TW202009277A - Colored resin composition,cured product,color filter and display device - Google Patents

Abstract

Provided is a colored resin composition comprising a polymer (A), a polymerizable compound (B), a polymerization initiator (C) and a color material (D), wherein the color material (D) comprises C.I. Pigment Red 291 and a diketopyrrolopyrrole-based pigment represented by the following chemical formula (D1):

Description

Colored resin composition, hardened material, color filter and display device

The invention relates to a coloring resin composition, a hardened product, a color filter and a display device.

In recent years, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays has been increasing. The penetration rate of mobile displays (mobile phones, smart phones, personal computers (PCs)) has also continued to increase, and the market for liquid crystal displays is expanding. In addition, organic light-emitting display devices such as organic electroluminescence (EL) displays with high visibility due to self-luminescence are also attracting attention as next-generation image display devices. In the performance of these image display devices, it is strongly expected that further high image quality or reduction in power consumption will be achieved, such as high color rendering, high brightness, and high contrast.

Color filters are used in such liquid crystal display devices or organic light emitting display devices. For example, the formation of a color image of a liquid crystal display device directly colors the light passing through the color filter into the color of each pixel constituting the color filter, and combines the light of these colors 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 can be formed by, for example, applying a coloring resin composition containing a color material and an adhesive component on a substrate, patterning by photolithography, and then performing heat treatment (post-baking) .

As the red color material used in the red coloring layer, in the past, in terms of high coloring power and the formation of a high-brightness coloring layer, pyrrolopyrrole dione pigments such as C.I. Pigment Red 254 have been used. However, regarding the pyrrolopyrrole-based pigments, if the pigments are made finer for higher contrast, the pigment particles are likely to aggregate during the high-temperature heating in the color filter manufacturing process, or the crystal growth is likely to occur during heating. After the step, the particles derived from the pigment on the surface of the colored layer are precipitated like foreign substances, and there is a problem that the brightness or contrast is lowered, or is recognized as a defect. As an attempt to suppress the precipitation of pigment-derived particles and to make the pigment finer, a pigment formulation composed of a combined pigment and a pigment derivative having a substituent group introduced into a part of the pigment skeleton is used. For example, Patent Document 1 describes a method for selecting or designing a pigment derivative that forms a pigment composition in which a pigment composition obtained by processing a pigment derivative and having good dispersibility is formed in a pigment And is characterized by the following steps: the step of measuring or calculating the dipole moment of the pigment derivative; and selecting the pigment derivative according to the value of the measured or calculated dipole moment, or designing the pigment derivative according to the value of the dipole moment Steps of things.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2012-77192

However, the coloring layer containing the pigment derivative tends to have lower optical characteristics than the coloring layer without the pigment derivative, especially the brightness and contrast tend to decrease.

The present invention was made in view of the above-mentioned actual circumstances, and its object 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 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. Furthermore, an object of the present invention is to provide a color filter having a coloring layer formed by using the above-mentioned colored resin composition to suppress precipitation of a compound derived from a color material, to suppress a decrease in brightness and a decrease in contrast, and to have the color filter Optical film display device.

The coloring resin composition of the present invention is characterized by comprising a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a color material (D), and

The color material (D) includes C.I. Pigment Red 291 and a pyrrolopyrrole dione pigment represented by the following chemical formula (D1).

[Chemical 1]

The cured product of the present invention is characterized in that it is the cured product of the coloring resin composition of the present invention described above.

The color filter of the present invention is characterized in that it is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the coloring resin composition of the present invention.

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

According to the present invention, it is possible to provide a coloring resin composition capable of forming a coloring layer that suppresses precipitation of a compound derived from a color material and suppresses reduction in brightness and contrast. Furthermore, according to the present invention, a cured product of the above colored resin composition can be provided. Furthermore, according to the present invention, there can be provided a color filter having a coloring layer formed by using the above-mentioned colored resin composition, which suppresses the precipitation of a compound derived from a color material, and suppresses a decrease in brightness and a decrease in contrast; and a color filter having the color filter The display device of the film.

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 showing an example of a color filter of the present invention.

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

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

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

Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible light ranges, and further includes radiation; radiation includes, for example, microwaves, electron beams, and the like. Specifically, it means an electromagnetic wave with a wavelength of 5 μm or less and an electron beam.

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

<<Coloring resin composition>>

The coloring resin composition of the present invention is characterized by comprising a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a color material (D), and

The color material (D) includes C.I. Pigment Red 291 and a pyrrolopyrrole dione pigment represented by the following chemical formula (D1).

[Chem 2]

The coloring layer formed using a conventional coloring resin composition containing a pyrrolopyrrole-based pigment is easy to agglomerate or crystallize due to heat due to the pyrrolopyrrole-based pigment. After baking, the compound derived from the color material is precipitated. As a result, there are problems such as a decrease in brightness or contrast, etc., a decrease in optical characteristics, or, in the appearance inspection, it is detected as an abnormal light spot, which causes the final The yield of color filter products is reduced. In order to suppress the precipitation of the compound derived from the color material, it is more effective to add a pigment derivative. On the other hand, if the amount of the pigment derivative is increased in order to sufficiently suppress the precipitation of the compound derived from the color material, it may cause brightness or contrast. The problem of degradation of optical characteristics such as degradation. Therefore, in the red colored layer containing the pyrrolopyrrole dione pigment, it is difficult to suppress the precipitation of the compound derived from the color material without impairing the optical properties.

On the other hand, the coloring resin composition of the present invention is a combination of CI Pigment Red 291 (PR291) containing a color material (D) as a pyrrolopyrrole dione pigment and pyrrolopyrrole II represented by the above chemical formula (D1) The ketone pigment can form a coloring layer that suppresses the precipitation of compounds derived from color materials and suppresses the decrease in brightness and contrast.

In addition, the coloring layer formed by using the coloring resin composition of the present invention can suppress the surface of the coloring layer from becoming rough by suppressing the precipitation of the compound derived from the coloring material, so that a coloring with higher productivity and lower surface roughness can be formed The layer can also improve the evenness of the colored layer.

The coloring resin composition of the present invention includes a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a color material (D), as long as the effect of the present invention is not impaired, it may further be Contains other ingredients.

The polymer (A), polymerizable compound (B), and polymerization initiator (C) contained in the coloring resin composition of the present invention are used as binder components of the colored resin composition to impart film-forming properties or to be coated The tightness of the applied surface.

As the above-mentioned binder component, a binder component used when forming a color layer of a conventionally known color filter can be suitably used, and there is no particular limitation, and examples thereof include visible light, ultraviolet rays, and electron beams. The polymerization hardening photosensitive adhesive component, or the thermosetting adhesive component that can be polymerized and hardened by heating, and a mixture of these can also be used.

Examples of the thermosetting adhesive component include a polymer containing at least a polymerizable functional group as the polymer (A), a compound having a polymerizable functional group in the molecule as the polymerizable compound (B), and The polymerization initiator (C) includes a thermal polymerization initiator including a hardener that reacts with the thermally polymerizable functional group and the like. Examples of the thermally polymerizable functional group include epoxy groups, isocyanate groups, carboxyl groups, amine groups, and hydroxyl groups.

When the photolithography step is used to form the coloring layer using the coloring resin composition of the present invention, a photosensitive adhesive component having alkaline developability can be suitably used. Furthermore, as the photosensitive adhesive component, a thermosetting adhesive component can be further used.

Examples of the photosensitive adhesive component include a positive photosensitive adhesive component and a negative photosensitive adhesive component. Examples of the positive photosensitive adhesive component include compounds containing an alkali-soluble resin as the polymer (A) and a polymerizable compound (B) having a bond cleaved by an acid and an ethylenically unsaturated group in the molecule, A thermal radical polymerization initiator as a polymerization initiator (C), and a system further containing a photoacid generator.

As the negative photosensitive adhesive component, a compound containing at least an alkali-soluble resin as the polymer (A), a compound having an ethylenically unsaturated group in the molecule as the polymerizable compound (B), and a polymerization start can be suitably used The photopolymerization initiator of agent (C).

As the adhesive component contained in the coloring resin composition of the present invention, in view of the fact that the pattern can be easily formed by the photolithography method using the existing process, the above-mentioned negative photosensitive adhesive component is preferred.

<Polymer (A)>

As the polymer (A), when the photolithography step is used when forming the colored layer, an alkali-soluble resin having solubility in an alkaline developer can be suitably used.

The alkali-soluble resin has an acidic group and functions as a binder resin, and as long as it is soluble in the alkaline developer used in pattern formation, it can be appropriately selected and used.

In the present invention, the so-called alkali-soluble resin may have an acid value of 30 mgKOH/g or more as a standard.

Examples of the acidic group possessed by the alkali-soluble resin include carboxyl groups. Examples of the alkali-soluble resin having a carboxyl group include a carboxyl group-containing copolymer having a carboxyl group or an epoxy (meth)acrylate resin having a carboxyl group. Examples of the carboxyl group-containing copolymer include acrylic copolymers having a carboxyl group and acrylic copolymers such as a styrene-acrylic copolymer having a carboxyl group. Among these, those having a carboxyl group in the side chain and further having an ethylenically unsaturated group in the side chain are particularly preferred. The reason is that the film strength of the cured film formed by containing an ethylenically unsaturated group is improved.

In addition, the ethylenically unsaturated group means a group containing a carbon-carbon double bond that can undergo radical polymerization, and examples thereof include (meth)acryloyl, vinyl, and allyl groups.

In addition, these acrylic copolymers and acrylic copolymers such as styrene-acrylic copolymers having a carboxyl group and epoxy acrylate resins may be used in combination of two or more.

Acrylic copolymers having a carboxyl group and acrylic copolymers such as a styrene-acrylic copolymer having a carboxyl group, for example, a carboxyl group-containing ethylenically unsaturated monomer, and others that can be copolymerized if necessary by a known method (Co)polymer obtained by (co)polymerization of monomers.

Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, and itaconic acid. Acid, crotonic acid, cinnamic acid, acrylic dimer, etc. In addition, the addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexane dicarboxylic anhydride can also be used. Substances, ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as a precursor of the carboxyl group, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

In terms of excellent adhesion to the substrate, the alkali-soluble resin preferably further has a hydrocarbon ring. By having a hydrocarbon ring as a bulky base in the alkali-soluble resin, it is possible to suppress shrinkage during curing, ease peeling from the substrate, and improve substrate adhesion. Furthermore, by using an alkali-soluble resin having a hydrocarbon ring as a bulky base, the solvent resistance of the obtained coloring layer is improved, and it is particularly preferable in terms of suppressing swelling of the coloring layer.

Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination of these. The hydrocarbon ring may have a carbonyl group, a carboxyl group, an oxycarbonyl group, or an acetyl group Substituents such as amine groups.

烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環；苯、萘、蒽、菲、茀等芳香族烴環；聯苯、聯三苯、二苯甲烷、三苯甲烷、茋等鏈狀多環、或酚酞基(cardo)構造(9,9-二芳基茀)等。 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, such as triphenyl, diphenylmethane, triphenylmethane, stilbene, or phenolphthalein (cardo) structure (9,9-diaryl stilbene), etc.

Among them, when an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained coloring layer is increased.

Also, in the case of a structure (phenolphthalein-based structure) in which two benzene rings are bonded to the stilbene skeleton shown in the following chemical formula (i), the hardening property of the colored layer is improved, and the solvent resistance is improved, especially suppression It is particularly preferable in terms of swelling of N-methylpyrrolidone (NMP, N-methyl-2-pyrrolidone).

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

[Chemical formula 3] Chemical formula (i)

Although the correct mechanism of the resin containing the above phenolphthalein group structure (referred to as phenolphthalein resin in the present invention) is not clear, the skeletal skeleton contains a π-conjugated system, so it is considered to be highly sensitive to free radicals. Among them, by combining the oxime ester-based photopolymerization initiator and the phenolphthalein-based resin, required performance such as sensitivity, developability, and development adhesion can be improved. In addition, the above phenolphthalein-based resin has high solvent resolubility, so it is also preferable in that it can be designed as a coloring resin composition having no agglomerates at a high color concentration.

In the alkali-soluble resin used in the present invention, in terms of easily adjusting the amount of each structural unit, easily increasing the amount of the structural unit having the above-mentioned hydrocarbon ring, and improving the function of the structural unit, it is preferable to use a different An acrylic copolymer having a structural unit of a carboxyl group and containing a structural unit of the above-mentioned hydrocarbon ring.

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

酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯、具有上述酚酞基構造與乙烯性不飽和基之單體等，就容易抑制源自色材之化合物之析出之方面而言，其中，較佳為(甲基)丙烯酸環己酯、(甲基)丙烯酸 二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、苯乙烯、具有上述酚酞基構造與乙烯性不飽和基之單體。 As the ethylenically unsaturated monomer having a hydrocarbon ring used in the alkali-soluble resin having a hydrocarbon ring, in terms of the combination with the following compound (E) having a fluorocarbon group and a crosslinked cyclic aliphatic group , For example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, isocyanate (meth)acrylate can be used well

Esters, phenoxyethyl (meth)acrylate, styrene, monomers having the above phenolphthalein group structure and ethylenically unsaturated groups, etc., in terms of easily suppressing precipitation of compounds derived from color materials, among them, Preferred are cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, a structure having the above phenolphthalein group and ethylene Monomer of unsaturated group.

In addition, 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, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond in the curing step of the resin composition at the time of color filter manufacturing. The film strength of the cured film is further improved, the development resistance is also improved, and the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.

The method of introducing an ethylenic unsaturated bond into an alkali-soluble resin should just select suitably from a well-known method. For example, a compound having an epoxy group and an ethylenically unsaturated bond in the carboxyl group added to the molecule of the alkali-soluble resin, for example, glycidyl (meth)acrylate, etc., and introducing ethylene into the side chain The method of saturating a bond; or the method of introducing a structural unit having a hydroxyl group into a copolymer in advance, 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 other structural units such as structural units having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate. The constituent unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition, but also functions as a component that improves solubility in a solvent and further improves solvent resolubility.

The alkali-soluble resin used in the present invention preferably contains an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and more preferably contains a carboxyl group Acrylic resins such as acrylic acid copolymers and styrene-acrylic acid copolymers such as structural units, structural units having a hydrocarbon ring, and structural units having an ethylenic unsaturated bond.

The alkali-soluble resin used in the present invention can be set to a desired performance by appropriately adjusting the addition amount of the monomer derived into each constituent unit.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer 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 carboxyl group-containing ethylenic unsaturated monomer is 5 mass% or more, the decrease in the solubility of the obtained coating film to the alkaline developer can be suppressed, and pattern formation can be easily performed. In addition, if the copolymerization ratio is 50% by mass or less, defects in the pattern or roughness of the film on the pattern surface are unlikely to occur during development with an alkaline developer. In addition, the said copolymerization ratio is the value calculated based on the addition amount of each monomer.

Also, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having ethylenic unsaturated bonds that can be better used as alkali-soluble resins, they have both epoxy and ethylene properties The addition amount of the unsaturated 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 with respect to the addition amount of the carboxyl group-containing ethylenically unsaturated monomer. %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 is sufficiently obtained, and if it is 50,000 or less, it is easy to form a pattern when developing with an alkaline developer.

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

Specific examples of the acrylic copolymer having a carboxyl group include those described in Japanese Patent Laid-Open No. 2013-029832.

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

As the epoxy (meth)acrylate resin having a carboxyl group, among them, in terms of showing an improvement in the effect of suppressing defects, the hardening of the colored layer is improved, and at the same time, the residual film rate of the colored layer is increased, it is preferably intramolecular Contains the above phenolphthalein-based structure.

Regarding the alkali-soluble resin, in terms of the developability (solubility) of the alkaline aqueous solution used in the developer, the acid value is preferably 30 mgKOH/g or more, and more preferably 40 mgKOH/g or more. Regarding the above-mentioned carboxyl group-containing copolymer, the acid value is preferably 50 mgKOH/g or more in terms of the developability (solubility) of the alkaline aqueous solution used in the developer and the adhesion to the substrate. And 300 mgKOH/g or less, more preferably 60 mgKOH/g or more and 280 mgKOH/g or less, and still more preferably 70 mgKOH/g or more and 250 mgKOH/g or less.

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

The equivalent of the ethylenically unsaturated bond in the case where the alkali-soluble resin has an ethylenically unsaturated group in the side chain is that the film strength of the cured film is improved and the precipitation of the compound derived from the color material can be further suppressed. The range of 100 to 2000 is preferable, and the range of 140 to 1500 is particularly preferable. When the ethylenically unsaturated bond equivalent is 100 or more, the development resistance or adhesion is excellent. Moreover, if it is 2000 or less, the ratio of the other structural units, such as the said structural unit which has a carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, and it is excellent in developing property and heat resistance. Here, the equivalent of an ethylenic unsaturated bond is the weight average molecular weight per 1 mole of the ethylenic unsaturated bond in the said alkali-soluble resin, and it is represented by the following formula (1).

[Number 1]

(In the above formula (1), W represents the mass (g) of the carboxyl-containing copolymer (M), and 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 can also be calculated by, for example, measuring the number of ethylenically unsaturated bonds contained in 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.

The content of the alkali-soluble resin 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 relative to 100 parts by mass of the total solid content of the colored resin composition. Within the range of more than 40 parts by mass. If the content of the alkali-soluble resin is above the above lower limit, sufficient alkaline developability is easily obtained, and if the content of the alkali-soluble resin is below the above upper limit, it is easy to suppress film roughness or pattern defects during development .

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

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

Furthermore, the coloring resin composition of the present invention may contain, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, cyclic Thermosetting polymers such as oxygen resins, amine alkyd resins, melamine-urea co-condensation resins, silicone resins, polysiloxane resins and the like are used as the above-mentioned polymer (A).

In addition, the said polymer (A) may be used individually by 1 type, and may use 2 or more types together.

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 content of the polymer is equal to or greater than the above lower limit, the decrease in film strength can be suppressed, and if the content of the polymer is equal to or less than the upper limit, components other than the polymer can be sufficiently contained.

<Polymerizable compound (B)>

The polymerizable compound is not particularly limited as long as it can be polymerized using the following polymerization initiator. For example, a photopolymerizable compound or a thermally polymerizable compound can be used. As the thermally polymerizable compound, a compound having a thermally polymerizable functional group such as a carboxyl group, an amine group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an 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, it can also be used as a thermally polymerizable compound. As the polymerizable compound, in view of the fact that it is possible to easily form a pattern by a photolithography method using an existing process, a photopolymerizable compound that can be polymerized using the following photopolymerization initiator is preferred. As the photopolymerizable compound, a compound having an ethylenically unsaturated group in the molecule can be used. As the photopolymerizable compound, a compound having two or more ethylenic unsaturated groups in the molecule is preferable, and a polyfunctional (meth)acrylic acid having two or more (meth)acryloyl groups in the molecule is particularly preferable. ester.

As such a polyfunctional (meth)acrylate, it can be used as long as it is appropriately selected from those skilled in the art. As specific examples, for example, those described in Japanese Patent Laid-Open No. 2013-029832 can be cited.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more. In addition, in the case where excellent photocurability (high sensitivity) is required for the coloring resin composition of the present invention, the multifunctional (meth)acrylate preferably has three or more (trifunctional) polymerizable double bonds , Preferably poly(meth)acrylates of polyhydric alcohols of three or more or modified products of these dicarboxylic acids, specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol Tris(meth)acrylate, pentaerythritol tri(meth)acrylate succinic acid modification, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , Modified succinic acid of dipentaerythritol 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, 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. It is 20 parts by mass or less and more preferably 40 parts by mass or less. If the content of the polymerizable compound is more than the above lower limit, the curing failure can be suppressed, so that the exposed portion can be suppressed from eluting during development, and if the content of the polymerizable compound is less than the above upper limit, the development failure can be suppressed And, it can suppress thermal shrinkage, so it is not easy to produce tiny wrinkles on the entire surface of the colored layer.

<polymerization initiator (C)>

The polymerization initiator is not particularly limited, and it can be used by using one kind or a combination of two or more kinds from various conventionally known initiators. Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators, and specific examples thereof include those described in Japanese Patent Laid-Open No. 2013-029832.

As a photopolymerization initiator, among them, the effect of hardening the film surface is high, the effect of suppressing the generation of defects in the pattern, the effect of suppressing the generation of water seepage, and the effect of suppressing the precipitation of the compound derived from the color material are high, It is preferable to include an oxime ester-based photopolymerization initiator. In addition, when two or more oxime ester-based photopolymerization initiators are used together, the precipitation of the compound derived from the color material can be further suppressed, so it is preferable to use two or more oxime ester-based photopolymerization initiators.

As the above-mentioned oxime ester-based photopolymerization initiator, in terms of reducing the contamination of the coloring resin composition or the pollution of the device caused by the decomposition products, among them, those having an aromatic ring are preferred, and those having an aromatic The condensed ring of the ring further preferably has a condensed ring containing a benzene ring and a heterocyclic ring.

Examples of the oxime ester-based photopolymerization initiator 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 oxime ester-based photoinitiator, etc.

As the above-mentioned oxime ester-based photopolymerization initiator, in order to achieve a wide range of color reproduction, the coloring resin composition with increased color material concentration is also excellent in curability, development resistance, suppression effect of pattern defects, and water penetration In terms of excellent suppression effect and easy suppression of precipitation of compounds derived from color materials, among them, it is preferable to use an oxime ester-based photoinitiator that generates alkyl radicals, and further use an oxime that generates methyl radicals Ester-based photopolymerization initiator. Compared with aryl radicals, it is presumed that alkyl radicals are easier to activate and activate free radicals. Examples of the oxime ester-based photopolymerization initiator that generates alkyl radicals include 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]- Acetophenone 1-(O-acetamide oxime) (trade name "Irgacure OXE-02", manufactured by BASF), [8-[[((acetoxy)imino)][2-(2,2,3 ,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-methanone (2,4,6- Trimethylphenyl) (trade name "Irgacure OXE-03", manufactured by BASF), 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxybenzene Oxy)-9H-carbazol-3-yl)-ethanone 1-(O-acetamide) (trade name "ADEKA ARKLS N-1919", manufactured by ADEKA), (9-ethyl-6-nitro Yl-9H-carbazol-3-yl) [4-(2-methoxy-1-methylethoxy-2-methylphenyl)-methanone O-acetoxime (trade name "ADEKA ARKLS NCI-831", manufactured by ADEKA), 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-acetone 1-(O-acetyl oxime) (trade name "TR-PBG-304", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H -Carbazol-3-yl]-1-acetone 1-(O-acetamide) (trade name "TR-PBG-314", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 2-cyclohexyl-1-[2 -(2-pyrimidinyloxy)-9H-carbazol-3-yl]-ethanone 1-(O-acetoxime) (trade name "TR-PBG-326", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-ethanone 1-(O-acetamidoxime) (trade name "TR-PBG-331" , Manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6][4-[(4,6-dimethyl -2-pyrimidinyl)thio]-2-methylbenzyl]-9H-carbazol-9-yl]phenyl]-1-octanone 1-(O-acetamido oxime) (brand name " EXTA-9", manufactured by UNION CHEMICAL), etc. In addition, as an initiator for generating phenyl radicals, specific examples include Irgacure OXE-01 (manufactured by BASF), etc. Furthermore, as a diphenylsulfide skeleton Examples of the oxime ester-based photopolymerization initiator include ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) and TR-PBG-3057 (manufactured by Changzhou Qiangli New Electronic Materials Co., Ltd.).

The oxime ester-based photopolymerization initiator having a diphenyl sulfide skeleton is preferable as compared with the case having a carbazole skeleton in terms of easily improving the brightness of the colored layer.

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

啉基苯基)-1-丁酮(例如，商品名「Irgacure 369」、BASF公司製造)、4,4’-雙(二乙基胺基)二苯甲酮(例如，商品名「Hicure ABP」、川口藥品公司製造)等。 In addition, the oxime ester-based photopolymerization initiator is preferably used in combination with a polymerization initiator having a tertiary amine structure in terms of improving sensitivity. The reason is that since the polymerization initiator having a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, the free radicals generated by the initiator are less likely to be deactivated by oxygen and can improve sensitivity. As the commercially available product of the photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthienyl)-2-

Prolin-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)benzophenone (for example, trade name "Hicure ABP"", manufactured by Kawaguchi Pharmaceutical Co., Ltd.).

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, relative to 100 parts by mass of the total solid content of the colored resin composition. 10 parts by mass or less. If the content of the polymerization initiator is more than the above lower limit, curing is sufficiently performed, and if the content of the polymerization initiator is less than the above upper limit, side reactions can be suppressed and stability over time can be maintained.

As a polymerization initiator used in the above colored resin composition, when two or more oxime ester-based photopolymerization initiators are used, in terms of sufficiently exerting the combined effect of these polymerization initiators 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, and more preferably 1.0 mass with respect to 100 parts by mass of the total solid content of the colored resin composition. Within a range of more than 8.0 parts by mass.

<color material (D)>

The coloring resin composition of the present invention contains at least CI Pigment Red 291 (PR291) and a pyrrolopyrrole dione-based pigment represented by the following chemical formula (D1) as a color material (D), which suppresses the occurrence of heating The effect of precipitation of the compound derived from the color material (in the present invention, there is a case called the precipitation inhibition effect). Therefore, the coloring layer formed using the coloring resin composition of the present invention suppresses the precipitation of the compound derived from the color material, and as a result, also suppresses the decrease in brightness and contrast. The coloring resin composition of the present invention may further contain other color materials as long as the effects of the present invention are not impaired.

[Chemical 4]

C.I. Pigment Red 291 (PR291) is a pyrrolopyrrole dione pigment. PR291 is monochromatic and appears bluish red, with relatively strong coloring power and high brightness. Furthermore, PR291 tends to have a better contrast than C.I. Pigment Red 254, which is a conventional pyrrolopyrrole-based pigment, and the like.

As a chromaticity coordinate in the XYZ color system of JIS Z8701 for color measurement using a single C light source, PR291 can display color materials with x=0.30 or more and 0.69 or less, y=0.30 or more and 0.35 or less, among which It can display color materials characterized by x=0.35 or more and 0.68 or less, y=0.30 or more and 0.34 or less.

PR291 is in the spectral transmittance spectrum of visible light range from 380nm to 780nm, when the transmittance of 430nm is set to 1%, the transmittance from 610nm to 780nm is 90%, and the penetration of 380nm The rate is 50% or less, and further, the transmittance at 500 nm is 10% or less.

In order to measure the color by coating the PR291 with monomers, it is necessary to prepare an appropriate amount of dispersant, binder component and solvent in PR291 to prepare a coating liquid, apply it to a transparent substrate and dry it, and harden it if necessary That's it. As a binder component, as long as a transparent coating film capable of color measurement can be formed, a non-curable thermoplastic resin composition may be used, and a photocurable (photosensitive) or thermosetting resin composition may also be used. As a transparent coating film capable of color measurement including a dispersant and a binder component, for example, the transmittance of the spectral transmittance spectrum with a film thickness of 2.0 μm, 380 nm or more and 780 nm or less can be set as a standard of 95% or more. In addition, the spectroscopic transmittance spectrum can be measured using a spectrometer (for example, OSP-SP200 manufactured by Olympus).

In the present invention, as PR291, a commercially available product can be used. Examples of commercially available products of PR291 include the product name Cinilex DPP Red MT-CF manufactured by CINIC Chemicals.

The pyrrolopyrrole dione pigment represented by the above chemical formula (D1) can be synthesized, for example, by referring to Japanese Patent No. 5619729.

In the coloring resin composition of the present invention, in the total 100% by mass of PR291 and the pyrrolopyrrole dione pigment represented by the above chemical formula (D1), the pyrrolopyrrole dione pigment represented by the above chemical formula (D1) The ratio is not particularly limited, and it is preferably 1% by mass or more, more preferably 2% by mass or more in terms of easily suppressing the precipitation of the compound derived from the color material and easily suppressing the reduction in the brightness and contrast of the colored layer. On the other hand, it is preferably 30% by mass or less, and more preferably 25% by mass or less.

In order to make the coloring layer the desired chroma, the coloring resin composition of the present invention can contain pyrrole pyrroldione different from PR291 and the above-mentioned chemical formula (D1) within the range not detracting from the effect of the present invention Other color materials of pigments.

The other color materials mentioned above are not particularly limited as long as they can perform the desired color development when forming the colored layer, and various organic pigments, inorganic pigments, dispersible dyes, or a mixture of two or more can be used alone . Among them, organic pigments can be used well because of their high color rendering and high heat resistance.

As the organic pigment that can be used as the other color material, for example, other pyrrolopyrrolodione pigments different from the pyrrolopyrrolodione pigments represented by PR291 and the above-mentioned chemical formula (D1) can be used favorably. The coloring resin composition of the present invention includes the combination of PR291 and the pyrrolopyrrole dione-based pigment represented by the above chemical formula (D1), and even if it further contains the aforementioned other pyrrolopyrrole-dione-based pigment, it is possible to suppress the color material-derived pigment Precipitation of compounds.

Specific examples of the other pyrrolopyrrole pigments include CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Orange 71, and CI Pigment Orange 73 etc.

When the coloring resin composition of the present invention contains the above-mentioned other pyrrolopyrrole-dione pigments as the color material (D), among the total 100% by mass of the pyrrolopyrrole-dione pigments, PR291 and the above-mentioned chemical formula (D1) The total ratio of the expressed pyrrolopyrrole-based pigments is preferably 40% by mass or more, and more preferably 50% by mass or more. With this, it is easy to suppress the precipitation of the compound derived from the color material, and it is easy to suppress the decrease in the brightness and contrast of the colored layer. The upper limit of the total ratio of the total amount of pyrrolopyrrole-based pigments, PR291 and the pyrrolopyrrole-based pigments represented by the above formula (D1) in 100% by mass of the pyrrolopyrrole-based pigments is not particularly limited. In terms of the effect of using the diketone pigment in combination, it is preferably 99% by mass or less, or 95% by mass or less.

The coloring resin composition of the present invention may contain a red color material other than the pyrrolopyrrole dione pigment as the color material (D). Examples of red color materials other than pyrrolopyrrole-based pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49 : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81 : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170 , 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226 , 242, 243, 245, 265, etc.

Examples of the above-mentioned dispersible dyes include dyes that can be dispersed insoluble in a solvent by imparting various substituents to the dye, or by using a well-known method of lake formation (salification); or Dispersible dyes in combination with solvents. By using such a dispersible dye in combination with the following dispersant, the dispersibility or dispersion stability of the dye can be improved.

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

Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, etc.

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

The color material (D) used in the present invention may further contain a yellow color material for toning. Examples of the yellow color material used in the present invention include the following yellow color material (D2) including the azo compound represented by the following general formula (I) and its tautomerism At least one anion selected from the group consisting of mono-, di-, tri-, and tetra anions of the structured azo compounds, composed of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn At least one metal ion selected from the group consisting of compounds represented by the following general formula (II).

The above-mentioned yellow color material (D2) is preferable in that crystal growth is not easy, and compounds derived from the color material are not easy to precipitate. Among them, in terms of obtaining a high-brightness coloring layer and suppressing crystal growth of the color material , Preferably the following yellow color material (D2), which comprises: the mono-, di-, tri- and tetra anions of the azo compound represented by the following general formula (I) and its tautomeric structure At least one anion selected from the group of ions; ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and The compound represented by the general formula (II).

[Chem 5]

In (Formula (I), R ^a each independently _{-OH, -NH 2, -NH-CN} , acyl group, alkyl group or aryl group, R ^b are independently -OH or -NH ₂ )

[化6]

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

The coloring resin composition of the present invention further includes the above yellow color material (D2), including the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn When the yellow color material (D2) of at least two kinds of metal ions is used as the yellow color material, even if the P/V ratio ((quality of color material component in the composition)/(other than the color material component in the composition is suppressed The solid content quality) ratio) can also produce red pixels contained in the chromaticity range of red with high color density. In addition, since the total content of the color material components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, so that a coloring layer can be formed which improves the plate-making property and further improves the adhesion with the substrate.

Examples of the acyl group in the acylamino group in the general formula (I) include, for example, alkylcarbonyl, phenylcarbonyl, alkylsulfonyl, phenylsulfonyl, alkyl, phenyl, or Naphthyl-substituted carbamoyl; sulfamoyl which may be substituted with alkyl, phenyl, or naphthyl; formamidinyl which may be substituted with alkyl, phenyl, or naphthyl, etc. The above-mentioned alkyl group preferably has 1 to 6 carbon atoms. In addition, the alkyl group may be substituted with at least one of halogen such as F, Cl, Br, -OH, -CN, -NH ₂ , and an alkoxy group having 1 to 6 carbon atoms. Further, the phenyl and naphthyl groups may be halogen, such as F, Cl, Br, etc., -OH, -CN, -NH ₂ , -NO ₂ , an alkyl group having a carbon number of 1 to 6, and a carbon number of 1 or more and At least one of the alkoxy groups below 6 is substituted.

The alkyl group in the alkylamine group in the general formula (I) is preferably 1 to 6 carbon atoms. The above-mentioned alkyl group may be substituted with at least one of halogen such as F, Cl, Br, —OH, —CN, —NH ₂ , and an alkoxy group having 1 to 6 carbon atoms.

Examples of the aryl group in the arylamine group in the general formula (I) include a phenyl group and a naphthyl group. These aryl groups may be halogenated by F, Cl, Br, etc.; -OH; carbon number 1 or more and 6 or less Alkyl groups, alkoxy groups with a carbon number of 1 or more and 6 or less; -NH ₂ , -NO ₂ and -CN are substituted.

Azo compounds and azo compounds mutual variation of the configuration is configured in the above general formula (I) in the represented as R ^a, it is presented in terms of the hue of reddish aspect, preferably each independently -OH, -NH _2, -NH-CN, or an alkyl group, two R ^a may be identical or different, respectively.

In the above general formula (I), regarding two ^Ra , in terms of hue, it is further preferred that both are -OH, both are -NH-CN, or 1 One is -OH and one is -NH-CN, and it is more preferable that both are -OH.

In addition, in the azo compound represented by the above general formula (I) and the azo compound having a tautomeric structure, it is more preferable that both of them are -OH in terms of hue as R ^b .

At least one metal selected as a group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, among which, it is preferable to include at least one metal to become divalent or trivalent The cationic metal preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably contains at least Ni. Regarding the above yellow color material (D2), in terms of obtaining a high-brightness coloring layer, suppressing the crystal growth of the color material, and suppressing the P/V ratio, it is preferred to include Cd, Co, The ions of at least two metals selected from the group consisting of Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, among which, it is preferable to include Ni and further composed of Cd, Co, Al, Cr, At least one metal selected from the group consisting of Sn, Pb, Zn, Fe, Cu, and Mn, and more preferably at least 1 selected from the group consisting of Ni and further consisting of Zn, Cu, Al, and Fe Kinds of metals. Among them, it is particularly preferred that the at least two metals are Ni and Zn or Ni and Cu.

In the yellow color material (D2), the content ratio of the metal may be adjusted appropriately.

In terms of the reddish hue, the yellow color material (D2) contains Ni and further consists of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn In the case of selecting at least one metal ion, the content ratio of Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn It is preferable to include Ni: the other at least one of the above metals at a molar ratio of 97:3 to 10:90, and further preferably at a molar ratio of 90:10 to 10:90.

Among them, in terms of the reddish hue, it is preferable to include Ni and Zn at a molar ratio of Ni:Zn of 90:10 to 10:90, and further preferably at a molar ratio of 80:20 to 20:80. The ear ratio contains Ni and Zn.

Or, in terms of the reddish hue, it is preferable to include Ni and Cu at a molar ratio of Ni:Cu of 97:3 to 10:90, and further preferably at a molar ratio of 96:4 to 20:80. The ear ratio contains Ni and Cu.

In the case where the yellow color material (D2) is a reddish hue, even if the above P/V ratio is suppressed, it is easy to produce red pixels included in the chromaticity range of high color density red.

In the above yellow color material (D2), it may further contain metal ions different from the above-mentioned specific metal ions, for example, it may include Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La At least one metal ion selected in the group.

Examples of the yellow color material (D2) include ions of at least two kinds of metals. Examples include the case where at least two kinds of ions are contained in a common crystal lattice, and one type is included in each of the other lattices. The state in which the crystals of metal ions are aggregated. Among them, in terms of further improvement in contrast, it is preferable to include ions of at least two metals in a common crystal lattice. In addition, in the case where a common crystal lattice contains ions of at least two kinds of metals, or in the case where crystals containing ions of one metal each in other lattices are aggregated, for example, refer to Japanese Patent Laid-Open No. 2014-12838 The bulletin is appropriately judged using the X-ray diffraction method.

The yellow color material (D2) includes a metal complex compound containing an anion of the azo compound represented by the general formula (I) and a tautomeric structure thereof and a specific metal ion, and the general formula (II ) Represents the compound molecule of the compound. Such intermolecular bonds can be formed by, for example, intermolecular interactions, Lewis acid-base interactions, or coordination bonds. In addition, it may be a structure of an inclusion compound in which a guest molecule is incorporated into a crystal lattice constituting a host molecule. Alternatively, it is possible to form a mixed substitution crystal in which two substances form a common crystal, and the atoms of the second component are located at the regular lattice positions of the first component.

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

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

啉、2,3-二羥基喹

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

-2,4-二胺、6-甲基-1,3,5-三

-2,4-二胺、三聚氰酸等。 In addition, the yellow color material (D2) may further include urea and substituted urea, such as phenylurea, dodecylurea, etc., and polycondensate with its aldehyde, especially formaldehyde; heterocycle, such as barbituric acid , Benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquin

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.

In addition, the yellow color material (D2) may further contain a water-soluble polymer, such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid, such as carboxymethyl cellulose, Modified cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxyethyl cellulose.

The yellow color material (D2) can be prepared by referring to Japanese Patent Laid-Open No. 2014-12838, for example.

In the case where the coloring resin composition of the present invention contains the above-mentioned yellow color material (D2), the content of the above-mentioned yellow color material (D2) in the total 100% by mass of the color material (D) realizes both chromaticity adjustment and In terms of brightness improvement, it is preferably 0.5% by mass or more. On the other hand, in terms of easily adjusting the chromaticity within the target range, it is preferably 20% by mass or less, and more preferably 10% by mass or less.

In addition, in terms of suppressing the precipitation of the compound derived from the color material, the content of the yellow color material (D2) is 100 parts by mass relative to the total of PR291 and the pyrrolopyrrole dione-based pigment represented by the chemical formula (D1) , Preferably 1% by mass or more. On the other hand, even if the content of the yellow color material (D2) is 10% by mass or less with respect to 100 parts by mass of the total amount of the pyrrolopyrrole-based pigment represented by the PR291 and the chemical formula (D1), the yellow color can be used. Precipitation suppression effect of color material (D2).

In addition, when the coloring resin composition of the present invention contains other color materials different from the pyrrolopyrrolodione pigment represented by PR291 and the above-mentioned chemical formula (D1), the effect of using the color materials in combination with the other color materials is obtained. , And it is easy to suppress the precipitation of the compound derived from the color material, and it is easy to suppress the reduction of the brightness and contrast of the colored layer. Of the total 100% by mass of the color material (D), PR291 and the chemical formula (D1) The total content of the pyrrolopyrrole dione-based pigment is preferably 40% by mass or more, and more preferably 50% by mass or more. On the other hand, in terms of sufficiently containing the above-mentioned other color materials, it is preferably 95% by mass or less , More preferably 90% 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 develop the required color when it is made into a color layer, and it is not particularly limited according to the type of color material used It is also different, preferably within a range from 10 nm to 100 nm, more preferably from 15 nm to 60 nm. 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 coloring resin composition of the present invention can be made to have high contrast and high quality.

In addition, the average dispersed particle diameter of the color material differs depending on the type of color material used, and is preferably in the range of 10 nm or more and 100 nm, and more preferably in the range of 15 nm or more and 60 nm or less.

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. As the measurement of the particle size using a laser light scattering particle size distribution meter, the solvent used in the colored resin composition can be used to appropriately dilute the color material dispersion liquid to a measurable concentration (eg 1000 times, etc.) using the laser light scattering particle size distribution meter ), and using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.), the dynamic light scattering method was used to measure at 23°C. The average distribution particle diameter here is a 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. Below. If the content of the color material is above the lower limit, the desired optical characteristics can be obtained and the desired function is exhibited, and if the content of the color material is below the above upper limit, it is easy to suppress the The precipitation of the compound can suppress the curing failure, and it is easy to pattern the coating film of the colored resin composition.

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

The coloring resin composition of the present invention is preferable in terms of suppressing the precipitation of the compound derived from the color material due to the heat treatment (post-baking) performed when the coloring layer is formed, and improving the brightness and contrast of the coloring layer. In order to further include a compound having a fluorocarbon group and a cross-linked cycloaliphatic group (hereinafter, this compound will be referred to as a "precipitation inhibiting compound").

The above-mentioned precipitation inhibiting compound is a compound having at least one fluorocarbon group and a cross-linked cycloaliphatic group in the molecule. The fluorocarbon group of the precipitation suppression compound tends to move to the surface of the coating film when heat is applied. Therefore, it is considered that the precipitation suppression compound moves to the surface direction of the coating film during heat treatment. On the other hand, since the cross-linked cycloaliphatic group included in the above precipitation inhibiting compound is bulky, it is believed that even if the compound derived from the color material reaches the surface, the cross-linking existing near the surface of the coating film The cyclic aliphatic group blocks the compound derived from the color material and suppresses the precipitation of the compound derived from the color material. In addition, it is presumed that the crystal growth of the color material itself is also suppressed near the surface of the coating film. Furthermore, in the coating film, the compound derived from the color material tends to accumulate in the weak part of the film, but due to the large volume of cross-linked cycloaliphatic groups present near the surface of the coating film, near the surface of the coating film Suppresses the decrease in film strength and also suppresses the aggregation of compounds derived from color materials. From this, it is presumed that by including the above-mentioned precipitation suppression compound, the precipitation of the compound derived from the color material can be suppressed in the colored layer. In addition, by using the above-mentioned precipitation-inhibiting compound, the precipitation of the compound derived from the color material is further suppressed to improve the brightness and contrast.

In addition, the compound has a fluorocarbon group and a cross-linked cyclic aliphatic group, which can be confirmed based on ¹ H- and ¹³ C-nuclear magnetic resonance (NMR) spectra measured using a nuclear magnetic resonance apparatus.

The fluorocarbon group possessed by the above-mentioned precipitation inhibiting compound refers to a group having a structure in which at least a part of hydrogen atoms having a hydrocarbon group are substituted with fluorine atoms. Furthermore, the fluorocarbon group may be a part of a fluorine atom or a hydrogen atom through a halogen atom such as a chlorine atom, a bromine atom, an iodine atom (excluding fluorine atoms), a hydroxyl group, a thiol group, an alkoxy group, an ether group, an amine group , Nitrile group, nitro group, sulfonyl group, sulfenyl group or ester group, amine group, acetyl group, amide group, carboxyl group and other substituents such as carbonyl-containing groups, may also have a part of the main chain Ether bond (-O-) or sulfonyl bond (-SO ₂ -).

From the viewpoint of improving the compatibility with other components and obtaining the best rheological properties when coating the colored resin composition, the carbon number of the fluorocarbon group in the above precipitation inhibiting compound is preferably 2 or more and 10 or less. The lower limit of the carbon number of the fluorocarbon group is more preferably 4 or more, and the upper limit is more preferably 7 or less.

The fluorocarbon group may be a fluorocarbon group in which a part of the hydrogen atoms of the hydrocarbon group is replaced by a fluorine atom. From the viewpoint of allowing the above-mentioned precipitation-inhibiting compound to exist on the surface of the colored layer and suppressing the precipitation of the compound derived from the color material, it is preferably A perfluorocarbon group in which the hydrogen atoms of the hydrocarbon group are all replaced by fluorine atoms.

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

Examples of the fluoroalkyl group include fluoroalkyl groups having a carbon number of 2 or more and 10 or less. Among perfluoroalkyl groups having a carbon number of 2 or more and 10 or less, from the viewpoint of allowing the above-mentioned precipitation-inhibiting compound to exist on the surface of the colored layer and suppressing the 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 perfluoro Heptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, etc.

Examples of the fluoroalkenyl group include a fluoroalkenyl group having 2 or more carbon atoms and 10 or less 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-inhibiting compound to exist on the surface of the colored layer and suppressing the precipitation of the compound derived from the color material, a perfluoroalkenyl group is preferred. Examples of perfluoroalkenyl groups having a carbon number of 2 or more and 10 or less include perfluoropropenyl, perfluoroisopropenyl, perfluorobutenyl, perfluoroisobutenyl, perfluoropentenyl, and perfluoroisoamyl Alkenyl, perfluorohexenyl, perfluoroheptenyl, perfluorooctenyl, perfluorononenyl, perfluorodecenyl, etc.

The cross-linked cycloaliphatic group possessed by the above precipitation inhibiting compound refers to an aliphatic group having a structure in which two or more rings share two or more atoms. From the viewpoint of compatibility with other materials or solubility with an alkaline developer, the carbon number of the cross-linked cycloaliphatic group is preferably 5 or more and 12 or less. 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.

基、可經取代之異

基、可經取代之金剛烷基、可經取代之三環癸基、可經取代之二環戊烯基、可經取代之二環戊基、可經取代之三環戊烯基、可經取代之三環戊基、可經取代之三環戊二烯基、及可經取代之二環戊二烯基等。該等之中，就耐熱性之方面及抑制源 自色材之化合物之析出之方面而言，較佳為可經取代之金剛烷基或可經取代之二環戊基，更佳為可經取代之金剛烷基。於該等基被取代之情形時，作為取代基，可列舉：烷基、環烷基、烷基環烷基、羥基、酮基、硝基、胺基、鹵素原子等。 Examples of the cross-linked cycloaliphatic group include:

The difference between base and substitutable

Group, substitutable adamantyl, substitutable tricyclodecyl, substitutable dicyclopentenyl, substitutable dicyclopentyl, substitutable tricyclopentenyl, substitutable Substituted tricyclopentyl, tricyclopentadienyl which may be substituted, and dicyclopentadienyl which may be substituted. Among these, in terms of heat resistance and the suppression of precipitation of compounds derived from color materials, adamantyl groups which may be substituted or dicyclopentyl groups which may be substituted are preferred, and more preferred are Substituted adamantyl. When such groups are substituted, examples of the substituent 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 inhibiting compound is preferably 150°C or higher and 250°C or lower. If the glass transition temperature of the precipitation-inhibiting compound is 150° C. or higher, after the precipitation-inhibiting compound oozes out onto the coating film surface, even if the coating film surface is rubbed, the abrasion resistance is higher, so the quality of the color filter can be improved, and If it is 250° C. or lower, the precipitation inhibiting compound easily moves (eases to bleed out) to the surface of the coating film, and the precipitation of the compound derived from the color material can be further suppressed. The glass transition temperature of the precipitation-inhibiting compound can be determined by a method according to JIS K7121-1987, which is measured by differential scanning calorimetry (DSC). The lower limit of the glass transition temperature of the precipitation inhibiting compound is more preferably 180°C or higher, and the upper limit is more preferably 230°C or lower.

The above precipitation inhibiting compound may be a copolymer containing a structural unit derived from a compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound derived from having a cross-linked cycloaliphatic group and ethylene Constituent unit of unsaturated group compound (E-2).

Among the above precipitation inhibiting compounds, the molar ratio (E-1:E-2) of the structural unit derived from the compound (E-1) to the structural unit derived from the compound (E-2) is preferably 5: 95~70:30, more preferably 10:90~50:50, still more preferably 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 become good. The molar ratio of each constituent unit in the above-mentioned precipitation-inhibiting compound can be obtained from the measurement results of nuclear magnetic resonance (NMR) analysis.

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

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

Examples of the alkylene group having 1 to 4 carbon atoms in X ¹ and X ² in the general formula (1) and the general formula (2) include, for example, methylene, ethyl, and propyl. , Stretching butyl, etc. Examples of the oxyalkylene group having 1 to 4 carbon atoms in X ¹ and X ² include oxymethylene, oxyethyl, oxypropyl, and oxybutyl groups. In addition, examples of the substituent that the alkylene group and the oxyalkylene group may have include a halogen atom, a hydroxyl group, an acid group, a nitro group, a carbonyl group, an amide group, and an amine group. Among them, X ¹ and X ^{2 are} preferably a direct bond or an alkylene group having 1 to 4 carbon atoms.

Examples of the hydrocarbon groups having 1 to 6 carbon atoms in R ¹¹ and R ¹² in the general formula (1) and the general formula (2) include methyl, ethyl, propyl, butyl, and iso Linear or branched alkyl groups such as propyl, tertiary butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl. In addition, examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxyl group, an acid group, a nitro group, and an amine group. Among them, R ¹¹ and R ^{12 are} preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

As the fluorocarbon group having a carbon number of 2 or more and 10 or less in Rf in the above general formula (1), for example, those having a carbon number of 2 or more and 10 or less in the fluorocarbon group can be used, and among them, the carbon number can be used favorably The above fluoroalkyl group of 2 or more and 10 or less.

As the cross-linked cycloaliphatic group in A ¹ in the above general formula (2), the above-mentioned cross-linked cycloaliphatic group can be used.

From the viewpoint of the precipitation inhibition effect, the precipitation prevention compound is preferably a block copolymer containing the structural unit derived from the compound (E-1) and the structural unit derived from the compound (E-2). When the precipitation suppression compound is a block copolymer, 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 range, it can be expressed without impairing the compatibility and rheological properties of the components of the colored resin composition Precipitation suppression effect.

The production method of the block copolymer is not particularly limited. The block copolymer can be produced by a well-known method, and it is preferably produced by a living polymerization method. The reason for this is that it is not easy to produce chain transfer or deactivation to produce a copolymer having a uniform molecular weight, and the dispersibility can be improved. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization method and radical transfer polymerization method, and living cationic polymerization methods. The copolymer can be produced by sequentially polymerizing monomers by using these methods. For example, by first producing a block (A block) containing a structural unit derived from the compound (E-1), the A block and the block (B) containing a structural unit derived from the compound (E-2) Block) polymerization to produce a block copolymer. In addition, in the above production method, the polymerization order may be reversed. Alternatively, the blocks may be manufactured separately, and then each block may be coupled.

The arrangement of each block of the block copolymer is not particularly limited. For example, it may be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Among them, in terms of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

In order to control the compatibility or glass transition point of the colored resin composition, the above-mentioned precipitation-inhibiting compound may further contain an ethylenically unsaturated group derived from the copolymerization with the above-mentioned compound (E-1) and the above-mentioned compound (E-2) The structural unit of the compound (E-3).

As a structural unit derived from the said compound (E-3), the structural unit represented by the following general formula (3) is mentioned, for example.

As the above-mentioned precipitation-inhibiting compound, a copolymer containing the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the following general formula (3) can be used favorably. Fit.

[Chem 8]

(In the general formula (3), R ¹³ is a hydrogen atom, or a hydrocarbon group which may be substituted with a carbon number of 1 to 6 or less, and A ² is a substituted aryl group, a substituted pyridyl group, or the following general (Base expressed by formula (4))

[化9]

(In the general formula (4), A ³ is a hydrogen atom, a substituted alkyl group, a substituted benzyl group, a substituted cyclopentyl group, a substituted cyclopentylalkyl group, a substituted Cyclohexyl, or cyclohexylalkyl which may be substituted. * indicates the bonding position)

As the substitutable hydrocarbon group having 1 to 6 carbon atoms in R ¹³ in the above general formula (3), R ¹¹ and R ¹² in the above general formula (1) and the above general formula (2) can be used The hydrocarbon groups in which carbon number is 1 or more and 6 or less are the same.

Examples of the aryl group in A ² in the general formula (3) include phenyl, biphenyl, naphthyl, tolyl, and xylyl. 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, examples of the substituent that the aryl group and pyridyl group in A ² in the general formula (3) may have include, for example, linear or branched alkyl groups and alkenes having 1 to 4 carbon atoms. Group, cycloalkyl group, nitro group, halogen atom, etc.

Examples of the substituent that A ³ in the general formula (4) may have include a hydroxyl group, an acetyl 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-mentioned precipitation inhibiting compound is a copolymer comprising a structural unit derived from the compound (E-1), a structural unit derived from the compound (E-2), and a structural unit derived from the compound (E-3) In this case, the ratio of the constituent units derived from the above compound (E-3) to the total of 100 moles of these constituent units is appropriately adjusted according to the compatibility of the colored resin composition and the glass transition point, and is not particularly limited. In terms of easily improving the precipitation inhibition effect, it is preferably 50 mol or less, more preferably 30 mol or less, and still more preferably 10 mol or less.

The above precipitation inhibiting compound can be obtained, for example, by including 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, depending on It is necessary to obtain by copolymerizing two or more monomers including the compound (E-3) having an ethylenically unsaturated group that can be copolymerized with the compound (E-1) and the compound (E-2). Examples of the compound (E-1) having a fluorocarbon group and an ethylenic saturated group include compounds represented by the following general formula (1-1). Examples of the compound (E-2) having a crosslinked cycloaliphatic group and an ethylenically unsaturated group include compounds represented by the following general formula (2-1).

[化10]

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

[Chem 11] General formula (2-1)

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

Specific examples of the compound (E-1) include, for example, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluoroisopropyl)ethyl (meth)acrylate, ( 2-(Perfluorobutyl)ethyl methacrylate, 2-(Perfluoropentyl)ethyl (meth)acrylate, 2-(Perfluorohexyl)ethyl (meth)acrylate, (methyl) 2-(Perfluoroheptyl) ethyl acrylate, 2-(perfluorooctyl) ethyl (meth)acrylate, 2-(perfluorononyl) ethyl (meth)acrylate, (meth)acrylic acid 2 -(Perfluorodecyl) ethyl ester, etc. Among these, from the viewpoint of the precipitation suppression effect and the rheological properties of the coloring resin composition, 2-(perfluorohexyl)ethyl (meth)acrylate is preferred.

酯、(甲基)丙烯酸異

酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸三環戊酯、(甲基)丙烯酸三環戊烯酯、(甲基)丙烯酸二環戊二烯酯、(甲基)丙烯酸三環戊二烯酯等。該等之中，就與著色樹脂組成物之各成分之相溶性或析出抑制效果之觀點而言，較佳為(甲基)丙烯酸1-金剛烷基酯及(甲基)丙烯酸二環戊酯。 Specific examples of the compound (E-2) include, for example, 1-adamantyl (meth)acrylate, 1-methyl-1-adamantyl (meth)acrylate, (meth)acrylic acid 2-methyl-2adamantyl ester, (meth)acrylic acid

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 or precipitation suppression effect, 1-adamantyl (meth)acrylate and dicyclopentyl (meth)acrylate are preferred .

In addition, in the case where the precipitation inhibition compound further includes a structural unit derived from the compound (E-3) having an ethylenically unsaturated group that can be copolymerized with the compound (E-1) and the compound (E-2) In this case, examples of the compound (E-3) include compounds represented by the following general formula (3-1).

[化12]

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

Specific examples of the compound (E-3) include, for example, methyl (meth)acrylate, (meth)acrylic acid, styrene, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, cyclopentylmethyl (meth)acrylate, cyclopentylethyl (meth)acrylate, cyclohexyl methyl (meth)acrylate, cyclohexyl (meth)acrylate, Vinylpyridine etc. Among these, from the viewpoint of the compatibility of the colored resin composition or the precipitation inhibition effect, 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 precipitation inhibiting compound is 3,000 or more and 10,000 or less, the affinity with other materials is excellent, and the viscosity of the colored resin composition does not become too high, so it does not hinder the heat during baking The surface bleed caused by the precipitation suppression effect is not easy to damage. The lower limit of the molecular weight of the precipitation suppressing compound is more preferably 4000 or more, and the upper limit of the molecular weight of the precipitation suppressing compound is more preferably 8000 or less.

In the case where the coloring resin composition of the present invention contains a precipitation inhibiting compound, regarding the content of the precipitation inhibiting compound, the effect of suppressing the precipitation of the compound derived from the color material is high, and the coating of the coloring resin composition applied can be improved In terms of the smoothness of the film, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the total solid content of the colored resin composition. On the other hand, in terms of suppressing separation of components or poor curing, it is preferably 12 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less .

<thiol compound (F)>

In terms of densifying the surface of the colored layer and further suppressing the precipitation of the compound derived from the color material, it is preferable that the coloring resin composition of the present invention further contains a thiol compound. When the coloring resin composition of the present invention further contains a thiol compound, it is presumed that the thiol compound functions as a crosslinking agent, and the bonding between the molecules of the polymer and the polymerizable compound becomes strong, thereby The surface of the colored layer can be densified and the crystallization of the color material can be suppressed.

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

、2-(N,N-二丁基胺基)-4,6-二巰基-s-三

等。作為硫醇化合物，其中，就反應速度提高之方面而言，較佳為使用2-巰基苯并噻唑。 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 bis(3-mercaptopropionate), ethylene glycol dimercaptoglycolate, 1,4-butanedi Alcohol dimercaptoglycolate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane trimercaptoglycolate, 2-mercaptobenzothiazole, trimethylolpropane tri(3 -Mercaptopropionate), pentaerythritol tetramercaptoglycolate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate), among others Various polyols, thioglycolic acid, mercaptopropionic acid and other thiol group-containing carboxylic acid esters, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene , 2,4,6-trimercapto-s-tri

, 2-(N,N-dibutylamino)-4,6-dimercapto-s-tri

Wait. Among the thiol compounds, 2-mercaptobenzothiazole is preferably used in terms of increasing the reaction rate.

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

As the thiol compound, among them, in terms of increasing the crosslinking density, the precipitation suppression effect can be further obtained and the surface roughness can be easily reduced, it is preferable to use a polyfunctional having two or more thiol groups in one molecule One or more selected from the group consisting of thiol compounds. In addition, in terms of easily maintaining a good precipitation suppression effect and low surface roughness even when the colored resin composition is stored for a long period of time, it is preferred that the carbon atom having a thiol group be bonded to a secondary carbon The secondary thiol compound of the atomic secondary thiol group is more preferably a polyfunctional secondary thiol compound having two or more secondary thiol groups in one molecule.

In the case where 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 0.05 part by mass relative to 100 parts by mass of the total solid content of the colored resin composition From 5 to 5 parts by mass or more, more preferably from 0.5 to 3 parts by mass. If the content of the thiol compound is more than the above lower limit, the coating film can be sufficiently cured by utilizing the curing promotion effect of the thiol compound, and if the content of the thiol compound is below the above upper limit, it can be controlled The acceleration of hardening can suppress the deterioration of the performance 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 to the color material, and improving the dispersibility and dispersion stability of the color material, it is preferable to use the following general formula (11) ) Represents the polymer constituting the unit. The structural unit represented by the following general formula (11) has basicity and functions as an adsorption site for the color material.

[Chem 13]

(In general formula (11), R ¹⁴ represents a hydrogen atom or a methyl group, L represents a divalent linking group, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, or a hydrocarbon group that may contain a hetero atom, and R ¹⁵ and R ¹⁶ may (Bound with each other to form a ring structure)

Examples of the divalent linking group in L in the general formula (11) include alkylene groups having 1 to 10 carbon atoms, aryl groups, -CONH- groups, -COO- groups, and carbon atoms. Number 1 or more and less than 10 ether groups (-R'-OR"-: R'and R" are each independently alkylene) and combinations thereof. Among these, in terms of dispersibility, L in the above formula (11) is preferably a divalent linking group containing a -CONH- group or a -COO- group.

The hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R ¹⁵ and R ¹⁶ may, for example, include an alkyl group, an aralkyl group, an aryl group, etc. The number of carbon atoms of the above-mentioned alkyl group is preferably 1 or more and 18 or less. Preferably, it is methyl or ethyl.

The hydrocarbon group containing a hetero atom in R ¹⁵ and R ¹⁶ has a structure in which the carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of heteroatoms that can be contained in the hydrocarbon group include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like.

啉環，其中，較佳為R¹⁵及R¹⁶中之至少1個為碳原子數1以上且5以下之烷基、苯基，或R¹⁵與R¹⁶進行鍵結而形成吡咯啶環、哌啶環、

啉環。 Among them, it is preferred that R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms and 5 or less, or R ¹⁵ and R ¹⁶ are bonded to form a pyrrolidine ring or a piperidine ring ,

Porphyrin ring, wherein at least one of R ¹⁵ and R ¹⁶ is preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ¹⁵ and R ¹⁶ are bonded to form a pyrrolidine ring or a piper Pyridine ring,

Oxo ring.

Examples of the structural unit represented by the general formula (11) include: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethyl (meth)acrylate Aminoethyl, diethylaminopropyl (meth)acrylate, etc. (meth)acrylates containing alkyl substituted amine groups, etc.; dimethylaminoethyl (meth)acrylamide, dimethyl Aminopropyl (meth)acrylamide and the like (meth)acrylamide containing alkyl substituted amine groups. Among them, in terms of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylamine can be used favorably Propyl propyl (meth) acrylamide.

The structural unit represented by the general formula (11) may include one kind, or may include two or more kinds of constitutional units.

In the polymer having the structural unit represented by the above general formula (11), the adsorption of the color material in the salt formation site is further improved, the dispersion stability of the color material, the suppression of development residue, and the solvent resolubility are excellent, and In terms of further suppressing the precipitation of the compound derived from the color material, it is preferable that at least a part of the nitrogen portion of the terminal possessed by the structural unit represented by the general formula (11) and the general formula (12) to (14) One or more compounds selected from the group consisting of the compounds represented form salts. The nitrogen portion of the terminal of the polymer represented by the general formula (11) having the structural unit represented by the general formula (11) is represented by the following general formulas (12) to (14) One or more compounds selected from the group consisting of compounds form salts and their ratio can be confirmed by a known method such as NMR.

[化14]

(In the general formula (12), R ¹⁷ represents a linear, branched or cyclic alkyl group having 1 or more carbon atoms and 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 1 or more carbon atoms and 20 or less, a vinyl group, a phenyl or benzyl group which may have a substituent, or a carbon atom having 1 or more and 4 The following alkylene (meth)acryloyl groups.

In the general formula (13), R ¹⁸ , R ¹⁹ , and R ²⁰ 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 Or a cyclic alkyl group, a vinyl group which may have a substituent, a phenyl or benzyl group which may have a substituent, or -OR", R" means a linear chain having 1 to 20 carbon atoms which may have a substituent , Branched or cyclic alkyl groups, vinyl groups which may have substituents, phenyl or benzyl groups which may have substituents, or (meth)acryloyl groups which extend through an alkylene group having 1 to 4 carbon atoms , 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 group having 1 or more carbons and 20 or less, vinyl, phenyl or benzyl which may have a substituent Group, or a (meth)acryloyl group through an alkylene group having 1 to 4 carbon atoms. (At least one of R ²¹ and R ²² contains a carbon atom)

In terms of improving the dispersibility and dispersion stability of the color material and the heat resistance of the coloring resin composition, and further suppressing the precipitation of the compound derived from the color material, it is possible to form a color layer with high brightness and high contrast. The polymer of the structural unit represented by the formula (11) is preferably at least a part of the nitrogen portion of the terminal possessed by the structural unit represented by the general formula (11), and the polymer represented by the general formulas (12) to (14) One or more compounds selected from the group consisting of the represented compounds form salt block copolymers of salts.

In the block copolymer, if the block containing the structural unit represented by the above general formula (11) is set as the A block, then in the A block, the structural unit represented by the above general formula (11) has a base The property functions as an adsorption site for the color material. In addition, at least a part of the nitrogen portion of the terminal possessed by the structural unit represented by the general formula (11) and one selected from the group consisting of the compounds represented by the general formulas (12) to (14) When the above compound forms a salt, the salt forming part functions as 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 general formula (11) functions as a block having solvent affinity. Therefore, in the block copolymer, the color material, the adsorbed A block, and the solvent-affinity B block share functions, and function as a color material dispersant.

The B block is a block that does not contain the structural unit represented by the general formula (11). The constituent unit constituting the B block is preferably a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer derived from the constituent unit represented by the above general formula (11), to have solvent affinity The method is appropriately selected and used according to the solvent. As a standard, it is preferable to introduce the solvent used in combination so that the solubility of the polymer at 23° C. becomes 50 (g/100 g solvent) or more, and the solvent affinity site is introduced. As the structural unit constituting the B block, it is preferable to include the structural unit represented by the following general formula (15).

[化15]

(In the general formula (15), L'is a direct bond or a divalent linking group, R ²³ is a hydrogen atom or a methyl group, R ²⁴ is a hydrocarbon group, -[CH(R ²⁵ )-CH(R ²⁶ )-O] _x -R ²⁷ or -[(CH ₂ ) _y -O] _z -R ²⁷ represents a monovalent group. R ²⁵ and R ²⁶ independently represent a hydrogen atom or a methyl group, R ²⁷ is a hydrogen atom, a hydrocarbon group, -CHO , -CH ₂ CHO, or -CH ₂ COOR ²⁸ represents a monovalent group, and R ²⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The above-mentioned hydrocarbon group may have a substituent.

x represents an integer from 1 to 18, y represents an integer from 1 to 5 and z represents an integer from 1 to 18)

The divalent linking group L'in the general formula (15) can be the same as L in the general formula (11). Among them, in terms of solubility in organic solvents, L'is preferably a direct bond, a divalent linking group containing a -CONH- group or a -COO- group. In terms of the heat resistance of the obtained polymer or the solubility to propylene glycol monomethyl ether acetate (PGMEA) which can be suitably used as a solvent, and is a relatively inexpensive material, L'is preferably -COO -base.

The hydrocarbon group in R ²⁴ is preferably an alkyl group having 1 or more carbon atoms and 18 or less, an alkenyl group having 2 or more carbon atoms and 18 or less, an aralkyl group, or an aryl group.

基、異

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

Base, different

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

The alkenyl group having 2 or more carbon atoms and 18 or less may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited, and in terms of the reactivity of the obtained polymer, it is preferable that a double bond exists at the end of the alkenyl group.

Examples of substituents for 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, which 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, examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, which 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.

Examples of substituents for aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, and examples include alkenyl groups, nitro groups, and halogen atoms.

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

In the above R ²⁴ , x is an integer of 1 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, and y is an integer of 1 or more and 5 or less, preferably It is 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 in the above R ²⁷ may be the same as the one represented in the above 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, R ²⁴ in the structural unit represented by the general formula (15) may be the same as or different from each other.

Among the above R ²⁴ , among them, it is preferably selected so as to be excellent in compatibility with the solvent contained in the coloring resin composition. Specifically, for example, when the colored resin composition contains a solvent such as glycol ether acetate, ether, or ester, which is generally used as a solvent for the colored resin composition for color filters, the above R ²⁴ It is preferably methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl and the like.

Furthermore, the R ²⁴ may be substituted with substituents such as alkoxy, hydroxyl, epoxy, and isocyanate groups in a range that does not hinder the dispersion performance of the block copolymer, etc., or may be embedded in the above After the synthesis of the segment copolymer, it reacts with the compound having the above substituents to add the above substituents.

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

1/Tg=Σ(Xi/Tgi)

Here, the block portion of the solvent affinity is set to n monomer components of i=1 to n for copolymerization. Xi is the weight fraction of No. i monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of No. i monomer homopolymer. Among them, Σ takes the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of constituent units constituting the solvent-affinity block portion may be appropriately adjusted within the range in which the dispersibility of the color material is improved. Among them, the number of constituent units of the block portion constituting the solvent affinity is preferably 10 or more and 200 or less in terms of the effective function of the solvent affinity portion and the color material affinity portion to improve the dispersibility of the color material , More preferably 10 or more and 100 or less, and still more preferably 10 or more and 70 or less.

The solvent-affinity block can be selected as long as it functions as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block may include one kind or two or more kinds of repeating units .

The weight average molecular weight Mw of the block copolymer is not particularly limited, and in terms of improving the dispersibility and dispersion stability of the color material, it is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less , And more preferably 3000 or more and 12000 or less.

The amine value of the block copolymer before salt formation is not particularly limited. In terms 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 More preferably, it is 60 mgKOH/g or more. The upper limit is more preferably 130 mgKOH/g or less, and still more preferably 120 mgKOH/g or less. If it is at least the above lower limit value, the dispersion stability is more excellent. Moreover, if it is below the said upper limit, compatibility with other components will be excellent, and solvent resolubility will become good. In this specification, the amine value of the block copolymer before salt formation means the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid equivalent to 1 g of the solid content of the block copolymer before neutralization of salt formation (mg ) Is the value measured by the method described in JIS K7237-1995.

The amine value of the obtained salt-type block copolymer is lower than that of the block copolymer before salt formation only in the part where the salt is formed. However, the salt formation site is the same as the nitrogen site corresponding to the terminal of the amine group, or rather becomes a strengthened color material adsorption site, so there is a tendency for the color material dispersion or color material dispersion stability to be improved by salt formation . Moreover, the salt formation site is the same as the amine group, and if it is too large, it will adversely affect the solvent resolubility. Therefore, the amine value of the block copolymer before salt formation can be used as an index for improving dispersion stability of the color material 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. If it is equal to or lower than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

In addition, the acid value of the dispersant used in the present invention is not particularly limited, and it is preferably 18 mgKOH/g or less, and more preferably 12 mgKOH/g in terms of developing adhesion and solvent resolubility being good. the following. In addition, if the acid value of the dispersant is 0 mgKOH/g, it is preferable in terms of further improving solvent resolubility and development adhesion, and in terms of substrate adhesion and dispersion stability. The smaller the acid value, the less likely it is to be attacked by the alkaline developing solution. Therefore, it is considered that the developing adhesion is good. On the other hand, in terms of the inhibitory effect of the development residue, it is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more.

In addition, in the present invention, the glass transition temperature of the dispersant is preferably 30° C. or higher in terms of improving the development adhesion. If the glass transition temperature of the dispersant is low, it is particularly close to the temperature of the developing solution (usually around 23°C), and there is a possibility that the development adhesiveness may decrease. In terms of developing 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 accurate weighing and the operability at the time of use.

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

Regarding the content of the dispersant, in terms of dispersibility and dispersion stability, it is preferably not less than 3 parts by mass and not more than 45 parts by mass, more preferably 100 parts by mass relative to the total solids in the colored resin composition. It is prepared at a ratio of 5 parts by mass or more and 35 parts by mass or less.

The production method of the block copolymer is not particularly limited, and the block copolymer can be produced by a known method. In addition, as a preparation method of the salt-type block copolymer, the following methods may be mentioned: To a solvent obtained by dissolving or dispersing a polymer having a structural unit represented by the above general formula (11), add the formula One or more compounds selected from the group consisting of the compounds represented by (12) to (14) are stirred and then heated as necessary.

<Solvent (H)>

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

Specific examples of the solvent include, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol solvents such as ethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, Ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-acetic acid Glycol ether acetate solvents such as butyl ester, 3-methoxybutyl acetate, ethoxyethyl acetate, etc.; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol acetate-based solvents such as carbitol acetate (BCA); diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethyl acetate Glycol ether solvents such as glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether ; Aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; tetrahydrofuran And other cyclic ether solvents; n-heptane, n-hexane, n-octane and other saturated hydrocarbon solvents; benzene, toluene, xylene, naphthalene and other aromatic hydrocarbons and other organic solvents. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used in terms of the solubility of other components. Among them, the solvent used in the present invention is preferably composed of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility of other components or coating suitability. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate Choose one or more.

The content of the solvent in the colored resin composition is generally preferably within a range of 55 mass% or more and 95 mass% or less relative to the total amount of the colored resin composition, and preferably 65 mass% or more and 90 mass% Within the following range, it is more preferably within a range of 70% by mass or more and 88% by mass or less. If the content of the solvent is 55% by mass or more, the decrease in the dispersibility caused by the increase in viscosity can be suppressed, and if the content of the solvent is 95% by mass or less, the decrease in the concentration of the color material can be suppressed, so it is easy to achieve the target color Degree coordinates.

<other ingredients>

In the coloring resin composition of the present invention, as long as the effect of the present invention is not impaired, other components may be further formulated as necessary. As other components, for example, a dispersion aid can be used.

Dispersing aids are used to improve the dispersibility of color materials. As the dispersion aid, a pigment derivative such as an acid pigment derivative is preferred. In addition to the function of improving the dispersibility of the color material, the pigment derivative has the effect of suppressing the precipitation of compounds derived from the color material. On the other hand, if the content of the pigment derivative is too large, the optical characteristics of the colored layer decrease. Therefore, in the case where the coloring resin composition of the present invention contains a pigment derivative, in terms of maintaining the optical characteristics of the colored layer, the pigment The content of the derivative is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the total solid content of the colored resin composition.

In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoamers, shrinkage inhibitors, antioxidants, anti-agglomeration agents, 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, and the like.

After preparing the color material dispersion liquid or color material solution, a polymer, a polymerizable compound, a polymerization initiator, a precipitation inhibiting compound, a thiol compound, etc. may be added to the color material dispersion liquid or color material solution, and The coloring resin composition is obtained by mixing using well-known mixing means.

<<hardened product>>

The cured product of the present invention is the cured product of the color resin composition of the present invention described above.

The hardened material of the present invention can be suitably used as a coloring layer of a color filter. Since it is a hardened product of the coloring resin composition of the present invention described above, it suppresses the precipitation of compounds derived from the color material and suppresses the brightness and contrast. reduce.

For example, in the case where the above-mentioned coloring resin composition of the present invention is a photosensitive colored resin composition containing a photopolymerizable compound, the cured product of the present invention can be coated by forming a coating film of the photosensitive colored resin composition After the film is dried, it is obtained by exposure and development if necessary. As the method of forming, exposing, and developing the coating film, for example, the same method as that used in the formation of the coloring layer included in the color filter of the present invention described below can be used.

In addition, when the color resin composition of the present invention is a thermosetting colored resin composition containing a thermopolymerizable compound, the coating film can be dried by forming a coating film of the thermosetting colored resin composition After that, heating is performed to obtain a hardened product.

<<Color filter>>

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the coloring 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 showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2, and a coloring layer 3.

(Coloring layer)

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

The colored layer is usually formed on the opening of the light-shielding portion on the substrate described below, and is usually composed of three or more coloring patterns.

In addition, the arrangement of the colored layer is not particularly limited, and for example, it can be a usual arrangement such as a stripe type, a mosaic type, a triangle type, a 4-pixel arrangement type, and the like. In addition, the width, area, etc. of the colored layer can be arbitrarily set.

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

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

First, using the spraying method, dip coating method, bar coating method, roll coating method, spin coating method, die coating method, etc., the above coloring resin composition of the present invention is applied to the following On the substrate, a wet coating film is formed. Among them, the spin coating method and the die coating method can be preferably used.

Then, using a hot plate or an oven to dry the wet coating film, it is exposed through a mask with a predetermined pattern, and the alkali-soluble resin and polyfunctional monomer are subjected to photopolymerization reaction to be hardened. Coated film. Examples of the light source used for exposure include ultraviolet rays and electron beams such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

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

Next, a developing solution is used to perform development processing to dissolve and remove unexposed portions, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent can be generally used. An appropriate amount of surfactant or the like can also be added to the alkaline solution. In addition, the usual method can be used as a developing method.

After the development process, the developer is usually washed, and the cured coating of the colored resin composition is dried to form a colored layer. In addition, after the development treatment, in order to sufficiently cure the coating film, a heat treatment may be performed. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

(Shade)

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

The pattern shape of the light-shielding portion is not particularly limited, and examples include stripes and matrix shapes. The light-shielding portion may be a metal thin film such as chromium using 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. In the case of a resin layer containing light-shielding particles, there are a method of patterning using photosensitive resist by development, a method of patterning using inkjet ink containing light-shielding particles, and heating the photosensitive resist Transfer method, etc.

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

(Substrate)

As the substrate, it can be used for a transparent substrate or a silicon substrate described below, on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed. On these substrates, other color filter layers, resin layers, thin film transistors (TFT, Thin Film Transistor) and other transistors, circuits, etc. can be formed.

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

The thickness of the transparent substrate is not particularly limited. According to the use 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, for example, a protective layer or a transparent electrode layer, an alignment film, an alignment protrusion, a column spacer, or the like in addition to the substrate, the light shielding portion, and the coloring layer.

<<Display device>>

The display device of the present invention is characterized by having the above-described color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples include 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 having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

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

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used in liquid crystal display devices can be adopted. As such a driving method, for example, a twisted nematic (TN) method, a transverse electric field effect (IPS, In-Plane Switching) method, an optically compensated birefringence (OCB, Optically Compensated Birefringence) method, and a multi-domain Vertical alignment (MVA, Multi-Domain Vertical Alignment) method, etc. In the present invention, any of these methods can be suitably used.

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

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

<Organic light-emitting display device>

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

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

As a method of stacking the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode are sequentially formed on the upper surface of the color filter The method of 76; or the method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60. In the organic light emitting body 80, 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, and other configurations can be used as appropriate. The organic light-emitting display device 100 manufactured in the above manner can be applied to, for example, an organic EL display of a passive driving method, or an organic EL display of an active driving method.

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

[Example]

Hereinafter, the present invention will be specifically described by showing examples. The invention is not limited by these descriptions.

(Synthesis Example 1: Synthesis of DPP pigment (D1))

To the reaction vessel, under a nitrogen atmosphere, 35 ml of third amyl alcohol and 2.5 parts by mass of sodium were added, and the mixture was stirred while being reacted at 100°C to produce the corresponding alcoholate, and then, at 90°C Add 2.6 parts by mass of benzonitrile. Then, 8.4 parts by mass of the compound represented by the following chemical formula (2) obtained by the method of Tetrahedron, 58 (2002) 5547-5565 was added to 35 ml of third amyl alcohol to prepare a slurry at 90°C The mixture was added to the reaction vessel at a constant speed while stirring for 30 minutes. After stirring it at 90°C for 18 hours, 136 parts by mass of ice/water, 27 parts by mass of methanol, 6.6 parts by mass of sulfuric acid (97%), and the implementation according to the specification of European Patent No. 0485337 over 50 minutes A mixture of 5 parts by mass of a 10% aqueous suspension of the product obtained in Example 2 was transferred to while stirring to 0°C in advance. At this time, adjust so that the temperature does not exceed 3°C. Thereafter, the mixture was further stirred at 0°C for 3 hours to complete the reaction. After filtering the reaction mixture with a suction funnel, it was washed with 200 ml of methanol and 500 ml of water, and dried to obtain a red solid. The obtained red solid was identified as a pyrrolopyrrole dione-based pigment represented by the above chemical formula (D1) based on the results of mass spectrometry using Time-Of-Flight Mass Spectrometry (TOF-MS).

[Chem 16]

(Synthesis Example 2: Preparation of azo derivative 1)

To 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. Then, potassium hydroxide aqueous solution was used so that it might become azobarbituric acid (0.3 mol), and it mixed with 750 mass parts of distilled water. By dropwise addition, 5 parts by mass of 30% hydrochloric acid was added. Thereafter, 38.7 parts by mass of melamine was introduced. Next, a nickel chloride solution of 0.60 mol was added and stirred at a temperature of 80°C for 8 hours. The pigment was separated by filtration, washed, dried at 120°C, and ground with a mortar to obtain an azo derivative 1.

(Synthesis Example 3: Preparation of azo derivative 2)

In Synthesis Example 2, 0.3 mole nickel chloride solution and 0.3 mole zinc chloride solution were used instead of 0.60 mole nickel chloride solution, except that the azo derivative was obtained in the same manner as in Synthesis Example 2. Article 2 (Ni:Zn=50:50 (mole ratio) azo pigment).

(Synthesis Example 4: Synthesis of precipitation inhibiting compound I)

After drying a 500 ml four-neck separable flask under reduced pressure, Ar (argon) was replaced. While flowing into Ar, add 100 parts by mass of dehydrated tetrahydrofuran (THF), 2.0 parts by mass of methyltrimethylsilyldimethylketene acetal, and 1M of tetrabutylammonium-3-chlorobenzoate (TBACB) Acetonitrile solution 0.15ml, mesitylene 0.2 parts by mass. Using a dropping funnel, 34.57 parts by mass of 2-(perfluorohexyl)ethyl methacrylate (FOEMA) was added dropwise thereto over 45 minutes. Since the reaction generates heat, the temperature is kept below 40°C by performing ice bath cooling. After 1 hour, 17.62 parts by mass of 1-adamantyl methacrylate (1-ADMA) was added dropwise over 15 minutes. After allowing to react for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain precipitation inhibitor compound I as a block copolymer. The weight average molecular weight of the precipitation suppression compound I determined by GPC measurement (NMP LiBr 10 mM) was 4,600.

By using thermal decomposition gas chromatography mass spectrometry (GCMS, Gas Chromatography Mass Spectrometry), Fourier transform infrared spectroscopy (FT-IR, Fourier Transform Infrared Radiation), ¹ H-NMR ¹³ C-NMR, and GPC, the obtained precipitation suppression Compound I was analyzed, and in precipitation inhibition compound I, it was confirmed that there was a structural unit derived from FOEMA and a structural unit derived from 1-ADMA, and it was confirmed that the structural unit derived from FOEMA and the structural unit derived from 1-ADMA The ear ratio is 1:6.

(Synthesis Example 5: Synthesis of Precipitation Inhibiting Compound II)

In Synthesis Example 4, dicyclopentyl methacrylate (DCPMA) (FA-513M manufactured by Hitachi Chemical Co., Ltd.) was used instead of 1-adamantyl methacrylate, except that it was the same as Synthesis Example 4. To obtain precipitation inhibition compound II. The weight average molecular weight of the precipitation inhibitory compound II determined by GPC measurement (NMP LiBr 10 mM) was 4,500.

By analyzing the obtained precipitation-inhibiting compound II by thermal decomposition GCMS, FT-IR, ¹ H-NMR, ¹³ C-NMR and GPC, in the precipitation-inhibiting compound II, it is confirmed that the constituent unit and source derived from FOEMA From the constituent unit of DCPMA, it was confirmed that the molar ratio of the constituent unit derived from FOEMA to the constituent unit derived from DCPMA was 1:6.

(Synthesis Example 6: Synthesis of Dispersant I)

After drying a 500 ml four-neck separable flask under reduced pressure, Ar (argon) was replaced. While flowing into Ar, add 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyltrimethylsilyldimethylketene acetal, and 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) , 0.2 parts by mass of mesitylene. Using a dropping funnel, 36.7 parts by mass of methyl methacrylate (MMA) was added dropwise thereto over 45 minutes. Since the reaction generates heat, the temperature is kept below 40°C by performing ice bath cooling. After 1 hour, 13.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After allowing to react for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain a block copolymer. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,600, and the amine value was 95 mgKOH/g.

In a 100 mL round bottom flask, in 29.35 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 29.35 parts by mass of the block copolymer obtained above was dissolved, and phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) 3.17 was added A mass part (0.20 mole relative to 1 mole of DMMA unit of the block copolymer) was stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining a salt type block copolymer (dispersant I) solution. Specifically, the amine value after salt formation is calculated as follows.

To the NMR sample tube, 9 parts by mass of the above salt-type block copolymer (solid matter after reprecipitation) and 1 part by mass of the resulting solution for 91 parts by mass of chloroform-D1NMR were mixed, and a nuclear magnetic resonance device (manufactured by Nippon Electronics Co., Ltd., FTNMR, JNM-AL400), and the ¹³ C-NMR spectrum was measured under the conditions of room temperature and a cumulative number of 10,000 times. Among the obtained spectral data, the nitrogen portion (amine group) at the terminal is based on the integral value of the carbon atom peak adjacent to the nitrogen atom that has not undergone salt formation and the carbon atom peak adjacent to the nitrogen atom that has undergone salt formation. The ratio is calculated by calculating the ratio of the number of amine groups for salt formation to the total number of amine groups, and it is confirmed that one acid group of each phenylphosphonic acid and the nitrogen portion at the end of the DMMA of the block copolymer form a salt.

From the amine value of 95 mgKOH/g before salt formation minus the amine value of 0.02 mole fraction of the DMMA unit (19 mgKOH/g), the amine value after salt formation was calculated as 76 mgKOH/g.

(Synthesis Example 7: Synthesis of alkali soluble resin I solution)

Under nitrogen flow at 100°C, 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 2,2 3 parts by mass of'-azobisisobutyronitrile (AIBM) was added dropwise to a polymerization tank to which 150 parts by mass of PGMEA was added. 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 7000.

Next, by adding 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol to the obtained polymer solution, at 110°C Under heating for 10 hours, the reaction of the carboxyl group of the main chain methacrylic acid and the epoxy group of GMA is carried out. During the reaction, in order to prevent the polymerization of GMA, air was passed into the reaction solution. Furthermore, the reaction is tracked by measuring the acid value of the solution. The obtained alkali-soluble resin I is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of BzMA with MMA and MAA using GMA. The solid content of the alkali-soluble resin I solution is 40% by mass, 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

The dispersant I solution obtained in Synthesis Example 6 as a dispersant was 8.8 parts by mass, and CI Pigment Red 291 (manufactured by CINIC Chemicals, product name Cinilex DPP Red MT-CF) as a color material was 11.94 parts by mass, Synthesis Example 1 0.06 parts by mass of the DPP pigment (D1) obtained in the above, 11.3 parts by mass of the alkali-soluble resin I solution obtained in Synthesis Example 7, 67.6 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a diameter of 2.0 mm were added to the mayonnaise bottle , Shake with a paint shaker (manufactured by Asada Iron Works) for 1 hour as pre-crushing, and then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly perform with a paint oscillator Dispersion for 4 hours was regarded as formal disintegration, and color material dispersion liquid R1 was obtained.

(2) Manufacture of colored resin composition R1

啉基苯基)-1-丁酮(光起始劑、商品名「Irgacure 369」、BASF公司製造)0.86質量份、3-環戊基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-丙酮1-(O-乙醯肟)(肟酯系光聚合起始 劑、商品名「TR-PBG-304」常州強力電子新材料公司製造)0.58質量份、PGMEA 9.10質量份，而獲得具有感光性之著色樹脂組成物R1。 Add 59.40 parts by mass of the color material dispersion liquid R1 obtained in (1) above, 4.83 parts by mass of the alkali-soluble resin I solution obtained in Synthesis Example 7, a photopolymerizable compound (trade name "ARONIX M-520D", East Asia Synthesis 5.28 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-1-butanone (photoinitiator, trade name "Irgacure 369", manufactured by BASF) 0.86 parts by mass, 3-cyclopentyl-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-1-acetone 1-(O-acetamido oxime) (oxime ester-based photopolymerization initiator, trade name "TR-PBG-304" Changzhou 0.58 parts by mass, PGMEA 9.10 parts by mass, to obtain a coloring resin composition R1 having photosensitivity.

(3) Formation of colored layer

On a glass substrate (trade name "NA35", manufactured by NH TECHNO GLASS) with a thickness of 0.7 mm and 100 mm x 100 mm, the film thickness after the subsequent baking is 2.2 μm and applied in the above (2) using a spin coater The obtained coloring resin composition R1 was dried under reduced pressure, heated at 80°C for 3 minutes using a hot plate, and dried to form a coating film. Then, ultraviolet light of 60 mJ/m ^{2 was} irradiated from the coating film side with a high-pressure mercury lamp, thereby performing exposure. After that, development was carried out for 60 seconds using a developing solution at a temperature of 23° C. and a KOH concentration of 0.05%, and further heated at 230° C. for 30 minutes in an oven for post-baking to form a colored layer.

<Examples 2-9, Comparative Examples RC1~RC6>

(1) Manufacturing of color material dispersion liquids R2~R9, color material dispersion liquids RC1~R6

In Examples 2 to 5, in the manufacture of the above-mentioned (1) color material dispersion liquid R1 in Example 1, the blending amount of CI Pigment Red 291 and the blending amount of DPP pigment (D1) were changed to Table 1. Except for the indicated amount (parts by mass), in the same manner as in the above (1) of Example 1, color material dispersion liquids R2 to R5 were obtained.

In Examples 6 to 9, in the manufacture of the above-mentioned (1) color material dispersion liquid R1 in Example 1, the formulation amount of CI Pigment Red 291 and the formulation amount of DPP pigment (D1) were changed to Table 2 respectively. The amount shown (parts by mass), and further, the amount (parts by mass) shown in Table 2 was prepared CI Pigment Red 254 (PR254, trade name: Hostaperm Red D2B-COF LV3781, CLARIANT), CI Pigment Red 264 (PR264, Trade name: SR6T, manufactured by CINIC Chemicals), the azo derivative 1 obtained in Synthesis Example 2, or the azo derivative 2 obtained in Synthesis Example 3, other than the above (1 ) In the same way, color material dispersions R6 to R9 are obtained.

In Comparative Example 1, in the production of the above-mentioned (1) color material dispersion liquid R1 of Example 1, the DPP pigment (D1) was not added, and the formulation amount of CI Pigment Red 291 was changed to 12.0 parts by mass. In the same manner as in the above (1) of Example 1, a color material dispersion liquid RC1 was obtained.

In Comparative Example 2, in the production of the above-mentioned (1) color material dispersion liquid R1 of Example 1, CI Pigment Red 291 was not added, and the formulation amount of the DPP pigment (D1) was changed to 12.0 parts by mass. In the same manner as in (1) above in Example 1, a color material dispersion liquid RC2 was obtained.

In Comparative Examples 3 to 6, in the production of the above-mentioned (1) color material dispersion liquid R1 of Example 1, the color material shown in Table 2 was prepared in the amount (parts by mass) shown in Table 2 instead of CI Pigment Red 291 Except for 11.94 parts by mass and 0.06 parts by mass of DPP pigment (D1), in the same manner as in (1) of Example 1, color material dispersion liquids RC3 to RC6 were obtained.

(2) Manufacture of colored resin compositions R2 to R9 and colored resin compositions RC1 to RC6

In the production of the above (2) colored resin composition R1 in Example 1, the color material dispersion liquids R2 to R9 and the color material dispersion liquids RC1 to RC6 obtained above were used instead of the color material dispersion liquid R1, respectively In the same manner as in the above (2) of Example 1, colored resin compositions R2 to R9 and coloring resin compositions RC1 to RC6 were obtained.

(3) Formation of colored layer

In the formation of the above-mentioned (3) colored layer in Example 1, the colored resin compositions R2 to R9 and the coloring resin compositions RC1 to RC6 were used instead of the colored resin composition R1. In the same manner as in (3) above, a colored layer is formed.

<Examples 10-12>

In Example 3, at the time of production of the colored resin composition R3, in Example 10, further addition of the precipitation inhibiting compound I obtained in Synthesis Example 4 was 0.02 parts by mass, and in Example 11 was further added in Synthesis Example 5. The obtained precipitation suppression compound I was 10.02 parts by mass, and in Example 12, 0.02 parts by mass was further added to the precipitation suppression compound III (MEGAFAC F575, fluorine-containing carbon group and cross-linked cyclic aliphatic group compound, manufactured by DIC), Except for this, in the same manner as in Example 3, colored resin compositions R10 to R12 were obtained. In addition, when forming the colored layer, the obtained colored resin compositions R10 to R12 were used instead of the colored resin composition R3, respectively, and the colored layer was formed in the same manner as in Example 3.

<Example 13>

(1) Manufacture of color material dispersion R13

In the production of the above-mentioned (1) color material dispersion liquid R1 in Example 1, the blending amount of CI Pigment Red 291 was changed to 6.84 parts by mass, and the blending amount of DPP pigment (D1) was changed to 0.36 parts by mass, and further, the blending Except for CI Pigment Red 177 (PR177, trade name: CHROMOFINE RED 6121EC, manufactured by Dairi Seiki) 4.8 parts by mass, in the same manner as in (1) of Example 1, color material dispersion R13 was obtained.

(2) Manufacture of colored resin composition R13

In the manufacture of the above-mentioned (2) colored resin composition R1 of Example 1, the color material dispersion liquid R13 obtained above was used in place of the color material dispersion liquid R1, except that it was the same as the above-mentioned (2) of Example 1. In this way, the colored resin composition R13 was obtained.

(3) Formation of colored layer

In the formation of the above-mentioned (3) colored layer in Example 1, the colored layer was formed in the same manner as in the above-mentioned (3) of Example 1 except that the colored resin composition R13 was used instead of the colored resin composition R1.

<Example 14>

In Example 13, the coloring resin was obtained in the same manner as in Example 13 except that 0.02 parts by mass of the precipitation suppression compound I obtained in Synthesis Example 4 was further added during the production of the colored resin composition R13. Composition R14. In addition, when forming the colored layer, the colored layer was formed in the same manner as in Example 13 except that the colored resin composition R14 was used instead of the colored resin composition R13.

<Example 15>

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

<Comparative Example 7>

In Comparative Example 1, at the time of manufacturing the colored resin composition RC1, 0.02 parts by mass of Comparative Compound IV (MEGAFAC F444, perfluoroalkyl ethylene oxide adduct, manufactured by DIC Corporation) was further added, in addition to The colored resin composition RC7 was obtained in the same manner as in Comparative Example 1. In addition, when forming the colored layer, the colored layer was formed in the same manner as in Comparative Example 1 except that the colored resin composition RC7 was used instead of the colored resin composition RC1.

<Evaluation of optical characteristics>

The chromaticity (x, y), brightness (Y) and contrast of the coloring layer formed in each example and each comparative example were measured. In addition, the chromaticity (x, y) and brightness were measured using the "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd., and the contrast was measured using the "contrast measuring device CT-" manufactured by TSUBOSAKA ELECTRIC Co., Ltd. 1B". The light source system uses a C light source.

Tables 1 and 3 show the measurement results of chromaticity (x, y) of each example and each comparative example.

In addition, Tables 1 to 3 show the measurement results of the brightness (Y) and the evaluation results of the contrast in each example and each comparative example.

The contrast was evaluated by the following evaluation criteria.

(Contrast evaluation criteria)

AAA: More than 95% relative to the target value

AA: Relative to the target value of 93% or more and less than 95%

A: Relative to the target value of 90% or more and less than 93%

B: Relative to the target value of 85% or more and less than 90%

C: Less than 85% relative to the target value

<precipitation evaluation>

The surface of the coloring layer produced in each example and each comparative example was observed with an optical microscope (product name "MX61L", manufactured by OLYMPUS) to confirm whether there was precipitation of a compound derived from a color material. The magnification was set to 100 times, and within the range of 500 μm×500 μm, the number of observable precipitates was measured by penetration measurement, and evaluated by the following evaluation criteria. The evaluation results are shown in Tables 1 to 3.

(Precipitation evaluation criteria)

AAA: 0 (very good)

AA: 1 or more and 3 or less (good)

A: 4 or more and 10 or less (levels with no problem in use)

B: 11 or more and 20 or less (a little precipitation can be observed, but there is no problem with the grade of use)

C: 21 or more and 100 or less (use problems)

D: more than 101 (there is a problem in use)

[Table 1]

[Table 2]

[table 3]

The "DPP pigment (D1) ratio (mass %)" in the table is the ratio (mass of DPP pigment (D1) in 100% by mass of the total of CI Pigment Red 291 and the DPP pigment (D1) obtained in Synthesis Example 1 %).

In addition, each abbreviation in the table is as follows.

‧PR291: C.I. Pigment Red 291 (trade name: Cinilex DPP Red MT-CF, manufactured by CINIC Chemicals)

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

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

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

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

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

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

[Summary of results]

The coloring resin composition of Examples 1 to 15 included in combination with CI Pigment Red 291 (PR291) and the pyrrolopyrrole dione pigment (DPP pigment (D1)) represented by the above chemical formula (D1) can form an inhibitor A coloring layer that suppresses the reduction of brightness and contrast due to the precipitation of compounds from color materials.

As shown in Table 1, Examples 1 to 5 containing PR291 and DPP pigment (D1) as a color material in combination with Comparative Example 1 containing only PR291 as a color material and Comparative Example containing only DPP pigment (D1) as a color material Compared with any of 2, the precipitation of compounds derived from color materials is also suppressed, and the brightness and contrast are improved. Among them, in the total 100% by mass of PR291 and DPP pigment (D1), the ratio of DPP pigment (D1) in the range of 1% by mass or more and 30% by mass or less in Examples 2 to 4 is compared with Examples 1 and 5 In addition, the precipitation of compounds derived from the color material is suppressed, and the brightness and contrast of the colored layer are further improved.

Furthermore, as shown in Table 2, even if pyrrolopyrrolodione-based pigments such as PR254 or PR264 are further included as color materials, Examples 6, 7 including PR291 and DPP pigment (D1) are combined with PR291 or DPP pigment (D1) ) Compared with Comparative Examples 3 to 6 of at least any one, the precipitation of compounds derived from the color material is also suppressed, and the brightness and contrast are improved. Furthermore, Example 6 and Comparative Examples 3 to 5, and Example 7 and Comparative Example 6 have the same chromaticity (x, y) values, but if the examples and the chromaticity (x, y) have the same value, Comparing the comparative examples, any of the examples has high brightness and the contrast is also improved.

Examples 8 and 9 include PR291 and DPP pigment (D1) as a color material, and further include azo derivative 1 or azo derivative 2 as the yellow color material (D2) as a yellow color material, thereby suppressing the source The precipitation of compounds from color materials also suppresses the decrease in brightness and contrast. Among them, in Example 9 using the azo derivative 2 containing ions of two specific metals as the yellow color material (D2), the brightness of the colored layer is improved.

In addition, as shown in Table 3, Examples 10 to 12 including PR291 and DPP pigment (D1) in combination as a color material, and further containing a precipitation suppressing compound, further suppressed the color-derived origin as compared to Example 3 containing no precipitation suppressing compound. The precipitation of the material compounds further improves the brightness and contrast. In addition to the precipitation inhibiting compound, Example 15 which further contained a thiol compound further suppressed the precipitation of the compound derived from the color material. On the other hand, in Comparative Example 7, Comparative Compound IV (trade name: MEGAFAC F444, perfluoroalkyl ethylene oxide adduct, manufactured by DIC Corporation) was used, but it was in phase with Comparative Example 1 where Comparative Compound IV was not used In contrast, it is impossible to suppress the precipitation of the compound derived from the color material, nor the decrease in brightness and contrast.

In addition, in Example 13 in which PR291 and DPP pigment (D1) were combined as a color material, and CI Pigment Red 177 (PR177) as an anthraquinone-based pigment was also combined, the precipitation of the compound derived from the color material was also suppressed and the brightness was suppressed And the reduction of contrast. In addition to PR177, Example 14 further containing a precipitation suppressing compound further suppresses the precipitation of the compound derived from the color material, and further suppresses the decrease in brightness and contrast.

Claims (12)

A coloring resin composition comprising: a polymer (A), a polymerizable compound (B), a polymerization initiator (C), and a color material (D), and The color material (D) includes C.I. Pigment Red 291 and a pyrrolopyrrole dione pigment represented by the following chemical formula (D1),

The coloring resin composition according to claim 1, wherein in the total 100% by mass of the above-mentioned CI Pigment Red 291 and the pyrrolopyrrole-based pigment represented by the above-mentioned chemical formula (D1), the pyrrole represented by the above-mentioned chemical formula (D1) The ratio of the pyrrolidinedione pigment is 1% by mass or more and 30% by mass or less. The coloring resin composition according to claim 1 or 2, which further includes a compound (E) having a fluorocarbon group and a cross-linked cycloaliphatic group. The coloring resin composition according to claim 1 or 2, wherein the carbon number of the fluorocarbon group in 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 in the compound (E) may have an adamantyl group having a substituent, or a dicyclopentyl group having a substituent. The coloring resin composition according to claim 1 or 2, wherein the compound (E) includes a structural unit derived from the compound (E-1) having the above fluorocarbon group and an ethylenically unsaturated group, and A copolymer of constituent units of a compound (E-2) that crosslinks a cyclic aliphatic group and an ethylenically unsaturated group. The coloring resin composition according to claim 1 or 2, wherein the color material (D) further includes a yellow color material, the yellow color material comprising: an azo compound represented by the following general formula (I) and its mutual variation At least one anion selected by the group consisting of mono-, di-, tri-, and tetra anions of the structured azo compounds, composed of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn At least one metal ion selected from the group consisting of, and a compound represented by the following general formula (II),

In (Formula (I), R ^a each independently _{-OH, -NH 2, -NH-CN} , acyl group, alkyl group or aryl group, R ^b are independently -OH or -NH ₂ )

(In the general formula (II), R ^{c is} independently a hydrogen atom or an 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 which is a hardened product of the coloring resin composition of any one of claims 1 to 9. A color filter comprising at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a hardened product of the coloring resin composition according to any one of claims 1 to 9. A display device having the color filter of claim 11.

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