KR20230081664A - Colored curable resin composition, cured film of colored curable resin composition, and display device - Google Patents

Abstract

[Problem] To provide a colored curable resin composition capable of providing a color filter capable of providing an organic EL display device capable of imparting a sufficiently good visual field even when viewed obliquely, and having sufficient curability.
[Solution Means] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein the scattering intensity of the inorganic fine particles in Mie scattering is set to X, and the colored curable resin When the content of the inorganic fine particles relative to the solid content of the composition is expressed as Y mass%, X is 4 or more and Y is 15 or less, formula (1):
a=X×Y (1)
The colored curable resin composition in which the value a computed by is 10 or more.

Description

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

[0001] The present invention relates to a colored curable resin composition, a cured film of the colored curable resin composition, and a display device.

[0002] An organic electroluminescence (EL) display device is a display device including, for example, an organic EL film formed on a substrate, and the organic EL film is for forming a hole transport layer and each pixel, for example, red (R), green (G), a light emitting layer that emits blue (B) light, and an electron transport layer. By applying a voltage to the electrodes at both ends of the organic EL film, electrons from the cathode and holes from the anode flow into the organic EL film, electrons and holes are recombinated in the light emitting molecules of the light emitting layer, and the light emitting molecules emit light. It is a device that uses In order to increase the light intensity of each color emitted, a micro cavity structure is employed in which the optical path length between the upper and lower electrodes is adjusted to the light wavelength of each color. By using the micro-cavity structure, the spectrum of the light extracted to the outside becomes steep and high-intensity by utilizing the resonance effect of light between the electrodes, and it is possible to increase the luminance and color purity of each color of RGB. It happens.

[0003] 1. Japanese Patent Laid-Open No. 2007-33963

[0004] Particularly, in an organic EL display device having an organic EL film having a micro-cavity structure, as described above, the spectrum of light extracted to the outside becomes steep and high-intensity, so that color intensity and color development can be improved. However, there was a case where a sufficient field of view could not be obtained when viewing the display device obliquely. In addition, as in Patent Document 1, although manufacturing a color filter using a resin composition containing organic particulates has been studied in order to achieve sufficient visual field, the addition of organic particulates makes it possible to manufacture a color filter from the resin composition. In some cases, sufficient curability was not obtained, or pattern formation with a predetermined resolution was difficult.

[0005] Therefore, an object of the present invention is to provide a colored curable resin composition capable of providing an organic EL display device capable of providing a sufficiently good visual field even when viewed obliquely, and having sufficient curability. is to provide

[0006] 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 following aspects are included in this invention.

[1] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein the scattering intensity of the inorganic fine particles in Mie scattering is set to X, and the colored curable resin composition When the content of the inorganic fine particles relative to the solid content of is expressed as Y mass%, X is 4 or more and Y is 15 or less, and formula (1):

a=X×Y (1)

The colored curable resin composition in which the value a computed by is 10 or more.

[2] The colored curable resin composition according to [1], wherein the inorganic fine particles are metal oxides.

[3] The colored curable resin composition according to [1] or [2], wherein the inorganic fine particles have a refractive index of 1.3 or higher.

[4] 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.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the polymerizable compound is 0 mass% to 50 mass% with respect to the solid content of the colored curable resin composition.

[6] The colored curable resin composition according to any one of [1] to [5], wherein the cured film of the curable resin composition has a haze value of 8 to 40% in terms of a thickness of 2 µm.

[7] A cured film of the colored curable resin composition according to any one of [1] to [6].

[8] The cured film according to [7], which has a haze value of 8 to 40% in terms of a thickness of 2 μm.

[9] The cured film according to [7] or [8], which constitutes a color filter included in the color filter substrate.

[10] A display device comprising the cured film according to any one of [7] to [9].

[0007] According to the present invention, a color filter capable of providing an organic EL display device having a sufficiently good visual field even when viewed obliquely can be provided, and a colored curable resin composition having sufficient curability can be provided. .

[0008] Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made without departing from the spirit of the present invention. In addition, when a plurality of upper limit values and lower limit values are described for a specific parameter, any upper limit value and lower limit value among these upper limit values and lower limit values can be combined to form a suitable numerical range.

[0009] <Colored Curable Resin Composition>

The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, and X is the scattering intensity in fine scattering of the inorganic fine particles, and the solid content of the colored curable resin composition When the content of the inorganic fine particles with respect to is Y mass%, X is 4 or more and Y is 15 or less, formula (1):

a=X×Y (1)

The value a calculated by is a colored curable resin composition of 10 or more. In addition, in the following, the colored curable resin composition of the present invention is also referred to as the composition of the present invention.

[0010] (inorganic fine particles)

The colored curable resin composition of the present invention contains at least one kind of inorganic fine particles. In the present specification, the inorganic fine particles are usually inorganic particles having an average particle diameter of 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 micro-level average particle diameter or a nano-level 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 one kind of inorganic fine particles, or may contain two or more kinds of inorganic fine particles. Here, when X is the scattering intensity in fine scattering of the inorganic fine particles, and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is set to Y mass%, X is 4 or more and Y is 15 or less. , equation (1):

a=X×Y (1)

The value a calculated by is 10 or more.

[0011] The scattering intensity (X) of fine scattering of inorganic fine particles is a value calculated under the conditions of non-polarized light, light source wavelength 550 nm, and scattering angle 0 degree, for example, scattering intensity in fine scattering. It can be calculated using Mieplot (refer to http://www.philiplaven.com/mieplot.htm), a calculation program of . The larger the scattering intensity (X) is, the higher the light scattering effect is. When the scattering intensity (X) is less than 4, the light scattering effect by the inorganic fine particles becomes insufficient, and it becomes difficult to sufficiently secure the field of view when the organic EL display device is viewed obliquely. From the viewpoint of ensuring visibility when viewing the organic EL display device obliquely, the inorganic fine particles included in the composition of the present invention have a scattering intensity of 4 or more. From the standpoint of easy visibility in the organic EL display device, the value of the scattering intensity (X) is 4 or more, preferably 5 or more, more preferably 6 or more, still more preferably 7 or more. Further, when the value of X is large, the visibility when the organic EL display device is viewed obliquely and the curability when forming a color filter from the composition of the present invention are easily improved. The upper limit of the scattering intensity (X) is not particularly limited, but from the viewpoint of interfacial reflection control, it is preferably 10,000 or less, more preferably 1,000 or less, still more preferably 300 or less, still more preferably 100 or less.

[0012] The content (Y mass%) of the inorganic fine particles relative 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% by mass, it is difficult to increase the curability when forming a color filter from the colored curable resin composition, and the color intensity of the obtained color filter tends to decrease. The content (Y mass%) of the inorganic fine particles relative to the solid content of the colored curable resin composition is preferably 15 mass% or less, more preferably 10 mass%, from the viewpoints of curability during formation of the color filter and color development of the color filter. % by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less.

[0013] From the scattering intensity (X) of fine scattering of inorganic fine particles and the content (Y mass%) of inorganic fine particles relative to the solid content of the colored curable resin composition, formula (1):

a=X×Y (1)

The value a calculated by is 10 or more. When the value a is less than 10, the light scattering effect by the inorganic fine particles becomes insufficient, and it becomes difficult to provide a sufficient visual field when the organic EL display device is viewed obliquely. The value a is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, from the standpoint of easily improving the visibility when viewing the organic EL display device from an angle. Also, from the viewpoint of interfacial reflection control, it is preferably 800 or less, more preferably 600 or less, still more preferably 450 or less, still more preferably 350 or less.

[0014] Examples of the inorganic fine particles include inorganic fine particles of metals, metal oxides, ceramics, and composite materials, and from the viewpoint of scattering intensity, preferable inorganic fine particles are metal oxides. The composition of the present invention may contain one type of inorganic fine particles, or may contain two or more kinds of inorganic fine particles. The inorganic fine particles may be surface-treated. By subjecting the inorganic fine particles to surface treatment, the 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 applied to the inorganic fine particles include treatment with a silane coupling agent, a silylating agent, an organic titanate-based coupling agent, and silicone oil.

Examples of the metal oxide include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide. The metal oxide is preferably titanium oxide, zinc oxide and/or silica, more preferably titanium oxide and/or silica, still more preferably titanium oxide. When the composition of the present invention contains a metal oxide as the inorganic fine particles, it may contain one type of metal oxide or two or more types of metal oxides.

[0016] The refractive index of the inorganic fine particles is the refractive index at 550 nm, and from the viewpoint of the scattering intensity, it is preferably 1.3 or more, more preferably 1.9 or more, still more preferably 2.2 or more, still more preferably 2.5 or more. . In addition, the refractive index of the inorganic fine particles is preferably 2.8 or less from the viewpoint of interfacial reflection control. The refractive index can be measured, for example, by ellipsometry.

[0017] 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, still more preferably 0.15 μm or more, from the viewpoint of scattering intensity. In addition, the average particle diameter of the inorganic fine particles is preferably 0.70 μm or less, more preferably 0.50 μm or less, still more preferably 0.30 μm or less, still more preferably 0.25 μm or less, especially from the viewpoint of suppressing particle sedimentation. Preferably it is 0.20 micrometer or less. The average particle diameter can be measured by, for example, a dynamic light scattering method.

[0018] (Suzy)

The resin contained in the composition of the present invention is not particularly limited, but is preferably an alkali-soluble resin. The composition of this invention may contain 1 type of resin, and may contain 2 or more types of resin. Examples of the resin include the following resins [K1] to [K6].

Resin [K1]; A structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"), and having 2 to 4 carbon atoms. copolymers having a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure and an ethylenically unsaturated bond;

Resin [K2]; A structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) (hereinafter “(c) a copolymer having a structural unit derived from);

Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

Resin [K4]; a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (b) to the structural unit derived from (a);

Resin [K5]; a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b);

Resin [K6]; Air having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a polyhydric carboxylic acid and/or carboxylic acid anhydride. coalescence.

[0020] As (a), specifically, for example,

unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

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, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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 bicyclo unsaturated compounds containing a carboxyl group such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyethyl of divalent or higher valent carboxylic acids such as succinate mono[2-(meth)acryloyloxyethyl] and phthalate mono[2-(meth)acryloyloxyethyl] alkyl] esters;

and unsaturated acrylates containing a hydroxyl group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, etc. are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in aqueous alkali solution.

[0021] (b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Eggplant refers to a polymerizable compound. As (b), a monomer having a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

In this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0022] As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (b2) ) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

[0023] As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), an alicyclic and a monomer (b1-2) having a structure in which an unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0024] As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (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(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene Cydyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) ) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene etc. can be mentioned.

[0025] As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (eg, Ceroxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) Acrylates (eg Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg Cyclomer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decyl (meth)acrylate, the compound represented by formula (BI), and the compound represented by formula (BII), etc. are mentioned.

[0026]

[In formula (BI) and formula (BII), R ^e and R ^f represent 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 hydroxy group.

X ^e and X ^f represent 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 a bond hand with O.]

[0027] 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 in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxyl group. A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^e and R ^f , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferably used, and a hydrogen atom and a methyl group are more preferable.

[0028] As the alkanediyl group, a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group etc. are mentioned.

Examples of X ^e and X ^f include preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *- and CH ₂ CH ₂ -O- (* indicates a bond with O).

[0029] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

[0030] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscott V#150, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), tetrahydrofurfuryl methacrylate and the like.

(b) is preferably (b1) in the case of Resin [K1] or Resin [K2] from the viewpoint of being able to further enhance the reliability of the obtained color filter in terms of heat resistance and chemical resistance.

[0032] As (c), for example, 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, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (as a common name in the art, "dicyclopentanyl (meth) acryl Also referred to as “tricyclodecyl (meth)acrylate”), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (the technical field , as a common name, it is referred to as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate (meth)acrylic acid esters such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxyl group-containing (meth)acrylic acid esters 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-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 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 -2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cicarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy bicyclo unsaturated compounds such as ccarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, (meth)acrylic acid esters are preferable.

[0033] In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is:

structural units derived from (a); 2 to 60 mol%

structural units derived from (b); 40 to 98 mol%

It is desirable that

structural units derived from (a); 10 to 50 mol%

structural units derived from (b); 50 to 90 mol%

is more preferable.

When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a pattern, and excellent solvent resistance of the resulting cured film.

[0034] The resin [K1], for example, is described in the document "Experimental Methods of Polymer Synthesis" (authored by Otsu Takayuki, published by Kagaku-Dojin Publishing Company, INC., 1st edition, 1st printing, March 1, 1972). It can be prepared by referring to the method and cited literature described in the literature.

[0035] Specifically, predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and, for example, by substituting oxygen with nitrogen, a deoxygenation atmosphere is set, and stirring ( The method of heating and keeping warm while exchanging is mentioned. In addition, the polymerization initiator and solvent used herein are not particularly limited, and those commonly used in the field can be used. For example, as a polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, t- butyl peroxy-2-ethylhexanoate, etc.), and the solvent may be one that dissolves each monomer. can

In addition, the obtained copolymer may be used as a solution after reaction, a concentrated or diluted solution may be used, or a copolymer extracted as a solid (powder) by a method such as re-precipitation is used. can also In particular, as a solvent during this polymerization, by using a solvent as described later, which is optionally included in the composition contained in the colored curable resin composition of the present invention, the solution after the reaction is prepared as it is in the colored curable resin composition of the present invention Since it can be used for, the manufacturing process of the colored curable resin composition of this invention can be simplified.

[0037] In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2] is:

structural units derived from (a); 2 to 45 mol%

structural units derived from (b); 2 to 95 mol%

structural units derived from (c); 1 to 65 mol%

It is desirable that

structural units derived from (a); 5 to 40 mol%

structural units derived from (b); 5 to 80 mol%

structural units derived from (c); 5 to 60 mol%

is more preferable.

When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to be excellent in storage stability, developability when forming a pattern, and solvent resistance, heat resistance and mechanical strength of the resulting cured film. there is.

[0038] Resin [K2] can be produced, for example, in the same manner as described as the method for producing resin [K1].

[0039] In the resin [K3], the ratio of the structural units derived from each is, among the total structural units constituting the resin [K3],

structural units derived from (a); 2 to 60 mol%

structural units derived from (c); 40 to 98 mol%

It is desirable that

structural units derived from (a); 10 to 50 mol%

structural units derived from (c); 50 to 90 mol%

is more preferable.

Resin [K3] can be produced, for example, similarly to the method described as the method for producing resin [K1].

Resin [K4] is obtained by obtaining a copolymer of (a) and (c), and the cyclic ether having 2 to 4 carbon atoms of (b) is a carboxylic acid and/or a carboxylic acid having (a) It can be prepared by adding to an anhydride.

First, a copolymer of (a) and (c) is prepared in the same manner as described for the production method of Resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as exemplified in relation to Resin [K3].

Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).

Following the preparation of the copolymers of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a catalyst for the reaction of a carboxylic acid or carboxylic anhydride with a cyclic ether (e.g. tris( dimethylaminomethyl) phenol, triphenylphosphine, etc.) and a polymerization inhibitor (eg, hydroquinone, methoquinone, etc.), etc. are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours, and the resin [K4 ] can be produced.

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it as this range, the balance of the storage stability of curable resin composition, the developability at the time of forming a pattern, pattern shape, hardenability at low temperature, and the solvent resistance of the pattern obtained, heat resistance, mechanical strength, and sensitivity tends to become favorable. there is. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b) used for resin [K4] is preferably (b1) and more preferably (b1-1).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).

Reaction conditions, such as a charging method and reaction temperature and time, can be appropriately adjusted in consideration of production equipment and the calorific value due to polymerization. In addition, similarly to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of manufacturing equipment and the calorific value due to polymerization.

[0042] Resin [K5], as a first step, is obtained in the same manner as in the production method for resin [K1] described above, to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as a solution after reaction, a concentrated or diluted solution, or extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is relative to the total number of moles of all the structural units constituting the above copolymer, respectively,

structural units derived from (b); 5 to 95 mol%

structural units derived from (c); 5 to 95 mol%

It is desirable that

structural units derived from (b); 10 to 90 mol%

structural units derived from (c); 10 to 90 mol%

is more preferable.

When the ratio of the structural unit of the resin [K5] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a pattern, the pattern shape, the curability at low temperatures, and the solvent resistance of the pattern obtained, The balance of heat resistance, mechanical strength and sensitivity tends to be good.

[0043] Further, under the same conditions as in the production method of resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is converted to the carboxylic acid or carboxyl ether of (a). Resin [K5] can be obtained by reacting boxylic acid anhydride.

The amount of (a) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], (b1) is preferable, and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting polyhydric carboxylic acid and/or carboxylic acid anhydride with Resin [K5]. A polyhydric carboxylic acid and/or a carboxylic acid anhydride is further reacted with a hydroxyl group generated by the reaction between the cyclic ether derived from (b) and the carboxylic acid or carboxylic acid anhydride derived from (a).

Examples of polyhydric carboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of the carboxylic acid 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. 0.05-1 mol is preferable with respect to 1 mol of usage-amounts of (a), and, as for the usage-amount of polyhydric carboxylic acid and/or carboxylic acid anhydride, 0.1-0.5 mol is more preferable.

[0045] As the resin contained in the colored curable resin composition of the present invention, a resin having a structural unit having an ethylenically unsaturated bond in the side chain (resin [K4] or resin [K5]) is preferable, and in the side chain (meta) A resin having a structural unit containing an acryloyl group is more preferred.

Examples of the resin having a structural unit containing a (meth)acryloyl group in the side chain include (b) glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3-methyl Resin [K4] using a monomer having a (meth)acryloyl group such as 3-methacryloyloxymethyloxetane or tetrahydrofurfuryl acrylate, and acrylic acid, methacrylic acid, or succinic acid mono as (a) Resin [K5] using a monomer having a (meth)acryloyl group such as [2-(meth)acryloyloxyethyl] is preferable.

In Resin [K4] and Resin [K5], as (c), dicarbonylimide derivatives and vinyltoluene 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 3,000 to 100,000, more preferably 4,000 to 50,000, still more preferably 5,000 to 30,000. When the weight average molecular weight of the resin is within the above range, the hardness of the cured film of the composition of the present invention is improved, the residual film rate is high, the solubility in the developing solution of the unexposed area is good, and the pattern shape is is improved, and the resolution of the pattern tends to be improved.

The degree of dispersion [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.

[0048] The acid value of the resin, in terms of solid content, is preferably 10 to 170 mg-KOH/g, more preferably 20 to 150 mg-KOH/g, still more preferably 30 to 135 mg-KOH/g. is g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

[0049] The content of the resin is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, still more preferably from 15 to 60% by mass, and still more preferably from the total amount of the solid content of the colored curable resin composition. More preferably, it is 20 to 50% by mass. When the content of the resin is within the above range, the curability of the colored curable resin composition is easily improved, patterns are easily formed, and the resolution and remaining film rate of the patterns tend to be improved. In addition, in this specification, "total amount of solid content" means the quantity remove|excluding content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and the content of each component thereof can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0050] (polymerizable compound)

The polymerizable compound is a compound that can be polymerized by an active radical generated from a polymerization initiator and/or an acid, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, etc., preferably (meta) It is an acrylic acid ester compound.

[0051] Especially, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate )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, caprolactone-modified dipentaerythritol hexa(meth)acrylate Acrylates are mentioned.

Especially, when it sees from a viewpoint of a pattern shape, dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate are preferable.

[0052] The weight average molecular weight of the polymerizable compound is preferably 150 or more and 2,900 or less, from the viewpoint of making it easy to improve the pattern shape and easily adjusting the curability of the colored curable resin composition to an appropriate range. Preferably they are 250 or more and 1,500 or less.

[0053] The content of the polymerizable compound is preferably 3% by mass or more, more preferably 6% by mass or more, still more preferably 9% by mass or more, with respect to the total amount of solids contained in the colored curable resin composition. Preferably it is 12 mass % or more. Further, the content of the polymerizable compound is preferably 50% by mass or less, more preferably 46% by mass or less, still more preferably 43% by mass or less, still more preferably, with respect to the total amount of solids contained in the colored curable resin composition. It is 40 mass % or less. When content of a polymeric compound is more than the said lower limit, sclerosis|hardenability of colored curable resin composition is easy to be improved, and it is easy to form a pattern. In addition, when the content of the polymerizable compound is equal to or less than the above upper limit, when the coating film of the colored curable resin composition is exposed to light and the coating film is cured, the degree of curing within the coating film is unlikely to vary, particularly the coating film. It becomes possible to sufficiently harden to the deep part of, and it is easy to obtain a favorable pattern shape.

When the sum of the mass of the resin (preferably the alkali-soluble resin, more preferably the resin [K1] to [K6]) and the mass of the polymerizable compound contained in the colored curable resin composition is 100% by mass, The content of the polymerizable compound is preferably 50% by mass or less, more preferably 47% by mass or less, even more preferably 45% by mass or less, still more preferably 43% by mass or less. When the content of the polymerizable compound is not more than the above upper limit, when the coating film of the colored curable resin composition is exposed to light and the coating film is cured, the degree of curing within the coating film is unlikely to vary, particularly to sufficiently cure the deep portion of the coating film. This becomes possible, and it is easy to obtain a good pattern shape.

[0055] (polymerization initiator)

A polymerization initiator is a compound capable of initiating polymerization by generating active radicals, acids, and the like under the action of light or heat. Although it does not specifically limit as a polymerization initiator, O-acyl oxime compound, an alkyl phenone compound, a biimidazole compound, a triazine compound, and an acyl phosphine oxide compound are mentioned. Especially, it is preferable that it is an O-acyl oxime compound. The polymerization initiator preferably has a maximum absorption wavelength in the range of 365 to 390 nm, and more preferably has a maximum absorption wavelength in the range of 370 to 390 nm, from the viewpoint of more easily improving the curability of the colored curable resin composition. . The colored curable resin composition of the present invention may contain one type of polymerization initiator or may contain two or more types of polymerization initiators.

[0056] As the polymerization initiator, an O-acyloxime compound is preferable. Further, the polymerization initiator is preferably a compound having a carbazole skeleton, and is also preferably a compound having a nitro group.

[0057] The O-acyloxime compound is formula (c1):

It is a compound having a structure represented by

[0058] The compound having a carbazole skeleton has the formula (c2):

It is a compound having a structure represented by Hereinafter, * represents a binding hand.

[0059] The compound having a nitro group (-N ₂ O) is preferably a compound having at least one nitro group bonded to an aromatic ring, more preferably at least one nitro group bonded to an aromatic ring included in the carbazole skeleton. It is a compound having a group.

[0060] The polymerization initiator is more preferably an O-acyloxime compound having a carbazole skeleton. Examples of such a compound include a compound represented by formula (c3) (hereinafter sometimes referred to as compound (c3)) and a compound represented by formula (c4) (hereinafter sometimes referred to as compound (c4)). At least 1 sort(s) selected from the group which consists of is mentioned.

[In formulas (c3) and (c4),

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, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is - It may be substituted with O-, -CO- or -S-, and the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group is It may be substituted with an OH group.

In addition, in this specification, when a methylene group ( _-CH2- ) etc. is substituted with -O-, -CO-, -S- etc., carbon number means the carbon number before substitution.

R ^b is 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 an aromatic hydrocarbon group and the alkyl group represents a group which may have a substituent in combination with an alkanediyl group derived from, and the methylene group (-CH ₂ -) contained in the alkyl group is -O-, -CO-, -S-, -SO ₂ - or -NR ^h - may be substituted. R ^h 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.

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 represents 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.

[0061] The number of carbon atoms of the aromatic hydrocarbon group represented by R ^a is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, more preferably a phenyl group and a naphthyl group, and still more preferably a phenyl group.

Moreover, the aromatic hydrocarbon group represented by R ^a may have one or two or more substituents. As this substituent, the same group as the substituent which the aromatic hydrocarbon group of R ^a may have is mentioned.

[0062] The number of carbon atoms in the aliphatic hydrocarbon group represented by R ^a is preferably 1 to 13, more preferably 2 to 10. As the aliphatic hydrocarbon group represented by R ^a , methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, Alkyl groups, such as a tridecyl group, a tetradecyl group, and a pentadecyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadecenyl group and pentadecenyl group Neil group; etc. can be mentioned. These aliphatic hydrocarbon groups may be chain (linear or branched) or cyclic, or may be a combination of a chain group and a cyclic group. In addition, in the aliphatic hydrocarbon group of R ^a , the methylene group (-CH ₂ -) may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) is -PO ₃ < may be substituted, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

[0063] Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^a include groups represented by the following formulas. In the formula, * represents a bonding hand.

[0064] R ^a is preferably a chain-like aliphatic hydrocarbon group which may have a substituent, more preferably a chain-like alkyl group without a substituent, still more preferably a straight-chain or branched-chain alkyl group without a substituent .

[0065] The number of carbon atoms of the aromatic hydrocarbon group represented by R ^b is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, with a phenyl group and a naphthyl group being more preferred, and a phenyl group being particularly preferred.

Moreover, the aromatic hydrocarbon group represented by R ^b may have one or two or more substituents. It is preferable that the substituent is substituted at the ortho position or para position of the aromatic hydrocarbon group. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. an alkyl group having 1 to 15 carbon atoms; Halogen atoms, such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; etc. can be mentioned.

It is preferable that it is 1-10, and, as for carbon number of the alkyl group as the said substituent, it is more preferable that it is 1-7. The alkyl group as the substituent may be straight-chain, branched-chain, or cyclic, or may be a combination of a chain-like group and a cyclic group. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent 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.

[0066] Examples of the alkyl group as a substituent for the aromatic hydrocarbon group represented by R ^b include groups represented by the following formulas. In the formula, * represents a bonding hand.

[0067]

[0068]

[0069] Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^b include groups represented by the following formulas. In the formula, * represents a bonding hand.

[0070]

[0071]

[0072] As the aromatic hydrocarbon group which may have a substituent represented by R ^b , a group represented by the following formula is preferable.

[In the formula, R ⁱ each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the methylene group (-CH ₂ -) contained in R ⁱ is -O- or -S- may be substituted, R ^j represents an alkyl group having 1 to 10 carbon atoms which may be each independently substituted with a halogen atom, q represents an integer of 1 to 5, and r represents an integer of 0 to 4. However, the sum of q+r is 5 or less.]

[0073] Examples of the alkyl group represented by R ⁱ and R ^j include the same groups as the alkyl groups exemplified as substituents of the aromatic hydrocarbon group represented by R ^b . As for carbon number of R ⁱ , it is preferable that it is 2-8, and it is more preferable that it is 2-6. In addition, the alkyl group represented by R ^<j> may be any of a linear, branched chain, and cyclic form, and a chain form is preferable. R ⁱ is preferably a group represented by the formula *-R ^j1 -OR ^j2 . Here, R ^j2 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R ^<j2> , it is preferable that it is a C1-C3 linear alkyl group. R ^j1 represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R ^<j1> , it is preferable that it is a C1-C3 linear alkylene group.

When R ⁱ and R ^j contain a halogen atom, examples of the halogen atom included in R ⁱ and R ^j include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, with a fluorine atom being particularly preferable.

Moreover, when a halogen atom is contained in R ⁱ and/or R ^j , the number is preferably 2 or more and 10 or less, and more preferably 3 or more and 6 or less. The substitution position of the R ⁱ O- group is preferably an ortho position or a para position. The substitution position of the R ^j - group is preferably an ortho position or a para position, and particularly preferably an ortho position.

Moreover, as for q, it is preferable that it is 1-2, and it is more preferable that it is 1. r is preferably 0 to 2, and particularly preferably 0 or 1.

[0074] The number of carbon atoms of the heterocyclic group represented by R ^b is preferably 3 to 20, more preferably 3 to 10, 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, and a carbazolyl group.

In addition, the heterocyclic group represented by R ^b may have one or two or more substituents. As this substituent, the group same as the group illustrated as the substituent which the aromatic hydrocarbon group represented by ^Rb may have is mentioned.

[0075] The number of carbon atoms of the alkyl group represented by R ^b is preferably 1 to 12. Examples of the alkyl group represented by R ^b include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and A pentadecyl group etc. are mentioned. These alkyl groups may be straight-chain, branched-chain, or cyclic, or a combination of a chain-like group and a cyclic group. In the alkyl group represented by R ^b , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^h -, and a hydrogen atom may be substituted with an OH group or an SH group.

[0076] R ^h represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be chain (linear or branched) or cyclic, may be any of linear, branched, and cyclic, or may be a combination of a chain and a cyclic group. In the alkyl group of R ^h , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

[0077] Specific examples of the alkyl group that may have a substituent represented by R ^b include groups represented by the formulas below. * represents a bonding hand.

[0078]

[0079] Further, the number of carbon atoms of the group combining the aromatic hydrocarbon group represented by R ^b and the alkanediyl group derived from the alkyl group represented by R ^b is preferably 7 to 33, more preferably 7 to 18 , and more preferably 7 to 12. The combined group may have one or two or more substituents, and examples of the substituents include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group and the alkyl group may have. Examples of the group combining an aromatic hydrocarbon group represented by R ^b and an alkanediyl group derived from an alkyl group represented by R ^b include an aralkyl group, and specifically, a group represented by the formula below. . In the formula, * represents a bonding hand.

[0080]

[0081] Especially, as R ^b , an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent is preferable, and an aromatic hydrocarbon group which may have a substituent is more preferable.

[0082] The number of carbon atoms of the aromatic hydrocarbon group represented by R ^c is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

The number of carbon atoms of the heterocyclic group represented by R ^c is preferably 3 to 20, more preferably 3 to 10, 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, and a carbazolyl group.

The number of carbon atoms of the alkyl group represented by R ^c is preferably 1 to 7, more preferably 1 to 5, still more preferably 1 to 3. Examples of the alkyl group include 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. The alkyl group may be straight-chain, branched-chain, or cyclic, or may be a combination of a chain-like group and a cyclic group.

[0083] As ^Rc , a chain-like alkyl group is preferable, more preferably a chain-like alkyl group having 1 to 5 carbon atoms, even more preferably a chain-like alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferable.

[0084] The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

In addition, the aromatic hydrocarbon group represented by R ^d may have one or two or more substituents. It is preferable that the substituent is substituted at the ortho position or para position of the aromatic hydrocarbon group. As the substituent, an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferable, and specifically, 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 having a carbon number of 1 an alkyl group of -15; alkenyl groups having 1 to 15 carbon atoms such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group and decenyl group; etc. can be mentioned.

It is more preferable that the number of carbon atoms of the aliphatic hydrocarbon group represented by R ^d is 1 to 7, and the aliphatic hydrocarbon group may be straight-chain, branched-chain, or cyclic. The contribution which combined group and ring-shaped group may also be sufficient. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) is substituted with -N< There may be.

[0085] Examples of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by ^Rd may have include groups represented by the following formulas. In the formula, * represents a bonding hand.

[0086]

[0087] Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d include groups represented by the formulas below. In the formula, * represents a bonding hand.

[0088]

[0089] The number of carbon atoms of the heterocyclic group represented by R ^d is preferably 3 to 20, more preferably 3 to 10, 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, and a carbazolyl group.

The heterocyclic group represented by ^Rd may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the substituents the aromatic hydrocarbon group represented by ^Rb may have.

[0090] Among them, R ^d is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of substituents is It is preferable that it is 2 or more and 5 or less.

[0091] Compound (c3) and compound (c4) can be produced by a production method described in Japanese Patent Publication No. 2014-500852 or International Publication No. 2008-078678.

[0092] In the compound (c3), preferably, R ^a is an alkyl group having 1 to 15 carbon atoms which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and R ^c is a carbon number An alkyl group of 1 to 10, and a compound in which p is 1 or 2,

More preferably, R ^a is an alkyl group having 1 to 4 carbon atoms which may have a substituent, and R ^b is the following formula:

[Wherein, R ^j is an alkyl group having 1 to 3 carbon atoms, and R ⁱ is a group represented by the formula *-R ^j1 -OR ^j2 [wherein R ^j1 is a linear or branched chain having 1 to 4 carbon atoms; represents an aliphatic hydrocarbon group which may be substituted with a halogen atom, and R ^j2 represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom], hydrogen atoms contained in R ⁱ and R ^j are halogen atoms May be substituted by atoms. q and r are 1.]

It is a group represented by , R ^c is an alkyl group having 1 to 4 carbon atoms, and p is a compound of 1.

As a commercial item of compound (c3), NCI-831 (made by ADEKA Corporation) is mentioned.

[0093] In the compound (c4), preferably, R ^a is an alkyl group having 1 to 10 carbon atoms which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ^c is a carbon number It is an alkyl group of 1 to 4, and is a compound in which R ^d represents an aromatic hydrocarbon group which may have a substituent.

As a commercial item of compound (c4), Irgacure OXE03 (made by BASF Corporation) is mentioned.

[0094] The alkylphenone compound is a compound having a partial structure represented by formula (d4) or a partial structure represented by formula (d5). Among these partial structures, the benzene ring may have a substituent.

[0095]

[0096] As the compound having the structure represented by formula (d4), 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane -1-one etc. are mentioned. You may use commercial items, such as Irgacure 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2-hydroxyl). Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α - Diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

From the viewpoint of sensitivity, as the alkylphenone compound, a compound having a structure represented by formula (d4) is preferable.

[0097] As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) Phenyl) -4,4', 5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. H06-75372, Japanese Patent Laid-Open No. H06-75373, etc.), 2,2'-bis (2 -Chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (di Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., Japanese Patent Publication No. S48-38403) , Japanese Patent Laid-Open No. S62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (for example, Japanese Patent Laid-Open No. H07-10913) See etc.) and the like. Especially, the compound represented by the following formula and mixtures thereof are preferable.

[0098]

[0099] As the triazine compound, 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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine; and the like.

[0100] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0101] The content of the polymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, still more preferably 2 to 30 parts by mass, based on the total amount of solids contained in the colored curable resin composition. am. When the content of the polymerization initiator is within the above range, it is easy to form a pattern of a good shape by exposure and development, and it is easy to improve the curability at low temperatures. In addition, since exposure time tends to be shortened due to increased sensitivity, productivity of color filters and the like is improved.

[0102] (colorant)

The colored curable resin composition of the present invention contains at least one colorant. The coloring agent may be either a dye or a pigment, but preferably contains a pigment. As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0103] Specifically, 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, yellow pigments such as 214;

C.I. orange pigments such as 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, red pigments such as 291;

C.I. blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 16, and 60;

C.I. Violet color pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments of Pigment Green 7, 36, 58, 59;

C.I. brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

[0104] The pigment, if necessary, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method An atomization treatment by the like, a washing treatment with an organic solvent or water, etc. to remove impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.

It is preferable that the pigment has a uniform particle size. Furthermore, by containing a pigment dispersant and carrying out dispersion treatment, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained.

[0105] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used independently or may be used in combination of 2 or more type. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Lubrizol Corporation), EFKA (manufactured by CIBA), Ajispa as trade names (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie), and the like.

[0106] When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

[0107] The content of the pigment is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, based on the total amount of the colorant, and 100 It may be mass %.

[0108] The colorant may contain a dye. The dye is not particularly limited, and known dyes can be used, and solvent dyes, acid dyes, direct dyes, mordant dyes, and the like are exemplified. As the dye, for example, a compound classified as having a color other than pigment in the color index (published by The Society of Dyers and Colourists), and a dyeing note (SHIKISENSHA CO., LTD. [color 染社]) The well-known dyes which have been described are mentioned. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium ) dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

[0109] Specifically, 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. Solvent 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, 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. C.I. solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. 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, 1 84, 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, 2 81, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 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, 90:1, 91, 92, 93, 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, 2 36, 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, 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 Orange 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, 1 96, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 2 46, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 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 dye,

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 Green 1 and other C.I. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. C.I., such as Reactive Red 36. reactive dyes,

C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern Trend 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. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Mordant 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. Modernt 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. C.I. mordant Dye,

C.I. C.I. of vat green 1 etc. Vat dye etc. are mentioned.

The content of the dye is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less with respect to the total amount of the colorant, It may be 0 mass %.

[0111] The content of the colorant is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, still more preferably 10 to 50% by mass, based on the total amount of solid content of the colored curable resin composition. If the content of the colorant is within the above range, the color density when used as a color filter is sufficient, and since a required amount of resin or polymeric compound can be contained in the composition, a pattern with sufficient mechanical strength can be formed.

[0112] In the colored curable resin composition that is required to be particularly darkened, the content of the colorant is preferably 4 to 60% by mass, more preferably 4 to 60% by mass, based on the total solid content of the curable resin composition. It is 6-56 mass %, More preferably, it is 8-53 mass %, More preferably, it is 10-50 mass %. When the content of the colorant is within the above range, a particularly high color density can be achieved when used as a color filter, and a required amount of resin or polymeric compound can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed. there is.

[0113] In the colored curable resin composition of the present invention, the colorant preferably contains a xanthene dye. A xanthene dye is a dye containing a compound having a xanthene skeleton in a molecule. As the xanthene dye, a dye containing a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)") is preferable.

[0114] [In formula (I), R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -.

R ⁵ is -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 ⁷ each independently represent 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 's may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ , or K ⁺ , and the four R ^11s may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- , -NH-, or -NR ⁸ -, or may be substituted with R ⁹ and R ¹⁰ to form a 3- to 10-membered heterocyclic 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.]

[0115] Compound (I) may be a tautomer thereof. When using Compound (I), the content of Compound (I) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more with respect to the solid content of the colorant contained in the colored curable resin composition. , more preferably 90% by mass or more, most preferably 100% by mass.

[0116] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ include a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Straight-chain alkyl groups, such as a dodecyl group, a hexadecyl group, and an icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and an alicyclic saturated hydrocarbon group having 2 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group. The number of carbon atoms of the saturated hydrocarbon group is a number including carbon atoms of the substituent when it has a substituent. Examples of substituents that the saturated hydrocarbon group may have are halogen atoms, -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 ¹⁴ each independently represent 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.

[0117] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R ¹ to ^{R 4} include a phenyl group. A toluyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group etc. are mentioned as a monovalent aromatic hydrocarbon group which has a substituent. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms in the aromatic hydrocarbon group includes carbon atoms in the substituent. As a substituent which an aromatic hydrocarbon group may have, a halogen atom, ^-R8 , -OH, ^-OR8 , _-SO3- ^, -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 ).

[0118] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include 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, straight-chain alkyl groups such as a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

[0119] The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may have a substituent. A hydroxyl group and a halogen atom are mentioned as this substituent.

Examples of the monovalent saturated hydrocarbon group having 1 to 4 carbon atoms in R ¹² to ^{R 14} include straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; C1-C4 alicyclic saturated hydrocarbon groups, such as a branched-chain alkyl group, such as an isopropyl group and an isobutyl group, are mentioned.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) Of the four R ¹¹ in ₄ , at least 2 are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, it is preferable that it is 20-80, and, as for the total number of carbon atoms of 4 R ^<11> , it is more preferable that it is 20-60. When ⁺ N(R ¹¹ ) ₄ is present in compound (I), if R ¹¹ is any of these groups, a color filter with fewer foreign substances can be formed from the negative resist composition of the present invention containing compound (I).

[0122] Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group. can be heard

[0123] Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0124] Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0125] Examples of -SO ₂ NR ⁹ R ¹⁰ include a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group diyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as a N,N-tert-butylmethylsulfamoyl group, a N,N-butylethylsulfamoyl group, a N,N-bis(1-methylpropyl)sulfamoyl group, a N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

[0126] Examples of -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ) include a trimethoxysilyl group and a triethoxysilyl group.

[0127] R ⁵ is preferably -CO ₂ H, -CO ₂ ^{-Z +} , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^{-Z +} , -SO ₃ H, or SO ₂ NHR ⁹ , SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ are more preferred.

m represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0129] Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the alkyl groups exemplified above, and the alkyl group having 1 to 2 carbon atoms is preferable. It is more preferable that R ⁶ and R ⁷ are hydrogen atoms.

[0130] Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0131] a represents an integer of 0 or 1, and 0 is preferable.

As the compound (I), a compound represented by formula (Ia) (hereinafter also referred to as “compound (Ia)”) is preferably exemplified. The compound represented by formula (Ia) may be used without being combined with a compound other than compound (Ia) in Compound (I) (hereinafter sometimes referred to as "compound (Ib)"), and may be used with Compound (Ia) You may use it combining the compound (Ib) mentioned later. In addition, you may use compound (Ia) in combination of 2 or more types.

[In formula (Ia),

R ^a1 and R ^a4 are each independently a monovalent aromatic hydrocarbon group which may have a monovalent saturated aliphatic hydrocarbon group having 2 or less carbon atoms and 1 to 4 carbon atoms.

R ^a2 and R ^a3 are each independently a hydrogen atom, a methyl group, or an ethyl group.

R ⁵ to R ⁷ , m, a, and X represent the same meanings as above.]

[0133] As R ^a1 and R ^a4 , among the same groups as R ¹ and R ⁴ above, 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 carbon atoms is used. A monovalent aromatic hydrocarbon group may be mentioned. Among them, a monovalent aromatic hydrocarbon group having 2 or less carbon atoms of a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable.

[0134] Examples of the monovalent aromatic hydrocarbon group having no substituent include a phenyl group. Examples of the monovalent aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms include a toluyl group, a xylyl group, and a mesityl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, even more preferably 7 to 10, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group is a number including carbon atoms in substituents. It is preferable that the said aromatic hydrocarbon group does not have a substituent other than the said saturated aliphatic hydrocarbon group.

[0135] The number of the saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, and more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded at an ortho position or meta position to the bond of the aromatic hydrocarbon group, more preferably at an ortho position. As this saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group which does not have a substituent is mentioned. 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.

[0136] Examples of R ^a2 and R ^a3 include a hydrogen atom, a methyl group, and an ethyl group, and among these, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

As the compound (Ib), a compound represented by formula (Ib1) (hereinafter sometimes referred to as “compound (Ib1)”) is preferable. Compound (Ib1) is preferably used in combination with compound (Ia), but may be used without being combined with compound (Ia). That is, the xanthene dye may be Compound (Ia) and/or Compound (Ib1), preferably Compound (Ia) or Compound (Ia) and Compound (Ib1), and more preferably Compound (Ia). .

[In formula (Ib1), R ^b1 to ^{R b4} are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent saturated hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represents an aromatic hydrocarbon group,

At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in ^Rb1 to ^Rb4 is 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 substituents Or, at least one aromatic hydrocarbon group contained in ^Rb1 to ^Rb4 has a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms of 1 to 4 as a substituent,

R ⁵ to ^{R 10} , R ¹² to ^{R 14} , m, a, and X have the same meaning as described above.]

[0138] As ^Rb1 and ^Rb4 , among the same groups as R ¹ and R ⁴ above, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a carbon number 6 to 20 which may have a substituent A monovalent aromatic hydrocarbon group or an aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms and having 1 to 4 carbon atoms as a substituent is exemplified. Among them, 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 having a substituent, or a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms and 1 to 4 carbon atoms, as a substituent group An aromatic hydrocarbon group having as is preferable.

[0139] The carbon number 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, still more preferably 2 to 7. The number of carbon atoms in the saturated aliphatic hydrocarbon group is a number including carbon atoms in substituents. As substituents, 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 ) are preferred, and 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 ), more 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 per one saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

[0140] The number of carbon atoms of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 12, still more preferably 7 to 10, particularly preferably 7 to 8, most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group is a number including carbon atoms in substituents. As the substituent, a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, 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 ) are preferred, more preferably is a monovalent ^saturated aliphatic hydrocarbon group having 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 . As for the number of substituents, per aromatic hydrocarbon group, 1-5 are preferable, 1-3 are more preferable, 1-2 are still more preferable, and 2 is the most preferable. The substituent is preferably bonded to the ortho position and/or meta position to the bond of the aromatic hydrocarbon group, and more preferably ortho position.

[0141] The number of carbon atoms of the aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms of 1 to 4 as a substituent is preferably 9 to 20, more preferably 9 to 13, still more preferably 9 to 12, most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group is a number including carbon atoms in substituents. It is preferable that the said aromatic hydrocarbon group does not have a substituent other than the said 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 per aromatic hydrocarbon group. The saturated aliphatic hydrocarbon group is preferably bonded to the ortho position and/or para position to the bond of the aromatic hydrocarbon group, and is more preferably bonded to the ortho position and para position. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

[0142] As R ^b2 and R ^b3 , among the same groups as R ² and R ³ above, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferably exemplified. Among these, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, is more preferable, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a substituent is still more preferable.

The number of carbon atoms in 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 in the saturated aliphatic hydrocarbon group is a number including carbon atoms in substituents. As substituents, 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 ) are preferred, and 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 ), more preferably -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), most preferably Preferably -CO ₂ H or -CO ₂ R ⁸ . The number of substituents per one saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

As compound (Ia), compound No. specified by formula (Iax) and Table 1. 1 to 15 are preferable.

[0145] [Table 1]

[0146] Symbols in the formula mean the following groups (hereafter, * represents a bonding hand).

As compound (Ib1), compound No. specified by formula (Ibx) and Table 2. Compounds represented by 16 to 35 and formulas A3-1 to A3-8 are preferred.

[0148] [Table 2]

[0149] Symbols in the formula mean the following groups (hereafter, * represents a bonding hand).

[0150]

[0151] (polymerization initiation aid)

The colored curable resin composition of the present invention may further contain at least one type of polymerization initiation assistant (E). The polymerization initiation aid is a compound or a sensitizer used to promote polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When a polymerization initiation aid (E) is included, it is usually used in combination with a polymerization initiator (C).

As the polymerization initiation aid (E), 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2 , 4-diethyl thioxanthone, N-phenylglycine, etc. are mentioned.

When using these polymerization initiation aids, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin and the polymerizable compound. When the amount of the polymerization initiation aid is within this range, patterns can be formed with higher sensitivity, and productivity of color filters and the like tends to improve.

[0153] (leveling agent)

The colored curable resin composition of the present invention may further contain at least one leveling agent. Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicon surfactants having a fluorine atom. These may have a polymeric group in a side chain.

[0154] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (Shin-ETSU Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF440, TSF4445 F4460 (Momentive Performance Materials JAPAN LLC manufactured) etc. can be mentioned.

[0155] Examples of the above fluorochemical surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC CORPORATION), Ftop (registered trademark) EF301, Ftop EF303, Ftop EF351, Ftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. manufactured), Suplon (registered trademark) S381, Suplon S382, Suplon SC101, Suplon SC105 (manufactured by AGC Inc. [former Asahi Glass Co., Ltd.]) and E5844 (Daikin Fine Chemical Genkyusho) production), etc.

[0156] Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC CORPORATION), etc. are mentioned specifically,.

[0157] When a leveling agent is included, the content of the leveling agent is preferably 0.0005 to 0.2% by mass, more preferably 0.0008 to 0.1% by mass, based on the total amount of the colored curable resin composition. When the content of the leveling agent is within the above range, the flatness of the color filter or the like can be improved.

[0158] The colored curable resin composition of the present invention containing the above components, when the composition is cured to form a cured film, the haze value of the cured film, converted to a thickness of 2 μm, is preferably 8 to 50%, More preferably, it is 10 to 45%, still more preferably 13 to 40%, still more preferably 17 to 35%. Curing conditions for forming a cured film by curing the composition are not particularly limited as long as sufficient curing is achieved, but is, for example, 15 minutes or longer under conditions of 70°C or higher. In addition, the haze value of a cured film can be measured with a haze meter.

[0159] (solvent)

The colored curable resin composition of the present invention may further contain at least one solvent. The solvent is not particularly limited, and solvents commonly used in the field may be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (containing OH in the molecule and -O- , solvents that do not contain -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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 γ-butyrolactone.

As the ether solvent, 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, tetra Hydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and Methylanisole etc. are mentioned.

[0162] As the ether ester solvent, methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxyacetic acid Methyl oxypropionate, 3-ethoxyethylpropionate, 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-methoxy -2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0163] As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane ion, cyclopentanone, cyclohexanone, diacetone alcohol, and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0165] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

[0166] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0167] The solvent preferably contains at least one selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably containing ether solvents and ether ester solvents, and propylene glycol monomethyl ether , And it is more preferable to include propylene glycol monomethyl ether acetate.

The content of the solvent is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, based on 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, the flatness at the time of application becomes good, and when a colorant is contained, for example, when a color filter is formed, the display characteristics tend to be good because the color density is not insufficient.

[0169] (other ingredients)

The curable resin composition of the present invention, if necessary, fillers, other high molecular compounds, adhesion promoters, antioxidants such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), You may also include additives known in the said technical field, such as a light stabilizer and chain transfer agents, such as n-dodecyl mercaptan.

[0170] <Method for producing colored curable resin composition>

The colored curable resin composition of the present invention can be prepared by mixing, for example, a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, and a polymerization initiation aid, a solvent, a leveling agent, and other components used as necessary. there is.

You may prepare a coloring agent using the above-mentioned pigment dispersion liquid. A desired curable resin composition can be prepared by mixing the remaining components with the pigment dispersion so as to have a predetermined concentration. In addition, it is preferable to filter the curable resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 µm.

[0171] <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 a photolithography method, an inkjet method, and a printing method. Especially, the photolithography method is preferable. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer through a photomask, and developing it. In the photolithography method, a colored coating film that is a cured film of the colored curable resin composition layer can be formed by not using a photomask at the time of exposure and/or not developing. Cured films such as colored patterns and colored coating films thus formed can be used as color filters.

The film thickness of the cured film, for example, the film thickness of the color filter, is not particularly limited and can be appropriately adjusted depending on the purpose or use, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm. .

[0172] As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass having a surface coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or the substrate What formed aluminum, silver, silver/copper/palladium alloy thin film, etc. on it is used. On these substrates, other color filter layers, resin layers, transistors, circuits and the like may be formed.

[0173] The formation of each color pixel by the photolithography method can be performed under known or conventional equipment and conditions. For example, it can manufacture as follows.

First, after applying the colored resin composition on a substrate, drying by heating (pre-bake) and/or drying under reduced pressure to remove volatile components such as solvents and drying, a smooth colored composition layer is obtained.

Examples of the coating method include spin coating, slit coating, and slit and spin coating.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Further, as the heating time, between 10 seconds and 60 minutes is preferable, and between 30 seconds and 30 minutes is more preferable.

When performing reduced pressure drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

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.

[0174] Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source generating light with a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, around 408 nm, and around 365 nm is selectively cut using a band pass filter that extracts these wavelength ranges. can be extracted or Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. In addition, the exposure amount on the basis of a wavelength of 365 nm is preferably 50 to 300 J/cm ² , more preferably 60 to 200 J/cm ² , and still more preferably 65 to 180 J/cm ² .

It is preferable to use an exposure device such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire exposure surface with parallel light rays and perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed. do.

[0175] A colored pattern is formed on the substrate by developing the colored composition layer after exposure in contact with a developing solution. By developing, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

After development, it is preferable to wash with water.

[0176] Further, it is preferable to perform a post bake on the obtained colored pattern. The post-baking temperature may be 200°C or less in order to form a color filter used in an organic EL display device, but is preferably 170°C or less, and more preferably 150°C or less. In the present invention, it is preferable to perform post-baking at a lower temperature, for example, at a temperature of 130°C or lower. The lower limit of the post-baking temperature is preferably 70°C or higher, more preferably 75°C or higher. The post-baking time is preferably from 1 to 120 minutes, and more preferably from 5 to 60 minutes.

[0177] The film thickness of the coating film after post-baking is, for example, preferably 3 μm or less, and more preferably 2.5 μm or less. Although the lower limit of the film thickness of a coating film is not specifically limited, It is 0.3 micrometer or more normally, and may be 0.5 micrometer or more.

[0178] The cured film of the colored curable resin composition of the present invention obtained after post-baking is preferably 8 to 50%, more preferably 10 to 45%, still more preferably 13 to 40%, in terms of a thickness of 2 μm, More preferably, it has a haze value of 17 to 35%. The haze value of a cured film can be measured with a haze meter. The present invention also provides a cured film of the colored curable resin composition of the present invention.

[0179] A 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, more preferably used as a color filter for an organic EL display device having a micro-cavity structure. do.

[Example]

[0180] Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples, but the present invention is not limited by these examples. In the examples, unless otherwise specified, % and parts representing content or amount used are based on mass.

[0181] <weight average molecular weight>

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using the GPC method under the following conditions. The ratio (Mw/Mn) between the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene obtained under the following conditions was used as the molecular weight distribution.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

column temperature; 40℃

solvent; tetrahydrofuran [THF]

flow rate; 1.0mL/min

solid content concentration of test solution; 0.001 to 0.01% by mass

injection amount; 50μL

detector; RI

standard materials for calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by TOSOH CORPORATION)

[0182] <Synthesis Example 1: Preparation of Pigment Dispersion (A1)>

C.I. Pigment Red 291 Part 8.6

C.I. Pigment Yellow 139 3.5 parts

3.9 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1).

[0183] <Synthesis Example 2: Preparation of Pigment Dispersion (A2)>

C.I. Pigment Green 59 Part 9.6

C.I. Pigment Yellow 150 1.7 parts

C.I. Pigment Yellow 139 1.5 parts

3.1 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed, and a pigment dispersion (A2) was obtained by sufficiently dispersing the pigment using a bead mill.

[0184] <Synthesis Example 3: Preparation of Pigment Dispersion (A3)>

C.I. Pigment Blue 16 9.8 parts

Pink Base (manufactured by TAIYO Fine Chemicals Co., Ltd.) 1.6 parts

4.6 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed, and a pigment dispersion (A3) was obtained by sufficiently dispersing the pigment using a bead mill.

[0185] <Synthesis Example 4: Preparation of Pigment Dispersion (A4)>

C.I. Pigment Green 36 3.9 parts

C.I. Pigment Yellow 185 7.9 parts

4.3 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed, and a pigment dispersion (A4) was obtained by sufficiently dispersing the pigment using a bead mill.

[0186] <Synthesis Example 5: Preparation of Pigment Dispersion (A5)>

C.I. Pigment Red 254 Part 6.2

C.I. Pigment Red 177 Part 6.2

3.6 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A5).

[0187] <Synthesis Example 6: Preparation of Pigment Dispersion (A6)>

C.I. Pigment Blue 15:6 Part 12.1

C.I. Pigment Violet 23 0.6 part

3.3 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84 parts

were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A6).

[0188] <Synthesis Example 7: Preparation of Resin>

277 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 120°C.

Subsequently, 35.3 parts of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate. This was added dropwise into the flask over 2 hours using a dropping funnel. After completion of the dropwise addition, a copolymerization reaction was conducted by stirring at 120°C for further 30 minutes to produce an addition copolymer.

Thereafter, the inside of the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine, and 0.8 part of methoquinone were introduced into the above addition copolymer solution, and the reaction was continued at 110°C for 10 hours, A polymerizable unsaturated bond was introduced into the side chain of the polymer while cleavage of the epoxy group by the reaction between the epoxy group derived from dil methacrylate and acrylic acid. Next, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110° C. for 1 hour to react the hydroxyl group generated by cleavage of the epoxy group with succinic anhydride to introduce a carboxyl group into the side chain, thereby forming a polymer. got it

Finally, 383.3 parts of propylene glycol monomethyl ether acetate was put into the reaction solution to obtain a polymer solution having a polymer solid content concentration of 40%. The weight average molecular weight of the obtained resin in terms of polystyrene was 6400.

[0189] <Scattering intensity in US spawning>

For the scattering intensity (X) of the fine scattering of the inorganic fine particles, using Mieplot (see http://www.philiplaven.com/mieplot.htm), a scattering intensity calculation program for the fine scattering, unpolarized light, It was calculated under conditions of a light source wavelength of 550 nm and a scattering angle of 0 degree.

[0190] <Examples 1 to 6, Reference Examples 1 to 3 and Comparative Examples 1 to 3>

(1) Preparation of colored curable resin composition

Each component shown in Table 3 was mixed so that it might become the compounding quantity shown in Table 3, and colored curable resin composition was obtained. Moreover, in preparation of colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that solid content of colored curable resin composition might be 14 weight%. The unit of the compounding amount of each component in Table 3 is "part by mass", and pigment dispersions (A1) to (A6), resin (B), polymerizable compound (C), polymerization initiator (D), metal oxide (E) ) and each compounding quantity of a leveling agent (F) is solid content conversion.

[0191] The polymerizable compound (C), polymerization initiator (D1), polymerization initiator (D2), inorganic fine particles (E) and leveling agent (F) used in Examples, Reference Examples and Comparative Examples are as follows.

Polymeric compound (C): dipentaerythritol hexaacrylate dipentaerythritol pentaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "A-9550")

Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; Changzhou Trolly New Electronic Materials Manufacturing Co., Ltd.)

Polymerization initiator (D-2): Compound represented by the following formula

Inorganic fine particles (E): Titanium oxide (metal oxide, average particle diameter 161 nm, scattering intensity 8.0, refractive index 2.7)

Leveling agent (F): Polyether modified silicone oil (made by Dow Corning Toray Co., Ltd., trade name "Toray Silicone SH8400").

[0192] [Table 3]

[0193] <Preparation of cured film>

The colored curable resin compositions of Examples, Comparative Examples, and Reference Examples prepared as described above were spun onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) so that the film thickness after post-baking was 2 μm. After applying by the coating method, it was prebaked at 90° C. for 1 minute to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was irradiated with light at an exposure amount of 100 mJ/cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION). After light irradiation, post-baking was performed in an oven at 85°C for 30 minutes to obtain a colored cured film. The haze of the obtained cured film and the visual field when viewed obliquely were evaluated according to the following criteria. The obtained results are shown in Table 4. In addition, about the cured films of Comparative Examples 1-3, since it was what could not form a pattern, evaluation of the visual field at the time of oblique viewing was not performed.

[0194] <Measurement of haze>

The haze of the obtained colored cured film was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.).

[0195] <Evaluation of patterning>

At the time of exposure to create a cured film, a 10 μm line-and-space pattern was used as a photomask, and the colored composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 24 hours. A colored pattern was obtained by immersion development at °C for 60 seconds and then washing with water.

○: A pattern was formed.

×: No pattern was formed.

[0196] <Evaluation of visual field when viewed obliquely>

A sheet having a specific pattern cut out was placed 5 cm below the colored cured film, and light was exposed from below the sheet, and light passing through the specific pattern was transmitted through the cured film. Next, the clarity of the pattern visually confirmed on the cured film surface was evaluated from an oblique direction of about 60 degrees with respect to the cured film plane above the cured film.

○: The shape can be visually confirmed.

×: Unable to discriminate the pattern.

[0197] [Table 4]

[0198] <Examples 7 to 12 and Comparative Examples 4 to 7>

A colored curable resin composition and a cured film were prepared in the same manner as in Example 3 except that the type of inorganic fine particles was changed to that shown in Table 5 and the addition amount of inorganic fine particles was changed to 5% by mass. Moreover, the haze of the obtained cured film and the visual field when viewed obliquely were evaluated in the same manner as above. The obtained results are shown in Table 5. In addition, the evaluation result of patterning was all ○. In the case of Example 12, since inorganic fine particles having a large particle size were used compared to other examples, a tendency for the particles to settle easily was observed.

[0199] [Table 5]

Claims (10)

A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein the scattering intensity in Mie scattering of the inorganic fine particles is X, and the solid content of the colored curable resin composition When the content of the inorganic fine particles relative to (formulation analysis) is expressed as Y mass%, X is 4 or more and Y is 15 or less, formula (1):
a=X×Y (1)
The colored curable resin composition in which the value a computed by is 10 or more. According to claim 1,
The colored curable resin composition in which the inorganic fine particles are metal oxides. According to claim 1,
The colored curable resin composition in which the inorganic fine particles have a refractive index of 1.3 or higher. According to claim 1,
A colored curable resin composition in which the inorganic fine particles have an average particle diameter of 0.05 μm to 0.70 μm. According to claim 1,
Colored curable resin composition whose content of a polymeric compound is 0.1 mass % - 50 mass % with respect to the solid content of colored curable resin composition. According to claim 1,
The colored curable resin composition in which the haze value of the cured film of the curable resin composition is 8 to 40% in terms of a thickness of 2 μm. A cured film of the colored curable resin composition according to any one of claims 1 to 6. According to claim 7,
A cured film having a haze value of 8 to 40% in terms of thickness of 2 μm. According to claim 7,
A cured film constituting a color filter included in a color filter substrate. A display device comprising the cured film according to claim 7 .