CN116203799A - Colored curable resin composition, cured film of colored curable resin composition, and display device - Google Patents

Colored curable resin composition, cured film of colored curable resin composition, and display device Download PDF

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CN116203799A
CN116203799A CN202211490090.8A CN202211490090A CN116203799A CN 116203799 A CN116203799 A CN 116203799A CN 202211490090 A CN202211490090 A CN 202211490090A CN 116203799 A CN116203799 A CN 116203799A
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group
resin composition
curable resin
colored curable
carbon atoms
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星隼人
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)
  • Electroluminescent Light Sources (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The invention relates to a colored curable resin composition, a cured film of the colored curable resin composition, and a display device. The present invention provides a colored curable resin composition which can provide a color filter and has sufficient curability, wherein the color filter can provide an organic EL display device which can provide a sufficiently good field of view even when viewed from an oblique direction. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein X is 4 or more, Y is 15 or less, and a value a calculated from formula (1) is 10 or more, when the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass% based on the scattering intensity of Mie scattering of the inorganic fine particles. a=x×y (1).

Description

Colored curable resin composition, cured film of colored curable resin composition, and display device
Technical Field
The invention relates to a colored curable resin composition, a cured film of the colored curable resin composition, and a display device.
Background
An organic Electroluminescence (EL) display device is, for example, a display device including an organic EL film formed on a substrate, the organic EL film including: a hole transport layer, a light emitting layer that emits, for example, red (R), green (G), blue (B) light for forming each pixel, and an electron transport layer. In the organic EL device, a voltage is applied to electrodes at both ends of an organic EL film to cause electrons to flow from a cathode to the organic EL film, holes to flow from an anode to the organic EL film, and light-emitting molecules of a light-emitting layer recombine with the electrons and holes, whereby the light-emitting molecules emit light. In order to increase the intensity of each emitted color light, a microcavity structure is employed in which the optical path length between the upper and lower electrodes is matched to the wavelength of each color light. By using the microcavity structure, the spectrum of light extracted to the outside can be made steep and high-intensity by utilizing the resonance effect of light between the electrodes, and the brightness and color purity of each color of RGB can be improved.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-33963
Disclosure of Invention
In particular, in the organic EL display device having the organic EL film with the microcavity structure, as described above, since the spectrum of light extracted to the outside becomes steep and high-intensity, the intensity and color development of the color can be improved, but there are cases where a sufficient field of view is not obtained when the display device is viewed obliquely. Further, as in patent document 1, it has been studied to manufacture a color filter using a resin composition containing organic fine particles for achieving a sufficient field of view, but if organic fine particles are added, sufficient curability may not be obtained in manufacturing a color filter from the resin composition, and it may be difficult to form a pattern of a predetermined resolution.
Accordingly, an object of the present invention is to provide a colored curable resin composition which can provide a color filter capable of providing a sufficiently good field of view even when viewed obliquely, and which has sufficient curability.
The present inventors have found that the above object can be achieved by the curable resin composition of the present invention described below. That is, the present invention includes the following aspects.
[ 1 ] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and inorganic fine particles, wherein X is 4 or more, Y is 15 or less, and the value a calculated from the formula (1) is 10 or more, when X is the scattering intensity of Mie scattering of the inorganic fine particles and Y is the content of the inorganic fine particles relative to the solid content of the colored curable resin composition.
a＝X×Y (1)
The colored curable resin composition according to [ 2 ], wherein the inorganic fine particles are metal oxides.
The colored curable resin composition according to [ 1 ] or [ 2 ], wherein the inorganic fine particles have a refractive index of 1.3 or more.
The colored curable resin composition according to any one of [ 1 ] to [ 3 ], wherein the inorganic fine particles have an average particle diameter of 0.05 μm to 0.70 μm.
The colored curable resin composition according to any one of [ 1 ] to [ 4 ], wherein the content of the polymerizable compound is 0 to 50% by mass relative to the solid content of the colored curable resin composition.
The colored curable resin composition according to any one of [ 1 ] to [ 5 ], wherein a haze value of a cured film of the curable resin composition is 8 to 40% in terms of a thickness of 2. Mu.m.
A cured film of the colored curable resin composition according to any one of [ 7 ] [ 1 ] to [ 6 ].
The cured film according to [ 7 ], wherein the cured film has a haze value of 8 to 40% in terms of a thickness of 2. Mu.m.
The cured film according to [ 7 ] or [ 8 ], which constitutes a color filter included in a color filter substrate.
A display device comprising the cured film of any one of [ 7 ] to [ 9 ].
According to the present invention, a colored curable resin composition having sufficient curability and capable of providing a color filter capable of providing an organic EL display device having a sufficiently good field of view even when viewed obliquely can be provided.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications may be made without departing from the scope of the present invention. When a plurality of upper and lower limits are described for a specific parameter, any of the upper and lower limits may be combined to an appropriate value range.
< coloring curable resin composition >
The colored curable resin composition of the present invention comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein X is 4 or more, Y is 15 or less, and a value a calculated from the formula (1) is 10 or more, when the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass%.
a＝X×Y (1)
Hereinafter, the colored curable resin composition of the present invention is also referred to as the composition of the present invention.
(inorganic particles)
The colored curable resin composition of the present invention contains at least 1 kind of inorganic fine particles. In the present specification, the inorganic fine particles are inorganic particles having an average particle diameter of usually 10 μm or less. The average particle diameter of the inorganic fine particles is not particularly limited as long as it is 10 μm or less, and may be a micrometer-sized average particle diameter or a nanometer-sized average particle diameter. The average particle diameter of the inorganic fine particles is preferably 1 μm or less, more preferably 0.70 μm or less. The composition of the present invention may contain 1 kind of inorganic fine particles, or may contain 2 or more kinds of inorganic fine particles. Here, when the scattering intensity of the mie scattering of the inorganic fine particles is X and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass%, X is 4 or more, Y is 15 or less, and the value a calculated from the formula (1) is 10 or more.
a＝X×Y (1)
The scattering intensity X of Mie scattering of the inorganic fine particles is a value calculated under the conditions of unpolarized light, light source wavelength of 550nm, and scattering angle of 0 degrees, and can be calculated by using, for example, a Mieplot (see http:// www.philiplaven.com/mieAN. Htm) which is a calculation program of the scattering intensity of Mie scattering. The larger the scattering intensity X, the higher the effect of light scattering. When the scattering intensity X is less than 4, the effect of light scattering by the inorganic fine particles becomes insufficient, and it is difficult to sufficiently secure a visual field when the organic EL display device is viewed obliquely. The scattering intensity of the inorganic fine particles contained in the composition of the present invention is 4 or more from the viewpoint of securing visibility when the organic EL display device is viewed obliquely. The value of the scattering intensity X is 4 or more, preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more, from the viewpoint of easy improvement of visibility of the organic EL display device. In addition, when the value of X is large, visibility when the organic EL display device is viewed obliquely and curability when a color filter is formed from the composition of the present invention are also easily improved. The upper limit of the scattering intensity X is not particularly limited, but is preferably 10000 or less, more preferably 1000 or less, further preferably 300 or less, and further preferably 100 or less from the viewpoint of controlling the interface reflection.
The content (Y mass%) of the inorganic fine particles with respect to the solid content of the colored curable resin composition is 15 mass% or less. When the content of the inorganic fine particles exceeds 15 mass%, it is difficult to improve the curability when forming a color filter from the colored curable resin composition, and the strength of the color tone in the obtained color filter is also easily lowered. The content (Y mass%) of the inorganic fine particles with respect to the solid content of the colored curable resin composition is preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 8 mass% or less, and still more preferably 6 mass% or less, from the viewpoints of curability at the time of forming the color filter and color development of the color filter.
The scattering intensity (X) of Mie scattering of the inorganic fine particles and the content (Y mass%) of the inorganic fine particles relative to the solid content of the colored curable resin composition are calculated according to the formula (1), and the value a is 10 or more.
a＝X×Y (1)
When the value a is less than 10, the effect of light scattering by the inorganic fine particles becomes insufficient, and it becomes difficult to provide a sufficient field of view when the organic EL display device is viewed obliquely. The value a is preferably 15 or more, more preferably 20 or more, and even more preferably 25 or more, from the viewpoint of easy improvement of visibility when the organic EL display device is viewed obliquely. From the viewpoint of controlling the interface reflection, it is preferably 800 or less, more preferably 600 or less, further preferably 450 or less, and further preferably 350 or less.
Examples of the inorganic fine particles include inorganic fine particles such as metals, metal oxides, ceramics, and composite materials, and the inorganic fine particles are preferably metal oxides from the viewpoint of scattering strength. The composition of the present invention may contain 1 kind of inorganic fine particles, or may contain 2 or more kinds of inorganic fine particles. The inorganic fine particles may be subjected to surface treatment. By surface-treating the inorganic fine particles, dispersibility in the resin composition is improved, and aggregation of the inorganic fine particles is easily prevented. Examples of the surface treatment that can be performed on the inorganic fine particles include treatment with a silane coupling agent, a silylating agent, an organic titanate coupling agent, a silicone oil, and the like.
Examples of the metal oxide include silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, cerium oxide, and the like. The metal oxide is preferably titanium oxide, zinc oxide and/or silicon dioxide, more preferably titanium oxide and/or silicon dioxide, and still more preferably titanium oxide. When the composition of the present invention contains a metal oxide as the inorganic fine particles, the composition may contain 1 metal oxide or 2 or more metal oxides.
The refractive index of the inorganic fine particles is preferably 1.3 or more, more preferably 1.9 or more, still more preferably 2.2 or more, and still more preferably 2.5 or more, from the viewpoint of scattering intensity. In addition, from the viewpoint of controlling the interface reflection, the refractive index of the inorganic fine particles is preferably 2.8 or less. The refractive index can be measured by an ellipsometer, for example.
The average particle diameter of the inorganic fine particles is preferably 0.05 μm or more, more preferably 0.10 μm or more, still more preferably 0.13 μm or more, and still more preferably 0.15 μm or more, from the viewpoint of scattering intensity. The average particle diameter of the inorganic fine particles is preferably 0.70 μm or less, more preferably 0.50 μm or less, further preferably 0.30 μm or less, further preferably 0.25 μm or less, and particularly preferably 0.20 μm or less, from the viewpoint of suppressing particle sedimentation. The average particle diameter can be measured by, for example, a dynamic light scattering method.
(resin)
The resin contained in the composition of the present invention is not particularly limited, but is preferably an alkali-soluble resin. The composition of the present invention may contain 1 resin or 2 or more resins. Examples of the resins include the following resins [ K1] to [ K6 ].
Resin [ K1]: a copolymer having a structural unit derived from at least 1 (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
resin [ K2]: copolymers having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (wherein the structural unit is different from (a) and (b) (hereinafter, sometimes referred to as "(c)");
resin [ K3]: a copolymer having structural units derived from (a) and structural units derived from (c);
resin [ K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);
resin [ K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);
resin [ K6]: a copolymer comprising a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or carboxylic anhydride, and a structural unit derived from (c).
Specific examples of (a) include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;
carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride;
unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as mono- [ 2- (meth) acryloyloxyethyl ] succinate and mono- [ 2- (meth) acryloyloxyethyl ] phthalate;
Unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.
Among them, acrylic acid, methacrylic acid, and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.
(b) Refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an ethylene oxide ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. As (b), monomers having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group are preferable.
In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The same meaning applies to the "(meth) acryl" and "(meth) acrylate" and the like.
Examples of (b) include a monomer (b 1) having an oxirane group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 1)"), a monomer (b 2) having an oxetane group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 2)"), a monomer (b 3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 3)"), and the like.
Examples of the (b 1) include a monomer (b 1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-1)") and a monomer (b 1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-2)").
Examples of (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2, 4-tris (glycidoxymethyl) styrene, and the like.
Examples of (b 1-2) include vinylcyclohexene monooxide and 1, 2-epoxy-4-vinylcyclohexane (for example, celloxide 2000, (product of Daicel) and 3, 4-epoxy (meth) acrylate)Cyclohexylmethyl ester (e.g., cyclomer A400; from Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (e.g., cyclomer M100; from Daicel), 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid 2,6 ]Decyl ester, a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.
Figure BDA0003964543160000071
[ formula (BI) and formula (BII), R e And R is f Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X e And X f Represents a single bond, -R g －、*－R g －O－、*－R g -S-or-R g －NH－。
R g Represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents the bonding site to O. ]
Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.
Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group.
As R e And R is f The hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group are preferable, and the hydrogen atom and methyl group are more preferable.
Examples of the alkanediyl group include methylene, ethylene, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.
As X e And X f A single bond, methylene, ethylene, or-CH may be preferably mentioned 2 -O-and-CH 2 CH 2 O-, more preferably a single bond, -CH 2 CH 2 -O- (x) represents a bonding site to O).
As (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.
As (b 3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V#150, manufactured by Osaka organic chemical industry Co., ltd.), tetrahydrofurfuryl methacrylate, and the like.
In the case where the resin [ K1] or the resin [ K2], the resin (b 1) is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be improved.
Examples of the (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo (5.2.1.0) acrylate 2,6 ]Decane-8-yl ester (which is known as dicyclopentyl (meth) acrylate ". Additionally, it is sometimes referred to as tricyclodecyl (meth) acrylate"), [5.2.1.0 ] tricyclo (meth) acrylate, as a conventional name in this technical field) 2,6 ]Decen-8-yl ester (known as "methyl" as a conventional name in this technical field) (meth) acrylic esters such as dicyclopentenyl acrylate "), (meth) dicyclopentenyl ethyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;
hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
bicyclo [2.2.1] hept-2-ene, 5-methylcyclo [2.2.1] hept-2-ene, 5-ethylcyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-diethoxy bicyclo [ 2.1] hept-2-ene, 5-diethoxy [ 2.1] bicyclohexa-2-ene, 5-hydroxy-2.1 ] hept-2-ene, 5-hydroxy-2.1-carbonyl, 5-di (hydroxymethyl) bicyclo [ 2.2.2.1 ] hept-2-ene, 5, 6-di (2.1 ] bicyclooxy-carbonyl-2.1 ] bicyclohept-2-ene, 5-bicyclooxy [ 2.1] hept-2-ene;
Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide;
styrene, alpha-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, and the like.
Among them, (meth) acrylic esters are preferable.
In the resin [ K1], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a), 40 to 98 mol% of the structural units derived from (b), more preferably 10 to 50 mol% of the structural units derived from (a), and 50 to 90 mol% of the structural units derived from (b), among all the structural units constituting the resin [ K1 ].
When the ratio of the structural units of the resin [ K1] is in the above range, the storage stability of the colored curable resin composition, the developability upon forming a pattern, and the solvent resistance of the resulting cured film tend to be excellent.
The resin [ K1] can be produced by, for example, a method described in the literature "experimental method for polymer synthesis" (release by 1 st printing 1972, 3 months and 1 days of the same chemical company, 1 st edition, division of the Ministry of Kagaku Kogyo Co., ltd.) or a cited literature described in the literature.
Specifically, the following method is mentioned: the predetermined amounts of (a) and (b), the polymerization initiator, the solvent, and the like are charged into a reaction vessel, and for example, a deoxidized atmosphere is produced by substituting oxygen with nitrogen, and heating and heat preservation are performed while stirring. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those commonly used in the art can be used. For example, the polymerization initiator may be an azo compound (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), or the like), an organic peroxide (e.g., benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate), or the like, and the solvent may be any solvent as long as it dissolves the monomers, and may be a solvent described below as an organic solvent contained in the colored curable resin composition of the present invention.
The copolymer obtained may be used as it is, a concentrated or diluted solution, or a solid (powder) extracted by a method such as reprecipitation. In particular, when the solvent as described later is used as a solvent in the composition contained in the colored curable resin composition of the present invention in the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, and thus the process for producing the colored curable resin composition of the present invention can be simplified.
In the resin [ K2], the ratio of the structural units derived from each unit is preferably 2 to 45 mol% of the structural units derived from (a), 2 to 95 mol% of the structural units derived from (b), 1 to 65 mol% of the structural units derived from (c), more preferably 5 to 40 mol% of the structural units derived from (a), 5 to 80 mol% of the structural units derived from (b), and 5 to 60 mol% of the structural units derived from (c), among all the structural units constituting the resin [ K2 ].
When the ratio of the structural units of the resin [ K2] is within the above range, there is a tendency that the color curable resin composition is excellent in storage stability, developability upon pattern formation, and solvent resistance, heat resistance and mechanical strength of the obtained cured film.
The resin [ K2] can be produced, for example, in the same manner as described as the method for producing the resin [ K1 ].
In the resin [ K3], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a), 40 to 98 mol% of the structural units derived from (c), more preferably 10 to 50 mol% of the structural units derived from (a), and 50 to 90 mol% of the structural units derived from (c), among all the structural units constituting the resin [ K3 ].
The resin [ K3] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
The resin [ K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or carboxylic anhydride of (a).
First, copolymers of (a) and (c) are produced in the same manner as described in the method for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from each unit is preferably the same ratio as the ratio exemplified for the resin [ K3 ].
Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms of (b).
After the production of the copolymer of (a) and (c), the atmosphere in the flask is then replaced with air from nitrogen, and the reaction catalyst (e.g., tris (dimethylaminomethyl) phenol, triphenylphosphine, etc.) for (b), carboxylic acid or carboxylic anhydride and cyclic ether, and a polymerization inhibitor (e.g., hydroquinone monomethyl ether, etc.) are placed in the flask and reacted at 60 to 130℃for 1 to 10 hours, for example, to produce the resin [ K4].
(b) The amount of (a) to be used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). In this range, there is a tendency that the balance of storage stability of the curable resin composition, developability at the time of forming a pattern, pattern shape, curability at low temperature, and solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern becomes good. Since the cyclic ether has high reactivity and unreacted (b) is not likely to remain, the (b) used in the resin [ K4] is preferably (b 1), and more preferably (b 1-1).
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature, and the time may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. The method of charging and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like, similarly to the polymerization conditions.
As the first stage, the copolymer of (b) and (c) was obtained in the same manner as the above-mentioned method for producing the resin [ K1 ]. As in the above, the copolymer obtained may be used as it is, or may be concentrated or diluted, or may be taken out as a solid (powder) by a method such as reprecipitation.
The ratio of the structural units derived from (b) and (c) is preferably 5 to 95 mol% of the structural units derived from (b) and 5 to 95 mol% of the structural units derived from (c), more preferably 10 to 90 mol% of the structural units derived from (b) and 10 to 90 mol% of the structural units derived from (c), respectively, based on the total mole number of all the structural units constituting the copolymer.
When the ratio of the structural units of the resin [ K5] is in the above range, there is a tendency that the balance of the storage stability of the colored curable resin composition, the developability at the time of forming a pattern, the pattern shape, the curability at low temperature, the solvent resistance, the heat resistance, the mechanical strength and the sensitivity of the obtained pattern becomes good.
Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride of (a) with the cyclic ether of (b) of the copolymer of (b) and (c) under the same conditions as those of the process for producing the resin [ K4 ].
The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 100 moles based on 100 moles of (b). Since the cyclic ether has high reactivity and unreacted (b) is not likely to remain, the (b) used in the resin [ K5] is preferably (b 1), and more preferably (b 1-1).
The resin [ K6] is a resin obtained by further reacting a polycarboxylic acid and/or carboxylic anhydride with the resin [ K5 ]. The polycarboxylic acid and/or carboxylic anhydride is further reacted with a hydroxyl group produced by the reaction of the cyclic ether from (b) with the carboxylic acid or carboxylic anhydride from (a).
Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarballylic acid. Examples of the carboxylic anhydride include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride. The amount of the polycarboxylic acid and/or carboxylic anhydride to be used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, based on 1 mol of the amount of (a) to be used.
The resin contained in the colored curable resin composition of the present invention is preferably a resin having a structural unit having an ethylenically unsaturated bond in a side chain (resin [ K4] or resin [ K5 ]), and more preferably a resin having a structural unit having a (meth) acryloyl group in a side chain.
As the resin having a structural unit having a (meth) acryloyl group in a side chain, for example, a resin [ K4] using a monomer having a (meth) acryloyl group such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-methacryloyloxymethyl oxetane, tetrahydrofurfuryl acrylate or the like as (b) and a resin [ K5] using a monomer having a (meth) acryloyl group such as acrylic acid, methacrylic acid, succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester or the like as (a) are preferable.
Among the resins [ K4] and [ K5], as (c), dicarbonyl imide derivatives and vinyl toluene are preferable.
The weight average molecular weight of the resin contained in the colored curable resin composition of the present invention in terms of polystyrene is preferably 3000 to 100000, more preferably 4000 to 50000, and even more preferably 5000 to 30000. When the weight average molecular weight of the resin is within the above range, the cured film of the composition of the present invention tends to have high hardness, high residual film ratio, good solubility of the unexposed portion in a developer, improved pattern shape, and improved pattern resolution.
The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin is preferably 1.1 to 6, more preferably 1.2 to 4.
The acid value of the resin is preferably 10 to 170mg-KOH/g, more preferably 20 to 150mg-KOH/g, still more preferably 30 to 135mg-KOH/g, in terms of solid content. The acid value is a value obtained by measuring the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.
The content of the resin is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total amount of the solid components of the colored curable resin composition. When the resin content is within the above range, the curability of the colored curable resin composition tends to be easily improved, patterns tend to be easily formed, and the resolution of the patterns and the film residue ratio tend to be improved. In the present specification, the term "total amount of solid components" means an amount obtained by removing the solvent content from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.
(polymerizable Compound)
The polymerizable compound is a compound capable of polymerizing by using a living radical and/or an acid generated by a polymerization initiator, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like, and is preferably a (meth) acrylate compound.
Among them, the polymerizable compound is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate.
Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable from the viewpoint of pattern shape.
The weight average molecular weight of the polymerizable compound is preferably 150 to 2900, more preferably 250 to 1500, from the viewpoints of easy improvement of the pattern shape and easy adjustment of the curability of the colored curable resin composition to an appropriate range.
The content of the polymerizable compound is preferably 3% by mass or more, more preferably 6% by mass or more, further preferably 9% by mass or more, and still further preferably 12% by mass or more, relative to the total amount of the solid components contained in the colored curable resin composition. The content of the polymerizable compound is preferably 50% by mass or less, more preferably 46% by mass or less, further preferably 43% by mass or less, and further preferably 40% by mass or less, based on the total amount of the solid components contained in the colored curable resin composition. When the content of the polymerizable compound is not less than the lower limit, the curability of the colored curable resin composition is easily improved, and a pattern is easily formed. When the content of the polymerizable compound is not more than the upper limit, the coating film of the colored curable resin composition is exposed to light and cured, whereby the degree of curing in the coating film is less likely to vary, and particularly, the coating film can be sufficiently cured to the deep portion of the coating film, and a good pattern shape is easily obtained.
The content of the polymerizable compound is preferably 50 mass% or less, more preferably 47 mass% or less, further preferably 45 mass% or less, further preferably 43 mass% or less, based on 100 mass% of the total of the mass of the resins (preferably alkali-soluble resins, more preferably the resins [ K1] to [ K6 ]) and the mass of the polymerizable compound contained in the colored curable resin composition. When the content of the polymerizable compound is not more than the upper limit, the coating film of the colored curable resin composition is exposed to light and cured, whereby the degree of curing in the coating film is less likely to vary, and particularly, the coating film can be sufficiently cured to the deep portion of the coating film, and a good pattern shape is easily obtained.
(polymerization initiator)
The polymerization initiator is a compound capable of generating a living radical, an acid, or the like under the action of light, heat, and initiating polymerization. The polymerization initiator is not particularly limited, and examples thereof include O-acyl oxime compounds, alkyl phenone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds. Among them, O-acyl oxime compounds are preferable. The polymerization initiator preferably has a maximum absorption wavelength in the range of 365 to 390nm, more preferably in the range of 370 to 390nm, from the viewpoint of easily further improving the curability of the colored curable resin composition. The colored curable resin composition of the present invention may contain 1 kind of polymerization initiator or 2 or more kinds of polymerization initiators.
As the polymerization initiator, an O-acyl oxime compound is preferable. The polymerization initiator is also preferably a compound having a carbazole skeleton, and is also preferably a compound having a nitro group.
The O-acyl oxime compound is a compound having a structure represented by the formula (c 1).
Figure BDA0003964543160000151
The compound having a carbazole skeleton is a compound having a structure represented by formula (c 2).
Figure BDA0003964543160000152
/>
Hereinafter, the bonding site is represented.
Having nitro (-N) 2 The compound of O) is preferably a compound having at least 1 nitro group bonded to an aromatic ring, more preferably a compound having at least 1 nitro group bonded to an aromatic ring contained in a carbazole skeleton.
The polymerization initiator is more preferably an O-acyl oxime compound having a carbazole skeleton. Examples of such a compound include at least 1 selected from the group consisting of a compound represented by formula (c 3) (hereinafter, sometimes referred to as a compound (c 3)) and a compound represented by formula (c 4) (hereinafter, sometimes referred to as a compound (c 4)).
Figure BDA0003964543160000161
[ in the formulae (c 3) and (c 4),
R a represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, wherein the methylene group (-CH) is contained in the aliphatic hydrocarbon group 2 (-) can be substituted by-O- -CO-or-S-, the methine group (-CH <) contained in the aliphatic hydrocarbon group may be substituted with-PO 3 The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
In the present specification, methylene (-CH) 2 (-) and the like are substituted with-O-, -CO-or-S-and the like, the number of carbon atoms indicates the number of carbon atoms before substitution.
R b Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a group which may have a substituent and which is formed by combining an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, a methylene group (-CH) contained in the alkyl group 2 (-) can be substituted by-O-, -CO-, -S-, -SO 2 -or-NR h －。R h An aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R c Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R d An aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
p represents an integer of 1 to 4, preferably an integer of 1 or 2, more preferably 1.
R a The number of carbon atoms of the represented aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, more preferably a phenyl group and a naphthyl group, and still more preferably a phenyl group.
In addition, R a The represented aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include R a The aromatic hydrocarbon groups of (2) may have the same substituent.
R a The number of carbon atoms of the aliphatic hydrocarbon group represented is preferably 1 to 13, more preferably 2 to 10. As R a Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl; alkenyl groups such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl; etc. These aliphatic hydrocarbon groups may be chain-shaped (straight-chain or branched), cyclic, or a combination of chain-shaped groups and cyclic groups. In addition, R a Methylene (-CH) in the aliphatic hydrocarbon group of (C) 2 (-) can be substituted by-O- -CO-or-S-, methine (-CH <) groups can be substituted with-PO 3 The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
As R a Examples of the aliphatic hydrocarbon group which may have a substituent(s) include a group represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000171
R a Preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which may have no substituent, and still more preferably a straight chain alkyl group which may have no substituentOr branched alkyl.
R b The number of carbon atoms of the represented aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and terphenyl, and phenyl and naphthyl are more preferable, and phenyl is particularly preferable.
In addition, R b The represented aromatic hydrocarbon group may have 1 or 2 or more substituents. The substituent is preferably substituted in the ortho-position and para-position of the aromatic hydrocarbon group. Examples of the substituent include alkyl groups having 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl; halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; etc.
The number of carbon atoms of the alkyl group as the substituent is preferably 1 to 10, more preferably 1 to 7. The alkyl group as the substituent may be any of a linear group, a branched group, and a cyclic group, or may be a group formed by combining a chain group and a cyclic group. Methylene (-CH) contained in the alkyl group as the substituent 2 (-) may be substituted with-O-or-S-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.
For R as b Examples of the alkyl group as a substituent of the aromatic hydrocarbon group include a group represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000181
As R b Examples of the aromatic hydrocarbon group which may have a substituent(s) include a group represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000191
As R b The aromatic hydrocarbon group which may have a substituent(s) represented by the following formula is preferable.
Figure BDA0003964543160000192
[ formula, R i Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, R i Methylene (-CH) group contained in 2 (-) may be substituted by-O-or-S-, R j Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, q represents an integer of 1 to 5, and r represents an integer of 0 to 4. Wherein the total of q+r is 5 or less. ]
As R i And R is j The alkyl group represented by R may be b The substituents of the represented aromatic hydrocarbon groups are the same as those exemplified by alkyl groups. R is R i The number of carbon atoms of (2) to (8) is preferable, and 2 to 6 is more preferable. In addition, R j The alkyl group may be any of linear, branched and cyclic, and is preferably chain. R is R i Preferably of formula j1 －O－R j2 A group represented by the formula (I). Here, R is j2 An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R j2 A linear alkyl group having 1 to 3 carbon atoms is preferable. R is R j1 An alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R j1 A linear alkylene group having 1 to 3 carbon atoms is preferable.
R i And R is j When containing halogen atoms, R is i And R is j Examples of the halogen atom contained in (a) include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom is particularly preferable.
In addition, R i And/or R j When the halogen atom is contained, the number thereof is preferably 2 to 10, more preferably 3 to 6. R is R i The substitution position of the O-group is preferably ortho-or para-position. R is R j The substitution position of the radicals is preferably ortho-or para-positionOrtho-positions are particularly preferred.
Q is preferably 1 to 2, more preferably 1.r is preferably from 0 to 2, particularly preferably 0 or 1.
R b The number of carbon atoms of the heterocyclic group represented is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like.
In addition, R b The heterocyclic group represented may have 1 or 2 or more substituents. Examples of the substituent include R b The represented aromatic hydrocarbon groups may have the same groups as exemplified by the substituents.
R b The number of carbon atoms of the alkyl group is preferably 1 to 12. As R b Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like. These alkyl groups may be any of linear, branched, and cyclic groups, or may be a combination of a chain group and a cyclic group. In addition, R b In the alkyl group represented, methylene (-CH) 2 (-) can be substituted by-O-, -CO-, -S-, -SO 2 -or-NR h The hydrogen atom may be substituted with an OH group or an SH group.
R h An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable. The alkyl group may be a chain (linear or branched), a cyclic group, any of linear, branched, and cyclic groups, or a combination of a chain group and a cyclic group. In addition, R h Methylene (-CH) in the alkyl group of (C) 2 (-) may be substituted with-O-or-CO-.
As R b The alkyl group which may have a substituent(s) is specifically represented by the following formula. * Represents the bonding site.
Figure BDA0003964543160000211
In addition, R b Represented by the formula (I) and R b The number of carbon atoms of the group formed by combining the alkyl-derived alkanediyl groups represented by the above is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. The group formed by the combination may have 1 or 2 or more substituents, and examples of the substituent include the same groups as exemplified as substituents which may be included as an aromatic hydrocarbon group or an alkyl group. As the R b Represented by the formula (I) and R b Examples of the group formed by combining alkyl-derived alkanediyl groups represented by the following formula include aralkyl groups, and more specifically, groups represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000212
Wherein R is as R b The aromatic hydrocarbon group which may have a substituent or the alkyl group which may have a substituent is preferable, and the aromatic hydrocarbon group which may have a substituent is more preferable.
R c The number of carbon atoms of the represented aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and terphenyl.
R c The number of carbon atoms of the heterocyclic group represented is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like.
R c The number of carbon atoms of the alkyl group is preferably 1 to 7, more preferably 1 to 5, and still more preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. The alkyl group may be any of linear, branched and cyclic, or may be a group having a chain shape and a cyclic shapeAnd a group formed by combining the groups.
As R c The chain alkyl group is preferable, the chain alkyl group having 1 to 5 carbon atoms is more preferable, the chain alkyl group having 1 to 3 carbon atoms is more preferable, and the methyl group is particularly preferable.
R d The number of carbon atoms of the represented aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and terphenyl, and phenyl and naphthyl are more preferable.
In addition, R d The represented aromatic hydrocarbon group may have 1 or 2 or more substituents. The substituent is preferably substituted in the ortho-position and para-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specifically, examples thereof include an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; alkenyl groups having 1 to 15 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl groups; etc.
R d The aliphatic hydrocarbon group which may be contained in the represented aromatic hydrocarbon group may have 1 to 7 carbon atoms, and the aliphatic hydrocarbon group may be any of a linear group, a branched group, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined. In addition, the methylene group (-CH) contained in the aliphatic hydrocarbon group 2 (-) can be substituted by-O- -CO-or-S-, the methine group (-CH <) may be substituted with-N <.
As R d Examples of the aliphatic hydrocarbon group that may be contained in the aromatic hydrocarbon group include a group represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000221
As R d Examples of the aromatic hydrocarbon group which may have a substituent(s) include a group represented by the following formula. Wherein, represents a bonding site.
Figure BDA0003964543160000231
R d The number of carbon atoms of the heterocyclic group represented is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like.
In addition, R d The heterocyclic group represented may have 1 or 2 or more substituents, and examples of the substituent include R b The represented aromatic hydrocarbon groups may have the same groups as exemplified by the substituents.
Wherein R is d An aromatic hydrocarbon group having a substituent is preferable, and the number of the substituent is preferably 2 to 5, and a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms) is preferable as the substituent.
The compound (c 3) and the compound (c 4) can be produced by a production method described in Japanese patent application laid-open No. 2014-500852 or International publication No. 2008-078678.
The compound (c 3) is preferably R a Is an alkyl group having 1 to 15 carbon atoms which may have a substituent, R b Is an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, R c A compound wherein p is 1 or 2 and is an alkyl group having 1 to 10 carbon atoms,
more preferably R a Is an optionally substituted alkyl group having 1 to 4 carbon atoms, R b Is a group represented by the formula R c A compound wherein p is 1 and is an alkyl group having 1 to 4 carbon atoms.
Figure BDA0003964543160000232
[ formula, R j Is C1-C3 alkyl, R i Is of the formula-R j1 －O－R j2 Represented radical [ here, R j1 Represents a straight chain or branched chain having 1 to 4 carbon atoms and can be usedHalogen atom-substituted aliphatic hydrocarbon group, R j2 Represents a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, R i And R is j The hydrogen atom contained in (b) may be substituted by a halogen atom. q and r are 1.]
As a commercially available product of the compound (c 3), NCI-831 (manufactured by ADEKA Co., ltd.) can be mentioned.
The compound (c 4) is preferably R a Is an optionally substituted alkyl group having 1 to 10 carbon atoms, R b Is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, R c Is C1-C4 alkyl and R d A compound which represents an aromatic hydrocarbon group which may have a substituent.
As a commercially available product of the compound (c 4), irgacure OXE03 (manufactured by BASF corporation) can be mentioned.
The alkylbenzene ketone compound is a compound having a partial structure represented by formula (d 4) or a partial structure represented by formula (d 5). In some of these structures, the benzene ring may have a substituent.
Figure BDA0003964543160000241
Examples of the compound having a structure represented by the formula (d 4) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one, and the like. Commercially available products such as Irgacure 369, 907 and 379 (all of which are manufactured by BASF corporation) may be used.
Examples of the compound having a structure represented by the formula (d 5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzil dimethyl ketal, and the like.
In terms of sensitivity, as the alkyl phenone compound, a compound having a structure represented by formula (d 4) is preferable.
Examples of the bisimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole (for example, reference is made to Japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetra (alkoxyphenyl) bisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent publication No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which phenyl groups at the 4,4', 5' -positions are substituted with carboalkoxy groups (for example, refer to Japanese patent application laid-open No. 7-10913, etc.), and the like. Among them, preferred are compounds represented by the following formula and mixtures thereof.
Figure BDA0003964543160000251
Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like.
The content of the polymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass, relative to the total amount of the solid components contained in the colored curable resin composition. When the content of the polymerization initiator is within the above range, a pattern having a good shape can be easily formed by exposure and development, and curability at low temperature can be easily improved. In addition, there is a tendency to shorten the exposure time by increasing the sensitivity, so that the productivity of color filters and the like is improved.
(colorant)
The colored curable resin composition of the present invention contains at least 1 colorant. The colorant may be any one of a dye and a pigment, and preferably contains a pigment. As the pigment, a known pigment can be used, and examples thereof include pigments classified as pigments (pigment) in the color index (The Society of Dyers and Colourists publication).
Specifically, examples thereof include yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
Orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291;
c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. blue pigments such as 16 and 60;
violet pigments such as c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;
green pigment of c.i. pigment green 7, 36, 58, 59;
brown pigments such as pigment brown 23, 25;
black pigments such as c.i. pigment black 1 and 7.
The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative having an acid group or a basic group introduced therein, a grafting treatment to the pigment surface with a polymer compound or the like, a micronization treatment by sulfuric acid micronization or the like, a washing treatment by an organic solvent, water or the like for removing impurities, a removal treatment by an ion exchange method or the like for ionic impurities, or the like, as required.
The pigment preferably has a uniform particle size. Further, by performing dispersion treatment by containing a pigment dispersing agent, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of 2 or more. Examples of pigment dispersants include KP (manufactured by Xinyue chemical industry Co., ltd.), FLOWLEN (manufactured by Kyowa Co., ltd.), solsperse (manufactured by Lubrizol Co., ltd.), EFKA (manufactured by CIBA Co.), AJISPER (manufactured by Weisu Fine chemical Co., ltd.), and Disperbyk (manufactured by BYK-Chemie Co., ltd.).
When the pigment dispersant is used, the amount thereof to be used is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, relative to the total amount of the pigment. When the amount of the pigment dispersant is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.
The content of the pigment in the total amount of the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass or more.
The colorant may also contain a dye. The dye is not particularly limited, and known dyes may be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples of dyes include compounds classified into substances having a color tone other than pigments in the color index (The Society of Dyers and Colourists publication) and known dyes described in dyeing guidelines (color dyeing company). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, and the like can be exemplified. Among them, organic solvent-soluble dyes are preferable.
Specifically, there may be mentioned: c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;
c.i. solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
c.i. solvents orange 2, 7, 11, 15, 26, 56, 77, 86;
c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
c.i. solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59: 1. 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. c.i. solvent dyes,
C.i. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 401, 412, 417, 418, 422, 426;
c.i. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
c.i. acid violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
c.i. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90: 1. 91, 92, 93: 1. 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1. 335, 340;
C.i. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50: 1. 58, 63, 65, 80, 104, 105, 106, 109, etc., c.i. acid dyes,
C.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
c.i. direct oranges 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
c.i. direct blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 259, 250, 251, 252, 256, 257, 259, 260, 268, 274, 293.
C.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. c.i. direct dye,
C.i. disperse yellow 51, 54, 76;
c.i. disperse violet 26, 27;
c.i. disperse blue 1, 14, 56, 60, etc. c.i. disperse dyes,
C.i. basic red 1, 10;
c.i. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
c.i. basic violet 2;
c.i. basic red 9;
C.I. basic dyes such as C.I. basic green 1,
C.i. active yellow 2, 76, 116;
c.i. active orange 16;
C.I. reactive dyes such as C.I. reactive red 36,
C.i. medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
c.i. media red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
c.i. medium oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
c.i. vehicle violet 1, 1: 1. 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C.i. medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
c.i. mediator dyes such as c.i. mediator green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53,
C.I. vat dyes such as C.I. vat green 1, etc.
The content of the dye is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and may be 0% by mass or less, based on the total amount of the colorant.
The content of the colorant is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass, based on the total amount of the solid components of the colored curable resin composition. When the content of the colorant is within the above range, the color density is sufficient when a color filter is produced, and the composition can contain a desired amount of the resin and the polymerizable compound, so that a pattern having sufficient mechanical strength can be formed.
In the colored curable resin composition particularly required to have a dark color, the content of the colorant is preferably 4 to 60% by mass, more preferably 6 to 56% by mass, still more preferably 8 to 53% by mass, and still more preferably 10 to 50% by mass, based on the total amount of the solid components of the curable resin composition. When the content of the colorant is within the above range, a particularly high color density can be achieved when a color filter is produced, and a desired amount of the resin or polymerizable compound can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.
In the colored curable resin composition of the present invention, the colorant preferably contains a xanthene dye. Xanthene dyes are dyes that contain compounds having a xanthene backbone within the molecule. The xanthene dye is preferably a dye containing a compound represented by the formula (I) (hereinafter, sometimes referred to as "compound (I)").
Figure BDA0003964543160000301
[ in formula (I), R 1 ～R 4 Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the saturated hydrocarbon group contains-CH 2 Can be substituted by-O-, -CO-or-NR 11 -substitution.
R 5 represents-OH, -SO 3 － 、－SO 3 H、－SO 3 － Z + 、－CO 2 H、－CO 2 － Z + 、－CO 2 R 8 、－SO 3 R 8 or-SO 2 NR 9 R 10 。
R 6 And R is 7 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, a plurality of R 5 May be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z + Representation of + N(R 11 ) 4 、Na + Or K + 4R 11 May be the same or different.
R 8 A monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R 9 And R is 10 Each independently represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms which may have a substituentMonovalent saturated hydrocarbon groups, the saturated hydrocarbon groups containing-CH 2 Can be replaced by-O-, -CO-, -NH-or-NR 8 -substitution, R 9 And R is 10 Heterocyclic rings which may be bonded and form a 3-to 10-membered ring together with the adjacent nitrogen atom.
R 11 Represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.]
The compound (I) may also be a tautomer thereof. When the compound (I) is used, the content of the compound (I) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass, based on the solid content of the colorant contained in the colored curable resin composition.
As R 1 ～R 4 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; alicyclic saturated hydrocarbon groups having 2 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl. The number of carbon atoms of the saturated hydrocarbon group is the number of carbon atoms including the substituent when the saturated hydrocarbon group has a substituent. Examples of the substituent which the saturated hydrocarbon group may have include a halogen atom, -OH, -OR 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－CO 2 H、－CO 2 R 8 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 、－SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 )。R 12 、R 13 And R is 14 Each independently represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
As R 1 ～R 4 Monovalent aromatic hydrocarbon having 6 to 20 carbon atomsExamples of the aromatic hydrocarbon group include phenyl groups. Examples of the monovalent aromatic hydrocarbon group having a substituent include tolyl group, xylyl group, and,
Figure BDA0003964543160000321
Radicals, propylphenyl, butylphenyl, and the like. The number of carbon atoms of the aromatic hydrocarbon group is the number of carbons including the substituent when the aromatic hydrocarbon group has a substituent. Examples of the substituent which may be contained in the aromatic hydrocarbon group include a halogen atom and-R 8 、－OH、－OR 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－CO 2 H、－CO 2 R 8 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 、－SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 )。
As R 8 ～R 11 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl.
R 9 And R is 10 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in (b) may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.
As R 12 ～R 14 Examples of the monovalent saturated hydrocarbon group having 1 to 4 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl and butyl; alicyclic saturated hydrocarbon groups having 1 to 4 carbon atoms such as branched alkyl groups such as isopropyl and isobutyl.
Z + Is that + N(R 11 ) 4 、Na + Or K + Preferably, it is + N(R 11 ) 4 . Preferably + N(R 11 ) 4 4R in (3) 11 At least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R 11 The total number of carbon atoms in (a) is preferably 20 to 80, more preferably 20 to 60. In the presence of the compound (I) + N(R 11 ) 4 In the case of R 11 When these groups are used, a color filter having less foreign matters can be formed from the negative resist composition of the present invention containing the compound (I).
as-OR 8 Examples thereof include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy and eicosoxy.
as-CO 2 R 8 Examples thereof include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.
as-SR 8 Examples thereof include methylthio, ethylthio, butylthio, hexylthio, decylthio and eicosylthio.
as-SO 2 R 8 Examples thereof include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosulfonyl.
as-SO 3 R 8 Examples thereof include methoxysulfonyl, ethoxysulfonyl, butoxysulfonyl, t-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.
as-SO 2 NR 9 R 10 For example, a sulfamoyl group; n-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N- (1-ethylpropyl) sulfamoyl, N- (1, 1-dimethylpropyl) sulfamoyl, N- (1, 2-dimethylpropyl) sulfamoyl, N- (2, 2-dimethylpropyl) sulfamoyl, N- (1-methylbutyl) sulfamoyl, N- (2-methylbutyl) sulfamoyl, N- (3-methylbutyl) sulfamoylN-1 substituted sulfamoyl groups such as a group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1, 3-dimethylbutyl) sulfamoyl group, N- (3, 3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1, 4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1, 5-dimethylbutyl) hexylsulfamoyl group, and N- (1, 2-tetramethylbutyl) sulfamoyl group; n, N-dimethyl sulfamoyl, N-ethyl methyl sulfamoyl, N-diethyl sulfamoyl, N-propyl methyl sulfamoyl, N-isopropyl methyl sulfamoyl, N, N-2 substituted sulfamoyl groups such as N-t-butylmethylsulfamoyl, N-butylethylsulfamoyl, N-bis (1-methylpropyl) sulfamoyl, N-heptylmethylsulfamoyl, and the like.
as-Si (OR) 12 )(OR 13 )(OR 14 ) Examples thereof include trimethoxysilyl and triethoxysilyl.
R 5 preferably-CO 2 H、－CO 2 － Z + 、－CO 2 R 8 、－SO 3 － 、－SO 3 － Z + 、－SO 3 H or SO 2 NHR 9 More preferably SO 3 － 、－SO 3 － Z + 、－SO 3 H or SO 2 NHR 9 。
m represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
As R 6 And R is 7 Examples of the alkyl group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms, preferably alkyl groups having 1 to 2 carbon atoms, among the above-mentioned alkyl groups. R is R 6 And R is 7 More preferably a hydrogen atom.
As R 11 Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl, phenylethyl, phenylbutyl and the like.
a represents an integer of 0 or 1, preferably 0.
The compound (I) is preferably a compound represented by the formula (Ia) (hereinafter also referred to as "compound (Ia)"). The compound represented by the formula (Ia) may be used in combination with a compound other than the compound (Ia) in the compound (I) (hereinafter, sometimes referred to as "compound (Ib)"), or the compound (Ia) may be used in combination with the compound (Ib) described later. In addition, 2 or more compounds (Ia) may be used in combination.
Figure BDA0003964543160000341
In the formula (Ia),
R a1 and R is a4 Each independently is a monovalent aromatic hydrocarbon group which may have 2 or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms.
R a2 And R is a3 Each independently is a hydrogen atom, methyl or ethyl.
R 5 ～R 7 M, a and X represent the same meanings as described above.]
As R a1 And R is a4 R is as described above 1 And R is 4 A monovalent aromatic hydrocarbon group having no substituent or a monovalent saturated aliphatic hydrocarbon group having 2 or less carbon atoms of 1 to 4 in the same group. Among them, monovalent aromatic hydrocarbon groups having 2 or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms are preferable.
Examples of the monovalent aromatic hydrocarbon group having no substituent include phenyl groups. Examples of the monovalent aromatic hydrocarbon group having 2 or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms include tolyl group, xylyl group, and the like,
Figure BDA0003964543160000342
A base, etc. The number of carbon atoms of the aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 10, and most preferably 8. The number of carbon atoms of the aromatic hydrocarbon group is the number of carbons including the substituent. The aromatic hydrocarbon group preferably has no substituent other than the saturated aliphatic hydrocarbon group.
The number of the saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded to an ortho-position or a meta-position, more preferably to an ortho-position, with respect to the bonding site of the aromatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a saturated aliphatic hydrocarbon group having no substituent. The number of carbon atoms of the saturated aliphatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.
As R a2 And R is a3 Among them, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is more preferable.
As the compound (Ib), a compound represented by the formula (Ib 1) (hereinafter, sometimes referred to as "compound (Ib 1)") is preferable. The compound (Ib 1) is preferably used in combination with the compound (Ia), or may be used in combination with the compound (Ia). That is, the xanthene dye may be the compound (Ia) and/or the compound (Ib 1), preferably the compound (Ia), or the compound (Ia) and the compound (Ib 1), more preferably the compound (Ia).
Figure BDA0003964543160000351
[ in formula (Ib 1), R b1 ～R b4 Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R b1 ～R b4 at least one saturated hydrocarbon group OR aromatic hydrocarbon group contained in the aromatic hydrocarbon compound has a halogen atom, -OH, -OR 8 、－CO 2 H、－CO 2 R 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 、－SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 ) As a substituent, or R b1 ～R b4 At least one aromatic hydrocarbon group contained therein has 3 or more carbonsMonovalent saturated aliphatic hydrocarbon groups having 1 to 4 atoms as substituents,
R 5 ～R 10 、R 12 ～R 14 m, a and X represent the same meanings as described above.]
As R b1 And R is b4 R is as described above 1 And R is 4 The same group may have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as a substituent. Among them, monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, or aromatic hydrocarbon groups having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, which may have a substituent, are preferable.
The number of carbon atoms of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferably 1 to 10, more preferably 2 to 8, and still more preferably 2 to 7. The number of carbon atoms of the saturated aliphatic hydrocarbon group is the number of carbon atoms including the substituent. As the substituent, halogen atoms, -OH, -OR are preferred 8 、－CO 2 H、－CO 2 R 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 、－SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 ) More preferably-OH, -OR 8 、－CO 2 H、－CO 2 R 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 OR-Si (OR) 12 )(OR 13 )(OR 14 ) Further preferably-OH, -OR 8 、－CO 2 H、－CO 2 R 8 OR-Si (OR) 12 )(OR 13 )(OR 14 ) Most preferably-Si(OR 12 )(OR 13 )(OR 14 ). The number of substituents is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1, relative to one saturated aliphatic hydrocarbon group.
The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent(s) preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 to 12 carbon atoms, still more preferably 7 to 10 carbon atoms, particularly preferably 7 to 8 carbon atoms, and most preferably 8 carbon atoms. The number of carbon atoms of the aromatic hydrocarbon group is the number of carbon atoms including the substituent. As the substituent, a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, -OH, -OR, OR is preferable 8 、－CO 2 H、－CO 2 R 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 、－SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 ) More preferably a monovalent saturated aliphatic hydrocarbon group of 1 to 4 carbon atoms, -OH, -OR 8 、－CO 2 H、－CO 2 R 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 or-SO 2 NR 9 R 10 . More preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, -OR 8 、－SO 3 － 、－SO 3 H、－SO 3 － Z + 、－SR 8 、－SO 2 R 8 、－SO 3 R 8 or-SO 2 NR 9 R 10 . The number of substituents is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 2, relative to one aromatic hydrocarbon group. The substituent is preferably bonded to the ortho-position and/or meta-position, more preferably to the ortho-position, relative to the bonding site of the aromatic hydrocarbon group.
The number of carbon atoms of the aromatic hydrocarbon group having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as a substituent is preferably 9 to 20, more preferably 9 to 13, still more preferably 9 to 12, and most preferably 9. The number of carbon atoms of the aromatic hydrocarbon group is the number of carbon atoms including the substituent. Preferably, the aromatic hydrocarbon group has no substituent other than the saturated aliphatic hydrocarbon group. The number of the saturated aliphatic hydrocarbon groups is preferably 3 to 5, more preferably 3 to 4, and most preferably 3, relative to one aromatic hydrocarbon group. The bonding site of the saturated aliphatic hydrocarbon group is preferably bonded to the ortho-position and/or para-position, more preferably bonded to the ortho-position and para-position, with respect to the bonding site of the aromatic hydrocarbon group. The number of carbon atoms of the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.
As R b2 And R is b3 R is preferably as defined above 2 And R is 3 The hydrogen atom in the same group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Of these, monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent are more preferable, and monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent are still more preferable.
The number of carbon atoms of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The number of carbon atoms of the saturated aliphatic hydrocarbon group is the number of carbon atoms including the substituent. As the substituent, a halogen atom, -OH, -OR is preferably mentioned 8 、-CO 2 H、-CO 2 R 8 、-SO 3 、-SO 3 H、-SO 3 - Z + 、-SR 8 、-SO 2 R 8 、-SO 3 R 8 、-SO 2 NR 9 R 10 OR-Si (OR) 12 )(OR 13 )(OR 14 ) More preferably-OH, -OR 8 、-CO 2 H、-CO 2 R 8 、-SO 3 - 、-SO 3 H、-SO 3 - Z + 、-SR 8 、-SO 2 R 8 、-SO 3 R 8 OR-Si (OR) 12 )(OR 13 )(OR 14 ) Further preferably-OH, -OR 8 、-CO 2 H、-CO 2 R 8 OR-Si (OR) 12 )(OR 13 )(OR 14 ) Most preferably-CO 2 H or-CO 2 R 8 . The number of substituents is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1, relative to one saturated aliphatic hydrocarbon group.
As the compound (Ia), preferred are compounds No.1 to 15 identified by the formula (Iax) and Table 1.
Figure BDA0003964543160000371
TABLE 1
No. R ax1 R ax2 R ax3 R ax4
1 Ph H H Ph
2 Ph CH 3 CH 3 Ph
3 Ph CH 3 CH 2 CH 3 CH 2 Ph
4 O-tolyl radical H H O-tolyl radical
5 O-tolyl radical CH 3 CH 3 O-tolyl radical
6 O-tolyl radical CH 3 CH 2 CH 3 CH 2 O-tolyl radical
7 M-tolyl radical H H M-tolyl radical
8 M-tolyl radical CH 3 CH 3 M-tolyl radical
9 M-tolyl radical CH 3 CH 2 CH 3 CH 2 M-tolyl radical
10 Para-tolyl group H H Para-tolyl group
11 Para-tolyl group CH 3 CH 3 Para-tolyl group
12 Para-tolyl group CH 3 CH 2 CH 3 CH 2 Para-tolyl group
13 2, 6-xylyl H H 2, 6-xylyl
14 2, 6-xylyl CH 3 CH 3 2, 6-xylyl
15 2, 6-xylyl CH 3 CH 2 CH 3 CH 2 2, 6-xylyl
The symbol descriptions in the formula represent the following groups (bond sites are indicated by the following).
Figure BDA0003964543160000381
As the compound (Ib 1), preferred are compounds represented by the formulae (Ibx) and the formulae (A3-1 to A3-8) of the formulae (16 to 35) and (B) shown in Table 2.
Figure BDA0003964543160000382
TABLE 2
No. R bx1 R bx2 R bx3 R bx4
16 CH 3 CH 3 CH 3 PrTMS
17 CH 3 CH 2 CH 3 CH 2 CH 3 PrTMS
18 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 PrTMS
19 Ph PrCOOH PrCOOH Ph
20 O-tolyl radical PrCOOH PrCOOH O-tolyl radical
21 M-tolyl radical PrCOOH PrCOOH M-tolyl radical
22 Para-tolyl group PrCOOH PrCOOH Para-tolyl group
23 2, 6-xylyl PrCOOH PrCOOH 2, 6-xylyl
24 MT1 H H MT1
25 MT1 CH 3 CH 3 MT1
26 MT1 CH 3 CH 2 CH 3 CH 2 MT1
27 MT2 H H MT2
28 MT2 CH 3 CH 3 MT2
29 MT2 CH 3 CH 2 CH 3 CH 2 MT2
30 MT3 H H MT3
31 MT3 CH 3 CH 3 MT3
32 MT3 CH 3 CH 2 CH 3 CH 2 MT3
33 2,4, 6-Triphenyl H H 2,4, 6-Triphenyl
34 2,4, 6-Triphenyl CH 3 CH 3 2,4, 6-Triphenyl
35 2,4, 6-Triphenyl CH 3 CH 2 CH 3 CH 2 2,4, 6-Triphenyl
The symbol descriptions in the formula represent the following groups (bond sites are indicated by the following).
Figure BDA0003964543160000401
/>
Figure BDA0003964543160000411
(polymerization initiation aid)
The colored curable resin composition of the present invention may further contain at least 1 polymerization initiator (E). The polymerization initiator aid is a compound or sensitizer for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator auxiliary (E) is contained, it is usually used in combination with the polymerization initiator (C).
Examples of the polymerization initiator (E) include 4,4' -bis (dimethylamino) benzophenone (known as Michaelis ' ketone), 4' -bis (diethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2, 4-diethylthioxanthone, and N-phenylglycine.
When these polymerization initiator additives are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin and the polymerizable compound. When the amount of the polymerization initiator is within this range, a pattern can be further formed with high sensitivity, and productivity of a color filter or the like tends to be improved.
(leveling agent)
The colored curable resin composition of the present invention may further contain at least 1 leveling agent. Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. They may have a polymerizable group in a side chain.
Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (trade name: dow Corning Toray, manufactured by Mitsui chemical Co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue chemical Co., ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by MOMENTIVE PERFORMANCE MATERIALS JAPAN contract Co., ltd.) and the like are exemplified.
The fluorine-based surfactant includes surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD FC430, FLUORAD FC431 (manufactured by Sumitomo 3M (Inc.), MEGAFAC F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Inc.), F-top EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi material electronics), surflon 382 (manufactured by registered trademark) S381, surflon S, surflon SC101, surflon SC105 (manufactured by AGC (manufactured by Asahi Nitri-seed (Inc.)) and E5844 (manufactured by David gold fine chemical research).
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there are exemplified MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (DIC corporation), and the like.
When the leveling agent is contained, the content of the leveling agent is preferably 0.0005 to 0.2 mass%, more preferably 0.0008 to 0.1 mass%, based on the total amount of the colored curable resin composition. When the content of the leveling agent is within the above range, flatness of the color filter or the like can be improved.
The colored curable resin composition of the present invention containing the above components, when the composition is cured to form a cured film, has a haze value of preferably 8 to 50%, more preferably 10 to 45%, still more preferably 13 to 40%, still more preferably 17 to 35%, in terms of a thickness of 2 μm. The curing conditions for curing the composition to form a cured film are not particularly limited as long as sufficient curing is achieved, and for example, the curing conditions are 15 minutes or longer at 70 ℃. The haze value of the cured film can be measured by a haze meter.
(solvent)
The colored curable resin composition of the present invention may further contain at least 1 solvent. The solvent is not particularly limited, and solvents generally used in this field can be used. For example, the number of the cells to be processed, examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule) an ether solvent (a solvent containing-O-and not-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a solvent containing-COO-in the molecule, and a solvent containing-COO-in the molecule an ether solvent (a solvent containing-O-and not-COO-in the molecule) ether ester solvents (solvents containing-COO-and-O-in the molecule).
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.
Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, and 1, 4-di-n
Figure BDA0003964543160000431
Alkyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole and the like.
Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, diacetone alcohol, isophorone, and the like.
Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
The solvent preferably contains 1 or more selected from the group consisting of an ether solvent, an ether ester solvent and a ketone solvent, more preferably contains an ether solvent and an ether ester solvent, and still more preferably contains propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
The content of the solvent is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, relative to the total amount of the colored curable resin composition of the present invention. In other words, the solid content of the colored curable resin composition is preferably 20 to 70% by mass, more preferably 25 to 65% by mass. When the content of the solvent is within the above range, flatness at the time of coating becomes good, and when the colorant is contained, for example, the color density at the time of forming a color filter is not insufficient, so that there is a tendency that display characteristics become good.
(other Components)
The curable resin composition of the present invention may contain, if necessary, additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants such as 2,2' -methylenebis (4-methyl-6-t-butylphenol), light stabilizers, and chain transfer agents such as n-dodecyl mercaptan.
Method for producing colored curable resin composition
The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, and if necessary, a polymerization initiator aid, a solvent, a leveling agent, and other components.
The colorant may be prepared using the pigment dispersion described above. The target curable resin composition can be prepared by mixing the remaining components in the pigment dispersion to achieve a prescribed concentration. The curable resin composition after mixing is preferably filtered by a filter having a pore size of about 0.01 to 10. Mu.m.
Method for producing cured film
Examples of the method for producing a cured film such as a colored pattern from the colored curable resin composition of the present invention include photolithography, inkjet method, and printing method. Among them, photolithography is preferable. Photolithography is a method of forming a colored composition layer by applying the colored curable composition to a substrate and drying the same, and exposing and developing the colored composition layer through a photomask. In the photolithography method, a colored coating film which is a cured film of the colored curable resin composition layer can be formed without using a photomask and/or without developing at the time of exposure. The cured film such as a colored pattern or a colored coating film thus formed can be used as a color filter.
The film thickness of the cured film, for example, the film thickness of the color filter is not particularly limited, and may be appropriately adjusted according to the purpose, use, and the like, and is, for example, 0.1 to 30. Mu.m, preferably 0.1 to 20. Mu.m, and more preferably 0.5 to 6. Mu.m.
As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like, silicon, a substrate having aluminum, silver/copper/palladium alloy thin films formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.
The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the production can be performed as follows.
First, the colored resin composition is applied onto a substrate, and then dried by heating (prebaking) and/or drying under reduced pressure, thereby removing volatile components such as a solvent and drying to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method.
The temperature at which the heat drying is carried out is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
In the case of drying under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150Pa at a temperature of 20 to 25 ℃.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
Next, the coloring composition layer is exposed to light via a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350nm may be cut off by a filter for cutting off the wavelength region, or light of around 436nm, around 408nm, or around 365nm may be selectively extracted by a band-pass filter for extracting the wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like are cited. The exposure amount at 365nm wavelength is preferably 50 to 300J/cm 2 More preferably 60 to 200J/cm 2 Further preferably 65 to 180J/cm 2 。
In order to uniformly irradiate the entire exposure surface with parallel light or to perform precise alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.
The exposed coloring composition layer is brought into contact with a developer to develop, thereby forming a coloring pattern on the substrate. The unexposed portion of the coloring composition layer is dissolved in a developer and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may contain a surfactant.
The developing method may be any of spin-coating immersing method, spraying method, and the like. Further, the substrate can be inclined at an arbitrary angle during development.
After development, washing with water is preferable.
Further, the resulting colored pattern is preferably post-baked. In order to form a color filter used in an organic EL display device, the post-baking temperature may be 200 ℃ or less, preferably 170 ℃ or less, and more preferably 150 ℃ or less. In the present invention, the post-baking is preferably performed at a lower temperature, for example, at 130 ℃ or lower. The lower limit of the post-baking temperature is preferably 70℃or higher, more preferably 75℃or higher. The post-baking time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.
The film thickness of the coating film after post-baking is, for example, preferably 3 μm or less, more preferably 2.5 μm or less. The lower limit of the film thickness of the coating film is not particularly limited, and is usually 0.3 μm or more, but may be 0.5 μm or more.
The cured film of the colored curable resin composition of the present invention obtained after post-baking has a haze value of preferably 8 to 50%, more preferably 10 to 45%, still more preferably 13 to 40%, still more preferably 17 to 35%, in terms of thickness of 2. Mu.m. The haze value of the cured film can be measured by a haze meter. The present invention also provides a cured film of the colored curable resin composition of the present invention.
The cured film obtained by curing the curable resin composition of the present invention is preferably used as a color filter included in a color filter substrate, and more preferably used as a color filter for an organic EL display device having a microcavity structure.
Examples (example)
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, the% and parts representing the content or the amount used are mass references unless otherwise specified.
< weight average molecular weight >
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC method under the following conditions. The molecular weight distribution was defined as the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene obtained under the following conditions.
The device comprises: HLC-8120GPC (manufactured by Tosoh Co., ltd.)
Column: TSK-GELG2000HXL
Column temperature: 40 DEG C
Solvent: tetrahydrofuran [ THF ]
Flow rate: 1.0mL/min
Detecting the concentration of the solid component of the liquid; 0.001 to 0.01 mass%
Sample injection amount: 50 mu L
A detector: RI (RI)
A calibration standard substance; TSK STANDARD PolySTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)
Synthesis example 1: preparation of pigment Dispersion (A1)
8.6 parts of c.i. pigment red 291, 3.5 parts of c.i. pigment yellow 139, 3.9 parts of an acrylic pigment dispersant, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A1).
< synthetic example 2: preparation of pigment Dispersion (A2)
9.6 parts of c.i. pigment green 59, 1.7 parts of c.i. pigment yellow 150, 1.5 parts of c.i. pigment yellow 139, 3.1 parts of an acrylic pigment dispersant, 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A2).
< synthesis example 3: preparation of pigment Dispersion (A3)
9.8 parts of c.i. pigment blue 16, 1.6 parts of Pink Base (manufactured by sun fine chemicals), 4.6 parts of an acrylic pigment dispersant, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A3).
Figure BDA0003964543160000481
< synthetic example 4: preparation of pigment Dispersion (A4)
3.9 parts of c.i. pigment green 36, 7.9 parts of c.i. pigment yellow, 4.3 parts of an acrylic pigment dispersant, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A4).
< synthesis example 5: preparation of pigment Dispersion (A5)
6.2 parts of c.i. pigment red 254, 6.2 parts of c.i. pigment red 177, 3.6 parts of an acrylic pigment dispersant, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A5).
< synthesis example 6: preparation of pigment Dispersion (A6)
12.1 parts of c.i. pigment blue 15: 6. 0.6 part of c.i. pigment violet 23, 3.3 parts of an acrylic pigment dispersant, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion (A6).
< synthesis example 7: preparation of resin >
277 parts of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while nitrogen was replaced, and the temperature was raised to 120 ℃.
Then, a mixed solution in which 35.3 parts of t-butyl peroxy-2-ethylhexanoate was added to a monomer mixture of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentyl methacrylate was added thereto by dropping the mixed solution from a dropping funnel into the flask over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 120℃for 30 minutes to carry out copolymerization to give an adduct copolymer.
Thereafter, the flask was replaced with air, 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine and 0.8 part of hydroquinone monomethyl ether were put into the above-mentioned adduct copolymer solution, and the reaction was continued at 110℃for 10 hours, whereby the epoxy group derived from glycidyl methacrylate was cleaved by the reaction of the epoxy group with acrylic acid, and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Then, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110℃for 1 hour, so that the hydroxyl group formed by cleavage of the epoxy group was reacted with succinic anhydride, and the carboxyl group was introduced into the side chain, to obtain a polymer.
Finally, 383.3 parts of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer solution having a polymer solid content of 40%. The polystyrene-equivalent weight average molecular weight of the obtained resin was 6400.
< scattering intensity of Mie scattering >
Miepsilon (see http:// www.philiplaven.com/mielist. Htm) as a calculation program of the scattering intensity of Mie scattering was used to calculate the scattering intensity X of Mie scattering of inorganic fine particles under the conditions of unpolarized light, light source wavelength of 550nm, and scattering angle of 0 degrees.
Examples 1 to 6, reference examples 1 to 3 and comparative examples 1 to 3 >, respectively
(1) Preparation of colored curable resin composition
The components shown in Table 3 were mixed so as to obtain the blending amounts shown in Table 3, thereby obtaining colored curable resin compositions. In the preparation of the curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the curable resin composition became 14% by weight. The unit of the amount of each component in table 3 is "parts by mass", and the amounts of each of the pigment dispersions (A1) to (A6), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the metal oxide (E) and the leveling agent (F) are calculated as solid components.
The polymerizable compound (C), the polymerization initiator (D1), the polymerization initiator (D2), the inorganic fine particles (E) and the leveling agent (F) used in examples, reference examples and comparative examples are as follows.
Polymerizable compound (C): dipentaerythritol hexaacrylate dipentaerythritol pentaacrylate (trade name "A-9550", manufactured by Xinzhou chemical industries, ltd.)
Polymerization initiator (D-1): n-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime Compound; new Strong electronics materials, inc. of Changzhou Co., ltd.)
Polymerization initiator (D-2): a compound represented by the formula
Figure BDA0003964543160000501
Inorganic fine particles (E): titanium oxide (metal oxide, average particle diameter 161nm, scattering intensity 8.0, refractive index 2.7) leveling agent (F): polyether modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Dow Corning Toray).
TABLE 3
Figure BDA0003964543160000502
< preparation of cured film >
The colored curable resin compositions of examples, comparative examples and reference examples prepared as described above were applied to a 5cm square glass substrate (EAGLE 2000; manufactured by Corning) by spin coating so that the film thickness after post-baking was 2. Mu.m, and then pre-baked at 90℃for 1 minute to form a colored composition layer. After cooling, the film was subjected to an exposure machine (TME-150 RSK; TOPCON, manufactured by TOPCON Co., ltd.) at a rate of 100mJ/cm under an atmospheric atmosphere 2 The colored composition layer formed on the substrate was irradiated with light (365 nm reference). After the light irradiation, post-baking was performed in an oven at 85 ℃ for 30 minutes to obtain a colored cured film. The haze and the visual field of the obtained cured film when viewed obliquely were evaluated according to the following criteria. The results obtained are shown in Table 4. Since the cured films of comparative examples 1 to 3 were not patterned, evaluation of the visual field when viewed from an oblique direction was not performed.
< determination of haze >)
The haze of the obtained colored cured film was measured by a haze meter HZ-2 (manufactured by SUGA tester Co., ltd.).
< evaluation of patterning >)
In the exposure for producing a cured film, a mask having 10 μm lines and space patterns formed thereon was used as a photomask, and the colored composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24℃for 60 seconds, followed by washing with water, whereby a colored pattern was obtained.
And (2) the following steps: a pattern can be formed.
X: no pattern can be formed.
< evaluation of field of view when viewed obliquely >
A sheet cut out with a specific pattern was placed 5cm below the colored cured film, and light was irradiated from below the sheet to transmit light having transmitted the specific pattern through the cured film. Next, the definition of a pattern visually recognizable on the cured film surface from an oblique direction of about 60 degrees with respect to the cured film surface above the cured film was evaluated.
And (2) the following steps: the pattern can be visually recognized.
X: the pattern cannot be discerned.
TABLE 4
Figure BDA0003964543160000521
Examples 7 to 12 and comparative examples 4 to 7 >, respectively
A colored curable resin composition and a cured film were produced in the same manner as in example 3, except that the types of the inorganic fine particles were changed to those shown in table 5 and the amount of the inorganic fine particles added was changed to 5 mass%. The haze and oblique view of the obtained cured film were evaluated in the same manner as described above. The results obtained are shown in Table 5. The evaluation results of patterning were all o. In the case of example 12, since inorganic fine particles having a larger particle diameter were used as compared with other examples, the tendency of the particles to settle was observed.
TABLE 5
Figure BDA0003964543160000522
/>

Claims (10)

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein X is 4 or more, Y is 15 or less, the value a calculated from formula (1) is 10 or more, when X is the scattering intensity of Mie scattering of the inorganic fine particles and Y is the content of the inorganic fine particles relative to the solid content of the colored curable resin composition,
a＝X×Y (1)。
2. the colored curable resin composition according to claim 1, wherein the inorganic fine particles are metal oxides.
3. The colored curable resin composition according to claim 1, wherein the inorganic fine particles have a refractive index of 1.3 or more.
4. The colored curable resin composition according to claim 1, wherein the inorganic fine particles have an average particle diameter of 0.05 μm to 0.70 μm.
5. The colored curable resin composition according to claim 1, wherein the content of the polymerizable compound is 0.1 to 50% by mass based on the solid content of the colored curable resin composition.
6. The colored curable resin composition according to claim 1, wherein the cured film of the curable resin composition has a haze value of 8 to 40% in terms of thickness of 2 μm.
7. A cured film of the colored curable resin composition according to any one of claims 1 to 6.
8. The cured film according to claim 7, wherein the cured film has a haze value of 8 to 40% in terms of a thickness of 2 μm.
9. The cured film according to claim 7, which constitutes a color filter included in a color filter substrate.
10. A display device comprising the cured film of claim 7.
CN202211490090.8A 2021-11-30 2022-11-25 Colored curable resin composition, cured film of colored curable resin composition, and display device Pending CN116203799A (en)

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