Colored resin composition, color filter formed therefrom, and display device containing the color filter

Abstract

An embodiment of the present invention provides a colored resin composition and its application. The colored resin composition comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). The epoxy equivalent number of the above-mentioned colored resin composition is 1.0E-02 to 2.0E-02. The epoxy equivalent number is defined as: epoxy equivalent number = Σ (weight % of each component having an epoxy group × 100 / epoxy equivalent of each component). Therefore, the colored resin composition of the present invention can improve the solvent resistance of the colored resin composition, optimize the performance, and suppress the image quality of the display device from being reduced.

Description

Technical Field

[0001] The present disclosure relates to a colored resin composition and its application. Background Art

[0002] In various display devices (such as liquid crystal display devices) and sensor devices (such as CCD and CMOS sensor devices), in order to display or sense light of a specific color, a color filter in the device is required. Generally speaking, a color filter can be formed by preparing a colored resin composition required for a color filter, forming a layer of the resin composition on a substrate, and then obtaining a desired pattern through exposure and development.

[0003] Although the existing colored resin compositions generally meet various requirements, they are not satisfactory in all aspects. Therefore, there is still a need for improvement of the colored resin compositions. Summary of the invention

[0004] The embodiment of the present invention provides a colored resin composition, which includes a colorant (A), an alkali-soluble resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). The epoxy equivalent number of the colored resin composition is 1.0E-02 to 2.0E-02, wherein the epoxy equivalent number is defined as:

[0005] Epoxy equivalent number=Σ(weight % of each component having an epoxy group×100 / epoxy equivalent of each component).

[0006] An embodiment of the present invention provides a color filter formed by the cured product of the above-mentioned colored resin composition.

[0007] An embodiment of the present invention provides a display device, which includes the above-mentioned color filter.

[0008] In order to make the features of the present disclosure clear and easy to understand, embodiments are specifically cited below and described in detail as follows. For other precautions, please refer to the technical field. DETAILED DESCRIPTION

[0009] The following is a detailed description of the colorant resin composition, color filter, and display device provided in this case. It should be understood that the following description provides many different embodiments or examples for implementing different modes of some embodiments of the present disclosure. The specific components and arrangements described below are only for simple and clear description of some embodiments of the present disclosure. Of course, these are only used for example and are not limitations of the present disclosure.

[0010] In the text, the terms "about", "approximately", and "substantially" generally mean within 5%, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5% of a given value or range. The quantities given here are approximate quantities, that is, in the absence of specific description of "about", "approximately", and "substantially", the meanings of "about", "approximately", and "substantially" can still be implied.

[0011] In this specification, the range represented by "a numerical value to another numerical value" is a summary representation method that avoids listing all the numerical values ​​in the range one by one in the specification. Therefore, unless there is a special additional description or it is obviously contrary to the reasonable common knowledge in the field, recording a specific numerical range in this case is equivalent to disclosing any numerical value in the numerical range and a smaller numerical range defined by any numerical value in the numerical range (including integers and numerical values ​​to the next decimal point), just as if the arbitrary numerical value and the smaller numerical range were written in the specification. For example, when only "1 to 10" is recorded, it can be equivalent to disclosing the range of "3 to 5" or "2.5-6.8", regardless of whether other numerical values ​​are listed in the specification.

[0012] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meanings as commonly understood by those skilled in the art to which the present disclosure belongs. It is understood that these terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with the background or context of the relevant technology and the present disclosure, and should not be interpreted in an idealized or overly formal manner unless specifically defined in the embodiments of the present disclosure.

[0013] In the color filter manufacturing process, the colored resin composition must go through multiple processes, such as forming a color resist pattern, a protective film (overcoat), polyimide (PI), etc., which use various solvents, such as propylene glycol methyl ether acetate (PGMEA), N-methyl pyrrolidone (N-Methyl-2-Pyrrolidone, NMP), acetone, etc., so that the colored resin composition is constantly exposed to the solvent, which can easily cause the color performance of the colored resin composition, such as chromaticity, brightness, or contrast value, to shift, resulting in color distortion.

[0014] The embodiment of the present invention provides a colored resin composition, which includes a colorant (A), an alkali-soluble resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). The colored resin composition of the present invention has an epoxy equivalent number of 1.0E-02 to 2.0E-02, which can improve the solvent resistance of the colored resin composition, optimize the performance, and suppress the image quality of the display device from being reduced.

[0015] The epoxy equivalent number of the colored resin composition is defined as:

[0016] Epoxy equivalent number=Σ(weight % of each component having an epoxy group×100 / epoxy equivalent of each component).

[0017] In the process of manufacturing color filters, the colored resin composition is easily exposed to various organic solvents, such as propylene glycol methyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), acetone, etc., which leads to poor colorability and poor color performance. Therefore, the embodiment of the present invention uses the epoxy equivalent number as an indicator of solvent resistance to ensure that the colored resin composition will not have color distortion.

[0018] Specifically, an alkali-soluble resin (B) having an epoxy group may be used to help improve solvent resistance. In some embodiments, an additive (F) having an epoxy group may be further used to further enhance solvent resistance.

[0019] First, let's explain the epoxy equivalent number:

[0020] [Epoxy equivalent number]

[0021] By measuring the weight % and epoxy equivalent of the component having an epoxy group in the colored resin composition of the present invention, the epoxy equivalent number of the composition is calculated to check whether the colored resin composition has color distortion. Specifically, the epoxy equivalent number is defined as Σ(weight % of each component having an epoxy group×100 / epoxy equivalent of each component).

[0022] The epoxy equivalent can be determined by a general method, such as potentiometric titration or spectral analysis.

[0023] In some embodiments, the epoxy equivalent can be determined by potentiometric titration, for example, the method according to JIS K7236.

[0024] In some embodiments, the spectral analysis method can be performed by infrared spectroscopy, Raman spectroscopy, or nuclear magnetic resonance spectroscopy to measure the epoxy equivalent of each component. For example, the infrared spectral absorption method uses the infrared spectra of a series of epoxy resins with known epoxy equivalents to obtain A910cm -1 / A1610cm -1(910cm -1 is the absorption peak of epoxy group, 1610cm -1 is the absorption peak of the benzene ring) baseline, and then make A910cm -1 / A1610cm -1 With the epoxy equivalent standard curve. In this way, when determining the epoxy equivalent of a certain epoxy group sample, it is only necessary to know the ratio of the epoxy resin A910 / M1610 to determine its epoxy equivalent.

[0025] It should be noted that, herein, the epoxy equivalent refers to the number of grams (g / eq) of a sample containing 1 gram equivalent of epoxy groups.

[0026] In some embodiments, the epoxy equivalent of the colored resin composition is 1.0E-02 to 2.0E-02, preferably 1.13E-02 to 1.95E-02, so as to achieve solvent resistance.

[0027] According to the inventor's research, if the epoxy equivalent number is greater than the upper limit of the above range, it can provide more epoxy groups, better cross-linking reactivity, and better solvent resistance. However, due to the secondary reaction in the high-temperature process (ring-opening reaction of epoxy groups at high temperatures), the photoresist material will produce a larger film shrinkage (or the photoresist surface roughness will increase), thereby affecting the color performance. If the epoxy equivalent number is less than the lower limit of the above range, it can be considered that the lower the epoxy group, the insufficient cross-linking reactivity, and the solvent resistance is not significantly improved, so it is easily affected by the solvent and the color performance is reduced.

[0028] In some embodiments, the epoxy groups in the colored resin composition are provided by the alkali-soluble resin (B). In the embodiment where the epoxy groups are provided only by the alkali-soluble resin (B), the epoxy equivalent number can be defined as:

[0029] Epoxy equivalent number=weight % of alkali-soluble resin (B)×100 / epoxy equivalent of alkali-soluble resin (B).

[0030] In some embodiments, the epoxy groups in the colored resin composition may also be provided by additives (F). In embodiments where the epoxy groups are provided only by additives (F), the epoxy equivalent number may be defined as:

[0031] Epoxy equivalent number=weight % of additive (F)×100 / epoxy equivalent of additive (F).

[0032] In some embodiments, the epoxy group in the colored resin composition is provided by the alkali-soluble resin (B) and the additive (F). In some embodiments, the colorant (A), the photopolymerizable monomer (C), the photopolymerization initiator (D), and the solvent (E) do not have an epoxy group, while the alkali-soluble resin (B) and the additive (F) have an epoxy group, so the epoxy equivalent number can be defined as:

[0033] Epoxy equivalent number=weight % of alkali-soluble resin (B)×100 / epoxy equivalent of alkali-soluble resin (B)+weight % of additive (F)×100 / epoxy equivalent of additive (F).

[0034] By maintaining the epoxy equivalent number within the above range, the colored resin composition can improve its solvent resistance and help maintain the color surface.

[0035] The following is a detailed description of each component in the colored resin composition:

[0036] [(A) Colorant]

[0037] According to some embodiments of the present invention, the colorant (A) comprises a pigment (A1) and / or a dye (A2).

[0038] In some embodiments, the pigment (A1) can use organic pigments or inorganic pigments commonly used in the field. The pigment (A1) can use various pigments used in printing inks, inkjet inks, etc., specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrenone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthraquinone anthraquinone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc. can be listed.

[0039] As inorganic pigments, metal compounds such as metal oxides and metal coordination compounds can be listed, and specifically, oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black can be listed. As organic pigments and inorganic pigments, specifically, CI pigment red, CI pigment violet, and CI pigment blue can be listed among compounds classified as pigments under the color rendering index (published by The society of Dyers and Colourists), and more specifically, pigments with the following color rendering index (CI) numbers can be listed, but they are not necessarily limited thereto, and they can be used alone or in combination of two or more.

[0040] In some embodiments, CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, and 185 can be listed.

[0041] In some embodiments, CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264, and 291 can be listed.

[0042] In some embodiments, CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76 may be listed.

[0043] In some embodiments, CI Pigment Green 7, 10, 15, 25, 36, 47, 58, and 59 may be listed.

[0044] In some embodiments, the pigment (A1) of the colorant (A) may be a known pigment, for example, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists).

[0045] In some embodiments, the content of the pigment (A1) is 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the solid components in the colorant (A). As long as the content of the above-mentioned pigment is within the range of 20 to 90% by weight based on the above-mentioned reference, the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the contrast is effectively improved, so it is preferred.

[0046] In certain embodiments, dye (A2) can be selected from acid dyes with acidic groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, etc. and their derivatives. In addition, azo, xanthene, phthalocyanine acid dyes and their derivatives can also be selected. As color, preferably blue, purple, crimson series dyes, compounds classified as dyes in the color rendering index (published by The Society of Dyers and Colourists), or dyeing notes (dying and weaving company) in the known dyes recorded, there are red, blue, purple dyes. These dyes can be used alone or in combination of two or more for use.

[0047] In some embodiments, the content of the dye (A2) in the colorant is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and particularly preferably 1 to 50% by weight, relative to the total weight of the solid content in the colorant (A). When the content of the dye in the colorant is within the above range, the problem of reduced reliability due to dissolution of the dye by an organic solvent after pattern formation can be prevented, and the sensitivity is excellent and preferred.

[0048] In some embodiments, the colorant (A) may further include a pigment dispersion (A3) whose particle size is uniformly dispersed. The pigment dispersant (A3) is added for deflocculation and stability maintenance of the pigment, and any pigment dispersant commonly used in the field may be used without limitation.

[0049] Specific examples of the pigment dispersant (A3) include cationic, anionic, nonionic, amphoteric, polyester, polyamine and other surfactants, and these pigment dispersants can be used alone or in combination of two or more.

[0050] In some embodiments, the content of the colorant (A) is preferably 10 to 45% by weight, more preferably 20 to 40% by weight, relative to the total weight of the colored resin composition.

[0051] In some embodiments, the content of the colorant (A) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight, based on the total weight of the solid content of the colored resin composition.

[0052] When the colorant (A) is contained in the above range, the color density of the pixel is sufficient even when a thin film is formed, and the defect property of the non-pixel portion is not reduced during development, so the generation of residue can be suppressed.

[0053] In some embodiments of the present invention, the total weight of the solid content in the colored resin composition refers to the total weight of the components remaining after removing the solvent (E) from the colored resin composition.

[0054] [Alkali-soluble resin (B)]

[0055] In some embodiments, the alkali-soluble resin (B) includes an epoxy-containing repeating unit (B1). The epoxy-containing repeating unit (B1) is an epoxy dicyclopentenyl (EDCP) repeating unit. In some embodiments, the epoxy dicyclopentenyl (EDCP) repeating unit can further improve solvent resistance to prevent color distortion.

[0056] Specifically, the repeating unit of epoxy dicyclopentenyl (EDCP) includes at least one of a first repeating unit having a structure as shown in Chemical Formula 1 and a second repeating unit having a structure as shown in Chemical Formula 2:

[0057] [Chemical formula 1]

[0058]

[0059] wherein R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms in the alkyl group are optionally substituted by hydroxyl groups, X1 represents a single bond, -R3-, -R3-O-, -R3-S-, or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer of 1 to 20;

[0060] [Chemical formula 2]

[0061]

[0062] Wherein, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms in the alkyl group are optionally substituted by hydroxyl groups, X2 represents a single bond, -R3-, -R3-O-, -R3-S-, or -R3-NH-, and m is a positive integer of 1-20.

[0063] The above repeating unit preferably has X1 and X2 as single bonds, R1 and R2 as hydrogen atoms, and may include a repeating unit having a structure as shown in Chemical Formula 1A and a repeating unit having a structure as shown in Chemical Formula 2A:

[0064] [Chemical Formula 1A]

[0065]

[0066] Wherein, p is a positive integer from 1 to 20;

[0067] [Chemical Formula 2A]

[0068]

[0069] Wherein, q is a positive integer from 1 to 20.

[0070] The repeating unit is more preferably derived from epoxydicyclopentenyl acrylate (EDCPA), which has a structure as shown in Chemical Formula 3:

[0071] [Chemical formula 3]

[0072]

[0073] In some embodiments, the content of the epoxy-containing repeating unit (B1) in the alkali-soluble resin (B) is preferably 40 to 90 wt %, more preferably 55 to 85 wt %, based on the total weight of the alkali-soluble resin (B).

[0074] When the content of the epoxy-containing repeating unit (B1) in the alkali-soluble resin (B) is within the above range, the alkali-soluble resin (B) can have high solvent resistance while providing alkaline developer solubility.

[0075] Next, the alkali-soluble resin (B) is a copolymer, which may include a structural unit derived from at least one monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "monomer (a)") and a structural unit derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"). The alkali-soluble resin (B) may further include other structural units, such as structural units of a monomer (c) different from monomer (a) and monomer (b) (hereinafter sometimes referred to as "monomer (c)"), or structural units having an ethylenically unsaturated bond. In the copolymer, the above structural units may contain only one type, or may contain two or more types.

[0076] Specific examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic 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, dimethyltetrahydrophthalic acid, Unsaturated dicarboxylic acids such as 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[2 .2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like; unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids having a valence of 2 or more such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; unsaturated acrylic esters containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid, etc.

[0077] Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

[0078] Monomer (b) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0079] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0080] Examples of monomer (b) include a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), and a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b3)"), etc.

[0081] Examples of the monomer (b1) include a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-1)") and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

[0082] Examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis( styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)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, and the like.

[0083] Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER M100; manufactured by Daicel Corporation), compounds represented by formula (I), and compounds represented by formula (II).

[0084]

[0085] In formula (I) and formula (II), R a and R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. a and X b Indicates a single bond, *-R c -、*-R c -O-, *-R c -S- or *-R c -NH-. Rc represents an alkylene group having 1 to 6 carbon atoms. * represents a bonding terminal to O.

[0086] As the compound represented by formula (I), there can be listed compounds represented by any one of formula (I-1) to formula (I-15). Among them, compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) are preferred.

[0087]

[0088] As the compound represented by formula (II), there can be listed compounds represented by any one of formula (II-1) to formula (II-15). Among them, compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) are preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) are more preferred.

[0089]

[0090] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more thereof. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the content ratio [compound represented by formula (I) : compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0091] As monomer (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. As monomer (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-methacryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. can be listed.

[0092] As the monomer (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of the monomer (b3) include tetrahydrofurfuryl acrylate (eg, VISCOAT V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0093] As the monomer (b), the monomer (b1) is preferred in that the reliability of the obtained color filter, such as heat resistance and chemical resistance, can be further improved. Furthermore, the monomer (b1-2) is more preferred in that the colored resin composition has excellent storage stability.

[0094] Examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate (referred to as "dicyclopentanyl (meth)acrylate" as a common name in the art).In addition, (meth)acrylates such as (sometimes referred to as “tricyclodecyl (meth)acrylate”), tricyclo[5.2.1.02,6]decen-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentenyl (meth)acrylate”), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, and diethyl itaconate carboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy bicyclic unsaturated compounds such as 5-(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[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-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0095] Among these, styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0096] In the embodiment where the monomer (c) is a structural unit having an ethylenically unsaturated bond, it may preferably be a structural unit having a (meth)acryloyl group. The alkali-soluble resin (B) having such a structural unit can be obtained by reacting a polymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b) with a monomer having a group reactive with the aforementioned structural unit and an ethylenically unsaturated bond.

[0097] Examples of the structural unit having an ethylenically unsaturated bond include a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth)acrylate to a maleic anhydride unit, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and a structural unit obtained by adding carboxylic anhydride to a structural unit having a hydroxyl group.

[0098] In some embodiments, the structural units from (a): 10 to 60 wt %; the structural units from (b): 40 to 90 wt %, more preferably the structural units from (a): 15 to 45 wt %; the structural units from (b): 55 to 85 wt %.

[0099] Alternatively, in an embodiment comprising structural units from (c), structural units from (a): 2 to 45 wt%; structural units from (b): 2 to 95 wt%; structural units from (c): 1 to 65 wt%, more preferably structural units from (a): 5 to 40 wt%; structural units from (b): 5 to 80 wt%; structural units from (c): 5 to 60 wt%.

[0100] In some embodiments, the epoxy-containing repeating unit (B1) is a structural unit derived from (b).

[0101] In some embodiments, the alkali-soluble resin (B) may include, for example, 3,4-epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.02.6]decyl(meth)acrylate / (meth)acrylic acid copolymer, and the like; glycidyl(meth)acrylate / benzyl(meth)acrylate / (meth)acrylic acid copolymer, glycidyl(meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.02.6]decyl(meth)acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, benzyl(meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, and the like.

[0102] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0103] The acid value (solid content conversion value) of the alkali-soluble resin (B) is preferably 10 to 300 mg-KOH / g, or 20 to 250 mg-KOH / g, or 20 to 200 mg-KOH / g, or 20 to 170 mg-KOH / g, or 30 to 170 mg-KOH / g. Here, the acid value is a measured value as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin (B), and can be obtained by titration using a potassium hydroxide aqueous solution, for example.

[0104] In some embodiments, the epoxy equivalent of the alkali-soluble resin (B) is 500 to 2000 (g / eq), preferably 600 to 1500 (g / eq). If it is less than the lower limit, it is difficult to maintain good heat yellowing resistance, and if it is greater than the upper limit, it may be difficult to form or coat.

[0105] In some embodiments, the content of the alkali-soluble resin (B) is preferably 10 to 45% by weight, more preferably 10 to 20% by weight, based on the total weight of the colored resin composition.

[0106] In some embodiments, the content of the alkali-soluble resin (B) is preferably 15 to 40% by weight, more preferably 20 to 35% by weight, based on the total weight of the solid content of the colored resin composition.

[0107] When the alkali-soluble resin (B) is contained in the above range, a colored pattern can be formed, and there is a tendency that the resolution and residual film rate of the colored pattern are improved.

[0108] [Photopolymerizable monomer (C)]

[0109] In some embodiments, the photopolymerizable monomer (C) is a monomer that can be polymerized by active free radicals and / or acids generated by a photopolymerization initiator (D), such as but not limited to ethylenically unsaturated bonds having polymerizable properties, such as (meth)acrylate compounds. Here, the compounds described in brackets mean that the presence and absence of the words in the brackets are included, such as the aforementioned (meth)acrylate compounds, including the case of acrylate compounds and methacrylate compounds. The photopolymerizable monomer (C) can also be called a polymerizable compound.

[0110] For example, the photopolymerizable monomer (C) may include but is not limited to at least one selected from the group consisting of the following options: polymerizable compounds having one ethylenically unsaturated bond, such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone; polymerizable compounds having two ethylenically unsaturated bonds, such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; and polymerizable compounds having trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like. The photopolymerizable monomer (C) may be a polymerizable compound having three ethylenically unsaturated bonds, such as 2-(2-(meth)acryloyloxyethyl)isocyanate, 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, pentaerythritol tetra(meth)acrylate, dipentaerythritol caprolactone-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol caprolactone-modified dipentaerythritol hexa(meth)acrylate. In some embodiments, the photopolymerizable monomer (C) is, for example, a compound having ethylenically unsaturated double bonds. In some embodiments, the photopolymerizable monomer (C) is, for example, a polymerizable compound having three ethylenically unsaturated double bonds.

[0111] Commercially available products of the photopolymerizable monomer (C) include KAYARAD (registered trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.), and A9500 (Shin-Nakamura Chemical Co., Ltd.).

[0112] The weight average molecular weight of the photopolymerizable monomer (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

[0113] In some embodiments, the content of the photopolymerizable monomer (C) is preferably 1 to 30% by weight, more preferably 1 to 20% by weight, based on the total weight of the colored resin composition.

[0114] In some embodiments, the content of the photopolymerizable monomer (C) is preferably 2 to 20% by weight, more preferably 4 to 10% by weight, based on the total weight of the solid content of the colored resin composition.

[0115] When the content of the photopolymerizable monomer (C) is within the above range, the residual film rate during color pattern formation and the chemical resistance of the color filter can be improved.

[0116] [Photopolymerization initiator (D)]

[0117] In some embodiments of the present invention, the photopolymerization initiator (D) may be any compound that can generate active free radicals, acids, etc. under the action of light, thereby initiating a photopolymerization reaction, and is not particularly limited.

[0118] For example, the photopolymerization initiator (D) may include but is not limited to at least one selected from the group consisting of: O-acyloxime compounds, alkylphenyl ketone compounds, bisimidazole compounds, triazine compounds, acyl phosphine oxides, benzoin compounds, diphenyl ketone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methyl phenylformate, acetophenone, and titanocene compounds.

[0119] In some embodiments, the photopolymerization initiator (D) preferably comprises at least one selected from the group consisting of: O-acyl oxime compounds, alkyl phenyl ketone compounds, bisimidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and bisimidazole compounds. For example, when an O-acyl oxime compound is used as the photopolymerization initiator (D), OXE-01 (BASF), Commercially available products include OXE-02 (from BASF) and N-1919 (from ADEKA).

[0120] The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding end.

[0121]

[0122] Examples of the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1 ...4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-[4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-[4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imide, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imide, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imide, etc. Commercially available products such as IRGACURE OXE01, OXE02 (both manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) can be used. Among them, the O-acyl oxime compound is preferably at least one selected from N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine is more preferred. These O-acyl oxime compounds tend to provide a color filter with high brightness.

[0123] The alkyl phenyl ketone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

[0124]

[0125] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, etc. Commercially available products such as IRGACURE 369, 907, and 379 (all manufactured by BASF) can be used.

[0126] Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0127] In terms of light sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

[0128] Examples of the triazine compound include 2,4-bis-trichloromethyl-6-[4-methoxyphenyl]-1,3,5-triazine, 2,4-bis-trichloromethyl-6-[4-methoxyphenyl]-1,3,5-triazine, 2,4-bis-trichloromethyl-6-[4-methoxyphenyl]-1,3,5-triazine, 2,4-bis-trichloromethyl-6-[4-methoxyphenyl]-1,3,5-triazine, 2,4-bis-trichloromethyl-6-[2-(5 -methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0129] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

[0130] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open No. 6-75372 and Japanese Patent Application Laid-Open No. 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.), and the like.

[0131] Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titanocene compounds, etc. Preferably, these polymerization initiators can be used in combination with the polymerization initiation aids (especially amines) described later.

[0132] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

[0133] In some embodiments, the content of the photopolymerization initiator (D) is preferably 0.1 to 2.5% by weight, more preferably 0.2 to 1.5% by weight, relative to the total weight of the colored resin composition.

[0134] In some embodiments, the content of the photopolymerization initiator (D) is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the total weight of the solid content of the colored resin composition.

[0135] When the content of the photopolymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so the productivity of the color filter can be improved.

[0136] [Solvent (E)]

[0137] In some embodiments, the solvent (E) may include but is not limited to at least one selected from the group consisting of the following options: ester solvent (herein means a solvent containing -COO- but not -O- in the molecule), ether solvent (herein means a solvent containing -O- but not -COO- in the molecule), ether ester solvent (herein means a solvent containing -COO- and -O- in the molecule), ketone solvent (herein means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (herein means a solvent containing OH but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc.

[0138] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0139] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methylanisole.

[0140] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0141] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0142] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0143] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0144] Among the above-mentioned solvents, organic solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferred from the viewpoint of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, and N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate, and ethyl 3-ethoxypropionate are more preferred.

[0145] In some embodiments, the content of the solvent (E) is preferably 35 to 80% by weight, more preferably 40 to 60% by weight, relative to the total weight of the colored resin composition. In other words, the total content of the solid content of the colored resin composition may be 20 to 65% by weight, more preferably 20 to 40% by weight.

[0146] When the solvent (E) is contained in the above range, the flatness during coating becomes good, and when a color filter is formed, there is no shortage of color density, so there is a tendency that display characteristics become good.

[0147] [Additives (F)]

[0148] In some embodiments, the colored resin composition may further include an additive (F). The additive (F) may include a filler, other polymer compounds, a curing agent, an adhesion promoter, an ultraviolet absorber, an anti-flocculating agent, etc. The additive (F) preferably includes an epoxy group, such as a glycidyl group, and may be combined with the alkali-soluble resin (B) to adjust the epoxy equivalent of the composition.

[0149] As the filler, specifically, glass, silica, alumina, etc. can be used, but the filler is not limited thereto.

[0150] As for the above-mentioned other polymer compounds, specifically, curable resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane can be used, but it is not limited thereto.

[0151] The curing agent is used to improve deep curing and mechanical strength. Specifically, epoxy compounds, multifunctional isocyanate compounds, melamine compounds, oxetane compounds, etc. can be used, but it is not limited thereto.

[0152] The curing agents exemplified above may be used alone or in combination of two or more.

[0153] Regarding the aforementioned adhesion promoter, specifically, one selected from the group consisting of the following adhesion promoters, either alone or in mixture, may be used: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content of the colored resin composition.

[0154] As for the aforementioned ultraviolet absorber, specifically, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. can be used, but it is not limited thereto.

[0155] As for the aforementioned deflocculant, specifically, sodium polyacrylate and the like may be used, but it is not limited thereto.

[0156] In some embodiments, the additive (F) helps improve solvent resistance. In some embodiments, the epoxy equivalent of the additive (F) is 0.5 to 300 (g / eq), preferably 0.5 to 200 (g / eq). If it is greater than the upper limit, the epoxy equivalent of the colored resin composition is small after conversion, the epoxy group is small and the cross-linking reactivity is low, which does not help improve solvent resistance.

[0157] In some embodiments, the content of the additive (F) is preferably 0.01 to 15 wt %, more preferably 0.01 to 5 wt %, and even more preferably 0.01 to 0.4 wt %, based on the total weight of the colored resin composition.

[0158] In some embodiments, the content of the additive (F) is preferably 0.01 to 30% by weight, more preferably 0.01 to 10% by weight, and even more preferably 0.01 to 0.8% by weight, based on the total weight of the solid content of the colored resin composition.

[0159] When the content of the additive (F) is within the above range, various properties such as dispersion, curing, and ultraviolet absorption can be provided without affecting the original properties of the colored resin composition.

[0160] [Color filter]

[0161] Another embodiment of the present disclosure is a color filter, which can be formed by a cured product of the colored resin composition according to any of the above embodiments. For example, the colored resin composition according to any of the above embodiments can be formed into the color filter by photolithography, inkjet, or printing, but the present disclosure is not limited thereto.

[0162] As a method for forming a color filter (color filter pattern) by a cured product of the colored resin composition of the present case, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed via light shielding. In the photolithography method, by not using light shielding and / or not developing during exposure, a colored coating film as a cured product of the above-mentioned colored composition layer can be formed. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention.

[0163] The film thickness of the color filter is not particularly limited and can be appropriately adjusted according to the purpose and application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm, and even more preferably 1.5 to 3.5 μm.

[0164] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or a product formed with a thin film of aluminum, silver, or a silver / copper / palladium alloy on the above substrates can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. can be formed on these substrates.

[0165] The formation of each color pattern (pixel) by photolithography can be performed using a known or customary apparatus and conditions. For example, it can be produced as follows.

[0166] First, the colored resin composition is applied on a substrate, and volatile components such as a solvent are removed by heating and drying (prebaking) and / or drying under reduced pressure to obtain a smooth colored resin composition layer. Examples of the coating method include spin coating, slit coating, and slit and spin coating.

[0167] Next, the colored resin composition layer is exposed through a light shield for forming a target colored pattern. Since parallel light can be uniformly irradiated to the entire exposure surface, light shielding and accurate alignment of the substrate on which the colored resin composition layer is formed can be performed, it is preferable to use an exposure device such as a shield aligner and a stepper.

[0168] The colored resin composition layer after exposure is contacted with a developer and developed to form a colored pattern on the substrate. By developing, the unexposed portion of the colored resin composition layer is dissolved in the developer and removed. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10 weight %, more preferably 0.03 to 5 weight %. Furthermore, the developer may contain a surfactant. The developing method may be any one of a capping immersion method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at an arbitrary angle during development. It may be washed with water after development.

[0169] The dose of the aforementioned exposure process is not particularly limited. In some embodiments, the present invention can be exposed at an exposure dose of 50 to 100 mJ.

[0170] Furthermore, the obtained colored pattern is preferably post-baked. The post-baking temperature is preferably 90° C. to 250° C., or 100° C. to 240° C. The post-baking time is preferably 1 to 120 minutes.

[0171] The cured product of the colored resin composition of the present invention can be used to prepare a color filter, which is a color filter or color filter that can be used in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[0172] [Display device]

[0173] Another embodiment of the present disclosure is a display device, which may include the aforementioned color filter, but the present disclosure is not limited thereto. According to some embodiments of the present disclosure, the display device may be a liquid crystal display device, an organic electroluminescent display device, or a plasma display device.

[0174] For example, the display device may include a backlight source, a TFT substrate, a color filter substrate, and a display medium (such as liquid crystal) disposed between the TFT substrate and the color filter substrate, wherein the color filter substrate may use a color filter formed by a cured product of the colored resin composition of the present invention.

[0175] Hereinafter, the present disclosure will provide several examples and comparative examples to more specifically illustrate the effects that can be achieved by the colored resin composition according to the examples of the present disclosure, as well as the characteristics of the colored resin composition obtained by applying the present disclosure. However, the following examples and comparative examples are only for illustrative purposes and should not be construed as limitations on the implementation of the present disclosure. The unit "part" used below represents parts by weight unless otherwise specified.

[0176] [Preparation Example 1]

[0177] Preparation Example 1 was prepared by mixing and dispersing 12.0 parts by weight of pigment CI Pigment Blue 15:6, 4.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK), 44 parts by weight of propylene glycol methyl ether acetate and 40 parts by weight of propylene glycol methyl ether as solvents in a bead mill for 12 hours.

[0178] [Synthesis example 1]

[0179] In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a proper amount of nitrogen gas was flowed to set a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85°C while being stirred. Then, a solution prepared by dissolving 19 parts of methacrylic acid and 171 parts of 2-hydroxyethyl methacrylate (2-HEMA) in 40 parts of propylene glycol monomethyl ether acetate was dripped into the flask using a drip pump for about 5 hours. On the other hand, a solution prepared by dissolving 26 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was dripped into the flask using another drip pump for about 5 hours. After the dripping of the polymerization initiator was completed, the same temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (alkali-soluble resin (B-1)) having a solid content of 50%. The obtained alkali-soluble resin (B-1) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH / g in terms of solid content. Here, the alkali-soluble resin (B-1) did not contain an epoxy group.

[0180] [Synthesis example 2]

[0181] In addition to replacing 2-methylpropene (2-hydroxyethyl) ester (2-HEMA) in Synthesis Example 1 with 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.0 2,6] In addition to a mixture of decane-9-yl ester (containing a ratio of 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Corporation) (containing epoxy dicyclopentene methacrylate (EDCPA), a monomer shown in the following chemical formula 3), the rest is the same as in Synthesis Example 1, and a solution of a copolymer (alkali-soluble resin (B-2)) with a solid content of 60% can be obtained. The obtained alkali-soluble resin (B-2) has a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value converted to solid content of 53 mg-KOH / g. Here, the alkali-soluble resin (B-2) has a repeating unit as shown in the following chemical formula 5, which can be used as an epoxy-containing repeating unit (B1) and accounts for 55% by weight of the alkali-soluble resin (B-2);

[0182] [Chemical formula 3]

[0183]

[0184] [Chemical formula 5]

[0185]

[0186] [Synthesis example 3]

[0187] Except that the weight portion of the mixture of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate in Synthesis Example 2 is 200 parts (containing epoxydicyclopentene methacrylate (EDCPA), a monomer as shown in Chemical Formula 3 above), the rest is the same as Synthesis Example 1, and a solution of a copolymer (alkali-soluble resin (B-3)) with a solid content of 80% can be obtained. The obtained alkali-soluble resin (B-3) has a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value converted to solid content of 53 mg-KOH / g. Here, the alkali-soluble resin (B-3) has a repeating unit as shown in Chemical Formula 5 above, which can be used as an epoxy-containing repeating unit (B1) and accounts for 65% by weight of the alkali-soluble resin (B-3).

[0188] [Synthesis Example 4]

[0189] Except that the weight portion of the mixture of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate in Synthesis Example 2 is 252 parts (containing epoxydicyclopentene methacrylate (EDCPA), a monomer as shown in Chemical Formula 3 above), the rest is the same as Synthesis Example 1, and a solution of a copolymer (alkali-soluble resin (B-4)) with a solid content of 90% can be obtained. The obtained alkali-soluble resin (B-4) has a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value converted to solid content of 53 mg-KOH / g. Here, the alkali-soluble resin (B-4) has a repeating unit as shown in Chemical Formula 5 above, which can be used as an epoxy-containing repeating unit (B1) and accounts for 85% by weight of the alkali-soluble resin (B-4).

[0190] [Synthesis Example 5]

[0191] In addition to the acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Except that the mixture of 9-decane ester is replaced by glycidylmethacrylate (GMA), the rest is the same as in Synthesis Example 2, and a solution of a copolymer (alkali-soluble resin (B-5)) with a solid content of 60% can be obtained. The weight average molecular weight of the obtained alkali-soluble resin (B-5) is 8000, the molecular weight distribution is 1.98, and the acid value converted to solid content is 53 mg-KOH / g. Here, although the alkali-soluble resin (B-5) contains an epoxy group, it does not have a repeating unit as shown in the above chemical formula 5. The repeating unit formed by glycidylmethacrylate (GMA) can be used as an epoxy-containing repeating unit (B1), which accounts for 50% by weight of the alkali-soluble resin (B-5).

[0192] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin (B) were measured by gel permeation chromatography (GPC method) under the following conditions.

[0193] Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

[0194] Column: TSK-GELG2000HXL

[0195] Column temperature: 40℃

[0196] Solvent: THF

[0197] Flow rate: 1.0mL / min

[0198] Solid content concentration of the test liquid: 0.001 to 0.01 mass%

[0199] Injection volume: 50μL

[0200] Detector: RI

[0201] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

[0202] The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

[0203] The ingredients of the following embodiments and comparative examples are shown in Tables 1-2, wherein the types of the ingredients selected are described below.

[0204] [Table 1]

[0205]

[0206] [Table 2]

[0207]

[0208] In Table 1 and Table 2, each component represents the following compound: Colorant (A): Colorant alkali-soluble resin obtained in Preparation Example 1 (B):

[0209] (B-1): Alkali-soluble resin (B-1) obtained in Synthesis Example 1 (B-2): Alkali-soluble resin (B-2) obtained in Synthesis Example 2

[0210] (B-3): Alkali-soluble resin (B-3) obtained in Synthesis Example 3

[0211] (B-4): Alkali-soluble resin (B-4) obtained in Synthesis Example 4

[0212] (B-5): Alkali-soluble resin (B-5) obtained in Synthesis Example 5

[0213] Photopolymerizable monomer (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.

[0214] Photopolymerization initiator (D): N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imide (trade name: TR-PBG-327; manufactured by TRONLY)

[0215] Solvent (E): propylene glycol monomethyl ether acetate (PGMEA; purchased from Shangren Chemical Co., Ltd.)

[0216] Additive (F): 3-Glycidoxypropyltrimethoxysilane (purchased from Sigma-Aldrich)

[0217] In addition, the epoxy equivalent is measured by infrared spectroscopy after each component is prepared. The epoxy equivalent is calculated by weight % of each component × 100 / epoxy equivalent.

[0218] [Preparation of Colored Resin Composition]

[0219] The colored resin composition can be obtained by mixing the compositions shown in Table 1 and Table 2 in proportion (weight %), dispersing and dissolving them. It should be noted that the solid composition of the examples and comparative examples of the present case is 51.4-51.5 weight % and the solvent is 48.5 weight %.

[0220] Specifically, a sample bottle is taken, and a powdered photopolymerization initiator (D) and additive (F) (if any) are added to the sample bottle, and a solvent (E) is added to the sample bottle, and the mixture is uniformly mixed with a shaker. After mixing for 20 minutes, when it is confirmed that the powder is completely dissolved, a photopolymerizable monomer (C), an alkali-soluble resin (B) and a colorant (A) are added in sequence, and the mixture is uniformly mixed with a shaker for 1 hour to obtain a colored resin composition.

[0221] [Production of color filters]

[0222] A 2 μm thick colored resin composition was applied on a 4-inch glass substrate (#1737; manufactured by Corning) by spin coating, and then pre-baked at 100°C to obtain a colored resin composition layer. After cooling, the substrate with the colored resin composition layer was placed in an exposure machine and exposed at 50 mJ / cm 2 The colored resin composition layer after light irradiation is immersed in an alkaline developer for development, and then washed with pure water for 40 seconds, and then placed in an oven for post-baking at 230° C. for 20 to 30 minutes to obtain a colored pattern.

[0223] [Solvent resistance test]

[0224] Use a colorimeter to locate the position on the colored pattern piece, and measure the chromaticity value (L*, a*, b*) and brightness (Y) of the position. Immerse the measured colored pattern piece in an organic solvent such as N-methylpyrrolidone (NMP), let it stand for 10 to 20 minutes, then take it out, remove the NMP with pure water, and then use an air spray gun to blow away the moisture on the surface of the colored pattern piece. Use a colorimeter to locate the position of the colored pattern piece before the NMP test, and measure the chromaticity value (L*, a*, b*) and brightness (Y) of the colored pattern piece after it is immersed in the solvent. Calculate the brightness change ΔY% and the color difference ΔE*ab, the formula is as follows:

[0225] ΔY%=(Y1-Y2) / Y1*100%

[0226]

[0227] Y1, Y2: brightness before and after solvent resistance test;

[0228] L1*: Brightness before solvent resistance test;

[0229] L2*: lightness after solvent resistance test;

[0230] a1*, b1*: Chromaticity index before solvent resistance test;

[0231] a2*, b2*: Chromaticity index after solvent resistance test.

[0232] [evaluate]

[0233] According to Table 3, the solvent resistance can be evaluated by the brightness change ΔY% and the color difference ΔE*ab.

[0234] [Table 3]

[0235]

[0236] O: Good, the change in brightness before and after the solvent test ΔY is less than 3%, and the color difference ΔE* ab Less than 0.8

[0237] Δ: Slightly better, the change in brightness before and after the solvent test ΔY is between 3% and 5%, or the color difference ΔE* ab Between 0.8 and 1.4.

[0238] X: Bad, the change in brightness before and after the solvent test ΔY is greater than 5%, or the color difference ΔE* ab Greater than 1.4.

[0239] As can be seen from Table 1, Examples 1 to 4 have good solvent resistance because the alkali-soluble resin (B) (especially EDCPA) and the additive (F) provide epoxy groups.

[0240] In contrast, it can be seen from Table 2 above that in Comparative Example 1, no component provides epoxy equivalents, so the solvent resistance is poor. In Comparative Example 2, epoxy equivalents are provided only by additive (F), and the obtained epoxy equivalent number is relatively low, so its solvent resistance is slightly better. In Comparative Example 3, the epoxy equivalent number is relatively high by using a higher weight % of additive (F) and a lower weight % of alkali-soluble resin (B) than other examples, so the solvent resistance is slightly better. In Comparative Example 4, the alkali-soluble resin (B) provides epoxy groups through repeating units formed by glycidyl methacrylate (GMA), which has a lower epoxy equivalent, so the epoxy equivalent number is relatively high, so its solvent resistance is slightly better.

[0241] In summary, by making the epoxy equivalent number of the colored resin composition within a specific range, the color filter formed from the colored resin composition can have good solvent resistance.

[0242] Several embodiments are summarized above so that those with ordinary knowledge in the art to which the present invention belongs can better understand the concepts of the embodiments of the present invention. Those with ordinary knowledge in the art to which the present invention belongs should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same purposes and / or advantages as the embodiments introduced herein. Those with ordinary knowledge in the art to which the present invention belongs should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present invention.

Claims

1. A colored resin composition comprising: (A) coloring agent; (B) an alkali-soluble resin, wherein the alkali-soluble resin (B) comprises repeating units containing epoxy groups, and provides the epoxy equivalent number, wherein the repeating units containing epoxy groups comprise repeating units of epoxydicyclopentenyl, wherein the repeating units containing epoxy groups account for 40-90 wt % of the alkali-soluble resin (B); (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E) solvent; as well as (F) an additive, wherein the (F) additive comprises a glycidyl group, wherein the (F) additive has an epoxy equivalent of 0.5-300 g / eq, wherein the additive (F) accounts for 0.01-15% by weight of the content of the colored resin composition, wherein the colorant (A), the photopolymerizable monomer (C), the photopolymerization initiator (D), and the solvent (E) do not have epoxy groups, The epoxy equivalent number of the colored resin composition is 1.0E-02 to 2.0E-02, wherein the epoxy equivalent number is defined as: epoxy equivalent number = weight % of the alkali-soluble resin (B) × 100 / epoxy equivalent of the alkali-soluble resin (B) + weight % of the additive (F) × 100 / epoxy equivalent of the additive (F).

2. The colored resin composition according to claim 1, wherein the repeating unit of the epoxydicyclopentenyl group includes at least one of a first repeating unit having a structure as shown in Chemical Formula 1 and a second repeating unit having a structure as shown in Chemical Formula 2: [Chemical formula 1] in, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atoms in the alkyl group are optionally substituted by hydroxyl groups, X1 represents a single bond, -R3-, -R3-O-, -R3-S-, or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer of 1 to 20; [Chemical formula 2] Wherein, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms in the alkyl group are optionally substituted by hydroxyl groups, X2 represents a single bond, -R3-, -R3-O-, -R3-S-, or -R3-NH-, and m is a positive integer of 1-20.

3. The colored resin composition according to claim 1, wherein the repeating unit of the epoxydicyclopentenyl group includes a repeating unit having a structure as shown in Chemical Formula 1A and a repeating unit having a structure as shown in Chemical Formula 2A: [Chemical Formula 1A] in, p is a positive integer from 1 to 20; [Chemical Formula 2A] Wherein, q is a positive integer from 1 to 20.

4. The colored resin composition of claim 1, wherein the epoxy functional group-containing repeating unit is derived from epoxy dicyclopentene methacrylate, which has a structure as shown in Chemical Formula 3: [Chemical formula 3] 5. The colored resin composition according to claim 1, wherein the epoxy equivalent of the alkali-soluble resin (B) is 500 to 2000 g / eq.

6. The colored resin composition according to claim 1, wherein the additive (F) accounts for 1% by weight or less of the content of the colored resin composition.

7. The colored resin composition according to claim 1, comprising: 10 to 45 wt % of the colorant (A); 5 to 30 wt % of the alkali-soluble resin (B); 1 to 30 wt % of the photopolymerizable monomer (C); 0.1 to 2.5 wt % of the photopolymerization initiator (D); and 35 to 80 wt % of the solvent (E).

8. A color filter formed from a cured product of the colored resin composition according to any one of claims 1 to 7. 9 . The color filter of claim 8 , wherein the color filter has a luminance variation ΔY%<5%, and / or a color difference ΔE*ab<1.

4.

10. A display device comprising the color filter according to claim 8 or 9.

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