TW201918531A - Colored resin composition, cured product, color filter and display device - Google Patents

Abstract

A colored resin composition comprising a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and a compound (E) containing a fluorocarbon group and a bridged alicyclic group, wherein the color material (D) contains a naphthol-based azo pigment (D1) represented by the following general formula (1): (symbols in the general formula (1) are as described in the Description).

Description

   Colored resin composition, hardened material, 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 (particularly the development of mobile personal computers), the demand for liquid crystal displays is increasing. The popularity of mobile displays (mobile phones, smartphones, tablets) has also increased, showing the growing market for LCDs. In addition, recently, organic light-emitting display devices, such as organic EL displays that use self-luminescence and have high visibility, have also become the next-generation image display devices that have attracted attention. The performance of these image display devices strongly desires high image quality, such as high color rendering, high luminance, and high contrast, and reduces power consumption.

These liquid crystal display devices and organic light-emitting display devices use color filters. For example, the formation of a color image in a liquid crystal display device is that the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and then the color light is synthesized to form a color image. In organic light-emitting display devices, color filters are used for color adjustment and the like.

The color filter is mainly composed of a substrate, a coloring 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 colored layer is formed by, for example, applying a coloring resin composition containing a color material and an adhesive component on a substrate, patterning by a lithography method, and then performing heat treatment (post-baking).

The red color material used in the red coloring layer is conventionally used from the viewpoint of forming a coloring layer with high color strength and high brightness. Pyrrolopyrrole dione pigments such as CI Pigment Red 254 are used. , There is a combination of CI Pigment Red 177, as a yellow color material for toning. Furthermore, in recent years, it has been proposed to use a color material having a naphthol-based azo skeleton for red color materials. For example, Patent Documents 1 and 2 describe that for the purpose of obtaining a coloring composition for a stable color filter with high brightness and contrast and excellent fluidity, a coloring agent, resin, and resin containing a naphthol azo pigment with a specific structure A resin-based dispersant with a basic substituent and a coloring composition for a solvent.

    [Prior Technical Literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 2014-67024

Patent Document 2: Japanese Patent Laid-Open No. 2014-149506

However, the color layer containing the color material with a naphthol-based azo skeleton will precipitate compounds derived from the color material during the heat treatment performed when the color layer is formed, resulting in reduced brightness and contrast, and reduced color filter performance The problem.

The present invention has been completed in view of the above circumstances, and an object thereof is to provide a coloring resin composition that can form a coloring layer that suppresses the precipitation of a compound derived from a color material and that suppresses the reduction in brightness and contrast. In addition, an object of the present invention is to provide a cured product of the colored resin composition. In addition, an object of the present invention is to provide a color filter having a colored layer that suppresses the precipitation of a compound derived from a color material using the above-mentioned colored resin composition and suppresses the reduction in brightness and contrast, and the color filter having the color filter Display device.

The coloring resin composition of the present invention contains: a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and a fluorocarbon group and a crosslinked cyclic aliphatic group Compound (E); wherein the color material (D) -based contains a naphthol-based azo pigment (D1) represented by the following general formula (1): (In general formula (1), R ¹ is a hydrogen atom, a methyl group, a methoxy group, or a methoxycarbonyl group; R ² and R ³ are independently hydrogen atoms or an aryl group which may have a substituent; R ² or R At least one of ³ is an aryl group which may have a substituent.)

The cured product of the present invention is characterized by the above-mentioned cured product of the colored resin composition of the present invention.

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

The display device of the present invention is characterized by being provided with the color filter of the present invention.

According to the present invention, it is possible to provide a coloring resin composition that can form a coloring layer that suppresses the precipitation of a compound derived from a color material and that suppresses brightness and contrast. In addition, according to the present invention, a cured product of the aforementioned colored resin composition can be provided. In addition, according to the present invention, there can be provided a color filter having a colored layer that suppresses the precipitation of a compound derived from a color material using the above-mentioned colored resin composition and suppresses the reduction in brightness and contrast, and provides the color filter Optical sheet display device.

1‧‧‧ substrate

2‧‧‧Shade

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧counter substrate

30‧‧‧Liquid crystal layer

40‧‧‧LCD display device

50‧‧‧ organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧hole injection layer

73‧‧‧Electric tunnel transmission layer

74‧‧‧luminous layer

75‧‧‧Electron injection layer

76‧‧‧Cathode

80‧‧‧ organic light emitting body

100‧‧‧ organic light-emitting display device

FIG. 1 is a schematic diagram of an example of a color filter of the present invention.

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

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

Hereinafter, the coloring resin composition, the cured product, the color filter, and the display device of the present invention will be described in detail in order.

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

In the present invention, the (meth) acryl group represents acryl and methacryl groups; the (meth) acryl group represents acryl and methacryl groups; the (meth) acrylate The series represent acrylate and methacrylate, respectively.

    << Coloring resin composition >>    

The coloring resin composition of the present invention contains: a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and a fluorocarbon group and a crosslinked cyclic aliphatic group Compound (E); wherein the color material (D) -based contains a naphthol-based azo pigment (D1) represented by the following general formula (1): (In general formula (1), R ¹ is a hydrogen atom, a methyl group, a methoxy group, or a methoxycarbonyl group; R ² and R ³ are independently hydrogen atoms or an aryl group which may have a substituent; R ² or R At least one of ³ is an aryl group which may have a substituent.)

Since the coloring resin composition of the present invention contains the compound (E) having a fluorocarbon group and a cross-linked cycloaliphatic group, it is possible to form a coloring layer that suppresses the precipitation of the compound derived from the coloring material and has reduced brightness and contrast. .

The reason why the coloring resin composition of the present invention can exert the effects as described above can be presumed as follows.

The coloring material (D) contained in the coloring resin composition of the present invention contains the naphthol-based azo pigment (D1) represented by the above general formula (1), and therefore is easily crystallized by heat. If it is contained in the colored layer In the case of heat treatment (post-baking) during the formation of the colored layer, the compound derived from the color material will be precipitated. As a result, the optical characteristics such as brightness and contrast will decrease, and unevenness will be detected in the appearance inspection. Abnormality causes problems such as a decrease in the yield of the final color filter product. In order to suppress the precipitation of the compound derived from the color material, the addition of the pigment derivative is effective. However, if the amount of the pigment derivative is increased to sufficiently suppress the precipitation of the compound derived from the color material, the optical characteristics will be reduced, which will damage the optical The characteristics make it more difficult to suppress the precipitation of compounds derived from color materials.

In contrast, the coloring resin composition of the present invention contains the compound (E) having a fluorocarbon group and a cross-linked cycloaliphatic group, which can suppress the heat treatment (post-baking) performed when the colored layer is formed Roasting), and compound precipitation from the color material occurs. The fluorocarbon group of the compound (E) has a tendency to move toward the surface of the coating film when heat is applied. Therefore, the compound (E) can be determined to move toward the surface of the coating film during heat treatment. On the other hand, because the cross-linked cycloaliphatic group of the compound (E) has a large barrier, even if the compound derived from the color material reaches the surface, it will still be present near the surface of the coating film. The cross-linked cyclic aliphatic group blocks the compound derived from the color material, and it is judged that the precipitation of the compound derived from the color material can be suppressed. In addition, it is estimated that the crystal growth of the color material itself is also suppressed near the surface of the coating film. In addition, in the coating film, although the compound derived from the color material tends to be concentrated in the place where the strength of the film is weak, by the presence of a large cross-linked cyclic aliphatic group near the surface of the coating film, the coating film can be In the vicinity of the surface, the reduction in film strength is suppressed, and the concentration of compounds derived from the color material can also be suppressed. From this, it is presumed that the precipitation of the compound derived from the color material in the colored layer can be suppressed. In addition, if a compound derived from a color material is precipitated in the color layer, the brightness and contrast of the color layer will decrease. However, the color layer formed using the color composition of the present invention suppresses the compound derived from the color material, It can also suppress the decrease of brightness and contrast.

Furthermore, the colored layer formed using the colored resin composition of the present invention can suppress the surface roughness of the colored layer by suppressing the precipitation of the compound derived from the color material, so that a colored layer with high productivity and low surface roughness can be formed. It can also improve the uniformity of the colored layer.

The coloring resin composition of the present invention contains: a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and a fluorocarbon group and a crosslinked cyclic aliphatic group The compound (E) mentioned above may be made to contain other components if necessary before harming the effects of the present invention.

The polymer (A), polymerizable compound (B), and polymerization initiator (C) contained in the colored resin composition of the present invention are used as a binding component of the colored resin composition to impart film-forming properties and Tackiness of coated surface.

The above-mentioned adhesive component can be appropriately used when forming a color layer of a color filter in conventional and well-known methods. The adhesive component used is not particularly limited. For example, it can be polymerized and hardened by visible light, ultraviolet rays, electron beams, etc. The adhesive component is a thermosetting adhesive component that can be polymerized and hardened by heating, and a mixture of these can also be used.

The thermosetting adhesive component may include, for example, a polymer containing at least the polymer (A) which may have a thermally polymerizable functional group, a compound having a thermally polymerizable functional group in the molecule of the polymerizable compound (B), and polymerization The initiator (C) includes a thermal polymerization initiator and the like containing a hardener that can react with the thermally polymerizable functional group. Examples of the thermally polymerizable functional group system include epoxy groups, isocyanate groups, carboxyl groups, amine groups, and hydroxyl groups.

When the colored resin composition of the present invention is used to form a colored layer, it is preferable to use a photosensitive adhesive component having alkali developability when the photoetching step is used. In addition, the photosensitive adhesive component may further use a thermosetting adhesive component.

The photosensitive adhesive component system may be, for example, a positive photosensitive adhesive component and a negative photosensitive adhesive component. The positive photosensitive adhesive component system may include, for example, the polymer (A) is an alkali-soluble resin, and the polymerizable compound (B) is a compound having a bond cut with an acid and an ethylenically unsaturated group in the molecule, and the polymerization is initiated The agent (C) is a thermal radical polymerization initiator, a photoacid generator, and the like.

The negative photosensitive adhesive component preferably contains at least: the polymer (A) is an alkali-soluble resin, the polymerizable compound (B) is a compound having an ethylenically unsaturated group in the molecule, and the polymerization initiator (C) is light Polymerization initiators and the like.

The adhesive component contained in the colored resin composition of the present invention is preferably the above-mentioned negative photosensitive adhesive component from the viewpoint that a pattern can be easily formed by a photolithography method using an existing process.

    <Polymer (A)>    

For the polymer (A), when the photoetching step is used when forming the colored layer, it is preferable to use an alkali-soluble resin soluble in an alkali developer.

The alkali-soluble resin can be appropriately selected and used before it has an acidic group, can play the role of a binder resin, and is soluble in the alkali developer used when forming the pattern.

In the present invention, the so-called alkali-soluble resin can be an index with an acid value of 30 mgKOH / g or more.

The acidic group possessed by the alkali-soluble resin may be, for example, a carboxyl group. Examples of the alkali-soluble resin system having a carboxyl group include a carboxyl group-containing copolymer having a carboxyl group, and an epoxy (meth) acrylate resin having a carboxyl group. Examples of the carboxyl group-containing copolymerization system include acrylic copolymers having a carboxyl group, acrylic copolymers such as a styrene-acrylic copolymer having a carboxyl group, and the like. Among these, the ultra good series has a carboxyl group in the side chain and further has an ethylenically unsaturated group in the side chain. The reason is that by containing an ethylenic unsaturated group, the film strength of the formed cured film can be improved.

In addition, the ethylenically unsaturated group refers to a group containing a carbon-carbon double bond capable of polymerizing with a radical, such as (meth) acryloyl group, vinyl group, allyl group and the like.

Furthermore, these acrylic copolymers, acrylic copolymers such as styrene-acrylic copolymers with carboxyl groups, and epoxy acrylate resins can be used in combination of two or more types.

Acrylic copolymers with carboxyl groups and acrylic copolymers with carboxyl groups such as styrene-acrylic copolymers are, for example, carboxyl group-containing ethylenically unsaturated monomers and other monomers that can be copolymerized as needed, (Co) polymer obtained by (co) polymerization by a known method.

The carboxyl group-containing ethylenically unsaturated monosystem can be, for example: (meth) acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, croton Acid, cinnamic acid, acrylic acid dimer, etc. In addition, addition of hydroxy monomers such as 2-hydroxyethyl (meth) acrylate and cyclic dehydrates such as maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride can also be used. Reactants; and ω-carboxy-polycaprolactone mono (meth) acrylate and so on. In addition, as the precursor of the carboxyl group, a monomer containing dehydrates such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, etc., particularly preferred (meth) acrylic acid.

The alkali-soluble resin preferably has a hydrocarbon ring from the viewpoint of excellent adhesion to the substrate. Since the alkali-soluble resin has a hydrocarbon ring with a large barrier, it can suppress shrinkage during hardening, ease peeling from the substrate, and improve substrate adhesion. In addition, it is also preferable to use an alkali-soluble resin having a barrier-based hydrocarbon ring to improve the solvent resistance of the obtained colored layer and to suppress swelling of the colored layer in particular.

Examples of such a hydrocarbon ring system include: a cyclic aliphatic hydrocarbon ring which may also have a substituent, an aromatic ring which may also have a substituent, and combinations thereof, and the hydrocarbon ring may also have, for example, a carbonyl group, a carboxyl group, and oxygen Substituents such as carbonyl and amide groups.

Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and Alkanes, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, stilbene and other aromatic hydrocarbon rings; biphenyl, biphenyl Chain polycyclic rings such as triphenyl, diphenylmethane, triphenylmethane and stilbene; suspension structure (9,9-diaryl stilbene) etc.

Among them, when the hydrocarbon ring system contains an aliphatic hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesiveness of the colored layer and improving the brightness of the obtained colored layer.

In addition, when a structure (suspending structure) in which two benzene rings are bonded to the stilbene skeleton shown in the following chemical formula (1) is included, the curability of the colored layer is improved, the solvent resistance is improved, and the NMP is particularly suppressed. The view of swelling is extremely good.

The hydrocarbon ring system may be contained in a monovalent group, or may be contained in a bivalent group or more.

The resin containing the above suspension structure (also referred to as "cardo resin" in the present invention), although the correct mechanism is not clear, but because the stilbene skeleton contains a π-conjugated system, it is judged to have a high sensitivity to free radicals. Among them, by combining the oxime ester-based photopolymerization initiator and the cardo resin, the required performances such as sensitivity, developability, and development adhesiveness can be improved. In addition, since the above-mentioned cardo resin has high solvent resolubility, it is possible to design a coloring resin composition without agglomerates even at a high color concentration, which is also preferable in this regard.

In the alkali-soluble resin used in the present invention, from the viewpoint of easily adjusting the amount of each structural unit, increasing the amount of the above-mentioned hydrocarbon ring-forming structural unit, and easily improving the function of the structural unit, it is preferable to exclude structural units having a carboxyl group The acrylic copolymer containing the above-mentioned hydrocarbon ring structural unit is still used.

The acrylic copolymer containing the carboxyl structural unit and the above-mentioned hydrocarbon ring can be prepared by using the above-mentioned "other copolymerizable monomer" using an ethylenically unsaturated monomer having a hydrocarbon ring.

The hydrocarbon ring-containing ethylenically unsaturated monomer used in the alkali-soluble resin having a hydrocarbon ring is preferably used from the viewpoint of combining with the compound (E) having a fluorocarbon group and a cross-linked cyclic aliphatic group For example: cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, isocyanate (meth) acrylate Ester, phenoxyethyl (meth) acrylate, styrene, monomers with the above-mentioned suspension structure and ethylenic unsaturated group, etc., can still suppress the precipitation of compounds derived from color materials after heat treatment ( (Hereinafter also referred to as "precipitation inhibiting effect") a larger viewpoint, particularly preferred are cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, (meth) Benzyl acrylate, styrene, monomer having the above-mentioned suspension structure and ethylenic unsaturated group.

The alkali-soluble resin used in the present invention preferably has an ethylenically unsaturated bond in the side chain. In the case of having an ethylenically unsaturated bond, in the manufacture of a color filter, the alkali-soluble resin may be between each other, even between the alkali-soluble resin and a multifunctional monomer, etc. in the curing step of the resin composition Form cross-linked bonds. The film strength of the cured film is further improved, the development resistance is improved, the thermal shrinkage of the cured film is suppressed, and the adhesion between the cured film and the substrate is excellent.

The method for introducing an ethylenically unsaturated bond into the alkali-soluble resin can be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and an ethylenically unsaturated bond is incorporated into the carboxyl group of the alkali-soluble resin (for example, glycidyl (meth) acrylate, etc.), and the ethylenic group is introduced into the side chain. A method of saturating a bond; and a method of introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenically unsaturated bond in the molecule, and introducing a method of introducing an ethylenically unsaturated bond into the side chain.

The alkali-soluble resin used in the present invention may further contain, for example, methyl (meth) acrylate, ethyl (meth) acrylate, etc., a structural unit having an ester group, and other structural units. The constituent unit having an ester group not only has a component function of suppressing alkali solubility of the colored resin composition, but also has a component function of improving solubility in solvents and resolubility of solvents.

The alkali-soluble resin used in the present invention preferably includes, for example, an acrylic copolymer containing a carboxyl constituent unit and a hydrocarbon ring constituent unit; and an acrylic resin such as a styrene-acrylic copolymer, and more preferably contains a carboxyl group Acrylic copolymers such as structural units, structural units with hydrocarbon rings, and structural units with ethylenic unsaturated bonds; and acrylic resins such as styrene-acrylic copolymers.

The alkali-soluble resin used in the present invention can achieve the desired performance by appropriately adjusting the loading amount of the monomer derived from each constituent unit.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is usually 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 40% by mass or less. In this case, if the copolymerization ratio of the ethylenically unsaturated monomer containing a carboxyl group is 5 mass% or more, the solubility of the obtained coating film to the alkali developer can be suppressed from decreasing, and pattern formation can be easily performed. In addition, if the copolymerization ratio is 50% by mass or less, it is less likely that pattern defects and film roughness on the pattern surface will occur during development due to the alkali developer. In addition, the above-mentioned copolymerization ratio is a value calculated from the loading amount of each monomer.

In addition, it is more preferable to use an acrylic resin containing an ethylenically unsaturated bond-containing structural unit as an alkali-soluble resin, and an acrylic resin such as a styrene-acrylic copolymer, in combination with an epoxy group and an ethylenic resin. The loading amount of the saturated bond monomer is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass relative to the loading amount of the carboxyl group-containing ethylenically unsaturated monomer by 100% by mass the following.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably 1,000 or more and 50,000 or less, and more preferably 3,000 or more and 20,000 or less. If the weight-average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, the curability of the coating film can be sufficiently obtained; and if it is 50,000 or less, pattern formation can be easily performed when developing with an alkali developer.

In addition, the weight average molecular weight (Mw) of the present invention is a standard polystyrene conversion value obtained by using a gel permeation chromatography analyzer (GPC).

Specific examples of the acrylic copolymer having a carboxyl group can be described in, for example, Japanese Patent Laid-Open No. 2013-029832.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and may be, for example, an epoxy (meth) obtained by reacting an epoxy compound with a reactant containing an unsaturated monocarboxylic acid and an acid anhydride Acrylate compounds. The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride system can be appropriately selected and used from known ones.

Epoxy (meth) acrylate resins with carboxyl groups, especially those containing the above-mentioned suspension structure in the molecule, from the viewpoint of improving the effect of suppressing display defects, improving the curability of the colored layer, and increasing the residual film rate of the colored layer, Is better.

The alkali-soluble resin is preferably an acid value of 30 mgKOH / g or more, and more preferably 40 mgKOH / g or more from the viewpoint of developability (solubility) of the alkali aqueous solution used in the developer. The carboxyl group-containing copolymer is preferably an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of the developability (solubility) of the alkaline aqueous solution used in the developer and the adhesion to the substrate The best series is 60 mgKOH / g or more and 280 mgKOH / g or less, and the special series is 70 mgKOH / g or more and 250 mgKOH / g or less.

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

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the equivalent of the ethylenically unsaturated bond is preferably in the range of 100 or more and 2000 or less from the viewpoint of improving the film strength of the cured film and suppressing the color material precipitation more. More preferably, it ranges from 140 to 1500. When the ethylenically unsaturated bond equivalent is 100 or more, both development resistance and adhesion are excellent. Moreover, if it is 2000 or less, the ratio of the said structural unit with a carboxyl group, the structural unit with a hydrocarbon ring, etc. can be increased relatively, and it is excellent in developing property and heat resistance. Here, the ethylenically unsaturated bond equivalent refers to the weight average molecular weight of the average ethylenically unsaturated bond in the above alkali-soluble resin of 1 mole, as shown in the following formula (1): (In the above formula (1), W represents the mass (g) of the carboxyl group-containing copolymer; M represents the mole number (mol) of the ethylenically unsaturated bond contained in the alkali-soluble resin W (g).)

The above-mentioned ethylenically unsaturated bond equivalent is calculated according to, for example, the iodine value test method described in JIS K 0070: 1992, by measuring the number of ethylenically unsaturated bonds contained in 1 g of the alkali-soluble resin.

The content of the alkali-soluble resin used in the colored resin composition is not particularly limited, and it is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. Within a range of not less than 40 parts by mass. If the content of the alkali-soluble resin exceeds the above lower limit, sufficient alkali developability can be easily obtained, and if the content of the alkali-soluble resin is below the above upper limit, it is easy to suppress the occurrence of film roughness and pattern defects during development situation.

In addition, in the present invention, the solid content is everything except the solvent, and also includes monomers and the like dissolved in the solvent.

Furthermore, in the colored resin composition, the polymer content having an ethylenically unsaturated group is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total solid content of the colored resin composition. It is 10 mass parts or more and 45 mass parts or less. If the content of the polymer having an ethylenic unsaturated group exceeds the above lower limit, sufficient curing can be achieved, and peeling of the patterned coloring resin composition coating film can be suppressed. In addition, if the content of the polymer having an ethylenically unsaturated group is below the above upper limit, peeling due to curing shrinkage can be suppressed.

Furthermore, in the coloring resin composition of the present invention, the polymer (A) may contain, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, Thermosetting polymers such as polyurethane resins, epoxy resins, amino alkyd resins, melamine-urea co-condensation resins, silicone resins, polysiloxane resins, etc.

In addition, the polymer (A) system may be used alone or in combination of two or more.

The content of the polymer in the colored resin composition is not particularly limited, and it is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the total solid content of the colored resin composition. And below 50 parts by mass. If the polymer content exceeds the above lower limit, the reduction in film strength can be suppressed, and if the polymer content is below the above upper limit, components other than the polymer can be sufficiently contained.

    <Polymerizable compound (B)>    

The polymerizable compound is mentioned before it can be polymerized using a polymerization initiator described later, and the rest is not particularly limited. For example, a photopolymerizable compound or a heat polymerizable compound can be used. As the thermally polymerizable compound, a compound having thermally polymerizable functional groups such as carboxyl group, amine group, epoxy group, hydroxyl group, glycidyl group, isocyanate group, and alkoxy group in the molecule can be used. In addition, by using a compound having an ethylenically unsaturated group in combination with a thermal radical polymerization initiator, a thermally polymerizable compound can also be used. In particular, the polymerizable compound is preferably a photopolymerizable compound that can be polymerized using a photopolymerization initiator, as will be described later, from the viewpoint that a photolithography method can easily form a pattern using an existing process. As the photopolymerizable compound, a compound having an ethylenically unsaturated group in the molecule can be used. The photopolymerizable compound is particularly preferably a compound having two or more ethylenic unsaturated groups in the molecule, and more preferably a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule.

Such a multifunctional (meth) acrylate system can be appropriately selected and used from conventionally known materials. As a specific example, the thing described in Unexamined-Japanese-Patent No. 2013-029832 etc. can be mentioned, for example.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition of the present invention, the polyfunctional (meth) acrylate preferably has three (trifunctional) or more polymerizable double bonds, more preferably Poly (meth) acrylates of polyhydric alcohols with a value of 3 or more, and these dicarboxylic acid-modified products. Specific preferred systems include, for example, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) Base) acrylate, pentaerythritol tri (meth) acrylate succinic acid modification, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Succinic acid modified product of penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.

The content of the polymerizable compound in the colored resin composition is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. Below, the ultra good series is 20 parts by mass or more and 40 parts by mass or less. If the content of the polymerizable compound exceeds the above-mentioned lower limit, the curing failure can be suppressed, so that the exposed portion can be suppressed from dissolving during development, and if the content of the polymerizable compound is below the above-mentioned upper limit, Suppression of poor development and thermal shrinkage can be suppressed, so that fine wrinkles are unlikely to occur on the entire surface of the colored layer.

    <Polymerization initiator (C)>    

The polymerization initiator is not particularly limited, and one kind may be used from various conventionally known initiators or two or more kinds may be used in combination. The polymerization initiator system may be, for example, a thermal polymerization initiator or a photopolymerization initiator, and the specific system may be, for example, those described in Japanese Patent Laid-Open No. 2013-029832.

In particular, the polymerization initiator preferably contains an oxime ester-based photopolymerization initiator from the viewpoints of high film surface hardening effect, effect of suppressing pattern defects, effect of suppressing the occurrence of water seepage, and high effect of suppressing color material precipitation. In addition, when two or more oxime ester-based photopolymerization initiators are used in combination, the precipitation of the color material can be more suppressed, so it is preferable to use two or more oxime ester-based photopolymerization initiators.

From the viewpoint of reducing the contamination of the coloring resin composition and the contamination of the device due to the decomposition products, the oxime ester-based photopolymerization initiator is particularly preferably an aromatic ring, more preferably an aromatic ring-containing condensation ring, Especially good ones have condensed rings containing benzene ring and heterocycle.

Examples of the oxime ester-based photopolymerization initiator system include: Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Laid-Open No. 2010-527339, Japanese Patent Laid-Open No. 2010-527338, Japanese Patent Laid-Open 2013 -041153, such as the oxime ester photoinitiator and the like.

The above-mentioned oxime ester-based photopolymerization initiator has excellent curability and development resistance for coloring resin compositions that increase the color material concentration to achieve a wide color reproduction range, and the effect of suppressing the occurrence of pattern defects is suppressed. From the viewpoint of the excellent effect of water penetration and the effect of suppressing precipitation, it is particularly preferable to use an oxime ester-based photoinitiator that generates alkyl radicals, and more preferably to use an oxime ester-based light that generates methyl radicals. Polymerization initiator. Alkyl radicals are presumed to be easier to activate free radical movement than aryl radicals. Examples of the oxime ester-based photopolymerization initiator system that generates alkyl radicals include acetone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Base]-, 1- (o-acetoxime) (trade name "IRGACURE OXE-02", manufactured by BASF); ketone, [8-[[((acetoxy) 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); ethyl ketone, 1- [9-ethyl-6- (1,3-dioxolane , 4- (2-methoxyphenoxy) -9H-carbazol-3-yl]-, 1- (o-acetoxime) (trade name "ADEKA ARKLS N-1919", manufactured by ADEKA Corporation); Methone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl)-, o-Acetyl oxime (trade name "ADEKA ARKLS NCI-831", manufactured by ADEKA); 1-acetone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzyl amide ) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime) (trade name "TR-PBG-304", manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.); 1-acetone, 3-cyclopentan Yl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime) (trade name "TR-PBG-314", Changzhou Power Electronics New Materials Co., Ltd.); Ethyl ketone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime) (trade name " TR-PBG-326 ", manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.); ethyl ketone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime) (trade name "TR-PBG-331", manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.); 1-octanone, 1- [4- [3- [1-[(acetyl oxy)) Imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl) thio] -2-methylbenzyl] -9H-carbazol-9-yl ] Phenyl]-, 1- (o-acetyl oxime) (trade name "EXTA-9", manufactured by UNION CHEMICAL), etc. In addition, specific examples of initiators that generate benzene radicals include, for example: IRGACURE OXE -01 (manufactured by BASF), etc. In addition, the oxime ester-based photopolymerization initiator system with a diphenyl sulfide skeleton can be, for example: ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation), TR-PBG-3057 (Changzhou Strong Electronic New Materials company) etc.

From the viewpoint that the oxime ester photopolymerization initiator can enhance brightness more than the case of having a carbazole skeleton, it is particularly preferable to use an oxime ester-based photopolymerization initiator having a diphenyl sulfide skeleton.

Furthermore, from the viewpoint of improving sensitivity, it is preferable to use a polymerization initiator having a tertiary amine structure in combination with the oxime ester-based photopolymerization initiator. The reason is a polymerization initiator with a tertiary amine structure. Since the molecule has a tertiary amine structure which is an oxygen matting agent, the free radicals generated from the initiator are not deactivated by oxygen, which can increase the sensitivity. The commercially available photoinitiator having a tertiary amine structure can be exemplified by 2-methyl-1- (4-methylthiophenyl) -2- Pynyl-1-propan-1-one (for example, IRGACURE 907, manufactured by BASF); 2-benzyl-2- (dimethylamino) -1- (4- Phenylphenyl) -1-butanone (for example, trade name "IRGACURE 369", manufactured by BASF); 4,4'-bis (diethylamino) diphenyl ketone (for example trade name "HICURE ABP", Kawaguchi Manufactured by pharmaceutical companies), etc.

The content of the polymerization initiator in the colored resin composition is preferably 0.1 part by mass or more and 15 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. Below. If the content of the polymerization initiator exceeds the above lower limit, curing can be sufficiently promoted, and if the content of the polymerization initiator is below the above upper limit, side reactions can be suppressed and stability over time can be maintained.

When the polymerization initiator used in the above-mentioned colored resin composition uses two or more kinds of oxime ester-based photopolymerization initiators, from the viewpoint of giving full play to the combined effect of these polymerization initiators, the composition of the colored resin The total solid content of the substance is 100 parts by mass, and the total content of the oxime ester-based photopolymerization initiator is preferably within a range of 0.1 parts by mass or more and 12.0 parts by mass or less, more preferably within a range of 1.0 parts by mass or more and 8.0 parts by mass or less .

    <Color material (D)>    

The coloring resin composition of the present invention contains a coloring material (D) of at least a naphthol-based azo pigment (D1) represented by the following general formula (1), and may further contain the effect of the present invention within the range not to damage it. Other color materials.

(In general formula (1), R ¹ is a hydrogen atom, a methyl group, a methoxy group, or a methoxycarbonyl group; R ² and R ³ are independently hydrogen atoms or an aryl group which may have a substituent; R ² or R At least one of ³ is an aryl group which may have a substituent.)

Although the naphthol-based azo pigment (D1) represented by the above general formula (1) is preferable from the viewpoint of high color rendering contribution, it is easy to crystallize, so there is a case where heat treatment is performed when the colored layer is formed , It is easy to be the cause of the precipitation of compounds derived from color materials. On the other hand, the coloring resin composition of the present invention uses the naphthol-based azo pigment (D1) represented by the above general formula (1) in combination with a compound having a fluorocarbon group and a cross-linked cycloaliphatic group described later (E ), It is possible to suppress the precipitation of the compound derived from the color material under the presence of the naphthol-based azo pigment (D1) represented by the general formula (1).

In the above general formula (1), R ¹ is a hydrogen atom, a methyl group, a methoxy group or a methoxycarbonyl group, and among them, from the viewpoint of dispersion stability, it is preferably a methoxy group.

In the above general formula (1), R ² and R ³ are each independently a hydrogen atom or an aryl group which may have a substituent; at least one of R ² or R ³ may be an aryl group which may have a substituent.

From the viewpoint of heat resistance, R ² and R ³ are preferably an aryl group which may have a substituent.

Examples of the aryl group of R ² and R ³ include phenyl, biphenyl, naphthyl, tolyl, and xylyl. In addition, the number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. From the viewpoint of heat resistance, the aryl group of R ² and R ³ is particularly preferably a phenyl group.

In R ² and R ³ , the substituents which the aryl group may have include, for example, linear or branched alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms ; Fluorine atom, chlorine atom, bromine atom and other halogen atoms; amine formyl, sulfo, sulfonate, nitro, cyano and so on.

Specific examples of the naphthol-based azo pigments (D1) represented by the above general formula (1) include, for example, they are classified as Pigments in the Pigment Index (CI; published by The Society of Dyers and Colourists). Compounds, for example: CI Pigment Red 31, 32, 146, 147, 150, 170, 184, 187, 188, 238, 245, 247, 268, 269, from the viewpoint of hue and brightness, preferably the following CI Pigment Red 269 represented by the chemical formula (D1-0).

Furthermore, specific examples of the naphthol-based azo pigment (D1) represented by the above general formula (1) include, for example, naphthol-based azo represented by the following chemical formulas (D1-1) to (D1-7) Pigments, etc.

In addition, the naphthol-based azo pigment (D1) represented by the general formula (1) above preferably uses the general formula (1) from the viewpoints of dispersion stability and optical characteristics, and from the viewpoint of exerting an effect of suppressing precipitation. R ^{3 in} ) is a monovalent naphthol-based azo pigment represented by the following general formula (2).

(In the general formula (2), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; R ⁵ is a nitro group, a sulfo group, or Sulfonate; * indicates the bonding position.)

In the above general formula (2), the halogen atom system of R ⁴ may include, for example, a chlorine atom, a bromine atom, a fluorine atom, etc. In particular, from the viewpoint of dispersion stability, it is preferably a chlorine atom.

In the above general formula (2), the alkyl group having a carbon number of 1 or more and 3 or less of R ⁴ may be exemplified by methyl, ethyl, n-propyl, and isopropyl groups. From the viewpoint of dispersion stability, Methyl is preferred.

In the above general formula (2), the alkoxy group having 1 or more carbon atoms and 3 or less carbon atoms in R ⁴ may be exemplified by methoxy, ethoxy, n-propoxy, and isopropoxy groups, among which From the viewpoint of stability, methoxy is preferred.

In the above general formula (2), the sulfonate of R ⁵ may be, for example, an alkali metal salt of sulfo group or an alkaline earth metal salt, and the alkali metal salt of sulfo group is particularly preferred, and sulfonic acid is particularly preferably used. Sodium base.

In the naphthol-based azo pigment (D1) represented by the general formula (1), R ³ in the general formula (1) is a monovalent naphthol-based azo pigment represented by the general formula (2) because The dispersion stability is easily improved, so the formed coloring layer easily suppresses the precipitation of the compound derived from the color material, and easily improves the optical properties. The substituent represented by R ⁵ in the above general formula (2) weakens the intermolecular bond, so the pigment is easily refined, and the dispersant described later is easily adsorbed on the substituent, and it is judged that the dispersion stability can be more easily improved and the color The dispersion stability of the material is excellent. As a result, the precipitation-preventing compound described later tends to move on the surface of the coating film, and it is judged that when the colored layer is formed, the precipitation-preventing compound is easily suppressed.

In the above general formula (1), R ³ is a specific example of the monovalent naphthol-based azo pigment (D1) represented by the above general formula (2), for example: the above chemical formulas (D1-1) to (D1- 6) The naphthol-based azo pigments shown.

Among them, the naphthol-based azo pigment represented by the above chemical formula (D1-1) is preferred from the viewpoint of dispersion stability and optical characteristics.

On the other hand, in the above general formula (1), from the viewpoint of hue and brightness, it is preferred that R ³ may have a halogen atom, an alkyl group having a carbon number of 1 or more and 3 or less, and a carbon number of 1 or more and The naphthol-based azo pigment (D1) in which the aryl group of at least one substituent is selected from alkoxy groups of 3 or less. Examples of such naphthol-based azo pigments (D1) include CI Pigment Red 269 and naphthol-based azo pigments represented by the above chemical formula (D1-7).

In the coloring resin composition of the present invention, from the viewpoint of optical characteristics, the content of the naphthol-based azo pigment (D1) represented by the general formula (1) is preferably 100% by mass of the color material (D) in total. 5% by mass or more, more preferably 10% by mass or more; on the other hand, from the viewpoint of further containing other color materials different from the naphthol-based azo pigment (D1) in order to improve the optical properties and suppress the source From the viewpoint of compound precipitation from the color material to improve optical properties, it is preferably 95% by mass or less, and more preferably 90% by mass or less.

The coloring resin composition of the present invention may further contain a naphthol-based coupler different from the above-mentioned general formula (1) so that the colored layer can have a desired chromaticity within the range not to impair the effects of the present invention. Nitrogen pigment (D1) other color materials.

The above-mentioned other color materials are not limited in particular as long as they can achieve the desired color development when forming the coloring layer, and can be used alone (or two or more types are mixed) of various organic pigments, inorganic pigments, and dispersible dyes . Among them, organic pigments are preferably used from the viewpoint of high color development and high heat resistance.

In addition, the above-mentioned dispersible dye system can be, for example, a dye that can be dispersed by imparting various substituents to the dye or insolubilized in a solvent using a well-known lake formation (salination) method; and by using a combination of low Dissolve the solvent and become a dispersible dye. By using such a dispersible dye in combination with a dispersant described later, the dispersibility and dispersion stability of the dye can be improved.

The dispersible dye system can be appropriately selected from conventionally known dyes. Examples of such a dye system include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, etc.

In addition, the indicator is that if the amount of the dye dissolved in 10 g of the solvent (or mixed solvent) is less than 10 mg, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

In particular, from the viewpoint of obtaining a high-luminance colored layer, the color material (D) used in the present invention preferably further contains a pyrrolopyrrole dione pigment (D2). In addition, because the pyrrolopyrrole-dione pigment (D2) is easily crystallized by heat and is easily precipitated when the colored layer is formed, when the color material (D) further contains the pyrrolopyrrole-dione pigment (D2) , Can more effectively exert the effect of suppressing precipitation caused by the colored resin composition of the present invention.

The pyrrolopyrrole dione pigment (D2) series can be represented by the following general formula (3 '): (In the general formula (3 '), R ^6' and R ^{7 '} each independently represent a halogen atom, a methyl group, an ethyl group, a third butyl group, a phenyl group, a N, N-dimethylamino group, and trifluoromethyl Group, or cyano group; k and k 'each independently represent an integer of 0 or more and 5 or less, when k and k' are each an integer of 2 or more, the plural R ^{6 '} and R ^7' may be the same or Mutually different.)

Among the pyrrolopyrrole dione pigments (D2), it is preferable to use the following general formula (3): [Chem 9] general formula (3) (In the general formula (3), R ⁶ and R ⁷ are each independently a chlorine atom, a bromine atom or a phenyl group.)

Pyrrolopyrrole dione pigment (D2) can be, for example, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 291, CI Pigment Orange 71, CI Pigment Orange 73, and pyrrolopyrrole dione pigment (BrDPP) shown in the following chemical formula (2), etc., but not limited to these.

When the coloring resin composition of the present invention contains the above-mentioned pyrrolopyrrole-dione pigment (D2), the total amount of color material (D) is 100% by mass. The content of D2) is preferably 5% by mass or more, and more preferably 10% by mass or more; on the other hand, it is easily obtained from the naphthol-based azo pigment (D1) represented by the above general formula (1). From the viewpoint of the effect of improving the optical properties caused by the naphthol-based azo pigment (D1) and the viewpoint of suppressing the precipitation of the compound derived from the color material to further improve the optical properties, it is preferably 95% by mass or less, and more preferably 90% by mass or less .

Furthermore, the color material (D) used in the present invention may further contain a yellow color material for toning. The yellow color material used in the present invention is preferably a yellow color material (D3). The yellow color material (D3) contains: from the group consisting of mono-, di-, tri- and tetravalent anions of the azo compound represented by the following general formula (4) and its tautomeric structure azo compound, at least 1 anion; and ions of at least 2 metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and represented by the following general formula (5) Compound.

(Formula (4), R ^a is each independently based _{-OH, -NH 2 -, - NH} -CN, acylated amino, an alkylamino group or an aryl group; R ^b are each independently -OH lines Or -NH _2. )

[Chem 12] General formula (5) (In the general formula (5), R ^c is an independent hydrogen atom or alkyl group.)

From the viewpoint of obtaining a high-luminance colored layer and the viewpoint of suppressing crystal growth of the color material, the yellow color material is preferably the above-mentioned yellow color material (D3). Furthermore, by further containing the above-mentioned yellow color material (D3), even if the P / V ratio [(quality of color material component in the composition) / (mass of solid content other than the color material component in the composition) ratio is suppressed] , You can still make red pixels that cover high-density red areas.

Furthermore, since the total content of the color material components in the colored resin composition can be suppressed, the content of the binding component can be relatively increased, so that a coloring layer can be formed that improves the plate-making property and can further improve the adhesion with the substrate.

In the general formula (4), the amide group of the amide group may be, for example, an amine substituted with an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a benzenesulfonyl group, an alkyl group, a phenyl group, or a naphthyl group Formyl; sulfamoyl which can be substituted with alkyl, phenyl, or naphthyl; guanidino substituted with alkyl, phenyl, or naphthyl, etc. The alkyl group is preferably a carbon number of 1 or more and 6 or less. In addition, the above-mentioned alkyl group may be substituted with at least one of halogen such as F, Cl, Br, and —OH, —CN, —NH ₂ , and alkoxy groups having 1 to 6 carbon atoms. In addition, the phenyl group and naphthyl group may be substituted with halogens such as F, Cl, Br, and -OH, -CN, -NH ₂ , -NO ₂ , alkyl groups with a carbon number of 1 to 6, and carbon numbers At least one of alkoxy groups of 1 or more and 6 or less is substituted.

In the general formula (4), the alkyl group of the alkylamine group preferably has a carbon number of 1 or more and 6 or less. The above-mentioned alkyl group may be substituted with at least one of halogen such as F, Cl, Br, and —OH, —CN, —NH ₂ , and alkoxy groups having 1 to 6 carbon atoms.

In the general formula (4), the aryl group of the arylamine group may be, for example, phenyl, naphthyl, and such aryl groups may also be halogenated by, for example, F, Cl, Br, etc., and -OH, carbon number 1 or more and Alkyl groups with 6 or less, alkoxy groups with 1 or more carbons and 6 or less, -NH ₂ , -NO ₂ and CN are substituted.

The above general formula (4) shown in FIG azo compound, and such tautomeric structure azo compound, R ^a is each independently based _{-OH, -NH 2, -NH-CN} , or alkyl group, but it becomes reddish hue from viewpoint, two each R ^a may be identical or different from each.

In the general formula (4), it is from the viewpoint of hue, two R ^a better system in the case where both are -OH, both of which are the case of -NH-CN or 1 and the other is -OH In the case of -NH-CN, the case of Tejia is -OH.

In addition, in the azo compound represented by the above general formula (4) and the azo compound of its tautomeric structure, from the viewpoint of hue, it is more preferable that both of R ^b are -OH.

Select at least two metals from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, preferably containing at least one metal that becomes a divalent or trivalent cation The more preferred system contains at least one selected from the group consisting of Ni, Cu, and Zn, and the more preferred system contains at least Ni.

Furthermore, the best system contains Ni, and at least one metal is selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and the best system contains Ni and At least one metal is selected from the group consisting of Zn, Cu, Al, and Fe. Among them, the above-mentioned at least two kinds of metal systems Ni and Zn, or Ni and Cu are more preferable.

In the above yellow color material (D3), the content ratio of at least two metals may be adjusted appropriately.

Among them, from the viewpoint of the reddish phase, in the above yellow color material (D3), Ni, and at least one selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn The content ratio of the metal is preferably Ni: other at least one of the above metals at a molar ratio of 97: 3 to 10:90, more preferably at a molar ratio of 90:10 to 10:90.

Among them, from the viewpoint of the reddish phase, Ni and Zn are preferably contained in a molar ratio of Ni: Zn = 90: 10 ~ 10: 90, more preferably in a molar ratio of 80: 20 ~ 20: 80 .

Or, from the viewpoint of the reddish phase, Ni and Cu are preferably contained in a molar ratio of Ni: Cu = 97: 3 ~ 10: 90, more preferably in a molar ratio of 96: 4 ~ 20: 80 .

When the yellow color material (D3) has a reddish phase, even if the P / V ratio is suppressed, red pixels belonging to a high-density redness region can be easily produced.

The yellow color material (D3) may further contain metal ions other than the specific metal ions, for example, Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La Select at least one metal ion in the group.

The above-mentioned yellow color material (D3) contains at least two kinds of metal ions. For example, when the common crystal lattice contains at least two kinds of metal ions, each of which contains one kind of metal ions in different lattices Crystallization. Among them, from the viewpoint of further enhancing the contrast, it is preferable that the common crystal lattice contains at least two kinds of metal ions. In addition, it belongs to a state in which at least two kinds of metal ions are contained in a common lattice, or a state in which crystals containing one kind of metal ions in different lattices are aggregated, for example, refer to Japanese Patent Laid-Open No. 2014- Gazette No. 12838 can be appropriately judged using the X-ray diffraction method.

The above-mentioned yellow color material (D3) contains: a metal complex [which is composed of anions of the azo compound represented by the above general formula (4) and its tautomeric structure, and a specific metal ion], and the above The compound molecule of the compound represented by formula (5). Such intermolecular bonding systems can be formed by, for example, intermolecular interactions, or Lewis acid-base interactions, or coordination bonds. Alternatively, it may be a structure such as an occlusion compound in which a guest molecule is attached to the crystal lattice constituting the host molecule. Alternatively, a mixed substitution crystal may be formed in which two substances form a common crystal and the atoms of the second component are located at regular lattice positions of the first component.

In the above general formula (5), the alkyl group of R ^c is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may also be substituted with -OH group. Among them, R ^{c is} preferably a hydrogen atom.

The content of the compound represented by the above general formula (5) is based on 1 mole of the azo compound represented by the above general formula (4) and its tautomeric structure, and it is generally 5 moles or more and 300 moles or less Preferably, it is 10 moles or more and 250 moles or less, and more preferably 100 moles or more and 200 moles or less.

In addition, the yellow color material (D3) may further contain: urea and substituted urea (such as phenylurea, dodecylurea, etc.), and its aldehyde (especially polycondensate with formaldehyde); Ring (for example: barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoline Porphyrin, 2,3-dihydroxyquin Quinoline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1, 3,5-three -2,4-diamine, 6-methyl-1,3,5-tri -2,4-diamine, cyanuric acid, etc.).

Furthermore, the yellow color material (D3) may further contain water-soluble polymers, such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly (meth) acrylic acid, and carboxyl, for example Modified cellulose such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxyethyl cellulose.

The above-mentioned yellow color material (D3) can be prepared by referring to, for example, Japanese Patent Laid-Open No. 2014-12838.

When the coloring resin composition of the present invention contains the above-mentioned yellow color material (D3), the above-mentioned yellow color material (D3) is 100% by mass of the color material (D) from the viewpoint of both chromaticity adjustment and brightness improvement. ) Is preferably 0.5% by mass or more. On the other hand, from the viewpoint that the chromaticity can be easily adjusted within the intended range, it is preferably 20% by mass or less, and more preferably 10% by mass or less.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it can achieve the desired color development when it becomes a colored layer, although it will vary according to the type of color material used, preferably 10 nm Within the range of 100 nm or less, more preferably 15 nm or more and 60 nm or less. When the average primary particle diameter of the color material is within the above range, a display device equipped with a color filter manufactured using the colored resin composition of the present invention can achieve high contrast and high quality.

In addition, the average dispersed particle diameter of the color material varies depending on the type of color material used, preferably within a range of 10 nm to 100 nm, more preferably within a range of 15 nm to 60 nm.

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

The content of the color material in the colored resin composition is preferably 15 parts by mass or more and 90 parts by mass or less, and more preferably 30 parts by mass or more and 80 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. . If the content of the color material is more than the above lower limit, the desired optical characteristics and the required performance are obtained, and if the content of the color material is less than the above upper limit, the effect of suppressing the precipitation of the color material compound is high and can be suppressed It is easy to pattern the coating film which is poorly cured and the colored resin composition.

    <Compound (E) having a fluorocarbon group and a cross-linked cycloaliphatic group>    

The compound having a fluorocarbon group and a cross-linked cycloaliphatic group used in the present invention (hereinafter also referred to as "precipitation inhibiting compound") contains one or more fluorocarbon groups and a cross-linked cycloaliphatic group in the molecule compound of. When the coloring resin composition of the present invention contains the above-mentioned precipitation-inhibiting compound, the precipitation of the coloring material-derived compound can also be suppressed in the formed coloring layer. In addition, the compound has a fluorocarbon group and a cross-linked cycloaliphatic group, which can be confirmed from ¹ H- and ¹³ C-NMR mass spectra measured using a nuclear magnetic resonance apparatus.

The fluorocarbon group included in the precipitation-preventing compound refers to a group in which at least a part of hydrogen atoms having a hydrocarbon group are replaced with fluorine atoms. In addition, the fluorocarbon group may have a part of a fluorine atom or a hydrogen atom such as a halogen atom such as a chlorine atom, a bromine atom, an iodine atom (but not a fluorine atom), a hydroxyl group, a thiol group, an alkoxy group, an ether group, an amine It can be substituted by various substituents such as carbonyl, nitrile, nitro, sulfonyl, sulfenyl or ester, amine, acetyl, amide, carboxyl and other groups, and may also have an ether in the main chain Bond (-O-), sulfonamide bond (-SO _2- ).

The carbon number of the fluorocarbon group in the above-mentioned suppression precipitation compound is preferably 2 or more and 10 or less from the viewpoint of improving the compatibility with other components and obtaining the best rheological properties when applying the colored resin composition. . The lower limit of the fluorocarbon-based carbon number 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 part of the hydrogen atoms of the hydrocarbon group are replaced by fluorine atoms. From the viewpoint of allowing the above-mentioned precipitation-preventing compound to exist on the surface of the colored layer and suppressing precipitation of the compound derived from the color material, the hydrogen of the hydrocarbon group is preferred A perfluorocarbon group in which all atoms are replaced by fluorine atoms.

Examples of the fluorocarbon-based system include fluoroalkyl groups having a saturated structure, fluoroalkenyl groups having an unsaturated structure, and fluoroalkylaryl groups having an aromatic skeleton. In particular, the synthesis of fluoroalkyl groups and fluoroalkenyl groups is relatively easy , Best to use.

Examples of the fluoroalkyl group include fluoroalkyl groups having 2 to 10 carbon atoms. Among the fluoroalkyl groups having a carbon number of 2 or more and 10 or less, from the viewpoint of allowing the above-mentioned precipitation-preventing compound to exist on the surface of the colored layer and suppressing precipitation of the compound derived from the color material, a perfluoroalkyl group is preferred. Examples of perfluoroalkyl groups having a carbon number of 2 or more and 10 or less include: perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, and perfluoroheptane Base, perfluorooctyl, perfluorononyl, perfluorodecyl, etc.

Examples of the fluoroalkenyl system include fluoroalkenyl groups having 2 to 10 carbon atoms. Among the fluoroalkenyl groups having a carbon number of 2 or more and 10 or less, from the viewpoint of allowing the above-mentioned precipitation-preventing compound to exist on the surface of the colored layer and suppressing precipitation of the compound derived from the color material, it is preferably a perfluoroalkenyl group. Examples of perfluoroalkenyl groups having a carbon number of 2 or more and 10 or less include: perfluoropropenyl, perfluoroisopropenyl, perfluorobutenyl, perfluoroisobutenyl, perfluoropentenyl, and perfluoroisopentene Group, perfluorohexenyl, perfluoroheptenyl, perfluorooctenyl, perfluorononenyl, perfluorodecenyl, etc.

The cross-linked cycloaliphatic group included in the precipitation-preventing compound refers to an aliphatic group in which two or more rings share a structure of two or more atoms. The carbon number of the cross-linked cyclic aliphatic group is preferably 5 or more and 12 or less from the viewpoint of compatibility with other materials and solubility in alkali developer. The lower limit of the carbon number of the cross-linked cycloaliphatic group is more preferably 7 or more, and the upper limit is more preferably 10 or less.

Examples of cross-linked cycloaliphatic radicals are: Alkyl and iso Group, adamantyl group which may be substituted, tricyclodecyl group which may be substituted, dicyclopentenyl group which may be substituted, dicyclopentyl group which may be substituted, tricyclopentyl group which may be substituted Alkenyl, optionally substituted tricyclopentyl, optionally substituted tricyclopentadienyl, and optionally substituted dicyclopentadienyl, etc. Among these, from the viewpoint of heat resistance and precipitation inhibition effect, adamantyl groups which may be substituted and dicyclopentyl groups which may be substituted are preferred, and adamantyl groups which may be substituted are more preferred. When such groups are substituted, examples of the substituent group include alkyl groups, cycloalkyl groups, alkylcycloalkyl groups, hydroxyl groups, ketone groups, nitro groups, amine groups, and halogen atoms.

The glass transition temperature of the precipitation-preventing compound is preferably 150 ° C or higher and 250 ° C or lower. If the glass transition temperature of the precipitated compound is suppressed to 150 ° C. or more, after the precipitated compound is suppressed from penetrating the coating film surface, even if the coating film surface is wiped, the abrasion resistance is still high, which can improve the quality of the color filter If the temperature is 250 ° C. or lower, the precipitation-preventing compound easily moves to the surface of the coating film (leaching easily occurs), and a better precipitation-preventing effect can be obtained. The glass transition temperature of the precipitation-preventing compound is determined according to JIS K 7121-1987 and can be determined by differential scanning calorimetry (DSC). The lower limit of the glass transition temperature to suppress precipitation of the compound is more preferably 180 ° C or higher, and the upper limit is more preferably 230 ° C or lower.

The above-mentioned precipitation-preventing compound may be a structural unit derived from a compound (E-1) derived from a fluorocarbon group and an ethylenically unsaturated group, and derived from a structural unit derived from a cross-linked cyclic aliphatic group and an ethylenically unsaturated group A copolymer of the constituent units of the compound (E-2).

Among the above compounds for inhibiting precipitation, the molar ratio (E-1: E-2) of the structural unit derived from the above-mentioned compound (E-1) to the structural unit derived from the above-mentioned compound (E-2) is preferably 5: 95 ~ 70: 30, the better system 10: 90 ~ 50: 50, the special system 13: 87 ~ 30: 70. When the molar ratio is within the above range, the compatibility with each component in the coloring resin composition, the precipitation suppression effect, and the rheological properties of the coloring resin composition are all good. The molar ratio of each constituent unit of the above-mentioned precipitation-preventing compound can be obtained from the measurement results of nuclear magnetic resonance (NMR) analysis.

The precipitation-preventing compound preferably contains, for example, a copolymer of a structural unit represented by the following general formula (6) and a structural unit represented by the following general formula (7).

(In the general formula (6) and the general formula (7), X ¹ and X ² are independent direct bonds, which may be substituted with an alkylene group having a carbon number of 1 or more and 4 or less, or may be substituted Oxyalkylene groups having a carbon number of 1 or more and 4 or less; Rf is a fluorocarbon group having a carbon number of 2 or more and 10 or less; R ¹¹ and R ¹² are independently hydrogen atoms, or a carbon number of 1 or more which may be substituted and Hydrocarbon groups of 6 or less; A ¹ is a cross-linked cycloaliphatic group.)

In the above general formula (6) and the above general formula (7), X ¹ and X ^{2 have} an alkylene group having a carbon number of 1 or more and 4 or less. Examples thereof include methylene, ethyl, propyl, Stretching butyl, etc. The oxyalkylene groups having X ¹ and X ² having a carbon number of 1 to 4 are exemplified by oxymethylene, oxyethyl, oxypropyl, oxybutyl and the like. In addition, the substituents that the alkylene group and the oxyalkylene group may have include, for example, halogen atoms, hydroxyl groups, acid groups, nitro groups, carbonyl groups, amide groups, and amine groups. Among X ¹ and X ² , it is preferably a direct bond or an alkylene group having 1 to 4 carbon atoms.

In the above general formula (6) and the above general formula (7), the hydrocarbon groups of R ¹¹ and R ¹² having a carbon number of 1 to 6 are, for example, methyl, ethyl, propyl, butyl, isopropyl Straight-chain or branched alkyl groups such as alkyl, tertiary butyl, pentyl and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and so on. In addition, the substituents that the hydrocarbon group may have include, for example, halogen atoms, hydroxyl groups, acid groups, nitro groups, and amine groups. R ¹¹ and R ¹² are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the above general formula (6), the fluorocarbon group of Rf having a carbon number of 2 or more and 10 or less can be used, for example, those in the fluorocarbon group having a carbon number of 2 or more and 10 or less, particularly preferably a carbon number of 2 or more and 10 or less of the above fluoroalkyl group.

In the above general formula (7), the cross-linked cycloaliphatic group of A ¹ can use the aforementioned cross-linked cycloaliphatic group.

From the viewpoint of the effect of suppressing precipitation, the above-mentioned compound for suppressing precipitation is preferably a block copolymer containing a structural unit derived from the compound (E-1) and a structural unit derived from the compound (E-2). When the precipitation of the compound-based block copolymer is suppressed, the structural unit derived from the above compound (E-1) is preferably 3 or more and 15 or less, and the structural unit derived from the above compound (E-2) is preferably 5 or more and 40 or less. If the structural unit derived from the above-mentioned compound (E-1) and the structural unit derived from the above-mentioned compound (E-2) are within the above-mentioned range, the compatibility of each component of the coloring resin composition with In the case of variable characteristics, the effect of suppressing precipitation is exhibited.

The production method of the block copolymer is not particularly limited. The block copolymer can be produced by a well-known method. Among them, the living polymerization method is preferably used. The reason is that it is possible to produce copolymers that are less prone to chain transfer and deactivation and have a uniform molecular weight, which can improve dispersibility. Examples of the living polymerization method system include living anionic polymerization methods such as living radical polymerization method and group transfer polymerization method; and living cationic polymerization method. Using these methods, a monomer can be polymerized in sequence to produce a copolymer. For example, first, the block (A block) derived from the structural unit of the compound (E-1) is produced, and then the block (B) formed from the structural unit of the compound (E-2) is polymerized on the A block Block) to produce block copolymers. In addition, the polymerization order in the above production method may be reversed from the above. Alternatively, each block may be manufactured separately, and then each block may be coupled.

The arrangement of each block of the block copolymer is not particularly limited, and it can be, for example, AB block copolymer, ABA block copolymer, BAB block copolymer, or the like. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The precipitation-preventing compound is capable of controlling the compatibility of the colored resin composition and the glass transition point, and may further contain a compound derived from being capable of copolymerizing with the compound (E-1) and the compound (E-2), and having The structural unit of the ethylenic unsaturated group compound (E-3).

The structural unit derived from the compound (E-3) can be, for example, a structural unit represented by the following general formula (8).

The precipitation-preventing compound is preferably a copolymer containing the structural unit represented by the general formula (6), the structural unit represented by the general formula (7), and the structural unit represented by the general formula (8) below.

[化 14] (In general formula (8), R ¹³ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted; A ² is an aryl group which may be substituted, or a pyridyl group which may be substituted, or The group represented by the following general formula (9).)

(In general formula (9), A ³ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted benzyl group, an optionally substituted cyclopentyl group, an optionally substituted cyclopentylalkyl group, (Cyclohexyl which may be substituted, or cyclohexylalkyl which may also be substituted. * Represents the bonding position.)

In the above general formula (8), R ¹³ may also be substituted with a hydrocarbon group having a carbon number of 1 or more and 6 or less, which can be used in the general formula (6) and the general formula (7) above, R ¹¹ and R ¹² The same is true for hydrocarbon groups with a carbon number of 1 or more and 6 or less.

In the general formula (8), the aryl group of A ² may be, for example, phenyl, biphenyl, naphthyl, tolyl, xylyl, or the like. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.

In addition, in the general formula (8), the substituents that the aryl group and pyridyl group of A ² may have may be exemplified by linear or branched alkyl groups having 1 to 4 carbon atoms and Alkenyl, cycloalkyl, nitro, halogen atoms, etc.

In the above general formula (9), the substituent groups that A ³ may have include, for example, a hydroxyl group, an acyl group, a nitro group, an amine group, a carboxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms.

The above precipitation-preventing compound is carried out by using a compound (E-1) having a fluorocarbon group and an ethylenic saturated group, and a compound (E-2) having a cross-linked cycloaliphatic group and an ethylenically unsaturated group. It can be obtained by copolymerization. The compound (E-1) having a fluorocarbon group and an ethylenic saturated group can be, for example, a compound represented by the following general formula (6-1). The compound (E-2) having a cross-linked cycloaliphatic group and an ethylenically unsaturated group can be, for example, a compound represented by the following general formula (7-1).

(In the general formula (6-1), X ¹ , Rf and R ¹¹ are the same as the general formula (6).)

[化 17] (In the general formula (7-1), X ² , A ¹ and R ¹² are the same as the above general formula (7).)

Specific examples of the above compound (E-1) include, for example, 2- (perfluoropropyl) ethyl (meth) acrylate and 2- (perfluoroisopropyl) ethyl (meth) acrylate , (Meth) acrylic acid-2- (perfluorobutyl) ethyl, (meth) acrylic acid-2- (perfluoropentyl) ethyl, (meth) acrylic acid-2- (perfluorohexyl) ethyl , (Meth) acrylic acid-2- (perfluoroheptyl) ethyl, (meth) acrylic acid-2- (perfluorooctyl) ethyl, (meth) acrylic acid-2- (perfluorononyl) ethyl Ester, 2- (perfluorodecyl) ethyl (meth) acrylate, etc. Among these, from the viewpoint of suppressing the precipitation effect and the rheological properties of the coloring resin composition, 2- (perfluorohexyl) ethyl (meth) acrylate is preferred.

Specific examples of the above compound (E-2) include, for example, 1-adamantane (meth) acrylate, 1-adamantane 1-methyl- (meth) acrylate, (meth) acrylic acid -2-methyl-2-adamantyl ester, (meth) acrylic acid Alkyl ester, (meth) acrylic acid Ester, tricyclodecyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclopentyl (meth) acrylate, tricyclo (meth) acrylate Pentenyl ester, dicyclopentadiene (meth) acrylate, tricyclopentadienyl (meth) acrylate, etc. Among these, from the viewpoint of compatibility with each component of the color resin composition and the effect of suppressing precipitation, 1-adamantanyl (meth) acrylate and dicyclopentyl (meth) acrylate are preferred.

Furthermore, when the precipitation-preventing compound further contains a compound (E-3) derived from an ethylenically unsaturated group that is copolymerized with the compound (E-1) and the compound (E-2), In the case of a unit, the compound (E-3) can be, for example, a compound represented by the following general formula (8-1): (In the general formula (8-1), A ² and R ¹³ are the same as the above general formula (8).)

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 (meth) acrylate, cyclopentylethyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, cyclohexyl (meth) acrylate, Vinylpyridine and so on. Among these, from the viewpoint of the compatibility of the colored resin composition and the effect of suppressing precipitation, methyl (meth) acrylate, (meth) acrylic acid, and styrene are preferred.

The weight average molecular weight (Mw) of the precipitation-preventing compound is preferably 3,000 or more and 10,000 or less. If the weight average molecular weight of the precipitated compound is suppressed to be 3,000 or more and 10,000 or less, the affinity with other materials is excellent, and the viscosity of the colored resin composition is not too high, so that it does not hinder the surface bleed out by heat during baking , And not easy to damage and inhibit precipitation effect. The lower limit of the molecular weight of the compound to suppress precipitation is more preferably 4,000 or more, and the upper limit of the molecular weight of the compound to suppress precipitation is more preferably 8,000 or less.

In the coloring resin composition of the present invention, from the viewpoint of a high effect of suppressing the precipitation of a compound derived from a color material and improving the smoothness of the coating film of the coloring resin composition applied, the total solid content of the coloring resin composition is 100 In terms of mass parts, the content of the precipitation-preventing compound is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more; on the other hand, from the viewpoint of suppressing component separation and poor curing, it is preferable 12 parts by mass or less, more preferably 10 parts by mass or less, particularly good 5 parts by mass or less, and most preferably 1 part by mass or less.

    <Thiol compound (F)>    

The thiol compound is a compound that has the function of a cross-linking agent and has one or more thiol groups in the molecule. By containing the thiol compound in the coloring resin composition of the present invention, the surface of the colored layer can be densified, and precipitation of compounds derived from the color material can be further suppressed.

The thiol compound system can be appropriately selected from known compounds having one or more thiol groups in the molecule. The thiol compound system 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 dimercaptoacetate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol dimercaptoacetate Ester, 1,4-butanediol dimercaptoacetate, 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tri (mercaptoacetate), 2-mercaptobenzene Thiazole, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetramercaptoacetate, pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate); and various other polyols, esters with thiol-containing carboxylic acids such as thioglycolic acid, mercaptopropionic acid, etc .; and trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate Ester, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-tri , 2- (N, N-Dibutylamino) -4,6-dimercapto-s-tri Wait. In particular, from the viewpoint of increasing the reaction rate, 2-mercaptobenzothiazole is preferably used as the thiol compound.

The thiol compound may be a thiol compound having a substituent on at least one carbon atom in the α position and β position relative to the thiol group. Examples of such specific examples include: 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, and bis (1-mercaptoethyl phthalate) ), Bis (2-mercaptopropyl phthalate), bis (3-mercaptobutyl phthalate), bis (3-mercaptoisobutyl phthalate), etc.

The thiol compound has a high cross-linking density, a better precipitation suppression effect, and a viewpoint of easily reducing the surface roughness. It is particularly preferable to use a polyfunctional sulfur having two or more thiol groups in one molecule. One or more types are selected from the group consisting of alcohol compounds. In addition, from the viewpoint of long-term storage of the colored resin composition, it is still possible to easily maintain a good precipitation suppression effect and a low surface roughness. Preferably, it is a secondary sulfur having a secondary carbon atom bonded to a thiol group. The secondary thiol compound of the alcohol group is more preferably a multifunctional secondary thiol compound having two or more secondary thiol groups in one molecule.

When the coloring resin composition of the present invention contains a thiol compound, the content of the thiol compound in the colored resin composition is preferably at least 0.05 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less. If the content of the thiol compound exceeds the above lower limit, the curing promotion effect caused by the thiol compound can be used to sufficiently cure the coating film, and if the content of the thiol compound is below the above upper limit, the curing can be controlled The promotion can suppress the performance degradation of the colored resin composition such as distortion of the shape of the end of the pattern.

    <Dispersant (G)>    

From the viewpoint of improving the dispersibility and dispersion stability of the color material, the coloring resin composition of the present invention preferably further contains a dispersant.

The dispersant used in the present invention is not particularly limited, and from the viewpoint of improving the adsorption performance of the color material, and improving the dispersibility and dispersion stability of the color material, it is preferable to use the following general formula (11) A polymer of constituent units. The structural unit system represented by the following general formula (11) has alkalinity and has a function of adsorbing a color material.

(In general formula (11), R ¹⁴ is a hydrogen atom or a methyl group; L is a divalent linking group; R ¹⁵ and R ¹⁶ are independently hydrogen atoms, or a hydrocarbon group that may also contain a hetero atom, or R ¹⁵ and R ^{16 is} bonded to each other to form a ring structure.)

In the general formula (11), the divalent linking system of L includes, for example, an alkylene group having 1 to 10 carbon atoms, an aryl group, a -CONH- group, a -COO- group, and 1 carbon atom Ether groups above and below 10 (-R'-OR "-: R 'and R" are independently alkylene groups) and combinations thereof. Among these, from the viewpoint of dispersibility, L of the above formula (11) is preferably a divalent linking group containing a -CONH- group or a -COO- group.

The hydrocarbon groups which may contain hetero atoms in R ¹⁵ and R ¹⁶ may be exemplified by alkyl groups, aralkyl groups, aryl groups, etc. The number of carbon atoms of the above-mentioned alkyl group is preferably 1 or more and 18 or less, and more particularly The best is methyl or ethyl.

In R ¹⁵ and R ¹⁶ , the hydrocarbon group containing a hetero atom means a structure in which the carbon atom in the above hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom system which the hydrocarbon group may contain include oxygen atom, nitrogen atom, sulfur atom, silicon atom and the like.

Among them, R ¹⁵ and R ^{16 are} preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group independently of each other, or R ¹⁵ and R ¹⁶ are bonded to form a pyrrolidine ring or a piperidine ring , A quinoline ring, particularly preferably at least one of R ¹⁵ and R ¹⁶ is an alkyl group or phenyl group having 1 to 5 carbon atoms, or a pyrrolidine ring or piper is formed by the bonding of R ¹⁵ and R ¹⁶ Pyridine ring, Oxo ring.

Examples of the structural unit system represented by the general formula (11) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminoethyl (meth) acrylate. , Diethylaminopropyl (meth) acrylate, etc. (Meth) acrylates containing alkyl substituted amine groups; dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) (Meth) acrylamide and the like (meth) acrylamide containing alkyl substituted amine groups. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to use, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (Meth) acrylamide.

The structural unit system represented by the general formula (11) may be constituted by a single type, or may contain two or more types of structural units.

In the polymer having the structural unit represented by the general formula (11), the absorption of the color material forming the salt portion is further improved, the color material dispersion stability, the development residue suppression, and the solvent resolubility are excellent, and From the viewpoint of combining the above-mentioned precipitation-inhibiting compound used in the present invention and further suppressing the precipitation of the color material compound, it is preferable that at least a part of terminal nitrogen sites included in the structural unit represented by the general formula (11) and from below The compounds represented by the general formulas (12) to (14) constitute a salt formed by selecting at least one compound from the group. In the polymer having the structural unit represented by the general formula (11), the terminal nitrogen site possessed by the structural unit represented by the general formula (11) and the group consisting of the following general formulas (12) to (14) The selection of one or more compounds to form a salt 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 a carbon number of 1 to 20 or less, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -O -R ';R' represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 20 or less, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 or more and (Meth) acryloyl group formed by alkylene extending below 4.

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, and may have a linear or branched carbon number of 1 to 20 Cyclic or cyclic alkyl, optionally substituted vinyl, optionally substituted phenyl or benzyl, or -OR ";R" represents, and may also have a substituted carbon number of 1 or more and 20 The following linear, branched or cyclic alkyl groups, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may also have a substituent, or an alkylene group having 1 to 4 carbon atoms The (meth) acryloyl group; Q represents a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (14), R ²¹ and R ²² each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having a carbon number of 1 to 20, a vinyl group, and may have a substituent Phenyl or benzyl, or -O-R ';R' represents a linear, branched or cyclic alkyl, vinyl, or optionally substituted phenyl or A benzyl group or a (meth) acryloyl group formed by 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 above general formula (11) can improve the dispersibility of the color material, the dispersion stability and the heat resistance of the coloring resin composition, and can be combined with the above-mentioned precipitation inhibiting compound used in the present invention. From the viewpoint of more suppressing the precipitation of the color material compound and forming a high-brightness and high-contrast colored layer, it is preferable that at least a part of terminal nitrogen sites included in the structural unit represented by the above general formula (11) and from the above general formula In the group consisting of the compounds represented by (12) to (14), one or more compounds form a salt-type block copolymer of a salt.

In the block copolymer, if the block containing the structural unit represented by the general formula (11) is designated as the A block, the structural unit represented by the general formula (11) of the A block is basic and has It becomes a function to attract the color material. In addition, when at least a part of the terminal nitrogen sites included in the structural unit represented by the general formula (11) form a salt with at least one compound selected from the group consisting of the general formulas (12) to (14), this The salt forming part has a function of becoming a stronger adsorption site for the color material. On the other hand, the B block that does not contain the structural unit represented by the above general formula (11) functions as a solvent-affinity block. Therefore, in the block copolymerization system, the A block that adsorbs the color material and the B block that has affinity for the solvent share functions, and the function of the color material dispersant is exerted.

The B block system does not contain the structural unit represented by the general formula (11). The structural unit constituting the B block is preferably compounded from a monomer having an ethylenically unsaturated bond which can be polymerized with a monomer derived from the structural unit represented by the above general formula (11) so as to have a solvent affinity The solvent is appropriately selected and used. The index is preferably to introduce the solvent affinity part to the solvent used in combination so that the polymer solubility at 23 ° C. becomes 50 (g / 100 g solvent) or more. The structural unit constituting the B block preferably contains a structural unit represented by the following general formula (15).

(In 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-[(CH ₂ ) _y -O] _z -R ²⁷ represents a monovalent group. R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group; R ²⁷ is a hydrogen atom, a hydrocarbon group, or -CHO, -CH ₂ CHO, or -CH ₂ COOR ^{28 is} a monovalent group; R ²⁸ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.

The above-mentioned hydrocarbon group may have a substituent.

The x system represents an integer of 1 or more and 18 or less; the y system represents an integer of 1 or more and 5 or less; and the z system represents an integer of 1 or more and 18 or less. )

The divalent linking group L 'in the general formula (15) may be the same as L in the general formula (11). Among them, from the viewpoint of solubility in organic solvents, L 'is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group. From the viewpoints of the heat resistance of the obtained polymer, the solubility of propylene glycol monomethyl ether acetate (PGMEA) in a preferred solvent, and the cheaper material, L 'is preferably a -COO- group.

The hydrocarbon group of 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 or more carbon atoms and 18 or less may be linear, branched, or cyclic, and may be, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl , 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, Base Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc.

The toxic alkenyl system having 2 or more carbon atoms and 18 or less may be linear, branched, or cyclic. Examples of such an alkenyl system include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited. From the viewpoint of the reactivity of the obtained polymer, it is preferable that the terminal of the alkenyl group has a double bond.

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

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

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

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

In addition, the above-mentioned preferable number of carbon atoms does not include the number of carbon atoms of the substituent.

In R ²⁴ above, x 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; y is an integer of 1 or more and 5 or less, preferably An integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group of R ²⁷ may be the same as that shown in 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.

In addition, the R ²⁴ series in the structural unit represented by the general formula (15) may be the same as or different from each other.

The above-mentioned R ^{24 is} preferably selected in accordance with an excellent compatibility with a solvent described later, specifically, for example, when the above-mentioned solvent system uses a solvent used in a general color filter composition for color filters, glycol ether acetate system, ether system, ester system In the case of solvents such as methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl and the like are preferred.

Furthermore, the above R ²⁴ can be substituted with substituents such as alkoxy, hydroxy, epoxy, isocyanate, etc. within the range that does not hinder the dispersibility of the block copolymer, etc. After the copolymer is synthesized, the compound with the above substituents can be reacted again to add the above substituents.

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

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

1 / Tg = Σ (Xi / Tgi)

Among them, the solvent-affinity block is set to copolymerize n monomer components from i = 1 to n. Xi is the weight fraction of the i-th monomer (ΣXi = 1); Tgi is the glass transition temperature (absolute temperature) of the monomer of the i-th monomer. However, Σ is a total of i = 1 to n. The glass transition temperature of the homopolymer of each monomer (Tgi) can be based ^{Polymer Handbook (3 rd Edition) (} J.Brandrup, EHImmergut the (Wiley-Interscience, 1989)) value.

The number of constituent units constituting the solvent-affinity block portion may be adjusted as long as the dispersibility of the color material is improved. In particular, the number of constituent units constituting the solvent-affinity block is preferably 10 or more and 200 or less, from the viewpoints of effectively functioning the solvent affinity portion and the color material affinity portion and improving the dispersibility of the color material. The system is 10 or more and 100 or less, and the ultra good system is 10 or more and 70 or less.

The solvent-affinity block system may be selected as long as it functions as a solvent-affinity site, and the repeating unit system constituting the solvent-affinity block may consist of only one type, or may contain two or more types of repeating units.

The weight average molecular weight Mw of the block copolymer is not particularly limited. From the viewpoint of making the color material dispersibility and dispersion stability good, it is preferably 1,000 or more and 20,000 or less, more preferably 2000 or more and 15,000 or less, and particularly The best line is above 3000 and below 12000.

The amine value of the block copolymer before salt formation is not particularly limited. From the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, and particularly preferably 60mgKOH / g or more. In addition, the upper limit is preferably 130 mgKOH / g or less, and more preferably 120 mgKOH / g or less. If it is more than the above lower limit, the dispersion stability is more excellent. Moreover, when it is below the said upper limit, compatibility with other components is excellent, and solvent resolubility is good. In this specification, the amine value of the block copolymer before salt formation refers to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation, which is equivalent to the mass (mg) of potassium hydroxide. The value measured by the method described in K 7237-1995.

The amine value of the obtained salt-type block copolymer is only a value that is less than the amount of salt formed in the block copolymer before salt formation. However, since the salt-forming site is the same as the terminal nitrogen site corresponding to the amine group, or instead it becomes a strengthened color material adsorption site, there is a tendency that the color-forming material dispersibility and color material dispersion stability can be improved by forming the salt. Also, the salt formation system is the same as the amine group, and if too much, it will adversely affect the solvent resolubility. Therefore, the amine value of the block copolymer that forms the pre-salt can be set as an index for the stability of color material dispersion and solvent resolubility. The amine value of the salt block copolymer obtained is preferably 0 mgKOH / g or more and 130 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 120 mgKOH / g or less. When it is below the above upper limit, it has excellent compatibility with other components and good solvent resolubility.

In addition, the acid value of the dispersant used in the present invention is not particularly limited. From the viewpoint of good development adhesiveness and solvent resolubility, it is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH / g or less. In addition, from the viewpoint of further improving the solvent resolubility and development adhesiveness, and the viewpoint of substrate adhesion and dispersion stability, the acid value of the dispersant is preferably 0 mgKOH / g. Because the lower the acid value, the less likely to be eroded by alkaline developer, so it can be judged that the better the development adhesion. On the other hand, from the viewpoint of suppressing the development residue effect, it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more.

Furthermore, in the present invention, from the viewpoint of improving the development adhesiveness, the glass transition temperature of the dispersant is preferably 30 ° C. or higher. If the glass transition temperature of the dispersant is low, especially close to the temperature of the developing solution (usually about 23 ° C), there is a possibility that the development adhesiveness will decrease. From the viewpoint of development adhesion, the glass transition temperature of the dispersant is preferably 32 ° C or higher, and more preferably 35 ° C or higher. On the other hand, it is preferably 200 ° C. or less from the viewpoint of ease of use when using a precision scale or the like.

The glass transition temperature of the dispersant of the present invention can be determined according to JIS K 7121 by differential scanning calorimetry (DSC).

The content of the dispersant is preferably 3 parts by mass or more and 45 parts by mass or less, and more preferably 5 parts by mass with respect to 100 parts by mass of the total solids in the colored resin composition from the viewpoint of dispersibility and dispersion stability. The ratio is more than 35 parts by mass.

The method for producing the above-mentioned block copolymer is not particularly limited, and the block copolymer can be produced by a known method. In addition, the preparation method of the salt-type block copolymer can be, for example, by adding a solvent from the above general formulas (12) to (14) in a solvent in which the polymer having the structural unit represented by the general formula (11) is dissolved or dispersed. Select one or more compounds in the composition group, stir them, and further apply the heating method if necessary.

    <Solvent (H)>    

The coloring resin composition of the present invention may further contain a solvent. The solvent system is not particularly limited as long as it does not react with the components of the coloring resin composition and can dissolve or disperse such organic solvents. The solvent system can be used alone or in combination of two or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxy ethoxy ethanol, ethoxy ethoxy ethanol, etc. Biol-based solvents; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, hydroxypropionic acid Ethyl ester, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclic Ketone solvents such as hexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxy acetate Glycol ether, ethoxyethyl acetate and other glycol ether acetate-based solvents; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA), etc. Carbitol acetate-based solvents; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol Ethylene glycol di Glycol ether solvents such as ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc .; N, N-dimethylformamide, N, N-dimethyl Aprotic amide solvents such as ethylacetamide and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; cyclic ether-based solvents such as tetrahydrofuran; unsaturated benzene, toluene, xylene, naphthalene Hydrocarbon solvents; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used from the viewpoint of solubility with other components. Among them, the solvent used in the present invention is preferably from the viewpoint of solubility with other components and coating suitability from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), Choose one or more of the group consisting of 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

The content of the solvent in the colored resin composition is usually preferably in the range of 55% by mass or more and 95% by mass or less relative to the total amount of the colored resin composition, and particularly preferably in the range of 65% by mass or more and 90% by mass or less Within the range of 5%, the ultra good series is within the range of 70% by mass or more and 88% by mass or less. If the solvent content is more than 55% by mass, the decrease in dispersion caused by the increase in viscosity can be suppressed, and if the solvent content is less than 95% by mass, the reduction in color material concentration can be suppressed, so it is easy to achieve the target chromaticity coordinates.

    <Other ingredients>    

In the coloring resin composition of the present invention, it may be further blended with other components as necessary before harming the effects of the present invention. For this other component system, for example, a dispersion aid can be used.

The dispersing aid is to improve the dispersibility of color materials. The dispersion aid is preferably a pigment derivative such as an acid pigment derivative. The pigment derivative system has the function of improving the dispersibility of the color material, and although the effect of suppressing the precipitation of the color material compound is weak, it is still considered to have the effect of suppressing the precipitation of the color material compound, so by using the above suppression together The precipitation of the compound and the pigment derivative can further suppress the precipitation of the color material compound.

Furthermore, the other components can be exemplified by surfactants for improving wettability, silane coupling agents for improving adhesion, defoamers, anti-collapse agents, antioxidants, anti-agglomeration agents, and ultraviolet absorbers Wait.

    <Manufacturing method of colored resin composition>    

The coloring resin composition of the present invention can be produced as follows, for example. First, a color material dispersion liquid or color material solution is prepared. The color material dispersion liquid contains at least a color material, a dispersant, and a solvent. The color material solution contains at least a color material and a solvent. The color material dispersion liquid or color material solution may further contain a polymer, a thiol compound, or the like.

After preparing the color material dispersion liquid or color material solution, a polymerizable compound, a precipitation-preventing compound, a polymerization initiator, and a polymer as needed are added to the color material dispersion liquid or color material solution, and a known mixing method is used By mixing, a colored resin composition can be obtained.

    << hardened product >>    

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

The cured product of the present invention is quite suitable as a coloring layer of a color filter. Since it is a cured product of the colored resin composition of the present invention described above, it is possible to suppress the precipitation of compounds derived from the color material, and to suppress the reduction in brightness and contrast.

The cured product of the present invention, for example, when the colored resin composition of the present invention is a photosensitive colored resin composition containing a photopolymerizable compound, after forming a coating film of the photosensitive colored resin composition and drying the coating film It can be obtained after exposure and development if necessary. The method for forming, exposing, and developing the coating film can be, for example, the same method as that used when the coloring layer included in the color filter of the present invention described later is used.

Furthermore, when the above-mentioned colored resin composition of the present invention is a thermosetting colored resin composition containing a thermopolymerizable compound, after forming the coating film of the thermosetting colored resin composition, after drying the coating film, the Can be obtained by heating.

Because the hardened system of the present invention suppresses the precipitation of compounds derived from color materials, the arithmetic average roughness Ra of the surface of the hardened product according to JIS B 0601 can be set below 50Å, and the preferred mode is set below 45Å, in a particularly good state The sample system is set below 25Å.

In addition, the arithmetic average roughness Ra system can be measured using an atomic force microscope.

    << Color filter >>    

The color filter of the present invention includes at least a substrate and a color filter provided with a colored layer on the substrate, wherein at least one of the colored layers is a cured product of the colored resin composition of the present invention.

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

    (Coloring layer)    

At least one of the coloring layers used in the color filter of the present invention is a hardened product of the colored resin composition of the present invention, that is, a colored layer formed by hardening the colored resin composition.

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

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

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the coloring resin composition, etc. It is usually preferably in the range of 1 μm or more and 5 μm or less.

Furthermore, the colored layer system suppresses the precipitation of the compound derived from the color material, so the arithmetic average roughness Ra of the surface according to JIS B 0601 can be set to 50 Å or less, the more preferred sample system is set to 40 Å or less, and the particularly preferred sample system Set below 25Å.

For example, when the colored resin composition is a photosensitive colored resin composition, the colored layer system can be formed by the following method.

First, the above-mentioned colored resin composition of the present invention is applied on a substrate to be described later 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, or a die coating method to form a wet type Coated film. Among them, the spin coating method and the die coating method are preferably used.

Secondly, using a hot plate, oven, etc. to dry the wet coating film, and then expose it through a mask with a predetermined pattern, so that the alkali-soluble resin and polyfunctional monomer etc. undergo photopolymerization reaction to form a hard coating membrane. The light source used in the exposure may be, for example, ultraviolet light such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halogen lamp, or an electron beam. The exposure amount is adjusted appropriately according to the light source used, the thickness of the coating film, etc.

Furthermore, in order to promote the polymerization reaction after exposure, heat treatment may also be performed. The heating conditions are appropriately selected according to the blending ratio of each component in the coloring resin composition used, the thickness of the coating film, and the like.

Next, the developing process is performed using a developing solution, and by dissolving and removing unexposed parts, a coating film is formed in accordance with a desired pattern. The developer is usually a solution in which alkali is dissolved in water or a water-soluble solvent. It is also possible to add an appropriate amount of surfactant to this alkaline solution. In addition, a general method can be used for the development 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. In addition, after the development treatment, in order to sufficiently harden the coating film, heat treatment may be performed. The heating conditions are not particularly limited, and can be appropriately selected in accordance with the application of the coating film.

    (Shade)    

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

The pattern shape of the light-shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light-shielding part can form a metal thin film such as chromium by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder. When the resin layer containing light-shielding particles is used, for example, a method of patterning using photosensitive photoresist for development, a method of patterning using inkjet ink containing light-shielding particles, and applying heat to the photosensitive photoresist Transfer method, etc.

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

    (Substrate)    

For the substrate system, for example, a transparent substrate, a silicon substrate, which will be described later, and a thin film of aluminum, silver, silver / copper / palladium alloy formed on the substrate are used. On these substrates, other color filter layers, resin layers, TFTs and other transistors, circuits, etc. may also be formed.

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

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

In addition, the color filter of the present invention may be formed with, for example, a protective layer, a transparent electrode layer, an alignment film, an alignment protrusion, a column spacer, etc. in addition to the above-mentioned substrate, light-shielding portion, and coloring layer.

    << Display device >>    

The display device of the present invention is characterized by having the above-described color filter of the present invention. The configuration of the display device of the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices, organic light-emitting display devices, and the like.

    <Liquid crystal display device>    

The liquid crystal display device of the present invention is characterized by including the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

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

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

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

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

The method for forming the liquid crystal layer can be a method used in a general method for manufacturing a liquid crystal cell, such as a vacuum injection method and a liquid crystal dropping method.

    <Organic light-emitting display device>    

The organic light emitting display device of the present invention is characterized by including the aforementioned color filter of the present invention and an organic light emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram of another example of the display device of the present invention, and a schematic diagram of 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 is provided with: a color filter 10 and an organic light-emitting body 80. Between the color filter 10 and the organic light-emitting body 80, an organic protective layer 50 and an inorganic oxide film 60 may also be provided.

The stacking method of the organic light-emitting body 80 may be, for example, a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the color filter ; The method of bonding the organic light-emitting body 80 that has been formed on another substrate to the inorganic oxide film 60; For 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 of the organic light-emitting body 80, other configurations can be used as appropriate. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, passively driven organic EL displays and active driven organic EL displays.

In addition, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and a generally known configuration of an organic light-emitting display device using a color filter may be adopted.

    [Example]    

Hereinafter, specific examples of the present invention will be described in detail. However, the present invention is not limited by these records.

    (Production Example 1: Preparation of naphthol-based azo pigment D1-1)    

To 573 parts by mass of toluene, 90 parts by mass of 2,3-hydroxynaphthoic acid and 1.2 parts by mass of N, N-dimethylformamide were added, and after heating to 85 ° C, thionyl chloride 556.3 was added dropwise over 15 minutes Quality parts. After the end of the dropwise addition, reflux for 1 hour. In a solution prepared by heating 62.8 parts by mass of the following compound (A) and 264 parts by mass of toluene to 85 ° C., the reaction solution was added dropwise over 30 minutes, and heating and refluxing were performed for 2 hours. After cooling the reaction liquid to 95 ° C, 8.0 parts by mass of 28% aqueous ammonia solution and 20 parts by mass of water were added, and after stirring at 95 to 100 ° C for 15 minutes, toluene and unreacted 2-methyl- were removed by steam distillation 5-nitroaniline. The precipitated reactant was collected by filtration, washed with hot water, and dried to obtain 134 parts by mass of the following compound (B) (yield: 95.8% by mass).

After adding 32 mass parts of the following compound (C) to 252.2 mass parts of glacial acetic acid, 39.1 mass parts of 35% hydrochloric acid was further added, and cooled to -2 to 0 ° C. After adding 42.2 parts by mass of a 25% sodium nitrite aqueous solution to this solution, the solution was kept at 0 to 5 ° C and stirred for 30 minutes. In a separately prepared mixed solution composed of 44.6 parts by mass of the compound (B) obtained in the above manner, 67.1 parts by mass of 25% sodium hydroxide solution, 772 parts by mass of water, and 680 parts by mass of isopropyl alcohol, the reaction was added dropwise over 15 minutes Solution. After the end of the dropwise addition, after stirring at room temperature for 30 minutes, it is further stirred while maintaining at 80 ° C, the precipitated reactant is collected by filtration, washed with hot water and methanol, and dried to obtain a naphthol-based azo Pigment D1-1: 79.9 parts by mass (yield: 98%). The obtained naphthol-based azo pigment D1-1 was subjected to mass analysis by TOF-MS. As a result, it was identified as the naphthol-based azo pigment represented by the above chemical formula (D1-1).

[化 22]

    (Production Example 2: Preparation of Azo Derivative 1)    

In 550 parts by mass of distilled water, 23.1 parts by mass of diazobarbituric acid and 19.2 parts by mass of barbituric acid were introduced. Next, it was adjusted to azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 parts by mass of distilled water. 5 parts by mass of 30% hydrochloric acid was added dropwise. Then, 38.7 parts by mass of melamine was introduced. Next, a 0.60 mole nickel chloride solution was added and stirred at 80 ° C for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C, and ground in a mortar to obtain Azo derivative 1.

    (Production Example 3: Preparation of Azo Derivative 2)    

Azo derivatives were obtained in the same manner as in Production Example 2 except that in Production Example 2, instead of 0.60 mole nickel chloride solution, 0.3 Mole nickel chloride solution and 0.3 mole zinc chloride solution were used. 2 (Ni: Zn = 50: 50 (mole ratio) Azo pigment).

    (Synthesis Example 1: Inhibition of synthesis of precipitated compound 1)    

After the 500 ml four-neck separable flask was dried under reduced pressure, Ar (argon) replacement was performed. While flowing into Ar, add: 100 parts by mass of dehydrated tetrahydrofuran (THF), 2.0 parts by mass of methyltrimethylsilyl dimethyl ketene diethanol, 1M acetonitrile of tetrabutylammonium-3-chlorobenzoate (TBACB) The solution was 0.15 ml and 0.2 parts by mass of mesitylene. Using a dropping funnel, 34.57 parts by mass of 2- (perfluorohexyl) ethyl (meth) acrylate (FOEMA) was added dropwise to this solution over 45 minutes. Since the reaction proceeds and heat is generated, the temperature is kept below 40 ° C by applying ice cooling. After 1 hour, 17.62 parts by mass of 1-adamantyl methacrylate (1-ADMA) was added dropwise over 15 minutes. After the reaction for 1 hour, 5 parts by mass of methanol was added to stop the reaction. After the solvent was removed under reduced pressure, Compound I, which was a block copolymer, was obtained to suppress precipitation. The weight-average molecular weight of the compound I was 4,600 determined by GPC measurement (NMP LiBr 10 mM).

The obtained precipitation-preventing compound I was analyzed by thermal decomposition GCMS, FT-IR, ¹ H-NMR, ¹³ C-NMR and GPC. As a result, in the precipitation-preventing compound I, it was confirmed that the structural unit derived from FOEMA and the source The structural unit of 1-ADMA, and the molar ratio of the structural unit derived from FOEMA and the structural unit derived from 1-ADMA was 1: 6.

    (Synthesis Example 2: Inhibition of synthesis of precipitated compound II)    

Except for the substitution of 1-adamantyl methacrylate in Synthesis Example 1, dicyclopentyl methacrylate (DCPMA) (FA-513M manufactured by Hitachi Chemical Co., Ltd.) was used. In the same manner, the precipitation-preventing compound II was obtained. The weight-average molecular weight of the compound II that inhibited precipitation was 4,500 determined by GPC measurement (NMP LiBr 10 mM).

The obtained precipitation-preventing compound II was analyzed by thermal decomposition GCMS, FT-IR, ¹ H-NMR, ¹³ C-NMR and GPC. As a result, in the precipitation-preventing compound II, it was confirmed that the constituent unit derived from FOEMA and The structural unit of DCPMA, and the molar ratio of the structural unit derived from FOEMA and the structural unit derived from DCPMA was 1: 6.

    (Synthesis Example 3: Synthesis of Dispersant I)    

After the 500 ml four-neck separable flask was dried under reduced pressure, Ar (argon) replacement was performed. While flowing into Ar, add: 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyltrimethylsilyl dimethyl ketene diethanol, 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), And 0.2 parts by mass of mesitylene. Using a dropping funnel, 36.7 parts by mass of methyl methacrylate (MMA) was added dropwise to this solution over 45 minutes. Since the reaction proceeds and heat is generated, the temperature is kept below 40 ° C by applying ice cooling. After 1 hour, 13.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After the reaction for 1 hour, 5 parts by mass of methanol was added to stop the reaction. After removing the solvent under reduced pressure, a block copolymer was obtained. The weight-average molecular weight system obtained by GPC measurement (NMP LiBr 10 mM) was 7,600, and the amine value system was 95 mgKOH / g.

In a 100 mL round bottom flask, 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), and 3.17 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) was added (relative to The DMMA unit 1 mole of the block copolymer was 0.20 mole), and the mixture was stirred at a reaction temperature of 30 ° C for 20 hours to obtain a salt-type block copolymer (dispersant I) solution. The amine value after salt formation is calculated as follows.

In an NMR sample tube, 9 parts by mass of the above-mentioned salt-type block copolymer (solid matter after reprecipitation) and 1 part by mass of a solution mixed with 91 parts by mass by chloroform-D1NMR were used. System, FT NMR, JNM-AL400), and the ¹³ C-NMR mass spectrum was measured under the conditions of room temperature and 10,000 integration times. In the obtained mass spectrometry data, for the terminal nitrogen site (amine group), the integral value ratio of the carbon atom spectrum peak adjacent to the nitrogen atom without salt formation and the carbon atom spectrum peak adjacent to the nitrogen atom with salt formation is calculated to form The ratio of the number of amine groups of the salt to the total number of amine groups confirmed that one acid group of each phenylphosphonic acid had a salt with the DMMA terminal nitrogen site of the block copolymer.

From the amine value of 95 mgKOH / g before salt formation, the amine value of 0.02 mol of the DMMA unit (19 mgKOH / g) was subtracted, and the amine value after salt formation was calculated to be 76 mgKOH / g.

    (Synthesis Example 4: Synthesis of alkali soluble resin I solution)    

40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methmethacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 2,2'-azobisisobutyronitrile ( (AIBN) 3 parts by mass of the mixed solution was added dropwise to a polymerization tank charged with 150 parts by mass of PGMEA under nitrogen flow at 100 ° C for 3 hours. After the dropwise addition was completed, it 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 epoxypropyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110 ° C for 10 hours. The carboxylic acid group of the main chain methacrylic acid reacts with the epoxy group of GMA. During the reaction, in order to prevent GMA from polymerizing, air foaming was carried out in the reaction solution. In addition, the reaction is followed by measuring the acid value of the solution. The obtained alkali-soluble resin I is a resin formed by introducing a side chain with an ethylenic double bond using GMA on the main chain formed by copolymerization of BzMA, MMA, and MAA. The solution of the alkali-soluble resin I is 40% by mass of solid content, the acid value is 74 mgKOH / g, and the weight-average molecular weight of the alkali-soluble resin I is 12,000.

    <Example 1>         (1) Manufacture of color material dispersion liquid R1    

8.8 parts by mass of the dispersant I solution obtained in Synthesis Example 3 of the dispersant, and 12.0 parts by mass of naphthol-based azo pigment (CI Pigment Red 269, trade name: Pigment Magenta 3810, manufactured by Sanyo Pigment) of color material, Synthesis Example 4 The obtained alkali-soluble resin I solution was 11.3 parts by mass, PGMEA: 67.6 parts by mass, and 100 parts by mass of zirconia balls with a diameter of 2.0 mm, which were placed in a mayonnaise bottle and were applied using a paint shaker (manufactured by Asada Iron Works) After 1 hour shaking pre-crushing, the zirconium dioxide balls with a particle size of 2.0 mm were taken out, and 200 parts by mass of zirconium dioxide balls with a particle size of 0.1 mm were added. Similarly, the powder was crushed by a paint shaker for 4 hours to form a formal crushing to obtain a color material. Dispersion R1.

    (2) Manufacture of colored resin composition R1    

Addition: color material dispersion liquid R1 obtained in the above (1): 59.40 parts by mass, 4.83 parts by mass of the alkali-soluble resin I solution obtained in Synthesis Example 4, photopolymerizable compound (trade name "Aronix M-520D", manufactured by East Asia Synthesizer) ) 5.82 parts by mass, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1 (photoinitiator, trade name "IRGACURE 369", manufactured by BASF) 0.86 parts by mass, 1-acetone, 3-cyclopentyl-1- [9-ethyl-6 -(2-Methylbenzyl) -9H-carbazol-3-yl]-, 1- (o-acetoxime) (oxime ester-based photopolymerization initiator, trade name "TR-PBG-304 "Changzhou Qiangli Electronic New Materials Co., Ltd.) 0.58 parts by mass, precipitation-preventing compound I: 0.02 parts by mass, and PGMEA: 9.10 parts by mass, to obtain a photosensitive colored resin composition R1.

    (3) Formation of colored layer    

The colored resin composition R1 obtained in the above (2) was applied on a 100 mm × 100 mm glass substrate (trade name “NA35”, manufactured by NH TECHNO GLASS) with a thickness of 0.7 mm using a spin coater, and then using a hot plate at 80 ° C. It was dried for 3 minutes, and then irradiated with 60mJ / cm ² ultraviolet rays using an ultra-high pressure mercury lamp, and heated for 30 minutes in a 230 ° C dust-free oven, whereby the film thickness was adjusted according to the way that the film thickness after curing became 2.2 μm to form a colored layer.

    <Example 2 ~ 7>         (1) Manufacture of color material dispersion liquids R2 ~ R7    

In Examples 2 to 4, except when manufacturing the color material dispersion liquid R1 in (1) above in Example 1, the color material was substituted for CI Pigment Red 269: 12.0 parts by mass, and CI Pigment Red 269: 6 parts by mass was used instead The coloring material dispersion liquids R2 to R4 were obtained in the same manner as in the above (1) of Example 1 except for 6 parts by mass of the pyrrolopyrrole-based pigment shown in Table 1.

In Examples 5 and 6, except for the production of the above-mentioned (1) color material dispersion liquid R1 in Example 1, the color material system used CI Pigment Red 269: 6 parts by mass, pyrrolopyrrole II represented by the above chemical formula (2) Ketone pigments (BrDPP, trade name "Irgaphor RED S 3621CF", manufactured by BASF): 5 parts by mass, and the yellow color material shown in Table 1: except 1 part by mass, the rest are in accordance with the above (1 ) Similarly, color material dispersion liquids R5 and R6 are obtained.

In Example 7, except for the production of the above-mentioned (1) color material dispersion R1 in Example 1, the color material system replaced CI Pigment Red 269: 12.0 parts by mass, and the naphthol-based azo obtained in Production Example 1 was used instead Pigment D1-1: 6 parts by mass, and the pyrrolopyrrole dione-based pigment (BrDPP) represented by the above chemical formula (2): 6 parts by mass, and the rest were obtained in the same manner as in the above (1) of Example 1 to obtain a color材 变 液 R7.

    (2) Manufacture of colored resin compositions R2 ~ R7    

Except that in the manufacture of the above (2) colored resin composition R1 in Example 1, instead of the color material dispersion liquid R1, the color material dispersion liquids R2 to R7 obtained above were used, the rest were in accordance with Example 1. Similarly to (2) above, colored resin compositions R2 to R7 are obtained.

    (3) Formation of colored layer    

Except for the coloring resin composition R1 instead of the coloring resin composition R1 when forming the coloring layer (3) of Example 1, the coloring resin compositions R2 to R7 were used in the same manner as in the above (3) of Example 1. Coloring layer.

    <Comparative Examples 1 ~ 5>    

Except that the precipitation inhibiting compound I was not added during the production of the coloring resin compositions R1 to R5 of Examples 1 to 5, the rest were obtained in the same manner as the production of the coloring resin compositions R1 to R5 of Examples 1 to 5. Coloring resin composition RC1 ~ RC5.

In addition, except for the formation of the colored layer in Examples 1 to 5, instead of the colored resin compositions R1 to R5, the colored resin compositions RC1 to RC5 were used, and the rest were formed in the same manner as in Examples 1 to 5. Coloring layer.

    <Comparative Example 6>    

A colored resin composition RC6 was obtained in the same manner as in the manufacture of the colored resin composition R7 of Example 7 except that the precipitation inhibiting compound I was not added during the manufacture of the colored resin composition R7 of Example 7.

In addition, the colored layer was formed in the same manner as in Example 7 except that instead of the colored resin composition R7 and the colored resin composition RC6 was used in the formation of the colored layer in Example 7.

    <Examples 8, 9 and Comparative Example 7>    

Except that in the manufacture of the coloring resin composition R1 of Example 1, instead of the precipitation suppression compound I, the precipitation suppression compound or the comparative compound shown in Table 1 was used, the rest were in accordance with the coloration resin composition R1 of Example 1. In the same manner as in the production, colored resin compositions R8, R9, and RC7 were obtained.

In addition, the colored layer was formed in the same manner as in Example 1, except that instead of the colored resin composition R1 and the colored resin compositions R8, R9, and RC7 were used in the formation of the colored layer in Example 1.

    <Comparative Example 8>    

Except that in the manufacture of the coloring resin composition R2 of Example 2, the precipitation-preventing compound I was not used, and the following pigment derivative I used 0.65 parts by mass, the rest was in accordance with the coloring resin composition R2 of Example 2. In the same manner as in the production, a colored resin composition RC8 was obtained.

In addition, the colored layer was formed in the same manner as in Example 2, except that instead of the colored resin composition R2 and the colored resin composition RC8 was used in the formation of the colored layer in Example 2.

    (Synthesis of pigment derivative I)    

374.76 parts by mass of fuming sulfuric acid with a sulfur trioxide content rate of 11% by mass was stirred while cooling to 10 ° C, and 74.96 parts by mass of C.I. Pigment Yellow 138 (trade name: Paliotol Yellow K0961HD, manufactured by BASF) was added. Next, it was stirred at 90 ° C for 6 hours. The obtained reaction liquid was added to 1600 parts by mass of ice water, and after stirring for 15 minutes, the precipitate was filtered.

The obtained wet cake was washed 3 times with 800 parts by mass of demineralized water. The washed wet cake was vacuum dried at 80 ° C. to obtain a pigment derivative I represented by the following chemical formula (3) and belonging to a yellow pigment sulfonated derivative. With regard to the obtained pigment derivative I, the molecular weight was measured by TOF-MS, and it was confirmed that it was a synthesis target.

[Chem. 25] Chemical formula (3)

    <Comparative Example 9>    

Except for the replacement of CI Pigment Red 269 in the manufacture of the color material dispersion R2 of Example 2, an anthraquinone pigment (CI Pigment Red 177, trade name: CHROMOFINE RED 6121EC, manufactured by Dairi Refining) was used. In the same manner as in the production of the color material dispersion liquid R2 of Example 2, the color material dispersion liquid RC9 was obtained. In addition, in order to adjust the chromaticity (x, y) of the colored layer measured using the "microscopic spectrophotometer OSP-SP200" manufactured by Olympus Co., Ltd., to adjust to the same as in Example 2, CI Pigment Red 177 was added The amount is set to 6 parts by mass.

In addition, the coloring resin composition RC9 was obtained in the same manner as in the production of the coloring resin composition R2 of Example 2 except that the coloring material dispersion liquid RC9 was used instead of the coloring material dispersion liquid R2. In addition, the colored layer was formed in the same manner as in Example 2 except that instead of the colored resin composition R2 and the colored resin composition RC9 was used.

    <Comparative Example 10>    

Except for the manufacture of the color material dispersion liquid RC2 of Comparative Example 2, instead of CI Pigment Red 269, an anthraquinone pigment (CI Pigment Red 177, trade name: CHROMOFINE RED 6121EC, manufactured by Dairi Seiki) was used. In the same manner as in the production of the color material dispersion liquid RC2 of Comparative Example 2, the color material dispersion liquid RC10 was obtained. In addition, in order to adjust the chromaticity (x, y) of the colored layer measured using the "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd., to adjust to the same as in Comparative Example 2, CI Pigment Red 177 was added The amount is set to 6 parts by mass.

In addition, the coloring resin composition RC10 was obtained in the same manner as the production of the coloring resin composition RC2 of Comparative Example 2 except that the coloring material dispersion RC2 was replaced with the coloring material dispersion RC10. In addition, the colored layer was formed in the same manner as in Comparative Example 2 except that instead of the colored resin composition RC2 and the colored resin composition RC10 was used.

    <Examples 10 and 11>    

Except for the addition of 0.2 parts by mass of Karenz MTPE1 (manufactured by Showa Denko) of the thiol compound in the manufacture of the coloring resin compositions R1 and R2 of Examples 1 and 2, the rest are in accordance with the coloring of Examples 1 and 2 Similarly to the production of the resin compositions R1 and R2, colored resin compositions R10 and R11 were obtained.

In addition, except for the formation of the coloring layer of Examples 1 and 2, instead of the colored resin compositions R1 and R2, the colored resin compositions R10 and R11 were used in the same manner as in Examples 1 and 2 Coloring layer.

    <Evaluation of optical characteristics>    

The contrast and brightness (Y) of the colored layer formed in each example and each comparative example were measured. In addition, the comparison system was measured using "Comparative Measurement Device CT-IB" manufactured by Husaka Electric Co., Ltd., and the luminance was measured using "Microscopic Spectroscopic Measurement Device OSP-SP200" manufactured by Olympus Corporation.

The comparison system was evaluated using the following evaluation criteria. The measurement results are shown in Tables 1 to 3.

    (Comparative evaluation criteria)    

A: More than 90% of the target value

B: More than 80% of the target value and less than 90%

C: Less than 80% of the target value

In addition, the measurement results of luminance (Y) are shown in Tables 1 to 3.

    <Precipitation evaluation>    

The coloring resin composition prepared in each example and each comparative example was formed into a coating liquid, which was applied on a glass substrate by spin coating method such that the film thickness after post-baking became 2.2 μm, and dried under reduced pressure After that, it was heated and dried at 80 ° C for 3 minutes using a hot plate to form a coating film. Next, 60 mJ / m ^{2 of} ultraviolet light was irradiated from the coating film side with a high-pressure mercury lamp to perform exposure. Then, it is developed with a developing solution at a temperature of 23 ° C. and a KOH concentration of 0.05% for 60 seconds, and is further heated in an oven at 230 ° C. for 30 minutes, and post-baked to form a colored layer. At this time, an optical microscope (product name "MX61L", manufactured by OLYMPUS) was used to confirm whether or not a compound derived from a color material precipitated on the surface of the colored layer, and evaluation was performed according to the following evaluation criteria. The evaluation results are shown in Tables 1-3.

A: The precipitation of the compound derived from the color material is not confirmed, or it is confirmed to be a little, but it is still to the extent that it does not pose a problem practically.

B: A part of the surface of the colored layer is confirmed to have precipitated a compound derived from the color material, which is a level that poses a practical problem.

C: Precipitation of the compound derived from the color material was confirmed on the entire surface of the colored layer.

    <Measurement of surface roughness>    

In Examples 1, 2, 7, 10, and 11, an atomic force microscope (product name "AS-7B-M", manufactured by TAKANO) was used for the surface of the colored layer evaluated by the above precipitation, and the arithmetic average was measured according to JIS B 0601 Roughness Ra. The measurement results are shown in Tables 3 and 4.

    <Dispersion stability evaluation>    

For the color material dispersion liquid R2 obtained in Example 2 and the color material dispersion liquid R7 obtained in Example 7, the viscosity immediately after preparation and after storage at 25 ° C for 2 weeks was measured, and the change in viscosity was calculated from the viscosity before and after storage Rate, the dispersion stability evaluation was carried out in accordance with the following evaluation criteria. The evaluation results are shown in Table 4. In addition, the viscosity measurement system uses a vibrating viscometer to measure the viscosity at 25.0 ± 0.5 ° C.

    (Decentralized stability evaluation criteria)    

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

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

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

D: The change rate of viscosity before and after storage is over 25%

However, the color material is set to a value at 12% by mass with respect to the total mass of the color material dispersion liquid including the solvent.

Even if the evaluation result is C, the color material dispersion liquid is practically usable, but if the evaluation result is B, the color material dispersion liquid is better, and if the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

    <Example 2 ', 7'>    

Except in the manufacture of the coloring composition R2 of the above Example 2 and the manufacture of the coloring composition R7 of the above Example 7, the color material dispersion liquids R2 and R7 immediately after preparation were replaced with the color material dispersion instead Except for the color material dispersion liquids R2 'and R7' after the liquids R2 and R7 were stored at 25 ° C for 2 weeks, the rest of the coloring resin compositions R2 'and R7' were produced in the same manner as in Examples 2 and 7 above. In addition, the colored layer was formed in the same manner as in Examples 2 and 7 above except that the colored resin compositions R2 and R7 were replaced with the obtained colored resin compositions R2 ′ and R7 ′.

With respect to the coloring layer formed using the colored resin compositions R2 'and R7', the luminance (Y) was measured in the same manner as the above-mentioned optical characteristic evaluation. The measurement results are shown in Table 4.

Furthermore, using the colored resin compositions R2 'and R7', a colored layer was formed in the same manner as in the above-mentioned precipitation evaluation, and the arithmetic average roughness Ra was measured in the same manner as in the above-described surface roughness measurement. The measurement results are shown in Table 4.

The code names in the table are as follows:

‧PR269: C.I. Pigment Red 269 (trade name: Pigment Magenta 3810, made by Shanyang Pigment)

‧Br-DPP: Pyrrolopyrrole diketone pigment shown in the above chemical formula (2), trade name "Irgaphor RED S 3621CF", manufactured by BASF

‧PR254: C.I. Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT)

‧PR264: C.I. Pigment Red 264 (trade name: SR6T, manufactured by CINIC)

‧PR177: C.I. Pigment Red 177 (trade name: CHROMOFINE RED 6121EC, manufactured by Dairi Seiki)

‧Precipitation inhibiting compound III: MEGAFAC F575 (compound containing fluorocarbon group and cross-linked cycloaliphatic group, manufactured by DIC)

‧Comparative compound IV: MEGAFAC F444 (perfluoroalkyl ethylene oxide adduct, manufactured by DIC Corporation)

‧ Thiol compound: Karenz MTPE1 (manufactured by Showa Denko)

    [Result sorting]    

The combination of the naphthol-based azo pigments represented by the above general formula (1) and the coloring resin compositions of Examples 1 to 11 that suppress the precipitation compound can form the compound that suppresses the precipitation of the color material and suppresses the brightness and contrast Reduced coloring layer.

On the other hand, in Comparative Examples 1 to 6 shown in Table 1, since no precipitation inhibiting compound was used, there was precipitation from the color material compound. Compared with the examples using the same color material, the brightness and contrast There is a decrease.

Furthermore, comparison between Comparative Example 1 and Comparative Examples 2 to 4 shows that when the color material further contains a pyrrolopyrrole dione pigment, the compound derived from the color material will be more likely to precipitate, but as in the example As shown in 1 to 4, the coloring resin composition of the present invention contains the precipitation-inhibiting compound, and even if it contains the pyrrolopyrrole dione-based pigment, the precipitation of the compound derived from the color material can be suppressed. That is, the coloring resin composition system of the present invention exhibits an effect of more effectively suppressing precipitation of the coloring material compound when the coloring material further contains a pyrrolopyrrole dione pigment. In addition, although the color material of Comparative Example 5 further contains a pyrrolopyrrole dione pigment, it is more likely to suppress precipitation than that of Comparative Examples 2 to 4. It is presumed that by further adding a yellow color material, It is due to the relative reduction in the content of the pyrrolopyrrole-dione pigments, as well as the dispersion and stabilization by coexistence with the yellow color material.

Furthermore, from the comparison between Example 5 and Example 6, when the colored resin composition of the present invention contains a yellow color material, if the yellow color material (D3) is used for the yellow color material system, the brightness of the colored layer is improved .

In Comparative Example 7, instead of the precipitation-preventing compound, Comparative Compound IV (trade name: MEGAFAC F444, perfluoroalkyl ethylene oxide adduct, manufactured by DIC) was used. Precipitation also cannot suppress the reduction in brightness and contrast.

In Comparative Example 8, the pigment derivative I was used instead of the precipitation-inhibiting compound. Therefore, both the brightness and the contrast were reduced, and the optical characteristics were reduced.

As shown in the comparison between Example 2 and Comparative Example 2 in Table 2 and the comparison between Comparative Example 9 and Comparative Example 10, instead of the naphthol-based azo pigment shown in the general formula (1) above, the In the case of using CI Pigment Red 177 in the same chromaticity (x, y) mode, even if the precipitation suppression compound is used in combination, the brightness has not been sufficiently improved.

Furthermore, as shown in the comparison between Example 1 and Example 10 in Table 3, and the comparison between Example 2 and Example 11, if the coloring resin composition of the present invention further contains a thiol compound, The precipitation of the color material compound is suppressed, and the surface roughness of the colored layer is reduced.

Furthermore, from the comparison between Examples 2 and 2 'shown in Table 4 and Examples 7 and 7', when using a naphthol-based azo pigment having a monovalent group represented by the above general formula (2) The dispersion stability is likely to be good. Even if the color material dispersion liquid after a certain period of storage is used, the surface roughness of the color layer formed is still small, and it is easy to suppress the precipitation of the color material compound.

Claims (13)

A coloring resin composition containing: a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and a fluorocarbon group and a cross-linked cyclic aliphatic group Compound (E); wherein the color material (D) -based contains a naphthol-based azo pigment (D1) represented by the following general formula (1): (In general formula (1), R ¹ is a hydrogen atom, a methyl group, a methoxy group, or a methoxycarbonyl group; R ² and R ³ are independently hydrogen atoms or an aryl group which may have a substituent; R ² or R At least any one of ³ is an aryl group which may have a substituent).     The coloring resin composition according to claim 1, wherein the carbon number of the fluorocarbon group of the compound (E) is 2 or more and 10 or less.         The coloring resin composition according to claim 1 or 2, wherein the cross-linked cycloaliphatic group of the compound (E) may be adamantyl which may have a substituent, or dicyclopentane which may also have a substituent base.         The coloring resin composition according to claim 1 or 2, wherein the above-mentioned compound (E) contains: a structural unit derived from the above-mentioned compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a source derived from the above Copolymer of the structural unit of the compound (E-2) with cross-linked cycloaliphatic group and ethylenically unsaturated group;     The coloring resin composition according to claim 1 or 2, wherein, in the above general formula (1), R ³ is a monovalent group represented by the following general formula (2): (In the general formula (2), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; R ⁵ is a nitro group, a sulfo group, or Sulfonate; * indicates the bonding position).     The coloring resin composition according to claim 1 or 2, wherein the color material (D) further contains a pyrrolopyrrole dione pigment (D2).     The coloring resin composition according to claim 6, wherein the pyrrolopyrrole dione pigment (D2) contains a pyrrolopyrrole dione pigment represented by the following general formula (3); (In the general formula (3), R ⁶ and R ⁷ are each independently a chlorine atom, a bromine atom or a phenyl group). The coloring resin composition according to claim 1 or 2, wherein the color material (D) further contains a yellow color material (D3); and the yellow color material (D3) contains: from the following general formula (4) At least one anion is selected from the group consisting of mono-, di-, tri-, and tetravalent anions of the azo compound and its tautomeric structure as shown; , Fe, Ni, Cu and Mn select at least two kinds of metal ions; and the compound represented by the following general formula (5); (Formula (4), R ^a is each independently based _{-OH, -NH 2, -NH-CN} , acylated amino, an alkylamino group or an aryl group; R ^b are each independently -OH or lines -NH ₂ ); (In the general formula (5), R ^c is an independent hydrogen atom or alkyl group).     The coloring resin composition according to claim 1 or 2, which further contains a thiol compound (F).         The coloring resin composition according to claim 1 or 2, wherein the polymerizable compound (B) is a photopolymerizable compound.         A hardened product is a hardened product of the coloring resin composition of any one of claims 1 to 10.         A color filter includes 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 any one of claims 1 to 10.         A display device is provided with the color filter of claim 12 above.