WO2020044975A1

WO2020044975A1 - Coloring resin composition, cured product, color filter and display device

Info

Publication number: WO2020044975A1
Application number: PCT/JP2019/030718
Authority: WO
Inventors: 琢実鈴木; 茉優松葉
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2018-08-27
Filing date: 2019-08-05
Publication date: 2020-03-05
Also published as: CN112585507A; CN112585507B; JPWO2020044975A1; TWI825150B; JP7308842B2; TW202009277A

Abstract

The present invention provides a coloring resin composition which contains (A) a polymer, (B) a polymerizable compound, (C) a polymerization initiator, and (D) a colorant; and the colorant (D) contains C. I. pigment red 291 and a diketopyrrolopyrrole pigment represented by chemical formula (D1).

Description

Colored resin composition, cured product, color filter, and display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Further, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission is attracting attention as a next-generation image display device. With regard to the performance of these image display devices, there is a strong demand for higher image quality such as higher color rendering, higher brightness, and higher contrast and reduction in power consumption.

カラー Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light that has passed through a color filter is directly colored into the color of each pixel constituting the color filter, and light of those colors is combined to form a color image. In an organic light emitting display device, a color filter is used for color adjustment and the like.

The color filter mainly includes a substrate, a colored layer formed on the substrate, a light-shielding layer disposed between the colored layers, and a transparent electrode layer formed on the colored layer. The coloring layer can be formed, for example, by applying a coloring resin composition containing a coloring material and a binder component on a substrate, patterning the coating by a photolithography method, and then performing a heat treatment (post-baking).

赤色 As the red coloring material used for the red coloring layer, C.I. has been conventionally used because it has a high coloring power and can form a high-luminance coloring layer. I. Diketopyrrolopyrrole pigments such as CI Pigment Red 254 are used. However, diketopyrrolopyrrole-based pigments, when the pigment is refined for high contrast, during high-temperature heating in the color filter manufacturing process, the pigment particles are likely to aggregate or crystal grow, after the heating process, There is a problem that particles derived from the pigment precipitate on the surface of the coloring layer like a foreign substance, thereby lowering the brightness and contrast or being recognized as a defect. In an attempt to reduce the size of a pigment while suppressing the precipitation of particles derived from the pigment, a pigment compound in which a pigment is combined with a pigment derivative having a substituent introduced into a part of the pigment skeleton has been used. For example, Patent Document 1 discloses a method for selecting or designing a pigment derivative that gives a pigment composition having good dispersibility in a pigment composition obtained by treating a pigment with a pigment derivative. Measuring or calculating, and selecting a pigment derivative from the measured or calculated numerical value of the dipole moment, or designing the pigment derivative from the numerical value of the dipole moment, a pigment derivative comprising: Is described.

JP 2012-77192 A

However, the coloring layer containing the pigment derivative tends to have lower optical characteristics than the coloring layer not containing the pigment derivative, and particularly tends to have lower luminance and contrast.
The present invention has been made in view of the above-described circumstances, and provides a colored resin composition capable of forming a colored layer in which precipitation of a compound derived from a coloring material is suppressed and a decrease in luminance and contrast is suppressed. The purpose is to do. Another object of the present invention is to provide a cured product of the colored resin composition. Further, the present invention provides a color filter having a coloring layer formed using the colored resin composition, in which precipitation of a compound derived from a coloring material is suppressed, and a decrease in luminance and a decrease in contrast are suppressed. It is an object to provide a display device having a filter.

The colored resin composition according to the present invention includes a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a coloring material (D),
The color material (D) is C.I. I. Pigment Red 291 and a diketopyrrolopyrrole-based pigment represented by the following chemical formula (D1).

硬化 The cured product according to the present invention is a cured product of the colored resin composition according to the present invention.

The color filter according to the present invention is a color filter including at least a substrate and a coloring layer provided on the substrate, wherein at least one of the coloring layers is a cured product of the coloring resin composition according to the present invention. There is a feature.

表示 A display device according to the present invention includes the color filter according to the present invention.

According to the present invention, it is possible to provide a colored resin composition capable of forming a colored layer in which precipitation of a compound derived from a coloring material is suppressed and a decrease in luminance and contrast is suppressed. Further, according to the present invention, a cured product of the colored resin composition can be provided. Further, according to the present invention, a color filter having a colored layer formed using the colored resin composition, in which precipitation of a compound derived from a coloring material is suppressed, and a decrease in luminance and a decrease in contrast are suppressed, and A display device having the color filter can be provided.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention. FIG. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the colored resin composition, the cured product, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and furthermore, 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) acryl represents each of acryl and methacryl, (meth) acryloyl represents each of acryloyl and methacryloyl, and (meth) acrylate represents each of acrylate and methacrylate.

<< colored resin composition >>
The colored resin composition according to the present invention includes a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a coloring material (D),
The color material (D) is C.I. I. Pigment Red 291 and a diketopyrrolopyrrole-based pigment represented by the following chemical formula (D1).

A colored layer formed using a conventional colored resin composition containing a diketopyrrolopyrrole-based pigment is likely to be agglomerated or crystallized by heat because the diketopyrrolopyrrole-based pigment is easily heat-treated at the time of forming the colored layer ( At the time of (post-baking), compounds derived from the coloring material are precipitated, and as a result, the optical characteristics are deteriorated, such as a decrease in luminance and contrast, and are also detected as irregularities in the appearance inspection. There is a problem that the yield of the color filter products is lowered. In order to suppress the precipitation of the compound derived from the coloring material, the addition of the pigment derivative is effective.On the other hand, when the addition amount of the pigment derivative is increased in order to sufficiently suppress the precipitation of the compound derived from the coloring material, There is a problem that optical characteristics such as luminance and contrast are lowered. Therefore, it has been difficult to suppress the precipitation of the compound derived from the coloring material in the red coloring layer containing the diketopyrrolopyrrole pigment without impairing the optical characteristics.
On the other hand, in the colored resin composition according to the present invention, the coloring material (D) is a C.I. I. Pigment Red 291 (PR291) and a diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) are included in combination, whereby precipitation of a compound derived from a coloring material is suppressed, and reduction in luminance and contrast is suppressed. Colored layer can be formed.
Further, the colored layer formed using the colored resin composition according to the present invention can suppress the surface of the colored layer from being roughened by suppressing the precipitation of the compound derived from the coloring material. A colored layer having high property and low surface roughness can be formed, and the leveling property of the colored layer can be improved.

The colored resin composition according to the present invention contains the polymer (A), the polymerizable compound (B), the polymerization initiator (C), and the coloring material (D), and the effect of the present invention is impaired. Unless otherwise specified, other components may be further contained as necessary.

The polymer (A), the polymerizable compound (B), and the polymerization initiator (C) contained in the colored resin composition according to the present invention serve as a binder component of the colored resin composition to form a film or adhere to a surface to be coated. Imparts properties.
As the binder component, a binder component used for forming a coloring layer of a conventionally known color filter can be appropriately used, and is not particularly limited. For example, visible light, ultraviolet light, and polymerized and cured by an electron beam or the like. And a thermosetting binder component which can be polymerized and cured by heating, and a mixture thereof can also be used.
As the thermosetting binder component, a polymer which may have a thermopolymerizable functional group as the polymer (A), a compound having a thermopolymerizable functional group in a molecule as the polymerizable compound (B), and a polymer Examples of the initiator (C) include a system containing at least a thermopolymerization initiator including a curing agent that reacts with the thermopolymerizable functional group. Examples of the thermopolymerizable functional group include an epoxy group, an isocyanate group, a carboxy group, an amino group, and a hydroxyl group.

When a photolithography step is used when forming a colored layer using the colored resin composition according to the present invention, a photosensitive binder component having alkali developability is preferably used. Note that a thermosetting binder component may be further used as the photosensitive binder component.
Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. As the positive photosensitive binder component, for example, an alkali-soluble resin as the polymer (A), a compound having a bond capable of being cleaved by an acid in the molecule and an ethylenically unsaturated group as the polymerizable compound (B) may be used. Examples of the initiator (C) include a system containing a thermal radical polymerization initiator and a photoacid generator.
As the negative photosensitive binder component, an alkali-soluble resin as the polymer (A), a compound having an ethylenically unsaturated group in the molecule as the polymerizable compound (B), and a photopolymerization initiator as the polymerization initiator (C) A system containing at least is preferably used.
As the binder component contained in the colored resin composition according to the present invention, the negative photosensitive binder component is preferable because a pattern can be easily formed by a photolithography method using an existing process.

<Polymer (A)>
When a photolithography step is used for forming the colored layer, an alkali-soluble resin that is soluble in an alkali developer is suitably used as the polymer (A).
The alkali-soluble resin has an acidic group, acts as a binder resin, and can be appropriately selected and used as long as it is soluble in an alkali developer used for forming a pattern.
In the present invention, the alkali-soluble resin can be determined based on an acid value of 30 mgKOH / g or more.

Examples of the acidic group of the alkali-soluble resin include a carboxy group. Examples of the alkali-soluble resin having a carboxy group include a carboxy group-containing copolymer having a carboxy group and an epoxy (meth) acrylate resin having a carboxy group. Examples of the carboxy group-containing copolymer include an acryl-based copolymer having a carboxy group and an acryl-based copolymer such as a styrene-acryl-based copolymer having a carboxy group. Among them, particularly preferred are those having a carboxy group on the side chain and further having an ethylenically unsaturated group on the side chain. This is because the film strength of the cured film formed by containing the ethylenically unsaturated group is improved.
The ethylenically unsaturated group means a group containing a radically polymerizable carbon-carbon double bond, and includes, for example, a (meth) acryloyl group, a vinyl group and an allyl group.
Further, these acrylic copolymers, acrylic copolymers such as styrene-acrylic copolymers having a carboxy group, and epoxy acrylate resins may be used in combination of two or more.

Acrylic copolymers such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group are, for example, carboxy group-containing ethylenically unsaturated monomers, and can be copolymerized if necessary. A (co) polymer obtained by (co) polymerizing other monomers by a known method.

Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Can be 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 anhydride, ω-carboxy-polycaprolactone mono ( (Meth) acrylate and the like can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of the carboxy group. Among them, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion to the substrate. By having a hydrocarbon ring which is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling off from the substrate is eased, and substrate adhesion is improved. Further, by using an alkali-soluble resin having a hydrocarbon ring which is a bulky group, the solvent resistance of the obtained colored layer is improved, and it is particularly preferable in that the swelling of the colored layer is suppressed.
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 carboxy group, an oxycarbonyl group, and an amide group.

Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Ring; aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and cardo structure (9,9-diarylfluorene) Is mentioned.

Among them, the case where an aliphatic hydrocarbon ring is contained as the hydrocarbon ring is preferable in that the heat resistance and adhesion of the colored layer are improved and the luminance of the obtained colored layer is improved.
When a fluorene skeleton represented by the following chemical formula (i) contains a structure in which two benzene rings are bonded (a cardo structure), the curability of the colored layer is improved, the solvent resistance is improved, and the swelling of NMP in particular is improved. Is particularly preferred from the standpoint of suppressing
The hydrocarbon ring may be contained as a monovalent group, or may be contained as a divalent or higher valent group.

The exact mechanism of the resin having the cardo structure (referred to as cardo resin in the present invention) is unknown, but is considered to be highly sensitive to radicals because the fluorene skeleton contains a π-conjugated system. Above all, by combining an oxime ester-based photopolymerization initiator with a cardo resin, required performance such as sensitivity, developability, and development adhesion can be improved. Further, since the cardo resin has high solvent resolubility, it is preferable from the viewpoint that a colored resin composition having no aggregate can be designed even at a high color density.

In the alkali-soluble resin used in the present invention, apart from the structural unit having a carboxy group, it is easy to adjust the amount of each structural unit by using an acrylic copolymer having the structural unit having a hydrocarbon ring, This is preferable because the function of the structural unit can be easily improved by increasing the amount of the structural unit having a hydrocarbon ring.
The acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the aforementioned “other copolymerizable monomer”. Can be.

As the ethylenically unsaturated monomer having a hydrocarbon ring used for the alkali-soluble resin having a hydrocarbon ring, for example, from the viewpoint of a combination with a compound (E) having a fluorocarbon group and a crosslinked cyclic aliphatic group described below, Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, a monomer having the cardo structure and an ethylenically unsaturated group, and the like Can be preferably used, and precipitation of a compound derived from a coloring material is easily suppressed. Among them, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, and benzyl (meth) acrylate are particularly preferred. , Styrene, a monomer having said cardo structure and an ethylenic unsaturated group are preferred.

The alkali-soluble resin used in the present invention preferably has an ethylenically unsaturated bond in a side chain. In the case of having an ethylenically unsaturated bond, in the curing step of the resin composition at the time of producing a color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer can form a cross-linking bond. The film strength of the cured film is further improved so that the development resistance is improved, and the heat shrinkage of the cured film is suppressed, so that the adhesion to the substrate is improved.
A method for introducing an ethylenically unsaturated bond into an 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 ethylenically unsaturated bond in the molecule, such as glycidyl (meth) acrylate, is added to the carboxy group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into a side chain. Or a method in which a structural unit having a hydroxyl group is introduced into a copolymer, and a compound having an isocyanate group and an ethylenically unsaturated bond in a molecule is added to introduce a ethylenically unsaturated bond into a side chain. And the like.

アルカリ The alkali-soluble resin used in the present invention may further contain other structural units such as a structural unit having an ester group, such as methyl (meth) acrylate and ethyl (meth) acrylate. The constituent unit having an ester group not only functions as a component for suppressing alkali solubility of the colored resin composition, but also functions as a component for improving solubility in a solvent and further improving solvent resolubility.

The alkali-soluble resin used in the present invention may be an acrylic resin such as an acrylic copolymer or a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring. Preferably, an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond. More preferably, there is.

アルカリ The alkali-soluble resin used in the present invention can have desired performance by appropriately adjusting the charged amount of a monomer for deriving each structural unit.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually from 5% by mass to 50% by mass, preferably from 10% by mass to 40% by mass. In this case, when the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is 5% by mass or more, a decrease in the solubility of the obtained coating film in an alkali developing solution can be suppressed, and pattern formation becomes easy. When the copolymerization ratio is 50% by mass or less, chipping of the pattern and roughening of the pattern surface hardly occur at the time of development with an alkaline developer. The copolymerization ratio is a value calculated from the charged amounts of the respective monomers.

In an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenically unsaturated bond or a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylenically unsaturated bond are used. The charged amount of the monomer having both of the above is preferably from 10% by weight to 95% by weight, and more preferably from 15% by weight to 90% by weight based on 100% by weight of the charged amount of the carboxy group-containing ethylenically unsaturated monomer. More preferably, there is.

The preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight of the carboxy group-containing copolymer is 1,000 or more, the curability of the coating film is sufficiently obtained.
In addition, the weight average molecular weight (Mw) in the present invention is determined as a standard polystyrene conversion value by gel permeation chromatography (GPC).

Specific examples of the acrylic copolymer having a carboxy group include, for example, those described in JP-A-2013-029832.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited. For example, an epoxy (meth) acrylate obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. ) Acrylate compounds are suitable. The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used.
Among the epoxy (meth) acrylate resins having a carboxy group, those containing the cardo structure in the molecule improve the effect of suppressing display defects, improve the curability of the colored layer, and improve the remaining of the colored layer. It is preferable because the film ratio increases.

The alkali-soluble resin preferably has an acid value of 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer. The carboxy group-containing copolymer has an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer and adhesion to a substrate. It is more preferably 60 mgKOH / g or more and 280 mgKOH / g or less, even more preferably 70 mgKOH / g or more and 250 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K0070.

The ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of the alkali-soluble resin is 100 or more from the viewpoint that the film strength of the cured film is improved and the precipitation of the coloring material-derived compound can be further suppressed. It is preferably in the range of 2000 or less, and particularly preferably in the range of 140 or more and 1500 or less. When the equivalent of the ethylenically unsaturated bond is 100 or more, development resistance and adhesion are excellent. Further, when the molecular weight is 2000 or less, the ratio of the structural unit having a carboxy group or the other structural unit such as a structural unit having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained. I have. Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

(In the above formula (1), W represents the mass (g) of the carboxy group-containing copolymer, and M represents the number of moles (mol) of the ethylenically unsaturated bond contained in the alkali-soluble resin W (g). Represents.)

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

The content of the alkali-soluble resin in the colored resin composition is not particularly limited, but is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or less based on 100 parts by mass of the solid content of the colored resin composition. It is in the range of from 40 parts by mass to 40 parts by mass. When the content of the alkali-soluble resin is equal to or more than the lower limit, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is equal to or less than the upper limit, film roughness or chipping of a pattern during development. Is easy to control.
In the present invention, the solid content is all other than the solvent, and includes monomers and the like dissolved in the solvent.

The content of the polymer having an ethylenically unsaturated group in the colored resin composition is preferably 5 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the solid content of the colored resin composition. Preferably it is 10 parts by mass or more and 45 parts by mass or less. When the content of the polymer having an ethylenically unsaturated group is at least the above lower limit, sufficient curing can be obtained, and peeling of the coating film of the patterned colored resin composition can be suppressed. When the content of the polymer having an ethylenically unsaturated group is equal to or less than the upper limit, peeling due to curing shrinkage can be suppressed.

In addition, the colored resin composition according to the present invention includes, as the polymer (A), for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd It may contain a thermosetting polymer such as a resin, a melamine-urea cocondensation resin, a silicon resin, and a polysiloxane resin.

In addition, the said polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the polymer in the colored resin composition is not particularly limited, but is preferably 5 parts by mass or more and 60 parts by mass or less, preferably 10 parts by mass or more based on 100 parts by mass of the total solid content of the colored resin composition. More preferably, it is 50 parts by mass or less. When the content of the polymer is equal to or more than the lower limit, a decrease in film strength can be suppressed, and when the content of the polymer is equal to or less than the upper limit, components other than the polymer can be sufficiently contained. .

<Polymerizable compound (B)>
The polymerizable compound is not particularly limited as long as it can be polymerized by a polymerization initiator described later, and for example, a photopolymerizable compound or a thermopolymerizable compound can be used. As the thermopolymerizable compound, a compound having a thermopolymerizable functional group such as a carboxy group, an amino group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an alkoxyl group in a molecule can be used. Further, by using a compound having an ethylenically unsaturated group in combination with a thermal radical polymerization initiator, it can be used as a thermopolymerizable compound. As the polymerizable compound, a photopolymerizable compound that can be polymerized by a photopolymerization initiator described later is particularly preferable because a pattern can be easily formed by a photolithography method using an existing process. As the photopolymerizable compound, a compound having an ethylenically unsaturated group in the molecule can be used. As the photopolymerizable compound, a compound having two or more ethylenically unsaturated groups in the molecule is preferable, and a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule is particularly preferable.

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

は One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. When the colored resin composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional (meth) acrylate has three or more polymerizable double bonds (trifunctional). And poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof. Specific examples thereof include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. ) Acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Modified succinic acid, dipentaerythri Ruhekisa (meth) acrylate are preferable.

The content of the polymerizable compound in the colored resin composition is preferably from 5 parts by mass to 60 parts by mass, and more preferably from 10 parts by mass to 50 parts by mass based on 100 parts by mass of the solid content of the colored resin composition. The content is more preferably at most 20 parts by mass and even more preferably at most 40 parts by mass. When the content of the polymerizable compound is equal to or more than the lower limit, curing failure can be suppressed, so that the exposed portion can be suppressed from being eluted during development, and the content of the polymerizable compound is equal to or less than the upper limit. In addition, since defective development can be suppressed and thermal shrinkage can be suppressed, fine wrinkles hardly occur on the entire surface of the colored layer.

<Polymerization initiator (C)>
The polymerization initiator is not particularly limited, and can be used alone or in combination of two or more of various conventionally known initiators. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and specific examples include those described in JP-A-2013-029832.

As the photopolymerization initiator, among others, the effect of curing the film surface is high, the effect of suppressing the occurrence of chipping of the pattern, and the effect of suppressing the occurrence of water stain, and the effect of suppressing the precipitation of the coloring material-derived compound are high. It is preferable to include an oxime ester-based photopolymerization initiator. Further, when two or more oxime ester-based photopolymerization initiators are used in combination, the precipitation of a compound derived from a coloring material can be further suppressed. Therefore, it is preferable to use two or more oxime ester-based photopolymerization initiators. .

As the oxime ester-based photopolymerization initiator, from the viewpoint of reducing the contamination of the colored resin composition and the contamination of the device by the decomposition product, among them, those having an aromatic ring are preferable, and those having a condensed ring containing an aromatic ring are preferable. It is more preferable to have a condensed ring containing a benzene ring and a hetero ring.

Examples of the oxime ester-based photopolymerization initiator include JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-523338, and JP-A-2013-041153. And the like.

As the oxime ester-based photopolymerization initiator, among others, it is possible to use an oxime ester-based photopolymerization initiator that generates an alkyl radical, and further to use an oxime ester-based photopolymerization initiator that generates a methyl radical. Excellent curability even for colored resin compositions with a high colorant concentration to achieve high resistance to development, excellent resistance to development of patterns, suppression of occurrence of chipping of patterns, excellent suppression of water stains, precipitation of compounds derived from colorants Is preferred because it is easily suppressed. It is presumed that the radical transfer is more easily activated in the alkyl radical than in the aryl radical. Examples of the oxime ester-based photopolymerization initiator that generates an alkyl radical include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime ) (Trade name "Irgacure OXE-02", manufactured by BASF), methanone, [8-[[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl]- 11- (2-ethylhexyl) -11H-benzo [a] carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name “Irgacure OXE-03”, manufactured by BASF), ethanone, 1 -[9-ethyl-6- (1,3-dioxolan, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxy ) (Trade name "ADEKA ARKULS N-1919", manufactured by ADEKA), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl]-, o-acetyloxime (trade name "ADEKA ARKULS NCI-831", manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name “TR-PBG-304”, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1 -[2- (2-Pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name "TR-PBG-314", Changzhou Strong Electron Materials), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name “TR-PBG-326”) , Changzhou Strong Electronics New Materials Co., Ltd.), Ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name) “TR-PBG-331”, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-octanone, 1- [4- [3- [1-[(acetyloxy) imino] ethyl] -6- [4-[(4 , 6-Dimethyl-2-pyrimidinyl) thio] -2-methylbenzoyl] -9H-carbazol-9-yl] phenyl]-, 1- (o-acetyloxime) (trade name "EXTA-9", manufactured by Union Chemical) ) And the like. Further, specific examples of the initiator that generates a phenyl radical include Irgacure OXE-01 (manufactured by BASF). Further, examples of the oxime ester-based photopolymerization initiator having a diphenyl sulfide skeleton include Adeka Aquel's NCI-930 (manufactured by ADEKA) and TR-PBG-3057 (manufactured by Changzhou Strong Electronics New Materials).

An oxime ester-based photopolymerization initiator having a diphenyl sulfide skeleton is preferable because it can easily improve the luminance of the colored layer as compared with a case having a carbazole skeleton.

In addition, it is preferable to use a polymerization initiator having a tertiary amine structure in combination with the oxime ester-based photopolymerization initiator from the viewpoint of improving sensitivity. Since the polymerization initiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and the sensitivity can be improved. is there. Commercially available photoinitiators having the tertiary amine structure include, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (eg, Irgacure 907, manufactured by BASF). 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, trade name “Irgacure 369”, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone ( For example, the trade name is “High Cure ABP”, manufactured by Kawaguchi Pharmaceutical Co., Ltd.).

The content of the polymerization initiator in the colored resin composition is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the solid content of the colored resin composition. More preferably, the amount is not more than part by mass. When the content of the polymerization initiator is equal to or higher than the lower limit, curing proceeds sufficiently, and when the content of the polymerization initiator is equal to or lower than the upper limit, side reactions can be suppressed, and the stability with time is maintained. Can be.

When two or more oxime ester-based photopolymerization initiators are used as the polymerization initiator used in the colored resin composition, the oxime ester-based photopolymerization initiator is used in order to sufficiently exhibit the combined effect of these polymerization initiators. Is preferably in the range of 0.1 to 12.0 parts by mass, and more preferably 1.0 to 8 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition. More preferably, the amount is within the range of 0 parts by mass or less.

<Color material (D)>
The colored resin composition according to the present invention contains at least C.I. I. Pigment Red 291 (PR291) in combination with a diketopyrrolopyrrole-based pigment represented by the following chemical formula (D1), thereby suppressing the deposition of a compound derived from a coloring material due to heating (in the present invention, the The effect may be referred to as a suppression effect.) Therefore, in the colored layer formed using the colored resin composition according to the present invention, the precipitation of the compound derived from the coloring material is suppressed, and as a result, the decrease in luminance and contrast is also suppressed. The colored resin composition according to the present invention may further contain another coloring material as long as the effects of the present invention are not impaired.

C. I. Pigment Red 291 (PR291) is a diketopyrrolopyrrole-based pigment. PR291 has a single color of bluish red, has relatively strong coloring power, and has high luminance. Furthermore, PR291 is a conventional diketopyrrolopyrrole-based pigment such as C.I. I. Pigment Red 254 and the like also tend to have good contrast.

PR291 displays x = 0.30 or more and 0.69 or less and y = 0.30 or more and 0.35 or less as chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source alone. It is a color material that is capable of displaying x = 0.35 to 0.68 and y = 0.30 to 0.34.

PR291 has a transmittance of 610 nm to 780 nm of 90% or more and a transmittance of 380 nm of 50% when a transmittance of 430 nm is 1% in a spectral transmittance spectrum of a visible light region of 380 nm to 780 nm. And the transmittance at 500 nm is 10% or less.

In order to form a coating film of PR291 alone and measure the color, PR291 is mixed with an appropriate dispersing agent, a binder component and a solvent to prepare a coating solution, which is coated on a transparent substrate, dried, and dried. It may be cured accordingly. As the binder component, a non-curable thermoplastic resin composition may be used, or a photo-curable (photosensitive) or thermo-curable resin composition as long as a transparent coating film capable of performing color measurement can be formed. May be used. As a transparent coating film capable of performing colorimetry containing a dispersant and a binder component, for example, a film having a thickness of 2.0 μm and a transmittance of a spectral transmittance spectrum at 380 nm to 780 nm of 95% or more is a standard. Can be Note that the spectral transmittance spectrum can be measured using a spectrophotometer (for example, Olympus microspectrophotometer OSP-SP200).

市販 In the present invention, a commercial product can be used as PR291. As a commercial product of PR291, for example, CINIC Chemicals Co., Ltd., product name Cinelex DPP Red MT-CF and the like can be mentioned.

The diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) can be synthesized with reference to, for example, Japanese Patent No. 5619729.

In the colored resin composition according to the present invention, in a total of 100% by mass of the PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1), the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) The ratio is not particularly limited, but is preferably 1% by mass or more, and more preferably 2% by mass, from the viewpoint that precipitation of a compound derived from a coloring material is easily suppressed and a decrease in luminance and contrast of the colored layer is easily suppressed. More preferably, it is at least 30% by mass, more preferably at most 25% by mass.

The colored resin composition according to the present invention includes PR291 and a diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) in a range that does not impair the effects of the present invention, so that the colored layer has a desired chromaticity. May further contain another different color material.
The other color material is not particularly limited as long as a desired color can be formed when a colored layer is formed, and is not particularly limited. Various organic pigments, inorganic pigments, dispersible dyes, alone or A mixture of more than one species can be used. Among them, organic pigments are preferably used because they have high coloring properties and high heat resistance.

As the organic pigment used as the another coloring material, for example, another diketopyrrolopyrrole-based pigment different from PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) can be preferably used. The colored resin composition according to the present invention may further include another diketopyrrolopyrrole-based pigment by including PR291 in combination with the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1). In addition, precipitation of a compound derived from a coloring material can be suppressed.
Specific examples of the other diketopyrrolopyrrole-based pigments include C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Pigment Red 272, C.I. I. Pigment Orange 71, and C.I. I. Pigment Orange 73 and the like.

When the colored resin composition according to the present invention contains the another diketopyrrolopyrrole-based pigment as the coloring material (D), PR291 and the chemical formula (D1) are used in 100% by mass of the total of the diketopyrrolopyrrole-based pigment. Is preferably 40% by mass or more, more preferably 50% by mass or more. Thereby, the precipitation of the compound derived from the coloring material is easily suppressed, and the decrease in luminance and contrast of the colored layer is easily suppressed. The upper limit of the total proportion of the PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) in the total of 100% by mass of the diketopyrrolopyrrole-based pigment is not particularly limited, but is not particularly limited. From the viewpoint of obtaining the effect of being used in combination with a pyrrolopyrrole-based pigment, the content is preferably 99% by mass or less, and may be 95% by mass or less.

着色 The colored resin composition according to the present invention may contain a red coloring material other than the diketopyrrolopyrrole pigment as the coloring material (D). Examples of red coloring materials other than diketopyrrolopyrrole pigments include C.I. 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, And the like can be given 06,207,208,209,215,216,220,224,226,242,243,245,265.

Examples of the dispersible dye include a dye that is dispersible by insolubilizing it in a solvent, by adding various substituents to the dye, or using a known lake formation (chlorination) technique, or a solvent having low solubility. Dyes which can be dispersed by using them in combination are exemplified. By using such a dispersible dye in combination with a dispersant described below, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of the dye dissolved in 10 g of the solvent (or the mixed solvent) is 10 mg or less, it can be determined that the dye is dispersible in the solvent (or the mixed solvent).

The coloring material (D) used in the present invention may further contain a yellow coloring material for toning. The yellow colorant used in the present invention is selected from, for example, the group consisting of mono-, di-, tri- and tetraanions of an azo compound represented by the following general formula (I) and an azo compound having a tautomeric structure thereof. At least one kind of anion and at least one kind of metal ion selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; And a yellow colorant (D2) containing the compound represented by the following formula:
The yellow color material (D2) is preferable because it hardly grows crystals and hardly precipitates a compound derived from the color material. Above all, from the viewpoint that a high-luminance colored layer is obtained and the crystal growth of the color material is suppressed. And at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (I) and an azo compound having a tautomeric structure thereof, and Cd, Co, Al , Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, a yellow color material containing ions of at least two kinds of metals and a compound represented by the following general formula (II) ( D2) is preferred.

(In the general formula (I), ^Ra is each independently -OH, -NH ₂ , -NH-CN, an acylamino group, an alkylamino group or an arylamino group, and R ^b is each independently -OH or —NH _2. )

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

The colored resin composition according to the present invention is a yellow color material selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn among the yellow color materials (D2). When further including a yellow color material (D2) containing at least two kinds of selected metal ions, the P / V ratio ((mass of the color material component in the composition) / (the color material component other than the color material component in the composition) Even if the (solid content mass) ratio is suppressed, a red pixel included in the red chromaticity region with high color density can be produced. Further, since the total content of the coloring material components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, so that the plate making property is improved and the adhesion to the substrate is improved. It is possible to form a higher colored layer.

The acyl group in the acylamino group in the general formula (I) includes, for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an alkyl, a phenyl, a carbamoyl group which may be substituted by naphthyl, an alkyl group Phenyl, or a sulfamoyl group which may be substituted with naphthyl; an alkyl, a guanyl group which may be substituted with phenyl or naphthyl. The alkyl group preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with at least one of halogen such as F, Cl, and Br, —OH, —CN, —NH ₂ , and an alkoxy group having 1 to 6 carbon atoms. Further, the phenyl group and the naphthyl group include, for example, halogen such as F, Cl, and Br, —OH, —CN, —NH ₂ , —NO ₂ , an alkyl group having 1 to 6 carbon atoms, and a 1 to 6 carbon atom. It may be substituted with at least one of the following alkoxy groups.
The alkyl group in the alkylamino group in the general formula (I) preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with at least one of halogens such as F, Cl, and Br, —OH, —CN, —NH ₂ , and an alkoxy group having 1 to 6 carbon atoms.
Examples of the aryl group in the arylamino group in the general formula (I) include a phenyl group and a naphthyl group. These aryl groups include, for example, halogens such as F, Cl, and Br, —OH, having 1 to 6 carbon atoms. May be substituted with an alkyl group having 1 to 6 carbon atoms, —NH ₂ , —NO _2, and —CN.

In the azo compound of the azo compound and its tautomeric structures represented by the general formula (I), as ^{R a,} independently, _-OH, -NH 2, is -NH-CN, or alkylamino it is preferable from the viewpoint comprising a reddish hue, the two R ^a may be different even in the same, respectively.
In the general formula (I), two ^Ra are, particularly from the viewpoint of hue, when both are —OH, when both are —NH—CN, or one is —OH and one is —NH— More preferably, it is CN, and even more preferably both are —OH.

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

Among the at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, a metal which becomes a divalent or trivalent cation is preferred. It is preferable to include at least one kind, more preferably at least one kind selected from the group consisting of Ni, Cu, and Zn, and further preferably contains at least Ni. The yellow color material (D2) is composed of Cd, Co, Al, and Cr from the viewpoint that a colored layer with high luminance is obtained, the crystal growth of the color material is suppressed, and the P / V ratio can be suppressed. , Sn, Pb, Zn, Fe, Ni, Cu and Mn, preferably containing ions of at least two kinds of metals. Among them, Ni and Cd, Co, Al, Cr, Sn , Pb, Zn, Fe, Cu and Mn, and preferably at least one metal selected from the group consisting of Ni and further selected from the group consisting of Zn, Cu, Al and Fe. And at least one metal. In particular, it is preferable that the at least two kinds of metals are Ni and Zn, or Ni and Cu.

In the yellow color material (D2), the content ratio of the metal may be appropriately adjusted.
Above all, the yellow color material (D2) is selected from the group consisting of Ni and Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn in terms of reddish hue. In the case of containing at least one metal ion, Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn Is preferably contained in a molar ratio of 97: 3 to 10:90, and more preferably in a molar ratio of 90:10 to 10:90.
Among them, from the viewpoint of reddish hue, it is preferable that Ni and Zn are contained in a molar ratio of 90:10 to 10:90, more preferably in a molar ratio of 80:20 to 20:80. preferable.
Alternatively, Ni and Cu are preferably contained in a molar ratio of 97: 3 to 10:90, and more preferably in a molar ratio of 96: 4 to 20:80, from the viewpoint of reddish hue. preferable.
When the yellow color material (D2) has a reddish hue, even if the P / V ratio is suppressed, it is easy to produce a red pixel included in a red chromaticity region having a high color density.

The yellow color material (D2) may further contain a metal ion different from the ion of the specific metal, for example, Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La. At least one metal ion selected from the group consisting of:

The yellow color material (D2) includes at least two kinds of metal ions in the case where at least two kinds of metal ions are included in a common crystal lattice, and one case where one kind of ion is included in another crystal lattice. The case where the crystals containing the respective metal ions are aggregated. Among them, a case where at least two kinds of metal ions are included in a common crystal lattice is preferable from the viewpoint of further improving the contrast. It should be noted that whether the common crystal lattice contains at least two kinds of metal ions or another crystal lattice containing one kind of metal ion is aggregated, For example, it can be appropriately determined using an X-ray diffraction method with reference to JP-A-2014-12838.

The yellow coloring material (D2) comprises a metal complex composed of an anion of the azo compound represented by the general formula (I) or an azo compound having a tautomeric structure thereof and a specific metal ion, and the general formula (II) And a complex molecule with the compound represented by The bonds between these molecules can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordination bonds. Further, the structure may be like an inclusion compound in which a guest molecule is incorporated in a lattice constituting a host molecule. Alternatively, the two substances may form a co-crystal and form a mixed substitution crystal in which atoms of the second component are located at regular lattice positions of the first component.

The alkyl group for R ^c in the general formula (II) is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be substituted with an —OH group. Among them, R ^c is preferably a hydrogen atom.

The content of the compound represented by the general formula (II) is generally based on 1 mol of the azo compound represented by the general formula (I) and the azo compound having a tautomeric structure thereof. 5 mol or more and 300 mol or less, preferably 10 mol or more and 250 mol or less, more preferably 100 mol or more and 200 mol or less.

The yellow colorant (D2) further includes urea and substituted ureas such as phenylurea and dodecylurea, and polycondensates thereof with aldehydes, particularly formaldehyde; heterocycles such as barbituric acid and benzimidazolone. , Benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxy Quinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid, etc. Is also good.
The yellow colorant (D2) further includes a water-soluble polymer, for example, ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly (meth) acrylic acid, for example, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methyl- And modified cellulose such as ethylhydroxyethylcellulose.

The yellow color material (D2) can be prepared by referring to, for example, JP-A-2014-12838.

When the colored resin composition according to the present invention contains the yellow color material (D2), the content of the yellow color material (D2) in the total 100% by mass of the color material (D) is determined by adjusting the chromaticity and the luminance. It is preferably 0.5% by mass or more from the viewpoint of compatibility, and on the other hand, preferably 20% by mass or less and 10% by mass or less from the viewpoint of easy chromaticity adjustment within the intended range. Is more preferable.
From the viewpoint of suppressing the precipitation of the compound derived from the coloring material, the content of the yellow coloring material (D2) is 100 masses in total of PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1). It is preferably 1% by mass or more based on parts. On the other hand, even if the content of the yellow colorant (D2) is 10% by mass or less based on 100 parts by mass of the total of PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1). The effect of suppressing precipitation by the yellow color material (D2) is obtained.

When the coloring resin composition according to the present invention contains another coloring material different from PR291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1), the coloring resin composition may be used in combination with the another coloring material. PR291 and the above-mentioned chemical formula (D1) in the total of 100% by mass of the coloring material (D) from the viewpoint that the precipitation of the compound derived from the coloring material is easily suppressed while obtaining the effect, and the decrease in the luminance and the contrast of the coloring layer is easily suppressed. The total content with the diketopyrrolopyrrole-based pigment represented by is preferably 40% by mass or more, more preferably 50% by mass or more, while the other colorant is sufficiently contained. In view of this, it is preferably 95% by mass or less, more preferably 90% by mass or less.

The average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can form a desired color when a colored layer is formed. The thickness is preferably in the range of not less than 100 nm and not more than 100 nm, and more preferably in the range of not less than 15 nm and not more than 60 nm. When the average primary particle size of the coloring material is in the above range, a display device including a color filter manufactured using the colored resin composition of the present invention can have high contrast and high quality. .

Further, the average dispersed particle size of the colorant varies depending on the type of the colorant used, but is preferably in the range of 10 nm to 100 nm, and more preferably in the range of 15 nm to 60 nm.
The average dispersed particle size of the coloring material is a dispersed particle size of the coloring material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. As the measurement of the particle size by the laser light scattering particle size distribution meter, the colorant dispersion is appropriately diluted with a solvent used for the colored resin composition to a concentration measurable by the laser light scattering particle size distribution meter (for example, 1000 times). And the like, and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). Here, the average distribution particle size is a volume average particle size.

The content of the coloring material in the colored resin composition is preferably from 15 parts by mass to 90 parts by mass, and more preferably from 30 parts by mass to 80 parts by mass with respect to 100 parts by mass of the solid content of the colored resin composition. Is more preferable. When the content of the coloring material is equal to or more than the above lower limit, desired optical characteristics are obtained, a desired function is exhibited, and when the content of the coloring material is equal to or less than the above upper limit, the coloring material-derived compound Precipitation is easily suppressed, poor curing can be suppressed, and patterning of the coating film of the colored resin composition becomes easy.

<Compound (E) having a fluorocarbon group and a crosslinked cyclic aliphatic group>
When forming the colored layer, the colored resin composition according to the present invention may further include a compound having a fluorocarbon group and a crosslinked cycloaliphatic group (hereinafter, this compound is referred to as a “precipitation inhibiting compound”). This is preferable from the viewpoint of suppressing the precipitation of the compound derived from the coloring material caused by the heat treatment (post-baking) and improving the brightness and contrast of the colored layer.
The precipitation inhibiting compound is a compound having at least one fluorocarbon group and at least one crosslinked cycloaliphatic group in the molecule. Since the fluorocarbon group of the precipitation suppressing compound tends to move to the surface of the coating film when heat is applied, it is considered that the precipitation suppressing compound moves toward the surface of the coating film during heat treatment. On the other hand, since the crosslinked cycloaliphatic group of the precipitation-inhibiting compound is bulky, the crosslinked cycloaliphatic group existing near the surface of the coating film is colored even if the coloring material-derived compound reaches near the surface. It is considered that the precipitation of the compound derived from the coloring material is suppressed by blocking the compound derived from the material. In addition, it is presumed that the crystal growth itself of the coloring material is suppressed near the surface of the coating film. In addition, compounds derived from coloring materials tend to collect in the coating film at locations where the film strength is weak, but due to the bulky cross-linked cycloaliphatic groups present near the surface of the coating film, the film strength decreases near the coating surface. Is suppressed, and the concentration of compounds derived from the coloring material is also suppressed. Thus, it is presumed that the precipitation of the compound derived from the coloring material in the colored layer can be suppressed by including the precipitation inhibiting compound. Further, it is preferable from the viewpoint of improving the luminance and the contrast by further suppressing the precipitation of the coloring material-derived compound by using the precipitation suppressing compound.
The fact that the compound has a fluorocarbon group and a crosslinked cyclic aliphatic group can be confirmed from ¹ H- and ¹³ C-NMR spectra measured using a nuclear magnetic resonance apparatus.

The fluorocarbon group contained in the precipitation-inhibiting compound means a group having a structure in which at least a part of a hydrogen atom of a hydrocarbon group is substituted with a fluorine atom. Note that a fluorocarbon group is a compound in which a part of a fluorine atom or a hydrogen atom is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom (however, a fluorine atom is excluded), a hydroxyl group, a thiol group, an alkoxy group, an ether group, an amino group, It may be substituted with various substituents such as a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group or a carbonyl-containing group such as an ester group, an amino group, an acyl group, an amide group, a carboxy group, or may be a part of the main chain. It may have an ether bond (—O—) or a sulfonyl bond (—SO ₂ —).

The carbon number of the fluorocarbon group in the precipitation-inhibiting compound is preferably 2 or more and 10 or less from the viewpoint of improving compatibility with other components and obtaining optimum rheological properties when applying the colored resin composition. preferable. The lower limit of the number of carbon atoms of the fluorocarbon group is more preferably 4 or more, and the upper limit is more preferably 7 or less.

The fluorocarbon group may be a fluorocarbon group in which a part of hydrogen atoms of a hydrocarbon group is substituted with a fluorine atom, but the precipitation suppressing compound is present on the surface of the coloring layer to precipitate a compound derived from a coloring material. From the viewpoint of suppressing the above, a perfluorocarbon group in which all the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms is preferable.

Examples of the fluorocarbon group include a fluoroalkyl group having a saturated structure, a fluoroalkenyl group having an unsaturated structure, and a fluoroalkylaryl group having an aromatic skeleton.In particular, a fluoroalkyl group and a fluoroalkenyl group are synthesized. Is easy and useful.

The fluoroalkyl group includes a fluoroalkyl group having 2 to 10 carbon atoms. Among the fluoroalkyl groups having 2 to 10 carbon atoms, a perfluoroalkyl group is preferable from the viewpoint of suppressing the precipitation of the compound derived from the coloring material by causing the precipitation suppressing compound to be present on the surface of the coloring layer. Examples of the perfluoroalkyl group having 2 to 10 carbon atoms include perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, and perfluoroheptyl. Group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group and the like.

Examples of the fluoroalkenyl group include fluoroalkenyl groups having 2 to 10 carbon atoms. Among the fluoroalkenyl groups having 2 to 10 carbon atoms, a perfulalkenyl group is preferable from the viewpoint of suppressing the precipitation of the compound derived from the coloring material by causing the precipitation suppressing compound to be present on the surface of the coloring layer. Examples of the perfluoroalkenyl group having 2 to 10 carbon atoms include a perfluoropropenyl group, a perfluoroisopropenyl group, a perfluorobutenyl group, a perfluoroisobutenyl group, a perfluoropentenyl group, and a perfluoroisopentenyl group. , A perfluorohexenyl group, a perfluoroheptenyl group, a perfluorooctenyl group, a perfluorononenyl group, a perfluorodecenyl group and the like.

架橋 The bridged cyclic aliphatic group of the precipitation inhibiting compound means an aliphatic group having a structure in which two or more rings share two or more atoms. The number of carbon atoms in the crosslinked cyclic aliphatic group is preferably 5 or more and 12 or less from the viewpoint of compatibility with other materials and solubility in an alkali developing solution. The lower limit of the number of carbon atoms in the crosslinked cyclic aliphatic group is more preferably 7 or more, and the upper limit is more preferably 10 or less.

Examples of the bridged cyclic aliphatic group include, for example, an optionally substituted norbornyl group, an optionally substituted isobornyl group, an optionally substituted adamantyl group, an optionally substituted tricyclodecyl group, a substituted Optionally substituted dicyclopentenyl group, optionally substituted dicyclopentanyl group, optionally substituted tricyclopentenyl group, optionally substituted tricyclopentenyl group, optionally substituted Good tricyclopentadiene groups and optionally substituted dicyclopentadiene groups are exemplified. Among these, an adamantyl group which may be substituted or a dicyclopentanyl group which may be substituted is preferable from the viewpoint of heat resistance and the point of suppressing precipitation of a compound derived from a coloring material, and even if substituted, Good adamantyl groups are more preferred. When these groups are substituted, examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a ketone group, a nitro group, an amine group, and a halogen atom.

ガラス The glass transition temperature of the precipitation-inhibiting compound is preferably from 150 ° C to 250 ° C. If the glass transition temperature of the precipitation-inhibiting compound is 150 ° C. or more, even if the precipitation-inhibiting compound bleeds out to the surface of the coating film and then the surface of the coating film is rubbed, the abrasion resistance is high, so the quality of the color filter is improved. When the temperature is 250 ° C. or lower, the precipitation inhibiting compound easily moves to the coating film surface (bleeding easily occurs), and the precipitation of the compound derived from the coloring material can be further suppressed. The glass transition temperature of the precipitation-inhibiting compound can be determined by measuring it by differential scanning calorimetry (DSC) according to JIS K7121-1987. The lower limit of the glass transition temperature of the precipitation inhibiting compound is more preferably 180 ° C. or higher, and the upper limit is more preferably 230 ° C. or lower.

The precipitation-inhibiting compound includes a structural unit derived from the compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound (E-2) having a crosslinked cyclic aliphatic group and an ethylenically unsaturated group. It is possible to obtain a copolymer containing a structural unit derived therefrom.

In the precipitation inhibiting compound, the molar ratio (E-1: E-2) of the structural unit derived from the compound (E-1) to the structural unit derived from the compound (E-2) is 5:95. The ratio is preferably from 70:30 to 30, more preferably from 10:90 to 50:50, and still more preferably from 13:87 to 30:70. When the molar ratio is within the above range, the compatibility with each component in the colored resin composition, the effect of suppressing precipitation, and the rheological properties of the colored resin composition are improved. The molar ratio of each structural unit in the precipitation-inhibiting compound can be determined from the result of nuclear magnetic resonance (NMR) analysis.

The precipitation-inhibiting compound is preferably, for example, a copolymer containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

(In the general formulas (1) and (2), X ¹ and X ² may be each independently a direct bond, an optionally substituted alkylene group having 1 to 4 carbon atoms, or an optionally substituted alkylene group. An oxyalkylene group having 1 to 4 carbon atoms, Rf is a fluorocarbon group having 2 to 10 carbon atoms, and R ¹¹ and R ¹² are each independently a hydrogen atom or an optionally substituted carbon number. It is a hydrocarbon group of 1 or more and 6 or less, and A ¹ is a crosslinked cyclic aliphatic group.)

Examples of the alkylene group having 1 to 4 carbon atoms in X ¹ and X ² in the general formulas (1) and (2) include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. . Examples of the oxyalkylene group having 1 to 4 carbon atoms in X ¹ and X ² include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. Examples of the substituent which the alkylene group and the oxyalkylene group may have include, for example, a halogen atom, a hydroxyl group, an acidic group, a nitro group, a carbonyl group, an amide group, an amino group and the like. X ¹ and X ² are particularly preferably a direct bond or an alkylene group having 1 to 4 carbon atoms.

Examples of the hydrocarbon group having 1 to 6 carbon atoms in R ¹¹ and R ¹² in the general formulas (1) and (2) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. And a linear or branched alkyl group such as tert-butyl group, pentyl group and hexyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; and aryl group such as phenyl group. Examples of the substituent which the hydrocarbon group may have include a halogen atom, a hydroxyl group, an acidic group, a nitro group and an amino group. Among them, R ¹¹ and R ¹² are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

As the fluorocarbon group having 2 to 10 carbon atoms for Rf in the general formula (1), for example, among the above-mentioned fluorocarbon groups, those having 2 to 10 carbon atoms can be used. More than 10 or less of the above fluoroalkyl groups can be preferably used.
As the crosslinked cyclic aliphatic group for A ¹ in the general formula (2), the above-mentioned crosslinked cyclic aliphatic group can be used.

The precipitation inhibiting compound may be a block copolymer containing a structural unit derived from the compound (E-1) and a structural unit derived from the compound (E-2) from the viewpoint of the precipitation suppressing effect. preferable. When the precipitation-preventing compound is a block copolymer, the number of structural units derived from the compound (E-1) is preferably from 3 to 15, and the structural unit derived from the compound (E-2) is preferred. Is preferably 5 or more and 40 or less. When the structural unit derived from the compound (E-1) and the structural unit derived from the compound (E-2) are within the above ranges, the compatibility and rheological properties of each component of the colored resin composition are not impaired. A precipitation suppressing effect can be exhibited.

製造 The method for producing the block copolymer is not particularly limited. Although a block copolymer can be produced by a known method, production by a living polymerization method is preferable. This is because chain transfer and deactivation hardly occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic 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 monomers by these methods. For example, a block (A block) composed of a structural unit derived from the compound (E-1) is first produced, and a block (B block) composed of a structural unit derived from the compound (E-2) is polymerized on the A block. Thereby, a block copolymer can be produced. In the above production method, the order of polymerization may be reversed. Alternatively, each block can be manufactured separately, and then each block can be coupled.

配置 The arrangement of each block of the block copolymer is not particularly limited, and may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Above all, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

The precipitation inhibiting compound has an ethylenically unsaturated group copolymerizable with the compound (E-1) and the compound (E-2) in order to control the compatibility and the glass transition point of the colored resin composition. It may further contain a structural unit derived from compound (E-3).

Examples of the structural unit derived from the compound (E-3) include a structural unit represented by the following general formula (3).
The precipitation inhibiting compound includes a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and a structural unit represented by the following general formula (3). A copolymer can be preferably used.

(In the general formula (3), R ¹³ is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and A ² is an optionally substituted aryl group, A pyridinyl group or a group represented by the following general formula (4))

(In the general formula (4), A ³ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted benzyl group, an optionally substituted cyclopentyl group, an optionally substituted cyclopentylalkyl A cyclohexyl group which may be substituted, or a cyclohexylalkyl group which may be substituted. * Indicates a bonding position.)

Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in R ¹³ in the general formula (3) include R ¹¹ and R ^{12 in the} general formulas (1) and (2). And the same hydrocarbon groups having 1 to 6 carbon atoms can be used.
The aryl group in A ² in formula (3), for example, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, xylyl group. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
Examples of the substituent which the aryl group and the pyridinyl group in A ² in the general formula (3) may have include, for example, a linear or branched alkyl group having 1 to 4 carbon atoms and Examples thereof include an alkenyl group, a cycloalkyl group, a nitro group, and a halogen atom.
Examples of the substituent which A ³ in the general formula (4) may have include, for example, a hydroxyl group, an acyl group, a nitro group, an amino group, a carboxy group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms. And the like.

The precipitation-inhibiting compound contains a structural unit derived from the compound (E-1), a structural unit derived from the compound (E-2), and a structural unit derived from the compound (E-3). In the case of a polymer, the ratio of the structural unit derived from the compound (E-3) to 100 mol of the total of these structural units is appropriately adjusted according to the compatibility and the glass transition point of the colored resin composition. Although not limited, the amount is preferably 50 mol or less, more preferably 30 mol or less, and even more preferably 10 mol or less, from the viewpoint of easily improving the effect of suppressing precipitation.

The precipitation inhibiting compound includes, for example, a compound (E-1) having a fluorocarbon group and an ethylenically saturated group, and a compound (E-2) having a crosslinked cycloaliphatic group and an ethylenically unsaturated group. In accordance with the above, by copolymerizing two or more monomers including a compound (E-3) having an ethylenically unsaturated group copolymerizable with the compound (E-1) and the compound (E-2) Obtainable. Examples of the compound (E-1) having a fluorocarbon group and an ethylenic saturated group include a compound represented by the following general formula (1-1). Examples of the compound (E-2) having a crosslinked cyclic aliphatic group and an ethylenically unsaturated group include a compound represented by the following general formula (2-1).

(In the general formula (1-1), X ¹ , Rf and R ¹¹ are the same as those in the general formula (1).)

(In the general formula (2-1), X ² , A ¹ and R ¹² are the same as those in the general formula (2).

Specific examples of the compound (E-1) include, for example, 2- (perfluoropropyl) ethyl (meth) acrylate, 2- (perfluoroisopropyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl ( (Meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluoroheptyl) ethyl (meth) acrylate, 2- (perfluorooctyl) Ethyl (meth) acrylate, 2- (perfluorononyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate and the like can be mentioned. Among these, 2- (perfluorohexyl) ethyl (meth) acrylate is preferred from the viewpoint of the precipitation suppressing effect and the rheological properties of the colored resin composition.

Specific examples of the compound (E-2) include 1-adamantyl (meth) acrylate, 1-methyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, norbornyl (meth) A) acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclopentanyl (meth) acrylate, tricyclopentenyl (meth) acrylate , Dicyclopentadienyl (meth) acrylate, tricyclopentadienyl (meth) acrylate and the like. Among these, 1-adamantyl (meth) acrylate and dicyclopentanyl (meth) acrylate are preferred from the viewpoint of compatibility with each component of the colored resin composition and the effect of suppressing precipitation.

Further, the precipitation-inhibiting compound further includes a structural unit derived from the compound (E-3) having an ethylenically unsaturated group copolymerizable with the compound (E-1) and the compound (E-2). In such cases, the compound (E-3) includes, for example, a compound represented by the following general formula (3-1).

(In the general formula (3-1), A ² and R ¹³ are the same as those in the general formula (3).)

Specific examples of the compound (E-3) include, for example, methyl (meth) acrylate, (meth) acrylic acid, styrene, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentylmethyl ( Examples include (meth) acrylate, cyclopentylethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexyl (meth) acrylate, and vinylpyridine. Among these, methyl (meth) acrylate, (meth) acrylic acid, and styrene are preferred from the viewpoint of the compatibility of the colored resin composition and the effect of suppressing precipitation.

(4) The weight average molecular weight (Mw) of the precipitation inhibiting compound is preferably 3,000 or more and 10,000 or less. When the weight average molecular weight of the precipitation inhibiting compound is 3,000 or more and 10,000 or less, the affinity with other materials is excellent, and the viscosity of the colored resin composition does not become too high. Does not inhibit surface bleeding, and the effect of suppressing precipitation is not easily impaired. The lower limit of the molecular weight of the precipitation inhibiting compound is more preferably 4000 or more, and the upper limit of the molecular weight of the precipitation inhibiting compound is more preferably 8000 or less.

When the colored resin composition according to the present invention contains a precipitation-inhibiting compound, the content of the precipitation-inhibiting compound has a high effect of suppressing the precipitation of the compound derived from the coloring material, and the coating of the applied colored resin composition is coated. From the viewpoint of improving smoothness, the total amount of the solid content of the colored resin composition is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the solid content. It is still more preferably 0.2 parts by mass or more, and on the other hand, it is preferably 12 parts by mass or less, and more preferably 10 parts by mass or less from the viewpoint of preventing separation of components and poor curing. More preferably, it is even more preferably 5 parts by mass or less, particularly preferably 1 part by mass or less.

<Thiol compound (F)>
It is preferable that the colored resin composition according to the present invention further contains a thiol compound because the surface of the colored layer can be densified and the precipitation of the compound derived from the coloring material can be further suppressed. When the colored resin composition according to the present invention further contains a thiol compound, the thiol compound functions as a cross-linking agent and bonds between molecules of the polymer and the polymerizable compound are strengthened, so that the surface of the colored layer is Can be densified, and crystallization of the coloring material is estimated to be suppressed.

The thiol compound is a compound having one or more thiol groups in the molecule, and can be appropriately selected from known compounds. The thiol compounds may be used alone or in combination of two or more.

Specific examples of the thiol compound include, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2- Cyclohexanedithiol, decanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-butanediol dithioglycolate, 1,4-butanediol bis ( 3-mercaptopropionate), trimethylolpropane tristhioglycolate, 2-mercaptobenzothiazole, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol Litol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate), and various other polyhydric alcohols and thioglycolic acid, mercaptopropion Ester with a thiol group-containing carboxylic acid such as an acid, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- ( (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. As the thiol compound, 2-mercaptobenzothiazole is particularly preferred from the viewpoint of improving the reaction rate.

The thiol compound may be a thiol compound having a substituent at at least one of the carbon atoms at the α-position and the β-position with respect to the thiol group. Such specific examples include, for example, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, phthalic acid di (1-mercaptoethyl ester), phthalic acid Examples thereof include di (2-mercaptopropyl ester), di (3-mercaptobutyl ester) phthalate, and di (3-mercaptoisobutyl ester) phthalate.

As the thiol compound, among others, the use of one or more selected from the group consisting of polyfunctional thiol compounds having two or more thiol groups in one molecule increases the crosslink density, and provides a more precipitation-preventing effect. It is preferable from the viewpoint of easily reducing the surface roughness and the surface roughness. Further, even when the colored resin composition is stored for a long period of time, a secondary thiol group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom is preferable from the viewpoint that a good precipitation suppressing effect and low surface roughness are easily maintained. Is preferred, and more preferably a polyfunctional secondary thiol compound having two or more such secondary thiol groups in one molecule.

When the colored resin composition according to the present invention contains a thiol compound, the content of the thiol compound in the colored resin composition is 0.05 parts by mass or more based on 100 parts by mass of the solid content of the colored resin composition. The amount is preferably 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the thiol compound is equal to or more than the lower limit, the coating film can be sufficiently cured by the curing promotion effect of the thiol compound, and when the content of the thiol compound is equal to or less than the upper limit, the curing is accelerated. This can control the performance of the colored resin composition, such as distorting the shape of the pattern edge, and can suppress the performance degradation of the colored resin composition.

<Dispersant (G)>
The colored resin composition according to the present invention preferably further contains a dispersant from the viewpoint of improving the dispersibility and dispersion stability of the coloring material.
The dispersant used in the present invention is not particularly limited, but is represented by the following general formula (11) from the viewpoint of improving the adsorption performance on the colorant and improving the dispersibility and dispersion stability of the colorant. It is preferable to use a polymer having a structural unit. The structural unit represented by the following general formula (11) has basicity and functions as an adsorption site for a coloring material.

(In the general formula (11), R ¹⁴ is a hydrogen atom or a methyl group, L is a divalent linking group, and R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a hydrocarbon which may contain a hetero atom. R ¹⁵ and R ¹⁶ may combine with each other to form a ring structure.)

Examples of the divalent linking group represented by L in the general formula (11) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and a carbon atom having 1 to 10 carbon atoms. The following ether groups (-R'-OR "-: R 'and R" are each independently an alkylene group) and combinations thereof and the like. Among these, from the viewpoint of dispersibility, L in the above formula (11) is preferably a divalent linking group containing a -CONH- group or a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group which may include a hetero atom in R ¹⁵ and R ¹⁶ include, for example, an alkyl group, an aralkyl group, and an aryl group, and the alkyl group has 1 to 18 carbon atoms. Is preferable, and among them, a methyl group or an ethyl group is more preferable.

The hydrocarbon group containing a hetero atom in R ¹⁵ and R ¹⁶ has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom which the hydrocarbon group may include include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.

Among them, R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ¹⁵ and R ¹⁶ are bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine. It is preferable that at least one of R ¹⁵ and R ¹⁶ is an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ¹⁵ and R ¹⁶ are bonded to form a pyrrolidine. It preferably forms a ring, a piperidine ring and a morpholine ring.

Examples of the structural unit represented by the general formula (11) include an alkyl-substituted amino such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Group-containing (meth) acrylates and the like, and alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide are exemplified. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used from the viewpoint of improving dispersibility and dispersion stability.

構成 The structural unit represented by the general formula (11) may be composed of one type, or may include two or more types of structural units.

In the polymer having the structural unit represented by the general formula (11), at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (11) and the following general formulas (12) to () The formation of a salt with at least one compound selected from the group consisting of the compounds represented by the formula (14) further enhances the colorant adsorption property at the salt formation site, and improves the colorant dispersion stability and development. It is excellent in suppressing the residue and in the solvent resolubility, and is preferable in that the precipitation of the compound derived from the coloring material can be further suppressed. A terminal nitrogen moiety of the structural unit represented by the general formula (11) of the polymer having the structural unit represented by the general formula (11), and a group consisting of the following general formulas (12) to (14) The formation of a salt with one or more compounds selected from the above and the ratio can be confirmed by a known method such as NMR.

(In the general formula (12), R ¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or- R ′ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, It represents a (meth) acryloyl group via 1 to 4 alkylene groups.
In the general formula (13), R ¹⁸ , R ¹⁹ , and R ²⁰ each independently represent a hydrogen atom, an acidic group or an ester group thereof, a linear group having 1 to 20 carbon atoms which may have a substituent, A branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR ", wherein R" has a substituent A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a phenyl group or a benzyl group optionally having a substituent, or a carbon number It represents a (meth) acryloyl group via 1 to 4 alkylene groups, and Q represents a chlorine atom, a bromine atom or an iodine atom.
In the general formula (14), R ²¹ and R ²² each independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, and a substituent. Represents a phenyl group or a benzyl group, or —OR ′, wherein R ′ may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. It represents a good phenyl or benzyl group or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ²¹ and R ²² contains a carbon atom. )

The polymer having the structural unit represented by the general formula (11) improves the dispersibility and dispersion stability of the coloring material and the heat resistance of the colored resin composition, and further suppresses the precipitation of the coloring material-derived compound. From the viewpoint that a colored layer having high luminance and high contrast can be formed, at least a part of the terminal nitrogen site of the structural unit represented by the general formula (11) and the general formula (12) to ( A salt-type block copolymer in which one or more compounds selected from the group consisting of the compounds represented by 14) form a salt is preferred.

In the block copolymer, when a block containing the structural unit represented by the general formula (11) is an A block, the A block has a basic structure in which the structural unit represented by the general formula (11) has basicity. , Functions as an adsorption site for the coloring material. In addition, at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (11) and one or more compounds selected from the group consisting of the general formulas (12) to (14) are salts. Is formed, the salt-forming portion functions as a stronger adsorption site for the coloring material. On the other hand, the B block not containing the structural unit represented by the general formula (11) functions as a block having a solvent affinity. Therefore, the block copolymer functions as a colorant dispersant by sharing the function of the A block adsorbing with the colorant and the B block having solvent affinity.

The B block is a block that does not include the structural unit represented by the general formula (11). The structural unit constituting the B block is selected from monomers having an ethylenically unsaturated bond, which are polymerizable with the monomer for deriving the structural unit represented by the general formula (11), so as to have a solvent affinity. It is preferable to select and use them appropriately according to the solvent. As a guide, it is preferable to introduce a solvent affinity site so that the solubility of the polymer at 23 ° C. in the solvent used in combination is 50 (g / 100 g solvent) or more. It is preferable that the structural unit constituting the B block includes a structural unit represented by the following general formula (15).

(In the general formula (15), L ′ is a direct bond or a divalent linking group, R ²³ is a hydrogen atom or a methyl group, R ²⁴ is a hydrocarbon group, — [CH (R ²⁵ ) —CH (R ²⁶ ) —O] _x —R ²⁷ or a monovalent group represented by — [(CH ₂ ) _y —O] _z —R ^27. R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group. R ²⁷ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ²⁸ , and R ²⁸ is a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. Is an alkyl group.
The hydrocarbon group may have a substituent.
x represents an integer of 1 to 18; y represents an integer of 1 to 5; z represents an integer of 1 to 18; )

The divalent linking group L in the general formula (15) can be the same as L in the general formula (11). Among them, L ′ is preferably a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group from the viewpoint of solubility in an organic solvent. In view of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and the fact that it is a relatively inexpensive material, L ′ may be a —COO— group. preferable.

The hydrocarbon group for R ²⁴ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples thereof include a 2-ethylhexyl group, a 2-ethoxyethyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, and a lower alkyl-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the terminal of the alkenyl group has a double bond from the viewpoint of the reactivity of the obtained polymer.
Examples of the substituent of an aliphatic hydrocarbon such as an alkyl group and an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 14 carbon atoms.
Examples of the substituent for an aromatic ring such as an aryl group or an aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ^24, x is an integer of 1-18, preferably 1 to 4 integer, more preferably 1 to 2 integer, y is 1 to 5 integer, preferably 1 to 4 And more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group for R ²⁷ can be the same as that shown by the R ^24.
R ²⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be linear, branched, or cyclic.
Further, R ²⁴ in the structural unit represented by the general formula (15) may be the same as or different from each other.

It is preferable that R ²⁴ be selected so as to have excellent compatibility with the solvent contained in the colored resin composition. Specifically, for example, when the colored resin composition contains a glycol ether acetate-based, ether-based, or ester-based solvent that is generally used as a solvent for the color filter colored resin composition, R ²⁴ is preferably a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group or the like.

Further, R ²⁴ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, an isocyanate group or the like as long as the dispersibility of the block copolymer is not impaired. After the synthesis of the polymer, the above substituent may be added by reacting with the compound having the above substituent.

In the present invention, the glass transition temperature (Tg) of the block portion having a solvent affinity of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-affinity block portion is preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the block portion having a solvent affinity in the present invention can be calculated by the following equation. Similarly, the glass transition temperature of the coloring 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 affinity 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. Where Σ is the sum of i = 1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer may be the value of Polymer Handbook (3rd Edition) (written by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). it can.

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

The solvent-affinity block may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block may be composed of one type or two or more types. May be included.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1,000 or more and 20,000 or less, and 2,000 or more and 15,000 or less, from the viewpoint of improving colorant dispersibility and dispersion stability. More preferably, it is more preferably 3,000 or more and 12,000 or less.

The amine value of the block copolymer before salt formation is not particularly limited, but from the viewpoint of colorant dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH / g or more, and more preferably 50 mgKOH / g or more. More preferably, it is even more preferably 60 mgKOH / g or more. In addition, the upper limit is more preferably 130 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. If it is not less than the lower limit, the dispersion stability is more excellent. Further, when the content is equal to or less than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good. In the present specification, the amine value of the block copolymer before salt formation refers to the potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation. It represents mass (mg) and is a value measured by the method described in JIS K7237-1995.

(4) The amine value of the obtained salt-type block copolymer is smaller than that of the block copolymer before salt formation by the amount of the salt formed. However, since the salt-forming site is similar to or rather an enhanced colorant-adsorbing site at the terminal nitrogen site corresponding to the amino group, the salt-forming tends to improve the colorant dispersibility and the colorant dispersion stability. is there. Further, as in the case of the amino group, if the content of the salt-forming site is too large, the solvent resolubility is adversely affected. Therefore, the amine value of the block copolymer before salt formation can be used as an index for improving the colorant dispersion stability and the solvent resolubility. The amine value of the obtained salt-type block copolymer is preferably from 0 mgKOH / g to 130 mgKOH / g, and more preferably from 0 mgKOH / g to 120 mgKOH / g. When the content is equal to or less than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

Further, the acid value of the dispersant used in the present invention is not particularly limited, but is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH / g or less from the viewpoint of improving development adhesion and solvent resolubility. More preferably, there is. Further, it is preferable that the acid value of the dispersant is 0 mgKOH / g, from the viewpoints of further improving the solvent resolubility and the developing adhesion, the substrate adhesion and the dispersion stability. It is considered that the lower the acid value, the less the erosion of the basic developer, and thus the better the adhesion to development. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably at least 1 mgKOH / g, more preferably at least 2 mgKOH / g.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C. or higher from the viewpoint of improving development adhesion. When the glass transition temperature of the dispersant is low, the temperature is particularly close to the temperature of the developer (usually about 23 ° C.), and the adhesiveness for development may be reduced. The glass transition temperature of the dispersant is preferably 32 ° C. or more, more preferably 35 ° C. or more, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200 ° C. or less from the viewpoint of operability at the time of use such as easy weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring it by differential scanning calorimetry (DSC) according to JIS K7121.

The content of the dispersant is preferably from 3 parts by mass to 45 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the total solid content in the colored resin composition, from the viewpoint of dispersibility and dispersion stability. It is blended at a ratio of at least 35 parts by mass.

方法 The method for producing the block copolymer is not particularly limited, and the block copolymer can be produced by a known method. Further, as a method for preparing the salt type block copolymer, the above-mentioned general formulas (12) to (14) are dissolved in a solvent in which a polymer having a structural unit represented by the general formula (11) is dissolved or dispersed. A method of adding one or more compounds selected from the group consisting of, stirring, and, if necessary, heating.

<Solvent (H)>
The colored resin composition according to the present invention may further contain a solvent. The solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the colored resin composition and can dissolve or disperse these components. The solvents can be used alone or in combination of two or more.

Specific examples of the solvent include, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxy ethoxy ethanol and ethoxy ethoxy ethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, and other glycol ether acetate solvents; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethyl Glycol ether solvents such as ethylene glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; γ-butyrolactone Lactone solvents such as tetrahydrofuran; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; organic solvents such as aromatic hydrocarbons such as benzene, toluene, xylene and naphthalene. Solvents. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in view of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, And it is preferable that it is at least one selected from the group consisting of 3-methoxybutyl acetate from the viewpoint of solubility of other components and applicability.

Usually, the content of the solvent in the colored resin composition is preferably in the range of 55% by mass or more and 95% by mass or less with respect to the total amount of the colored resin composition, and particularly preferably 65% by mass or more and 90% by mass or less. It is preferably in the range, more preferably in the range of 70% by mass to 88% by mass. When the content of the solvent is 55% by mass or more, a decrease in dispersibility due to an increase in viscosity can be suppressed, and when the content of the solvent is 95% by mass or less, a decrease in the colorant concentration can be suppressed. , It is easy to achieve the target chromaticity coordinates.

<Other ingredients>
Other components may be further added to the colored resin composition according to the present invention, if necessary, as long as the effects of the present invention are not impaired. As other components, for example, a dispersing aid can be used.

The dispersing aid is for improving the dispersibility of the coloring material. As the dispersing aid, a dye derivative such as an acidic dye derivative is preferable. The dye derivative has a function of improving the dispersibility of the coloring material and an effect of suppressing precipitation of a compound derived from the coloring material. On the other hand, if the content of the dye derivative is too large, the optical properties of the coloring layer are reduced. Therefore, when the coloring resin composition of the present invention contains the coloring matter derivative, the coloring properties of the coloring layer are maintained. The content of the derivative is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the solid content of the colored resin composition. Even more preferred.

Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cissing agent, an antioxidant, an anti-agglomerating agent, and an ultraviolet absorber. And the like.

<Method for producing colored resin composition>
The colored resin composition according to the present invention can be produced, for example, as follows. First, a colorant dispersion or a colorant solution is prepared. The colorant dispersion contains at least a colorant, a dispersant, and a solvent. The coloring material solution contains at least a coloring material and a solvent. The coloring material dispersion or the coloring material solution may further contain a polymer, a thiol compound, or the like.

After preparing a colorant dispersion or a colorant solution, a polymer, a polymerizable compound, a polymerization initiator, and, if necessary, a precipitation inhibiting compound, a thiol compound, etc. are added to the colorant dispersion or the colorant solution. To obtain a colored resin composition.

<< Cured product >>
The cured product according to the present invention is a cured product of the colored resin composition according to the present invention.
The cured product according to the present invention is suitably used as a colored layer of a color filter, and is a cured product of the colored resin composition according to the present invention. And a decrease in contrast is suppressed.
The cured product according to the present invention, for example, when the colored resin composition according to the present invention is a photosensitive colored resin composition containing a photopolymerizable compound, forms a coating film of the photosensitive colored resin composition. After drying the coating film, it can be obtained by exposure and, if necessary, development. As a method of forming a coating film, exposing, and developing, for example, a method similar to a method used in forming a colored layer included in a color filter according to the present invention described later can be used.
When the colored resin composition according to the present invention is a thermosetting colored resin composition containing a thermopolymerizable compound, a coating film of the thermosetting colored resin composition is formed, and the coating film is dried. After being heated, a cured product can be obtained by heating.

<< Color filter >>
The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the colored resin composition according to the present invention. It is.

カラー The color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, a color filter 10 of the present invention has a substrate 1, a light shielding part 2, and a coloring layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a cured product of the colored resin composition according to the present invention, that is, a colored layer obtained by curing the colored resin composition.
The coloring layer is usually formed in an opening of a light-shielding portion on a substrate described later, and usually includes a coloring pattern of three or more colors.
The arrangement of the coloring layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. Further, the width, the area, and the like of the coloring 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.

For example, when the colored resin composition is a photosensitive colored resin composition, the colored layer can be formed by the following method.
First, the above-described colored resin composition of the present invention is applied to a substrate described below using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. To form a wet coating film. Among them, a spin coating method and a die coating method can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, and cured by a photopolymerization reaction of an alkali-soluble resin and a polyfunctional monomer. Make a coating. 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.
Further, heat treatment may be performed after the exposure in order to accelerate the polymerization reaction. The heating conditions are appropriately selected depending on the mixing ratio of each component in the coloring resin composition to be used, the thickness of the coating film, and the like.

Next, the coating film is formed in a desired pattern by performing a development process using a developer and dissolving and removing the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. In addition, a general method can be adopted as a developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the use of the coating film.

(Light shield)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and may 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 stripe shape and a matrix shape. The light shielding portion may be a thin metal film of chromium or the like by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, and the like are described. is there.

The thickness of the light-shielding portion is set at about 0.2 μm or more and 0.4 μm or less for a metal thin film, and about 0.5 μm or more and 2 μm or less for a black pigment dispersed or dissolved in a binder resin. Is set by

(substrate)
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or a substrate on which aluminum, silver, a silver / copper / palladium alloy thin film, or the like is formed, is used. On these substrates, other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, and synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, and flexible glass. Materials.
The thickness of the transparent substrate is not particularly limited, but a thickness of, for example, about 100 μm or more and 1 mm or less can be used according to the use of the color filter of the present invention.
The color filter of the present invention is, in addition to the substrate, the light-shielding portion and the coloring layer, formed with, for example, an overcoat layer and a transparent electrode layer, and further, an alignment film, alignment protrusions, columnar spacers, and the like. Is also good.

<< Display device >>
A display device according to the present invention includes 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, and examples thereof include a liquid crystal display device and an organic light emitting display device.

<Liquid crystal display device>
A liquid crystal display device according to the present invention includes the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
The configuration of the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be adopted. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
The counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention and the like.

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

<Organic light emitting display>
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitting body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of the 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 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic luminous body 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. And a method of bonding the organic light emitting body 80 formed on another substrate to 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, and the cathode 76 in the organic light emitting body 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3, but may have a structure generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be described specifically with reference to examples. The description is not intended to limit the invention.

(Synthesis Example 1: Synthesis of DPP pigment (D1))
Under a nitrogen atmosphere, 35 ml of tert-amyl alcohol and 2.5 parts by weight of sodium are added to the reaction vessel and reacted at 100 ° C. with stirring to form the corresponding alcoholate, and then 2.6 parts by weight. Some benzonitrile was added at 90 ° C. Next, 8.4 parts by mass of the compound represented by the following chemical formula (2) obtained by the method of Tetrahedron, 58 (2002) 5547-5565 is put into 35 ml of tert-amyl alcohol to make a slurry, and the slurry is made at 90 ° C. for 30 minutes. And added to the reaction vessel at a constant rate with stirring. After stirring at 90 ° C. for 18 hours, 136 parts by weight of ice / water, 27 parts by weight of methanol, 6.6 parts by weight of sulfuric acid (97%) and EP 0 485 337 are taken over 50 minutes. A mixture of the product obtained according to Example 2 of the specification with 5 parts by weight of a 10% aqueous suspension was transferred with stirring while previously cooling to 0 ° C. At that time, the temperature was adjusted so as not to exceed 3 ° C. Thereafter, stirring was further performed at 0 ° C. for 3 hours to complete the reaction. The reaction mixture was filtered with a suction funnel, washed with 200 ml of methanol and 500 ml of water, and dried to obtain a red solid. The obtained red solid was identified to be a diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) based on the result of mass spectrometry by TOF-MS.

(Synthesis Example 2: Preparation of Azo derivative 1)
23.1 parts by weight of diazobarbituric acid and 19.2 parts by weight of barbituric acid were introduced into 550 parts by weight of distilled water. Then, it was adjusted to be azobarbituric acid (0.3 mol) using an aqueous solution of potassium hydroxide and mixed with 750 parts by mass of distilled water. 5 parts by weight of 30% hydrochloric acid were added dropwise. Thereafter, 38.7 parts by weight of melamine were introduced. Next, a 0.60 mol nickel chloride solution was added, and the mixture was stirred at a temperature of 80 ° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C. and triturated in a mortar to give the Azo derivative 1.

(Synthesis Example 3: Preparation of Azo Derivative 2)
An Azo derivative was prepared in the same manner as in Synthesis Example 2 except that a 0.3 mol nickel chloride solution and a 0.3 mol zinc chloride solution were used instead of the 0.60 mol nickel chloride solution in Synthesis Example 2. 2 (azo pigment of Ni: Zn = 50: 50 (molar ratio)) was obtained.

(Synthesis Example 4: Synthesis of Precipitation Inhibiting Compound I)
A 500-ml four-neck separable flask was dried under reduced pressure, and then replaced with Ar (argon). While flowing Ar, 100 parts by mass of dehydrated tetrahydrofuran (THF), 2.0 parts by mass of methyltrimethylsilyldimethylketene acetal, 0.15 ml of a 1 M solution of tetrabutylammonium-3-chlorobenzoate (TBACB) in acetonitrile, 0.2 part by mass of mesitylene Was added. Using a dropping funnel, 34.57 parts by mass of 2- (perfluorohexyl) ethyl methacrylate (FOEMA) was added dropwise over 45 minutes. Since the reaction generates heat as the reaction proceeds, the temperature was kept below 40 ° C. by cooling with ice. One hour later, 17.62 parts by mass of 1-adamantyl methacrylate (1-ADMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain a precipitation inhibiting compound I which was a block copolymer. The weight average molecular weight of the precipitation inhibiting compound I determined by GPC measurement (NMP LiBr 10 mM) was 4,600.

The obtained precipitation inhibiting compound I was analyzed by pyrolysis GCMS, FT-IR, ¹ H-NMR, ¹³ C-NMR and GPC, whereby the structural unit derived from FOEMA in the precipitation inhibiting compound I and 1-ADMA The structural unit derived from FOEMA was confirmed, and the molar ratio of the structural unit derived from FOEMA to the structural unit derived from 1-ADMA was confirmed to be 1: 6.

(Synthesis Example 5: Synthesis of Precipitation Inhibiting Compound II)
A precipitation inhibiting compound II was obtained in the same manner as in Synthesis Example 4 except that dicyclopentanyl methacrylate (DCPMA) (FA-513M manufactured by Hitachi Chemical Co., Ltd.) was used instead of 1-adamantyl methacrylate. . The weight average molecular weight of Precipitation Inhibiting Compound II determined by GPC measurement (NMP LiBr 10 mM) was 4,500.

The resulting precipitation-inhibiting compound II is analyzed by pyrolysis GCMS, FT-IR, ¹ H-NMR, ¹³ C-NMR, and GPC to find that the structural unit derived from FOEMA and the one derived from DCPMA in the precipitation-inhibiting compound II The structural units were confirmed, and the molar ratio of the structural units derived from FOEMA to the structural units derived from DCPMA was 1: 6.

(Synthesis Example 6: Synthesis of Dispersant I)
A 500-ml four-neck separable flask was dried under reduced pressure, and then replaced with Ar (argon). While flowing Ar, 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyltrimethylsilyldimethylketene acetal, 0.15 ml of a 1 M solution of tetrabutylammonium-3-chlorobenzoate (TBACB) in acetonitrile, and 0.2 parts by mass of mesitylene were added. Using a dropping funnel, 36.7 parts by mass of methyl methacrylate (MMA) was added dropwise over 45 minutes. Since the reaction generates heat as the reaction proceeds, the temperature was kept below 40 ° C. by cooling with ice. One hour later, 13.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain a block copolymer. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,600, and the amine value was 95 mgKOH / g.
29.35 parts by mass of the block copolymer obtained above was dissolved in 29.35 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) in a 100 mL round bottom flask, and phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) 3 .17 parts by mass (0.20 mol based on 1 mol of DMMA unit of the block copolymer) and stirring at a reaction temperature of 30 ° C. for 20 hours to obtain a salt-type block copolymer (dispersant I) solution. Was. The amine value after salt formation was specifically calculated as follows.
One part by mass of a solution obtained by mixing 9 parts by mass of the salt-type block copolymer (solid after reprecipitation) and 91 parts by mass of chloroform-D1NMR was put into an NMR sample tube, and the 13C-NMR spectrum was subjected to nuclear magnetic resonance. The measurement was performed using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400) under the conditions of room temperature and 10,000 times of integration. In the obtained spectral data, at the terminal nitrogen site (amino group), the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom was calculated. From the ratio, the ratio of the number of amino groups formed into salts to the total number of amino groups was calculated, and it was confirmed that one acidic group of each phenylphosphonic acid formed a salt with the nitrogen moiety at the terminal of DMMA of the block copolymer. did.
The amine value after the salt formation (76 mg KOH / g) was calculated by subtracting the amine value (19 mg KOH / g) for 0.02 mol of the DMMA unit from the amine value before the salt formation of 95 mg KOH / g.

(Synthesis Example 7: Synthesis of alkali-soluble resin I solution)
A mixture of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) In a polymerization tank containing 150 parts by mass of PGMEA, the mixture was added dropwise at 100 ° C. over 3 hours under a nitrogen stream. After completion of the dropwise addition, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution, and the mixture is heated at 110 ° C. for 10 hours. Then, a carboxy group of the main chain methacrylic acid was reacted with an epoxy group of GMA. During the reaction, air was bubbled through the reaction solution to prevent polymerization of GMA. The reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin I was a resin in which a side chain having an ethylenic double bond was introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA. The alkali-soluble resin I solution had a solid content of 40% by mass, an acid value of 74 mgKOH / g, and a weight average molecular weight of the alkali-soluble resin I of 12,000.

<Example 1>
(1) Production of Coloring Material Dispersion R1 As a dispersing agent, 8.8 parts by mass of the dispersing agent I solution obtained in Synthesis Example 6 was used. I. Pigment Red 291 (manufactured by CINIC Chemicals, product name: Cinilex DPP Red MT-CF) is 11.94 parts by mass, the DPP pigment (D1) obtained in Synthesis Example 1 is 0.06 parts by mass, and obtained in Synthesis Example 7. 11.3 parts by mass of the alkali-soluble resin I solution, 67.6 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm in a mayonnaise bottle. A pre-crusher was used as a paint shaker (manufactured by Asada Iron Works). For 1 hour, then take out the zirconia beads having a particle diameter of 2.0 mm, add 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as the main disintegration, A colorant dispersion R1 was obtained.

(2) Production of Colored Resin Composition R1 59.40 parts by mass of the coloring material dispersion R1 obtained in (1) above, 4.83 parts by mass of the alkali-soluble resin I solution obtained in Synthesis Example 7, and 5.82 parts by mass of a polymerizable compound (trade name “Aronix M-520D”, manufactured by Toagosei Co., Ltd.) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiation) 0.86 parts by mass of an agent, trade name “Irgacure 369”, manufactured by BASF), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Il]-, 1- (o-acetyloxime) (0.58 parts by mass of oxime ester-based photopolymerization initiator, trade name "TR-PBG-304" manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) and 9.10 of PGMEA Parts by mass, Thus, a colored resin composition R1 having photosensitivity was obtained.

(3) Formation of Colored Layer The colored resin composition R1 obtained in the above (2) was post-formed on a glass substrate (trade name “NA35”, manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. The film was applied using a spin coater so that the film thickness after baking became 2.2 μm, dried under reduced pressure, and then heated and dried at 80 ° C. for 3 minutes using a hot plate to form a coating film. Next, exposure was performed by irradiating 60 mJ / m ^{2 of} ultraviolet light from the coating film side with a high-pressure mercury lamp. Thereafter, the film was developed with a developer having a temperature of 23 ° C. and a KOH concentration of 0.05% for 60 seconds, further heated in an oven at 230 ° C. for 30 minutes, and post-baked to form a colored layer.

<Examples 2 to 9, Comparative Examples RC1 to RC6>
(1) Production of Coloring Material Dispersions R2 to R9 and Coloring Material Dispersions RC1 to R6 In Examples 2 to 5, in the production of the above (1) Coloring Material Dispersion R1 of Example 1, C.I. I. Pigment Red 291 and the amount of the DPP pigment (D1) were changed to the amounts (parts by mass) shown in Table 1, respectively, in the same manner as in the above (1) of Example 1 to disperse the colorant. Liquids R2 to R5 were obtained.
In Examples 6 to 9, in the above (1) production of the colorant dispersion R1 of Example 1, I. Pigment Red 291 and the DPP pigment (D1) were changed to the amounts (parts by mass) shown in Table 2, respectively. I. Pigment Red 254 (PR254, trade name: Hostaperm Red D2B-COF LV3781, CLARIANT), C.I. I. Pigment Red 264 (PR264, trade name: SR6T, manufactured by CINIC Chemicals), Azo Derivative 1 obtained in Synthesis Example 2, or Azo Derivative 2 obtained in Synthesis Example 3 in an amount (parts by mass) shown in Table 2. Coloring material dispersions R6 to R9 were obtained in the same manner as in the above (1) of Example 1, except for mixing.
In Comparative Example 1, in the production of the above (1) colorant dispersion R1 of Example 1, the DPP pigment (D1) was not added, and C.I. I. Pigment Red 291 was changed to 12.0 parts by mass, and a colorant dispersion liquid RC1 was obtained in the same manner as in the above (1) of Example 1.
In Comparative Example 2, in the production of (1) the colorant dispersion R1 in Example 1, C.I. I. Pigment Red 291 was not used, and the amount of the DPP pigment (D1) was changed to 12.0 parts by mass in the same manner as in the above (1) of Example 1 to obtain a colorant dispersion liquid RC2.
In Comparative Examples 3 to 6, C.I. I. Pigment Red 291 (11.94 parts by mass) and DPP pigment (D1) 0.06 parts by mass in place of the coloring materials shown in Table 2 in the amounts (parts by mass) shown in Table 2 except for the above. In the same manner as in (1), color material dispersions RC3 to RC6 were obtained.

(2) Production of Colored Resin Compositions R2 to R9 and Colored Resin Compositions RC1 to RC6 In the production of the above (2) Colored Resin Composition R1 of Example 1, instead of the coloring material dispersion R1, the above obtained components were obtained. Colored resin compositions R2 to R9, and colored resin compositions in the same manner as in the above (2) of Example 1, except that the colorant dispersions R2 to R9 and RC1 to RC6 were used. RC1 to RC6 were obtained.

(3) Formation of Colored Layer In the formation of the colored layer (3) in Example 1, the colored resin composition R2 to R9 and the colored resin composition RC1 to RC6 were used instead of the colored resin composition R1. Except for the above, a colored layer was formed in the same manner as in the above (3) of Example 1.

<Examples 10 to 12>
In Example 3, during the production of the colored resin composition R3, in Example 10, 0.02 parts by mass of the precipitation-inhibiting compound I obtained in Synthesis Example 4 was used, and in Example 11, the precipitation-obtained compound obtained in Synthesis Example 5 was used. 0.02 parts by mass of inhibitory compound II and 0.02 parts by mass of precipitation inhibitory compound III (Megafac F575, a compound containing a fluorocarbon group and a crosslinked cycloaliphatic group, manufactured by DIC) in Example 12 except that it was further added. In the same manner as in Example 3, colored resin compositions R10 to R12 were obtained. A colored layer was formed in the same manner as in Example 3, except that the obtained colored resin compositions R10 to R12 were used instead of the colored resin composition R3 when forming the colored layer.

<Example 13>
(1) Production of Coloring Material Dispersion R13 In the production of (1) Coloring Material Dispersion R1 in Example 1, C.I. I. Pigment Red 291 and the DPP pigment (D1) were changed to 6.84 parts by mass and 0.36 parts by mass, respectively. I. Pigment Red 177 (PR177, trade name: Chromofine Red 6121EC, manufactured by Dainichi Seika) was prepared in the same manner as in the above (1) of Example 1 except that 4.8 parts by mass of colorant dispersion R13 was obtained. Was.
(2) Production of Colored Resin Composition R13 Except that, in the production of (2) Colored Resin Composition R1 in Example 1, the colorant dispersion R13 obtained above was used instead of the colorant dispersion R1. In the same manner as in the above (2) of Example 1, a colored resin composition R13 was obtained.
(3) Formation of Colored Layer In the formation of the colored layer (3) in Example 1, except that the colored resin composition R13 was used instead of the colored resin composition R1, Similarly, a colored layer was formed.

<Example 14>
In Example 13, a colored resin composition was prepared in the same manner as in Example 13 except that 0.02 parts by mass of the precipitation-inhibiting compound I obtained in Synthesis Example 4 was further added during the production of the colored resin composition R13. The product R14 was obtained. Further, a colored layer was formed in the same manner as in Example 13 except that a colored resin composition R14 was used instead of the colored resin composition R13 when forming the colored layer.

<Example 15>
A colored resin composition was prepared in the same manner as in Example 10, except that 0.2 part by mass of a thiol compound (Karenz MTPE1, manufactured by Showa Denko) was further added during the production of the colored resin composition R10. R15 was obtained. Further, a colored layer was formed in the same manner as in Example 10 except that a colored resin composition R15 was used instead of the colored resin composition R10 when forming the colored layer.

<Comparative Example 7>
Comparative Example 1 was prepared in the same manner as in Comparative Example 1, except that 0.02 parts by mass of Comparative Compound IV (Megafac F444, a perfluoroalkylethylene oxide adduct, manufactured by DIC) was further added when producing the colored resin composition RC1. In the same manner as in the above, a colored resin composition RC7 was obtained. Further, a colored layer was formed in the same manner as in Comparative Example 1, except that a colored resin composition RC7 was used instead of the colored resin composition RC1 when forming the colored layer.

<Evaluation of optical characteristics>
The chromaticity (x, y), luminance (Y), and contrast of the colored layers formed in each of the examples and comparative examples were measured. The chromaticity (x, y) and the luminance were measured using a “spectrophotometer OSP-SP200” manufactured by Olympus Corporation, and the contrast was measured using a “contrast measurement device CT-1B” manufactured by Tsubosaka Electric Co., Ltd. Measured. The light source used was a C light source.
Tables 1 and 3 show the measurement results of the chromaticity (x, y) of each example and each comparative example.
Tables 1 to 3 show the measurement results of the luminance (Y) and the evaluation results of the contrast in each of the examples and the comparative examples.
The contrast was evaluated according to the following evaluation criteria.
(Contrast evaluation criteria)
AAA: 95% or more to the target value AA: 93% to less than 95% of the target value A: 90% to less than 93% of the target value B: 85% to less than 90% of the target value C : Less than 85% of target value

<Precipitation evaluation>
The surface of the colored layer produced in each of the examples and comparative examples was observed with an optical microscope (product name “MX61L”, manufactured by OLYMPUS) to confirm whether or not a compound derived from the coloring material was deposited. The magnification was 100 times, and the number of precipitates observable by transmission was measured in a region of 500 μm × 500 μm, and evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 3.
(Precipitation evaluation criteria)
AAA: 0 (very good)
AA: 1 or more and 3 or less (good)
A: 4 or more and 10 or less (no problem in use)
B: 11 or more and 20 or less (although slight precipitation is observed, there is no problem in use)
C: 21 or more and 100 or less (there is a problem in use)
D: 101 or more (there is a problem in use)

The “DPP pigment (D1) ratio (% by mass)” in the table refers to C.I. I. The ratio (% by mass) of the DPP pigment (D1) to the total 100% by mass of C.I. Pigment Red 291 and the DPP pigment (D1) obtained in Synthesis Example 1.
The abbreviations in the table are as follows.
* PR291: C.I. I. Pigment Red 291 (trade name: Cinilex DPP Red MT-CF, manufactured by CINIC Chemicals)
* PR254: C.I. I. Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781 manufactured by CLARIANT)
* PR264: C.I. I. Pigment Red 264 (trade name: SR6T, manufactured by CINIC Chemicals)
* PR177: C.I. I. Pigment Red 177 (trade name: Chromo Fine Red 6121EC, manufactured by Dainichi Seika)
-Precipitation inhibiting compound III: Megafac F575 (compound containing fluorocarbon group and crosslinked cyclic aliphatic group, manufactured by DIC)
-Thiol compound: Karenz MTPE1 (manufactured by Showa Denko)
Comparative compound IV: Megafac F444 (perfluoroalkyl ethylene oxide adduct, manufactured by DIC)

[Summary of results]
C. I. Pigment Red 291 (PR291) and a diketopyrrolopyrrole-based pigment (DPP pigment (D1)) represented by the chemical formula (D1) in the coloring resin compositions of Examples 1 to 15, The formation of a colored layer in which the precipitation of the compound was suppressed and the decrease in brightness and contrast was suppressed was able to be formed.
As shown in Table 1, Examples 1 to 5 including the combination of PR291 and the DPP pigment (D1) as the colorant were Comparative Examples 1 including only PR291 as the colorant, and DPP pigment (as the colorant). Compared with any of Comparative Example 2 including only D1), precipitation of the compound derived from the coloring material was suppressed, and luminance and contrast were improved. Among them, Examples 2 to 4 in which the ratio of the DPP pigment (D1) is in the range of 1% by mass or more and 30% by mass or less in the total of 100% by mass of the PR291 and the DPP pigment (D1) are Examples 1 and 5. As compared with Comparative Example 2, precipitation of the compound derived from the coloring material was further suppressed, and the luminance and the contrast of the colored layer were further improved.
Further, as shown in Table 2, Examples 6 and 7 in which PR291 and DPP pigment (D1) are combined, even though diketopyrrolopyrrole-based pigments such as PR254 and PR264 are further included as coloring materials. As compared with Comparative Examples 3 to 6, which did not contain at least either PR291 or DPP pigment (D1), precipitation of compounds derived from coloring materials was suppressed, and luminance and contrast were improved. The chromaticity (x, y) of Example 6 and Comparative Examples 3 to 5 and the chromaticity (x, y) of Example 7 and Comparative Example 6 are the same, respectively. In comparison with the examples, all of the examples had higher luminance and improved contrast.
Examples 8 and 9 include a combination of PR291 and a DPP pigment (D1) as a coloring material, and further include an Azo derivative 1 or an Azo derivative 2 as the yellow coloring material (D2) as a yellow coloring material. Precipitation of the compound derived from the material was further suppressed, and reductions in luminance and contrast were also suppressed. Above all, in Example 9 using the Azo derivative 2 containing two kinds of specific metal ions as the yellow color material (D2), the luminance of the colored layer was improved.
Further, as shown in Table 3, Examples 10 to 12 containing a combination of PR291 and DPP pigment (D1) as coloring materials and further containing a precipitation-inhibiting compound were Examples 3 and 4 containing no precipitation-inhibiting compound. In comparison with the above, the precipitation of the compound derived from the coloring material was further suppressed, and the luminance and the contrast were further improved. In Example 15, which further contained a thiol compound in addition to the precipitation suppressing compound, the precipitation of the compound derived from the coloring material was further suppressed. On the other hand, in Comparative Example 7, the comparative compound IV (trade name: Megafac F444, perfluoroalkylethylene oxide adduct, manufactured by DIC) was used. Was not able to suppress the precipitation of the compound, and was not able to suppress the decrease in brightness and contrast.
Further, it contains PR291 and DPP pigment (D1) in combination as coloring materials, and further contains C.I. I. Also in Example 13 including Pigment Red 177 (PR177), the precipitation of the compound derived from the coloring material was suppressed, and the decrease in luminance and contrast was suppressed. In Example 14, which further contained a precipitation-inhibiting compound in addition to PR177, the precipitation of the coloring material-derived compound was further suppressed, and the reduction in luminance and contrast was further suppressed.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display 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 luminous body 100 Organic luminous display

Claims

A polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a coloring material (D);
The color material (D) is C.I. I. Pigment Red 291 and a diketopyrrolopyrrole-based pigment represented by the following chemical formula (D1).
{C. I. Pigment Red 291 and the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) in a total of 100% by mass, and the proportion of the diketopyrrolopyrrole-based pigment represented by the chemical formula (D1) is 1% by mass or more. The colored resin composition according to claim 1, wherein the content is 30% by mass or less.
3. The colored resin composition according to claim 1, further comprising a compound (E) having a fluorocarbon group and a crosslinked cyclic aliphatic group. 4.
The colored resin composition according to any one of claims 1 to 3, wherein the number of carbon atoms of the fluorocarbon group in the compound (E) is 2 or more and 10 or less.
5. The compound (E), wherein the bridged cyclic aliphatic group is an adamantyl group which may have a substituent or a dicyclopentanyl group which may have a substituent. The colored resin composition according to any one of the above.
The compound (E) comprises a structural unit derived from the compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound (E- The colored resin composition according to any one of claims 1 to 5, which is a copolymer containing a structural unit derived from 2).
The coloring material (D) is at least one selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (I) and an azo compound having a tautomeric structure thereof. An anion, at least one metal ion selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (II) The colored resin composition according to any one of claims 1 to 6, further comprising a yellow coloring material containing:

(In the general formula (I), Ra is each independently —OH, —NH 2 , —NH—CN, acylamino, alkylamino or arylamino, and R b is each independently —OH or —NH 2 Is.)

(In the general formula (II), R c is each independently a hydrogen atom or an alkyl group.)
The colored resin composition according to any one of claims 1 to 7, further comprising a thiol compound (F).
着色 The colored resin composition according to any one of claims 1 to 8, wherein the polymerizable compound (B) is a photopolymerizable compound.
(10) A cured product of the colored resin composition according to any one of (1) to (9).
A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the colored resin composition according to any one of claims 1 to 9. There is a color filter.
A display device having the color filter according to claim 11.