by mass of PGMEA, 587.3 parts by mass (0.80 mol parts) of IPDI3N, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 499. 1 part by mass (2.52 mol parts) was added, and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of isocyanate groups of 2270 cm-1 completely disappeared, and the absorption of imide groups was absorbed in 1780 cm ^-1 and 1720 cm ^-1. confirmed.
After lowering the temperature to 110 ° C, 1.2 parts by mass of p-methoxyphenol, 153.5 parts by mass (1.08 mol) of glycidyl methacrylate (GMA), and 9.6 parts by mass of triethylamine were added and added at 110 ° C for 15 hours. It was reacted. As a result of measuring the characteristic absorption by the infrared spectrum, the absorption of 1860 cm ^-1 , which is the characteristic absorption of the acid anhydride group, completely disappeared. The acid value was 148 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 5000 in terms of polystyrene. The concentration of the resin content was 51.3% by mass. This was used as a resin E solution.

(Synthesis Example 6: Synthesis of Resin F)
After charging 150 parts by mass of PGMEA in a polymerization tank and heating the temperature to 100 ° C. in a nitrogen atmosphere, 32 parts by mass of methacrylic acid (MAA), 52 parts by mass of cyclohexyl methacrylate (CHMA) and perbutyl O (manufactured by Nichiyu Co., Ltd.) ) 6 parts by mass and 2 parts by mass of the chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the reaction was continued at 100 ° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of dropping of the main chain forming mixture to terminate the polymerization.
Next, while blowing air, 16 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110 ° C., 0.8 parts by mass of triethylamine was added, and the temperature was 110 ° C. for 15 hours. The addition reaction was carried out to obtain a resin F solution (weight average molecular weight (Mw) 9,000, acid value 145 mgKOH / g in terms of solid content, solid content 40% by mass).
The weight average molecular weight was measured by a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent.

(Synthesis Example 7: Synthesis of Resin G)
1464 parts by mass of PGMEA, 888 parts by mass (2 mol) of IPDI (isophorone diisocyanate), 412 parts by mass (2 mol) of NBDI (norbornan diisocyanate) and 960 parts by mass of trimellitic anhydride in a flask equipped with a stirrer, a thermometer and a condenser. Parts (5 mol parts) were added, and the temperature was raised to 130 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid, and as a result of measuring the characteristic absorption by infrared spectrum, the characteristic absorption of the isocyanate group, 2270 cm-1, completely disappeared to 725 cm-1, 1780 cm-1, and 1720 cm-1. Absorption of imide groups was confirmed. The acid value was 90 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 1500 in terms of polystyrene. The resin content was 59.7% by mass. This was used as a resin G solution.

(Synthesis Example 8: Synthesis of Resin H)
A flask equipped with a stirrer, a thermometer, and a condenser contains 96.1 parts by mass (0.5 mol) of trimellitic acid anhydride, 86.1 parts by mass (0.5 mol) of cyclohexanedicarboxylic acid, and Isophorone diisocyanate 222. 2 parts by mass (1 mol part) and 404.4 parts by mass of dimethylimidazolidinone as a polymerization solvent were charged, the temperature was raised to 150 ° C. and reacted for 5 hours, and then 0.3 mol of glycidyl methacrylate was cooled to 100 ° C. The reaction was continued for 3 hours at a concentration of 30% by mass by adding a portion and dimethylimidazolidinone. The obtained polymer solution was cooled to room temperature, poured into a large amount of water to solidify, thoroughly washed with water, and then dried to obtain a powder. The obtained unsaturated group-containing polyamide-imide resin was dissolved in an equal amount mixed solvent of toluene and ethanol so as to have a concentration of 10% by mass, and this was used as a resin H solution.

In addition, a commercially available polyamide-imide resin containing an aliphatic carboxylic acid, trade name EMG-1015 (manufactured by DIC Corporation) was prepared.

(Synthesis Example 9: Synthesis of Block Copolymer 1)
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round bottom 4-port separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen substitution. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2- (trimethylsilyloxy) ethyl methacrylate (TMSMA), and 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA) of the B-block monomer. Parts, 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) over 60 minutes using an addition funnel. Dropped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content of 30% by mass. Add 32.5 parts by mass of water, raise the temperature to 100 ° C. and react for 7 hours to deprotect the constituent units derived from EEMA to make them constituent units derived from methacrylic acid (MAA), and deprotect the constituent units derived from TEMSMA. It was used as a constituent unit derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, filtered, and vacuum dried to purify the block copolymer 1 (acid value 8 mgKOH / g) containing the structure represented by the general formula (1). , Tg 38 ° C.) was obtained. When the block copolymer 1 thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Synthesis Example 10: Synthesis of Color Material A)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g (yield) of Intermediate 1 represented by the following chemical formula (1) was obtained. Rate 70%) Obtained.
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 511 (+), divalent / elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Coloring Material A 5.00 g (4.58 mmol) of Intermediate 1 was added to 300 ml of water and dissolved at 90 ° C. to prepare an Intermediate 2 solution. Next, add 10.44 g (3.05 mmol) of phosphotungstic acid / n-hydrate H ₃ [PW ₁₂ O ₄₀ ] / nH ₂ O (n = 30) manufactured by Nippon Inorganic Chemicals Co., Ltd. to 100 mL of water and stir at 90 ° C. Then, an aqueous solution of phosphotungstic acid was prepared. An aqueous solution of phosphotungstic acid was mixed with the above two intermediate solutions at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of the coloring material A represented by the following chemical formula (2).
It was confirmed from the following analysis results that the obtained compound was the target compound. (Mole ratio W / Mo = 100/0)
-MS (ESI) (m / z): 510 (+), divalent / elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) 5.17%, 4.11%)
Further, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained even after becoming the coloring material A.

(Synthesis Example 11: Synthesis of Color Material B)
Acid Red 289 5.0 g was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.85 g of polyaluminum chloride (“trade name: Takibine # 1500” manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5 mass%, alumina content 23.5 mass%) in 200 ml of water The mixture was added and stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. over 15 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a metal lake coloring material B of a rhodamine-based acid dye.

(Preparation Example 1: Preparation of Photosensitive Binder Component CR-1)
Dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toa Synthetic Co., Ltd.)) as a polyfunctional monomer with respect to 16.6 parts by mass of the resin A solution (solid content 47.4% by mass) obtained in Synthesis Example 1. 23.5 parts by mass, 5.9 parts by mass of Irgacure 907 (manufactured by BASF) as an initiator, 2.0 parts by mass of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), antioxidant IRGANOX1010 (manufactured by BASF) 0. 8 parts by mass and 51.3 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-1.

(Preparation Examples 2 to 8: Preparation of photosensitive binder components CR-2 to CR-5 and CR-8 to CR-10)
In Preparation Example 1, the same as in Preparation Example 1 except that the resin B to H solutions of Synthesis Examples 2 to 8 were used instead of the resin A solution and adjusted so that the weight ratio of each component was the same. Photosensitive binder components CR-2 to CR-5 and CR-8 to CR-10 were obtained.

(Example 1: Preparation of colored resin composition)
(1) Preparation of Coloring Material Dispersion Solution A In a 225 mL mayonnaise bottle, 63.3 parts by mass of PGMEA, 13.0 parts by mass of a resin F solution (solid content 40% by mass), and block copolymer 1 (solid content) of Synthesis Example 9 45% by mass) 9.96 parts by mass was added and stirred. 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalent with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
13.0 parts by mass of the coloring material A of Synthesis Example 10 and 100 parts by mass of zirconia beads having a particle size of 2.0 mm were added, and the mixture was shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size was 0. The beads were changed to 200 parts of 1 mm zirconia beads and dispersed with a paint shaker for 4 hours as the main crushing to obtain a color material dispersion liquid A.

(2) Preparation of Colored Resin Composition for Color Filter 30.9 parts by mass of color material dispersion A obtained in (1) above, 26.9 parts by mass of photosensitive binder component CR-1 of Preparation Example 1, surface activity Agent Megafuck R08MH (manufactured by DIC) 0.01 parts by mass and 42.1 parts by mass of PGMEA were mixed to obtain a colored resin composition for a color filter of Example 1. The colored resin composition is a photosensitive colored resin composition.

(Examples 2 to 5: Preparation of colored resin composition for color filter)
The color filters of Examples 2 to 5 are the same as in Example 1 except that the photosensitive binder components CR-1 are replaced with the photosensitive binder components CR-2 to CR-5 in Example 1. A colored resin composition for use was obtained.

(Example 6: Preparation of colored resin composition for color filter)
(1) Preparation of Coloring Material Dispersion Solution B 76.3 parts by mass of PGMEA and 9.96 parts by mass of block copolymer 1 (solid content 45% by mass) of Synthesis Example 9 were placed in a 225 mL mayonnaise bottle and stirred. 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalent with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
13.0 parts by mass of the coloring material A of Synthesis Example 10 and 100 parts by mass of zirconia beads having a particle size of 2.0 mm were added, and the mixture was shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size was 0. The beads were changed to 200 parts of 1 mm zirconia beads and dispersed with a paint shaker for 4 hours as the main crushing to obtain a color material dispersion liquid B.

(2) Preparation of Colored Resin Composition for Color Filter 30.9 parts by mass of color material dispersion B obtained in (1) above, 31.0 parts by mass of photosensitive binder component CR-2 of Preparation Example 2, surface activity Agent Megafuck R08MH (manufactured by DIC) 0.01 part by mass and PGMEA38.1 part by mass were mixed to obtain a colored resin composition for a color filter of Example 6.

(Example 7: Preparation of colored resin composition for color filter)
(1) Preparation of Photosensitive Binder Component CR-6 In Preparation Example 1, a polyamide-imide resin solution (solid content 44.1% by mass) having the repeating unit of the general formula (A) instead of the resin A solution (commodity). Name: EMG-1015, manufactured by DIC Co., Ltd., polyamide-imide containing aliphatic carboxylic acid, acid value of 149 KOHmg / g in terms of solid content, number average molecular weight of 4900), adjusted so that the weight ratio of each component is the same. A photosensitive binder component CR-6 was obtained in the same manner as in Preparation Example 1.
(2) Preparation of Colored Resin Composition for Color Filter In Example 1, the same procedure as in Example 1 was carried out except that the photosensitive binder component CR-1 was changed to the photosensitive binder component CR-6. A colored resin composition for a color filter of Example 7 was obtained.

(Example 8: Preparation of colored resin composition for color filter)
(1) Preparation of Photosensitive Binder Component CR-7 Dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate) as a polyfunctional monomer with respect to 15.7 parts by mass of the resin E solution (solid content 51.3% by mass) obtained in Synthesis Example 5. DPHA) (Aronix M402 (manufactured by Toa Synthetic Co., Ltd.)) 24.1 parts by mass, Irgacure 907 (manufactured by BASF) 5.9 parts by mass as an initiator, TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.) 1.2 A photosensitive binder component CR-7 was obtained by adding 0.8 parts by mass, 0.8 parts by mass of the antioxidant IRGANOX1010 (manufactured by BASF), and 52.4 parts by mass of PGMEA.
(2) Preparation of Colored Resin Composition for Color Filter In Example 1, the same procedure as in Example 1 was carried out except that the photosensitive binder component CR-1 was changed to the photosensitive binder component CR-7. A colored resin composition for a color filter of Example 8 was obtained.

(Comparative Examples 1 to 3: Preparation of Colored Resin Composition for Color Filter)
In Example 1, the photosensitive binder component CR-8 (resin F: acrylic resin), CR-9 (resin G), and CR-10 (resin H) were changed instead of the photosensitive binder component CR-1. Colored resin compositions for color filters of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except for the above.
However, the colored resin composition of Comparative Example 3 could not be evaluated because it gelled significantly within 1 day after preparation.

[Evaluation]
<Brightness and contrast evaluation>
The colored resin compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were each used as a glass substrate having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.). A colored layer was formed by applying the above using a spin coater so that the chromaticity after post-baking was y = 0.089, and then drying at 80 ° C. for 3 minutes using a hot plate. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp.
Next, the colored substrate was post-baked in a clean oven at 230 ° C. for 75 minutes, and the contrast and brightness (Y) of the obtained colored substrate were measured by Tsubosaka Electric's contrast measuring device CT-1B and Olympus's microspectroscopy measuring device OSP. -Measured using SP200. The results are shown in Table 2.

<Development time evaluation>
The colored resin compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were each used as a glass substrate having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.). After coating with a spin coater on the top, a colored layer having a thickness of 2.5 μm was formed by drying at 80 ° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp via a photomask. Then, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and the unexposed portion of the colored layer was completely dissolved to form the colored layer. The time until the glass surface of the formed portion appeared was measured as the developing time (seconds). The results are shown in Table 2.

<Residual film ratio after development>
The colored resin compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 and 2 are placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm, respectively, on a spin coater. Was applied using. After heat-drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 60 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Then, shower development was carried out using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). The calculated value of T2 / T1 × 100 (%) was used as the residual film ratio after development.

<Water stain evaluation>
The colored resin compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 and 2 are post-baked on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater. After coating with a film thickness to form a colored layer with a thickness of 2.5 μm, it is dried at 80 ° C. for 3 minutes using a hot plate, and ultraviolet rays of 30 mJ / cm ² are used using an ultrahigh pressure mercury lamp without using a photomask. A colored layer was formed on the glass substrate by irradiating the entire surface with. Next, spin-development is performed using a 0.05 mass% potassium hydroxide aqueous solution as a developer, the developer is indirectly liquidated for 60 seconds, and then washed with pure water for development treatment. The washed substrate is rotated for 10 seconds and water is used. Immediately after the water stain was removed by centrifugation, the contact angle of pure water was measured as follows to evaluate water stain.
To measure the contact angle of pure water, 1.0 μL of pure water is dropped on the surface of the colored layer immediately after the water is centrifugally removed, and the static contact angle 10 seconds after the drip is measured according to the θ / 2 method. I measured it. The measuring device was a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd..
(Evaluation criteria)
AA: Contact angle 80 degrees or more A: Contact angle 65 degrees or more and less than 80 degrees B: Contact angle less than 65 degrees If the water stain evaluation standard is AA or A, it can be used practically, but if the evaluation result is AA The effect is excellent.

<Stability of colored resin composition over time>
The colored resin compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were stored at room temperature (25 ° C.), respectively, and their viscosities were measured 1 day and 2 weeks after preparation. The viscosity was measured at 25.0 ± 1.0 ° C. using a vibration viscometer (VM-200T2 manufactured by SEKONIC), and the value 30 seconds after the start of measurement was adopted.
(Criteria for evaluating stability over time)
AA: Viscosity change is less than 3% by comparing the viscosity 1 day after preparation and viscosity after 2 weeks storage A: Viscosity change by comparing the viscosity 1 day after preparation and the viscosity after 2 weeks storage B: 3% or more and less than 10% B: Viscosity change is 10% or more by comparing the viscosity 1 day after preparation and the viscosity after 2 weeks storage.

<Solvent resolubility evaluation of colored resin composition>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored resin composition for a color filter obtained in Examples and Comparative Examples, and applied to a 1 cm long portion of the glass substrate. The pulled glass substrate was placed in a constant temperature and humidity chamber so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dry coating film was visually discriminated and evaluated. The results are also shown in Table 2.
(Solvent resolubility evaluation standard)
AA: All dry coatings are dissolved A: Fragments of dry coating are formed in the solvent, but the flakes dissolve within 5 minutes B: Fragments of dry coating are formed in the solvent, and the flakes are within 5 minutes If the evaluation standard for solvent resolubility that does not dissolve is AA or A, it is evaluated as having good solvent resolubility and can be used without any problem in practical use.

(Example 9: Preparation of colored resin composition for color filter)
Preparation of coloring material dispersion C In a 225 mL mayonnaise bottle, 62.9 parts by mass of PGMEA, 13.0 parts by mass of resin F solution (solid content 40% by mass), and block copolymer 1 (solid content 45% by mass) of Synthesis Example 9 ) 10.7 parts by mass was added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.3 molar equivalents with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
9.1 parts by mass of color material A of Synthesis Example 10, 3.9 parts by mass of color material B of Synthesis Example 11, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and a paint shaker (manufactured by Asada Iron Works Co., Ltd.) was added as preliminary crushing. ) Was shaken for 1 hour, then changed to 200 parts of zirconia beads having a particle size of 0.1 mm and dispersed for 8 hours with a paint shaker as the main crushing to obtain a color material dispersion liquid C.
(2) Preparation of Colored Resin Composition for Color Filter In Example 1, the same as in Example 1 except that the color material dispersion A was changed to the color material dispersion C obtained in (1) above. A colored resin composition for a color filter of Example 9 was obtained.

(Examples 10 to 13: Preparation of colored resin composition for color filter)
The color filters of Examples 10 to 13 are the same as in Example 9 except that the photosensitive binder components CR-1 are changed to the photosensitive binder components CR-2 to CR-5 in Example 9. A colored resin composition for use was obtained.

(Example 14: Preparation of colored resin composition for color filter)
(1) Preparation of Coloring Material Dispersion Solution D 75.9 parts by mass of PGMEA and 10.7 parts by mass of block copolymer 1 (solid content 45% by mass) of Synthesis Example 9 were placed in a 225 mL mayonnaise bottle and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.3 molar equivalents with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
9.1 parts by mass of color material A of Synthesis Example 10, 3.9 parts by mass of color material B of Synthesis Example 11, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and a paint shaker (manufactured by Asada Iron Works Co., Ltd.) was added as preliminary crushing. ) Was shaken for 1 hour, then changed to 200 parts of zirconia beads having a particle size of 0.1 mm and dispersed for 8 hours with a paint shaker as the main crushing to obtain a color material dispersion liquid D.

(2) Preparation of Colored Resin Composition for Color Filter 30.9 parts by mass of color material dispersion D obtained in (1) above, 31.0 parts by mass of photosensitive binder component CR-2 of Preparation Example 2, surface activity Agent Megafuck R08MH (manufactured by DIC) 0.01 part by mass and PGMEA 38.1 part by mass were mixed to obtain a colored resin composition for a color filter of Example 14.

(Example 15: Preparation of colored resin composition for color filter)
A colored resin composition for a color filter of Example 15 was obtained in the same manner as in Example 9 except that the photosensitive binder component CR-1 was changed to the photosensitive binder component CR-6 in Example 9. It was.

(Comparative Example 4: Preparation of Colored Resin Composition for Color Filter)
In Example 9, in the same manner as in Example 9, Comparative Example 4 was changed to the photosensitive binder component CR-8 (resin F: containing an acrylic resin) instead of the photosensitive binder component CR-1. A colored resin composition for a color filter was obtained.

[Evaluation]
The brightness and contrast of Examples 9 to 15 and Comparative Example 4 were evaluated in the same manner as in Example 1 except that they were applied so that the chromaticity was y = 0.048.
The development time, the residual film ratio after development, water stain, stability over time, and resolubility were evaluated in the same manner as in Example 1.
The evaluation results of Examples 9 to 15 and Comparative Example 4 are shown in Table 3.

(Example 16: Preparation of colored resin composition for color filter)
(1) Preparation of Coloring Material Dispersion Solution E In a 225 mL mayonnaise bottle, 63.3 parts by mass of PGMEA, 13.0 parts by mass of a resin F solution (solid content 40% by mass), and block copolymer 1 (solid content) of Synthesis Example 9 45% by mass) 9.96 parts by mass was added and stirred. 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalent with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
There C. I. Pigment Green 58 (FASTOGEN GREEN A350, manufactured by DIC) 9.75 parts by mass, C.I. I. Add 3.25 parts by mass of Pigment Yellow 138 and 100 parts by mass of zirconia beads with a particle size of 2.0 mm, shake with a paint shaker (manufactured by Asada Iron Works) for 1 hour as preliminary crushing, and then zirconia with a particle size of 0.1 mm. The beads were changed to 200 parts and dispersed for 4 hours with a paint shaker as the main crushing to obtain a color material dispersion liquid E.

(2) Preparation of Colored Resin Composition for Color Filter 44.0 parts by mass of color material dispersion E obtained in (1) above, 24.3 parts by mass of photosensitive binder component CR-1 of Preparation Example 1, surface activity Agent Megafuck R08MH (manufactured by DIC) 0.01 part by mass and 31.7 part by mass of PGMEA were mixed to obtain a colored resin composition for a color filter of Example 16.

(Examples 17 to 18: Preparation of colored resin composition for color filter)
In Example 16, the same as in Example 16 except that the photosensitive binder component CR-1 was changed to the photosensitive binder components CR-2 and CR-6, respectively, of Examples 17 and 18. A colored resin composition for a color filter was obtained.

(Comparative Example 5: Preparation of Colored Resin Composition for Color Filter)
In Example 16, the same as in Example 16 except that the photosensitive binder component CR-8 (resin F: containing an acrylic resin) was used instead of the photosensitive binder component CR-1. A colored resin composition for a color filter was obtained.

[Evaluation]
With respect to Examples 16 to 18 and Comparative Example 5, the luminance was evaluated in the same manner as in Example 1 except that the chromaticity after post-baking was applied so as to be y = 0.575.
The development time, water stain, and stability over time were evaluated in the same manner as in Example 1.
The evaluation results of Examples 16 to 18 and Comparative Example 5 are shown in Table 4.

(Example 19: Preparation of colored resin composition for color filter)
In the preparation of the colored resin composition for the color filter of Example 13, instead of the solvent PGMEA 42.1 parts by mass, the solvent was used, PGMEA 33.9 parts by mass and 3-methoxy-3-methyl-1-butanol (trade name Sol). A colored resin composition for a color filter of Example 19 was obtained in the same manner as in Example 13 except that it was prepared using 8.2 parts by mass of Fit Clare).

(Example 20: Preparation of colored resin composition for color filter)
In the preparation of the colored resin composition for a color filter of Example 13, instead of 42.1 parts by mass of the solvent PGMEA, 33.9 parts by mass of PGMEA and 8.2 parts by mass of diethylene glycol ethyl methyl ether (EMDG) were used. A colored resin composition for a color filter of Example 20 was obtained in the same manner as in Example 13 except that it was prepared.

(Example 21: Preparation of colored resin composition for color filter)
In the preparation of the colored resin composition for a color filter of Example 13, instead of the solvent PGMEA 42.1 parts by mass, 33.9 parts by mass of PGMEA and 8.2 parts by mass of propylene glycol monomethyl ether (PGME) were used. A colored resin composition for a color filter of Example 21 was obtained in the same manner as in Example 13 except that it was prepared.

(Example 22: Preparation of colored resin composition for color filter)
In the preparation of the colored resin composition for a color filter of Example 9, instead of 42.1 parts by mass of the solvent PGMEA, 33.9 parts by mass of PGMEA and 8.2 parts by mass of diethylene glycol ethyl methyl ether (EMDG) were used. A colored resin composition for a color filter of Example 22 was obtained in the same manner as in Example 9 except that it was prepared.

(Example 23: Preparation of colored resin composition for color filter)
In the preparation of the colored resin composition for the color filter of Example 15, instead of the solvent PGMEA 42.1 parts by mass, the solvent was used, PGMEA 33.9 parts by mass and 3-methoxy-3-methyl-1-butanol (trade name Sol). A colored resin composition for a color filter of Example 23 was obtained in the same manner as in Example 15 except that it was prepared using 8.2 parts by mass of Fit Clare).

[Evaluation]
In Examples 19 to 23, the brightness, contrast, development time, residual film ratio after development, water stain, stability over time, and solvent resolubility were evaluated in the same manner as in Example 9.
The evaluation results of Examples 19 to 23 are shown in Table 5.

(Summary of results)
Examples 1 to 23 corresponding to the colored resin composition for a color filter of the present invention using the polyamideimide resin having the repeating unit represented by the general formula (A) as the alkali-soluble resin have improved brightness and contrast. It is a colored resin composition for a color filter that can form a colored layer, has good developability, and suppresses the occurrence of water stains after development, and provides a color filter with improved brightness and contrast with excellent productivity. It was revealed that it can be formed.
On the other hand, the colored resin compositions of Comparative Examples 1, 4 and 5 in which only the acrylic resin, which has been frequently used as the alkali-soluble resin, is used as the alkali-soluble resin, are inferior in brightness and contrast of the colored layer as compared with Examples. Moreover, water stains occurred after development.
Further, the colored resin composition of Comparative Example 2 using the polyamide-imide resin having no repeating unit represented by the general formula (A) was inferior in brightness and contrast of the colored layer as compared with Examples.
Further, the colored resin composition of Comparative Example 3 using the polyamide-imide resin having no repeating unit represented by the general formula (A) is a composition having poor stability so that it gels significantly one day after preparation. Therefore, it could not be evaluated as in the examples.

Among the polyamide-imide resins having the repeating unit represented by the general formula (A), those in which the terminal carboxyl group is modified with alcohol have further shortened the development time and are excellent in solvent resolubility. (Comparison of Examples 2, 4 and 5 with respect to Examples 1 and 3; Comparison of Examples 10, 12 and 13 with respect to Examples 9 and 11).
Further, it was clarified that when the colored resin composition contains not only a polyamide-imide resin but also an acrylic resin as an alkali-soluble resin, it is excellent in stability over time and solvent resolubility (Example). Comparison of Example 2 with respect to 6; Comparison of Example 10 with respect to Example 14).

1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposing substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emission display device 201 Divalent or higher cation 202 Divalent or higher anion 203 Ionic bond 210 Molecular assembly

Claims (13)

It contains a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent, and the total content of the coloring materials is the total solid content of the colored resin composition. 4 is the mass% to 55 mass%, the content of the polyamide-imide resin Ri 10% to 40% by mass relative to the total solid content of the colored resin composition with respect to,
A colored resin composition for a color filter , wherein the dispersant is a polymer having a structure represented by the following general formula (1) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less .
(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)
(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) , And (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.)
(In the general formula (1), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ⁵ )). -CH (R ⁶ ) -O] _x- CH (R ⁵ ) -CH (R ⁶ )-or -[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- divalent organic group , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R ⁶ is an independent hydrogen atom or methyl group, respectively.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) The polyamide-imide resin is represented by the general formula (C4), (C5), (C6), (C9), or (C10) at least one of the Rc and the resin terminal of the general formula (A). The colored resin composition for a color filter according to claim 1, which comprises a structural unit. The colored resin composition for a color filter according to claim 1 or 2, wherein the polyamide-imide resin contains an unsaturated double bond group. The colored resin composition for a color filter according to any one of claims 1 to 3, further comprising an acrylic resin having an acid value of 50 KOH mg / g or more. The colored resin composition for a color filter according to any one of claims 1 to 4, wherein the coloring material is a rake coloring material. The colored resin composition for a color filter according to any one of claims 1 to 5, wherein the coloring material is a rake coloring material represented by the following general formula (I).
(In the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. ^Bc− contains at least tungsten. Represents a c-valent polyacid anion. R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱ . R ⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ^{i to} R ^v and Ar ¹ may be the same or different, respectively. A and c represent two or more integers, b and d represent one or more integers. E is 0 or 1, and when e is 0, the coupling is It does not exist. Multiple e may be the same or different.) The solvent contains propylene glycol monomethyl ether acetate, and further contains 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol. The colored resin composition for a color filter according to any one of claims 1 to 6 , which may contain at least one solvent selected from monomethyl ether. It contains a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent, and further contains an acrylic resin having an acid value of 50 KOHmg / g or more. Colored resin composition for color filters.
(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)
(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) , And (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.) The color material contains a color material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent, and the color material is a rake color represented by the following general formula (I). A colored resin composition for a color filter, which is a material.
(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)
(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) , And (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.)
(In the general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. ^Bc− contains at least tungsten. Represents a c-valent polyacid anion. R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱ . R ⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ^{i to} R ^v and Ar ¹ may be the same or different, respectively. A and c represent two or more integers, b and d represent one or more integers. E is 0 or 1, and when e is 0, the coupling is It does not exist. Multiple e may be the same or different.) It contains a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent, and the total content of the coloring materials is the total solid content of the colored resin composition. The content of the polyamide-imide resin is 10% by mass to 40% by mass with respect to the total solid content of the colored resin composition.
The polyamide-imide resin is represented by the general formula (C4), (C5), (C6), (C9), or (C10) at least one of the Rc and the resin terminal of the general formula (A). A colored resin composition for a color filter, which comprises a structural unit.
(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)
(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) In (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.) It contains a coloring material, a dispersant, a polyamide-imide resin having a repeating unit represented by the following general formula (A), and a solvent, and the total content of the coloring materials is the total solid content of the colored resin composition. The content of the polyamide-imide resin is 10% by mass to 40% by mass with respect to the total solid content of the colored resin composition.
A colored resin composition for a color filter, wherein the coloring material is a rake coloring material.
(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)
(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) In (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.) A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the colored resin composition for a color filter according to any one of claims 1 to 11. A color filter characterized by having a colored layer made of a cured product of a product. A display device comprising the color filter according to claim 12.