Xanthene compound, resin composition, cured product, method for producing cured product, organic el display device, and display device

Abstract

An object of the present application is to provide a xanthene compound having high heat resistance and capable of blocking light in a long wavelength region up to the visible light region compared with conventional xanthene compounds. To solve the above problem, the xanthene compound (b) of the present application is a xanthene compound (b) represented by formula (1).

Description

Technical Field

[0001] This invention relates to xaton compounds, resin compositions using xaton compounds, and organic EL display devices using resin compositions. Background Technology

[0002] In display devices with thin displays, such as smartphones, tablets, and televisions, many products using organic electroluminescent (hereinafter "organic EL") display devices have been developed. Typically, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and emits light by applying a voltage between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet light irradiation are commonly used as materials for the planarization layer and the insulating layer. Of these, photosensitive resin compositions using polyimide-based resins are preferred because the resin has high heat resistance and produces fewer gaseous components from the cured product, resulting in a highly reliable organic EL display device.

[0003] In recent years, with the aim of improving the light extraction efficiency of organic EL display devices, thin-film polarizing plates and polarizer-free display devices have been developed. In order to improve contrast, it is required to reduce the visible light transmittance of the insulating layer and planarization layer.

[0004] As a technique to reduce the transmittance of visible light in a cured material and increase its blackness, as seen in black matrix materials for liquid crystal display devices and RGB paste materials, one example is the method of adding colorants such as carbon black, organic and inorganic pigments, and dyes to a resin composition.

[0005] As a technique for improving the blackness of cured products in positive photosensitive resin compositions, there are methods such as: adding quinone diazide compounds and black pigments to Novolac resin and / or alkali-soluble resins formed from vinyl polymers (see Patent Document 1); adding photosensitizers and black pigments to soluble polyimides (see Patent Document 2); adding photosensitizers and yellow, red, and blue dyes and / or pigments to alkali-soluble resins formed from polyimides and / or polyimide precursors (see Patent Document 3); and so on. Additionally, xaton compounds are known as dyes with high heat resistance and high molar absorptivity (see Patent Documents 4 and 5).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 6-230215

[0009] Patent Document 2: Japanese Patent Application Publication No. 2003-119381

[0010] Patent Document 3: Japanese Patent Application Publication No. 2018-63433

[0011] Patent Document 4: Japanese Patent Application Publication No. 2014-9330

[0012] Patent Document 5: Japanese Patent Application Publication No. 2020-111627 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] While previous oxane compounds had high heat resistance, they had a maximum absorption wavelength around 550 nm, and their light-shielding properties in the visible light region, especially in the long wavelength region, were insufficient.

[0015] Methods for solving problems

[0016] To address the aforementioned issues, the present invention has the following configuration.

[0017] [1] The thallium compound (b) represented by formula (1).

[0018] [Chemical Formula 1]

[0019]

[0020] (In formula (1), A) 1 ~A 4 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms that may have electron-donating substituents. Among them, A... 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents has an electron-donating substituent. R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 A monovalent hydrocarbon group with 1 to 20 carbon atoms. R 5 Represents hydrogen atom, -SO3H, -SO3 - -SO3NR 6 R 7 -COOH, -COO- -COOR 8 -CONR 9 R 10 R 6 ~R 10 Each group independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. Z represents anionic compounds, and n represents 0 or 1. Among them, the xaton compound (b) represented by formula (1) is an electrically neutral compound overall.

[0021] [2] The thallium compound (b) as described in [1] above, wherein the substituent constant σ of the Hammett rule for the aforementioned electron-donating substituents. p The value is below -0.20.

[0022] [3] The thallium compound (b) as described in [1] or [2] above, wherein n is 0 in the aforementioned formula (1).

[0023] [4] The sulfonate compound (b) as described in [1] or [2] above, wherein in the aforementioned formula (1), n ​​is 1 and Z is an aliphatic or aromatic sulfonate ion.

[0024] [5] A resin composition comprising the thiamethoxam compound (b) and the alkali-soluble resin (a) described in any one of [1] to [4] above.

[0025] [6] The resin composition as described in [5] above further comprises a photosensitive compound (c).

[0026] [7] The resin composition as described in [6] above, wherein the aforementioned photosensitive compound (c) comprises a quinone diazide compound.

[0027] [8] The resin composition as described in any one of [5] to [7] above further contains a colorant (d-2) having a maximum absorption wavelength at any point in the range of 350 to 800 nm, above 490 nm and below 580 nm.

[0028] [9] The resin composition as described in any one of [5] to [7] above comprises a thallium compound (b1) in which n is 1 and Z is an organic anion in the aforementioned formula (1), and an ionic dye (d10) that forms an ion pair of organic ions, wherein the aforementioned organic anion is one type.

[0029]

[10] The resin composition as described in any one of [5] to [9] above, wherein the aforementioned alkali-soluble resin (a) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide, polyamide imide precursor and copolymers thereof.

[0030]

[11] The resin composition as described in any one of [5] to

[10] above, wherein the total mass of all chlorine atoms and all bromine atoms contained in the aforementioned resin composition is 150 ppm or less relative to the total mass of the solid components of the resin composition.

[0031]

[12] A cured product, which is obtained by curing the resin composition described in any one of [5] to

[10] above.

[0032]

[13] A solidified compound containing a thallium compound (b') represented by formula (2).

[0033] [Chemical Formula 2]

[0034]

[0035] (In equation (2), A) 1 ~A 4 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms that may have electron-donating substituents. Among them, A... 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents has an electron-donating substituent. R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 A monovalent hydrocarbon group with 1 to 20 carbon atoms. R 5 Represents hydrogen atom, -SO3H, -SO3 - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 R 6 ~R 10 Each group independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. Among them, the oxonium compound (b') represented by formula (2) is an electrically neutral or cationic compound.

[0036]

[14] A method for manufacturing a cured product includes: a step of forming a resin film on a substrate formed of the resin composition described in any one of [6] to

[11] above; a step of exposing the resin film; a step of developing the exposed resin film; and a step of heat-treating the developed resin film.

[0037]

[15] In the method for manufacturing the cured material as described in

[14] above, in the process of exposing the aforementioned resin film, the photomask used during exposure is a halftone photomask having a light-transmitting part, a light-blocking part and a semi-transmitting part, and the transmittance of the semi-transmitting part is 5% to 30% when the transmittance of the light-transmitting part is set to 100%.

[0038]

[16] An organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, wherein the planarization layer and / or the insulating layer have the cured material described in

[12] or

[13] above.

[0039]

[17] The organic EL display device as described in

[16] above, wherein the aforementioned insulating layer has the aforementioned cured material, and the optical density under visible light per 1 μm film thickness of the aforementioned insulating layer is 0.5 to 1.5.

[0040]

[18] The organic EL display device described above in

[16] or

[17] also includes a color filter with a black matrix.

[0041]

[19] A display device having at least metal wiring, the curing material described in

[12] or

[13] above, and a plurality of light-emitting elements, wherein the display device is configured such that the light-emitting elements have a pair of electrode terminals on any side, the pair of electrode terminals are connected to a plurality of metal wirings extending in the curing material, and the plurality of metal wirings are electrically insulated by the curing material.

[0042] Invention Effects

[0043] A xaton compound is provided that has high heat resistance and can block light up to the long wavelength region of visible light, compared with previous xaton compounds. Attached Figure Description

[0044] [ Figure 1 [This is a cross-sectional view of an example of an organic EL display device.]

[0045] [ Figure 2 [This is a cross-sectional view of an example of a display device.] Detailed Implementation

[0046] The embodiments of the present invention will be described in detail.

[0047] <Xanton compound(b)>

[0048] The pyrithione compound (b) of the present invention is a compound represented by formula (1).

[0049] [Chemical Formula 3]

[0050]

[0051] In equation (1), A 1 ~A 4 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms that may have electron-donating substituents. Among them, A... 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents has an electron-donating substituent. R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 A monovalent hydrocarbon group with 1 to 20 carbon atoms. R 5 Represents hydrogen atom, -SO3H, -SO3 - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 R 6 ~R 10 Each group independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. Z represents an anionic compound, and n represents 0 or 1. Among them, the thallium compound (b) represented by formula (1) is an electrically neutral compound as a whole.

[0052] With regard to the thallium compound (b) of the present invention, in formula (1), A 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents has an electron-donating substituent. Thus, compared with xaton compounds that are not so, the maximum absorption wavelength in the range of 350 to 800 nm can be extended.

[0053] The aryl group having 6 to 10 carbon atoms, which may have an electron-donating substituent, may contain, for example, phenyl or naphthyl groups. In formula (1), from the viewpoint of further extending the maximum absorption wavelength in the 350-800 nm range, A is preferred. 1 ~A 4 All four of them are aryl.

[0054] At least one of the aryl groups with 6 to 10 carbon atoms among the above-mentioned at least three electron-donating substituents has an electron-donating substituent. By making the aryl group on the nitrogen atom in formula (1) have an electron-donating substituent, the maximum absorption wavelength in the 350 to 800 nm range of the zeatane compound (b) can be further extended. In organic electronic theory, an electron-donating substituent is an atomic group that donates electrons to the substituted atomic group through inductive or resonance effects. As an electron-donating substituent, the substituent constant σ, which is the Hammett rule, can be cited as an example. p Substituents that take negative values. The substituent constant σ in Hammett's rule. p The value can be cited from the Chemical Handbook Fundamentals, Revised 5th Edition (II-380). As a specific example of an electron-donating substituent, for example, it can have an alkyl group (σ of methyl). p Value: -0.17), alkoxy (σ of methoxy) p Value: -0.27), aryloxy group (-OC6H5) σ p Value: -0.32), σ of hydroxyl group (-OH) p Value: -0.37), σ of amino (-NH2) p Value: -0.66), σ of alkylamino (-N(CH3)2 p Value: -0.83, etc.

[0055] From the viewpoint of being able to extend the maximum absorption wavelength of 350–800 nm in the thallium compound (b), the substituent constant σ of the Hammett rule for electron-donating substituents... p The value is preferably below -0.20, more preferably below -0.25, and even more preferably below -0.30. The substituent constant σ of the Hammett rule. p There is no particular restriction on the lower limit of the value, but it is preferred to be above -0.90.

[0056] A 1 ~A 4When three of the aryl groups are 6 to 10 carbon atoms that can have electron-donating substituents, it is preferable that two or more aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents have electron-donating substituents, and more preferably that three aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents have electron-donating substituents.

[0057] A 1 ~A 4 When the four aryl groups are 6 to 10 carbon atoms that can have electron-donating substituents, it is preferable that two or more aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents have electron-donating substituents, more preferably that three or more aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents have electron-donating substituents, and even more preferably that four aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents have electron-donating substituents.

[0058] The preferred substitution position for the electron-donating substituent is preferably para or ortho relative to the carbon atom bonded between the nitrogen atom and the thallium compound (b), and more preferably para.

[0059] The aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents can also have substituents other than the aforementioned electron-donating substituents. Examples of substituents other than electron-donating substituents include, for example, aryl groups, halogen atoms, -COORa, -OCORa, and -SO3. - The compounds represented by formula (1) are generally electrically neutral; therefore, the aryl groups with 6 to 10 carbon atoms have a -SO3 group. - In the case of -SO3 - The substitution number is 1, R 1 ~R 5 It has a neutral group. Ra represents an alkyl group. From the viewpoint of reducing the molecular weight of the thallium compound (b) and increasing the proportion of coloring component per unit mass, the number of carbon atoms of the substituents other than the electron-donating substituents is preferably 20 or less, and more preferably 10 or less. From the same viewpoint, the number of carbon atoms of Ra is preferably 20 or less, and more preferably 10 or less. The substituent constant σ according to Hammett's rule for bonding to the aryl group with 6 to 10 carbon atoms of the electron-donating substituents mentioned above. p The sum of the values ​​is preferably below -0.20.

[0060] A 1 With A 2 and / or A 3 With A 4Each atom can bond together to form a ring. These rings can be formed by single bonds or by bonding between any one of nitrogen, oxygen, or sulfur atoms. Furthermore, 5-membered or 6-membered rings are preferred as the rings formed in this case. Examples of the formed rings include, for instance, a carbazole ring containing two aryl groups (6 to 10 carbon atoms) bonded together by single bonds, and an indole ring containing an aryl group (6 to 10 carbon atoms) bonded together by single bonds, and an alkyl group (1 to 10 carbon atoms).

[0061] R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 A monovalent hydrocarbon group with 1 to 20 carbon atoms. R 6 ~R 10 Each group independently represents a hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms can contain alkyl, cycloalkyl, aryl, etc.

[0062] R 5 Represents hydrogen atom, -SO3H, -SO3 - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 R 6 ~R 10 Each group independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. From the perspective of improving heat resistance, R... 5 Preferably, hydrogen atoms, -SO3H, or -SO3 - -SO3NR 6 R 7 -COOR 8 -CONR 9 R 10 Further preferred are -SO3H and -SO3 - -SO3NR 6 R 7 -CONR 9 R 10 R 5 -SO3NR 6 R 7In this case, from the viewpoint of improving heat resistance, R is preferred. 6 R 7 Any one of them is aryl, and R is further preferred. 6 and R 7 It is aryl. R 5 For -CONR 9 R 10 In this case, from the viewpoint of improving heat resistance, R is preferred. 9 R 10 Any one of them is aryl, and R is further preferred. 9 and R 10 It is an aryl group.

[0063] Z represents an anionic compound. When the compound represented by formula (1) is an anionic compound represented by Z, n is 1. The anionic compound can be any of inorganic or organic anions. As an inorganic ion, it can contain halide ions such as chlorine or bromine. As an organic ion, it can contain sulfonamide anions [(RSO2)2N] in addition to aliphatic or aromatic sulfonate ions and aliphatic or aromatic carboxylate ions. - , borate anion (BR4) -In the ionic formula, each R is independently a monovalent hydrocarbon group with 1 to 20 carbon atoms that may have substituents or heteroatoms in the carbon chain. Examples of substituents for R include alkyl groups with 1 to 10 carbon atoms, aryl groups with 1 to 10 carbon atoms, halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, etc. Examples of heteroatoms include nitrogen atoms, oxygen atoms, halogen atoms, etc. From the viewpoint of suppressing the deterioration of the electrodes and light-emitting layers of an organic EL display device when a cured product formed from a resin composition having sulfonate compound (b) is applied to an organic EL display device, the anionic compounds n=1 and Z in formula (1) are preferably organic anions, preferably aliphatic or aromatic sulfonate ions, aliphatic or aromatic carboxylate ions, sulfonamide anions, or borate anions. Furthermore, from the viewpoint of improving sensitivity and reducing residue when preparing a resin composition comprising the alkali-soluble resin (a) and the photosensitive compound (c) described later, in formula (1), n ​​is 1, and Z is preferably an aliphatic or aromatic sulfonate ion or an aliphatic or aromatic carboxylate ion, and Z is more preferably an aliphatic or aromatic sulfonate ion. As an aliphatic group, a monovalent alkyl group with 1 to 20 carbon atoms is preferred, and in addition to methyl, ethyl, propyl, and butyl, groups formed by substituting some hydrogen atoms of these alkyl groups with halogen atoms are also possible. As an aromatic group, a monovalent aryl group with 1 to 20 carbon atoms is preferred, and phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, dodecylphenyl, etc. are possible. From the viewpoint of improving sensitivity by increasing the proportion of the coloring component per molecule and reducing the amount of ionic dye added, the molecular weight of Z is preferably 1000 or less, preferably 700 or less, and more preferably 300 or less. The lower limit of the molecular weight of Z is not particularly limited, but it is preferably 1 or more, and more preferably 100 or more.

[0064] n represents 0 or 1. The compound represented by formula (1) is electrically neutral overall. Electroneutrality means that the number of positive charges and negative charges in the compound represented by formula (1) are equal. Since the compound represented by formula (1) is electrically neutral overall, therefore, in R... 1 ~R 5 In the case of anions, R 1 ~R 5 Only one of them becomes -SO3 - or -COO - In compound (b) R 1 ~R 5 Only one of them is -SO3 - or -COO - In cases where the aryl group has 6 to 10 carbon atoms and possesses -SO3 -In the case where there is a counter anion among the substituents in the molecule, the compound represented by formula (1) is electrically neutral overall even without Z, and n becomes 0. On the other hand, in the thallium compound (b), R 1 ~R 5 In cases where neither contains anion, or where the aryl group with 6 to 10 carbon atoms does not have -SO3 - In the case where n is 1, the compound represented by formula (1) is electrically neutral overall, and therefore n becomes 1. When n is 1, the compound represented by formula (1) has Z. From the viewpoint of preventing the incorporation of halide ions into the cured product formed from the resin composition having alkali-soluble compound (b), n in formula (1) is preferably 0. On the other hand, from the viewpoint of improving sensitivity when preparing a resin composition containing the alkali-soluble resin (a) and the photosensitive compound (c) described later, n is preferably 1.

[0065] Xanthones compound (b) preferably has a maximum absorption wavelength in the range of 350–800 nm and between 580 nm and 700 nm. Generally, xanthones with alkyl groups substituted at the nitrogen atom can obtain a red spectrum with a maximum absorption wavelength in the range of 350–800 nm around 550 nm, but for xanthones compound (b) represented by formula (1), A… 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents has an electron-donating substituent. This results in a longer maximum absorption wavelength, thus obtaining a blue spectrum. The sulfonium compound (b) more preferably has a maximum absorption wavelength at any point in the range of 590 nm to 700 nm, and even more preferably at any point in the range of 600 nm to 700 nm.

[0066] From the viewpoint of improving the light-shielding properties of visible light, the resin composition contains a thallium compound (b) having a maximum absorption wavelength at any point in the wavelength range of 580 nm to 700 nm and a colorant (d-2) having a maximum absorption wavelength at any point in the range of 350 to 800 nm, above 490 nm and below 580 nm, as described later. More preferably, it contains a colorant (d-1) having a maximum absorption wavelength in the range of 350 to 800 nm, above 400 nm and below 490 nm, as described later, or a thermochromic compound, as described later.

[0067] The xaton compound (b) of the present invention can be manufactured according to known methods for manufacturing xaton compounds, without particular limitation.

[0068] For example, the dichloride of sulfonylfluorescein and the corresponding aromatic amine compound are heated and stirred in a solvent. After cooling to room temperature, the reaction solution is injected into an aqueous hydrochloric acid solution and stirred. The precipitate is then filtered, washed with water and hot water, and dried to obtain a xanthonium compound in which two identical aryl groups are substituted at the nitrogen atom. To prepare xanthonium compounds in which two different aryl groups are substituted at the nitrogen atom, the corresponding half of the aromatic amine compound is added dropwise in small amounts to a solvent containing the dichloride of sulfonylfluorescein. After the reaction, the remaining half of the aromatic amine compound is added dropwise.

[0069] Next, the xanthones compound with two aryl groups substituted at the nitrogen atom and the corresponding aromatic halide were heated and stirred in a solvent containing a copper catalyst and a base. The reaction solution was filtered to remove insoluble matter, then injected into an aqueous hydrochloric acid solution and stirred. The precipitate was then filtered off, washed with water and hot water, and dried to obtain xanthones compounds with three or four aryl groups substituted at the nitrogen atom. In the case of xanthones compounds with three aryl groups substituted at the nitrogen atom, different aromatic halides or aliphatic halides can be used to similarly carry out the reaction, thereby obtaining xanthones compounds with four aryl groups substituted at the nitrogen atom or xanthones compounds with three aryl groups and one alkyl group substituted at the nitrogen atom.

[0070] <Alkali-soluble resin (a)>

[0071] The resin composition of the present invention comprises the succinate compound (b) of the present invention and an alkali-soluble resin (a). Alkali-soluble means that a pre-baked film with a thickness of 10 μm ± 0.5 μm is formed by coating a silicon wafer with a solution obtained by dissolving the resin in γ-butyrolactone, pre-baking at 120°C for 4 minutes, immersing the pre-baked film in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23 ± 1°C for 1 minute, and then rinsing with pure water. The dissolution rate, calculated based on the reduction in film thickness at this point, is 50 nm / min or higher.

[0072] To make the alkali-soluble resin (a) alkali-soluble, hydroxyl groups and / or acidic groups are present in the structural units of the resin and / or at the ends of its main chain. For example, acidic groups may include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, etc.

[0073] As an alkali-soluble resin (a), it may contain, but is not limited to, polyimide, polyimide precursor, polybenzoxazole precursor, polyamide-imide, polyamide-imide precursor, polyamide, polymers of free radical polymerizable monomers having acidic groups, phenolic resins, etc. The resin composition may contain two or more of these resins.

[0074] From the perspective of high adhesion, excellent heat resistance, and low gas escape at high temperatures, resulting in high long-term reliability when the cured product is used in organic EL display devices, the alkali-soluble resin (a) preferably includes one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, polyamide-imide precursor, and copolymers thereof, more preferably polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers thereof. Furthermore, from the viewpoint of further improving sensitivity, polyimide precursor or polybenzoxazole precursor is further preferred. Here, polyimide precursor refers to a resin that is converted into polyimide through heat treatment or chemical treatment. Examples of polyimide precursors include, for example, polyamic acid and polyamic acid ester. Polybenzoxazole precursor refers to a resin that is converted into polybenzoxazole through heat treatment or chemical treatment, for example, polyhydroxyamide.

[0075] The aforementioned polyimide precursor and polybenzoxazole precursor have structural units represented by formula (3) below, and the polyimide has structural units represented by formula (4) below. It may contain two or more of them, or it may contain a resin copolymerized from structural units represented by formula (3) and structural units represented by formula (4).

[0076] [Chemical Formula 4]

[0077]

[0078] In formula (3), X represents an organic group with 4 to 40 carbon atoms and a valence of 2 to 8, and Y represents an organic group with 6 to 40 carbon atoms and a valence of 2 to 11. 11 and R 13 Each can independently represent a hydroxyl group or a sulfonic acid group. R 12 and R 14 Each of these can independently represent a monovalent hydrocarbon group with 1 to 20 hydrogen or carbon atoms. t, u, and w represent integers from 0 to 3, and v represents an integer from 0 to 6. Where t + u + v + w > 0.

[0079] [Chemical Formula 5]

[0080]

[0081] In formula (4), E represents an organic group with 4 to 40 carbon atoms and a valence of 4 to 10, and G represents an organic group with 6 to 40 carbon atoms and a valence of 2 to 8. R 15 and R 16 Each group independently represents a carboxyl group, a sulfonic acid group, or a hydroxyl group. x and y each independently represent an integer from 0 to 6. Where x + y > 0.

[0082] Polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably have 5 to 100,000 structural units represented by formula (3) or formula (4). Alternatively, other structural units may be present in addition to those represented by formula (3) or formula (4). In this case, it is preferable that the structural units represented by formula (3) or formula (4) are present in an amount of 50 mol% or more of all structural units.

[0083] In the above formula (3), X(R) 11 ) t (COOR 12 ) u Residues representing acids. X is an organic group having 4 to 40 carbon atoms and a valence of 2 to 8, preferably an organic group with a valence of 2 to 8 containing an aromatic ring or a cyclic aliphatic group.

[0084] Examples of acid residues include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; pyromellitic tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane. (2,3-Dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and aromatic tetracarboxylic acids with structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid and other aliphatic tetracarboxylic acids containing cyclic aliphatic groups, etc. X(R) 11 ) t (COOR 12 ) u It can have more than two of these residues.

[0085] [Chemical Formula 6]

[0086]

[0087] R 20 Represents an oxygen atom, C(CF3)2, or C(CH3)2. R 21 and R 22Each can be used independently to represent a hydrogen atom or a hydroxyl group.

[0088] In the case of tricarboxylic or tetracarboxylic acid residues, one or two carboxyl groups are equivalent to (COOR) in formula (3). 12 ).

[0089] In equation (4) above, E(R) 15 ) x Represents a dianhydride residue. E is an organic group with 4 to 40 carbon atoms and a valence of 4 to 10, preferably an organic group containing an aromatic ring or a cyclic aliphatic group.

[0090] Specifically, examples of dianhydride residues include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, and bis(2,3-dicarboxyphenyl) Methane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and other aromatic tetracarboxylic dianhydrides with structures shown below, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, and residues of aliphatic tetracarboxylic dianhydrides containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. E(R) 15 ) x It can have more than two of these residues.

[0091] [Chemical Formula 7]

[0092]

[0093] R 20 Represents an oxygen atom, C(CF3)2, or C(CH3)2. R 21 and R 22 Each can be used independently to represent a hydrogen atom or a hydroxyl group.

[0094] Y(R) in equation (3) above 13 ) v(COOR 14 ) w and G(R) of equation (4) above 16 ) y This represents a residue of a diamine. Y is an organic group having 6 to 40 carbon atoms and a valence of 2 to 11, preferably an organic group having a valence of 2 to 11 containing an aromatic ring or a cyclic aliphatic group. G is an organic group having 6 to 40 carbon atoms and a valence of 2 to 8, preferably an organic group having a valence of 2 to 8 containing an aromatic ring or a cyclic aliphatic group.

[0095] Specific examples of diamine residues may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diamino Residues of aromatic diamines such as biphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds formed by substituting at least a portion of the hydrogen atoms of their aromatic rings with alkyl or halogen atoms; residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexanediamine and methylene dicyclohexaneamine; and residues of diamines with structures shown below. Y(R) 13 ) v (COOR 14 ) w and G(R) 16 ) y It can have more than two of these residues.

[0096] [Chemical Formula 8]

[0097]

[0098] R 20 Represents an oxygen atom, C(CF3)2, or C(CH3)2. R 21 ~R 24 Each can be used independently to represent a hydrogen atom or a hydroxyl group.

[0099] In addition, the ends of alkali-soluble resin (a) can be blocked using known monoamines, acid anhydrides, acyl chlorides, monocarboxylic acids, and active ester compounds with acidic groups.

[0100] Alkali-soluble resin (a) can be synthesized using known methods.

[0101] Regarding methods for manufacturing polyamic acid as a precursor of polyimide, for example, one method is to react tetracarboxylic dianhydride with a diamine compound in a solvent at low temperature.

[0102] Regarding methods for manufacturing polyamic acid esters, which are also precursors to polyimides, in addition to the aforementioned method of reacting polyamic acid with an esterifying agent, there are also methods such as: obtaining a diester using tetracarboxylic acid dianhydride and an alcohol, and then reacting it with an amine in a solvent in the presence of a condensing agent. Examples include: obtaining a diester using tetracarboxylic acid dianhydride and an alcohol, then acylchlorinating the remaining dicarboxylic acid, and reacting it with an amine in a solvent. From the viewpoint of ease of synthesis, a step including the reaction of polyamic acid with an esterifying agent is preferred. There are no particular limitations on the esterifying agent; known methods can be used, but from the perspective of ease of purification of the obtained resin, N,N-dimethylformamide dialkyl acetal is preferred.

[0103] Regarding methods for manufacturing polyhydroxyamides as precursors of polybenzoxazole, one example is a method involving a condensation reaction of a bisaminophenol compound with a dicarboxylic acid in a solvent. Specifically, one example is a method in which a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and then a bisaminophenol compound is added thereto. Another example is a method in which a solution of dicarboxylic acid acyl chloride is added dropwise to a solution of a bisaminophenol compound containing a tertiary amine such as pyridine.

[0104] As a method for manufacturing polyimide, examples include dehydrating and ring-closing polyamic acid or polyamic ester obtained by the aforementioned method in a solvent. Examples of dehydration and ring-closing methods include chemical treatment using acids or alkalis, and heat treatment.

[0105] Examples of methods for manufacturing polybenzoxazole include dehydrating and ring-closing the polyhydroxyamide obtained by the aforementioned method in a solvent. Examples of dehydration and ring-closing methods include chemical treatment using acids or alkalis, and heat treatment.

[0106] Examples of polyamide-imide precursors include polymers of tricarboxylic acids, corresponding tricarboxylic anhydrides, tricarboxylic anhydride halides, and diamine compounds, with polymers of trimellitic anhydride chloride and aromatic diamine compounds being preferred. Methods for manufacturing polyamide-imide precursors include, for example, reacting tricarboxylic acids, corresponding tricarboxylic anhydrides, tricarboxylic anhydride halides, etc., with diamine compounds in a solvent at low temperature.

[0107] Examples of methods for manufacturing polyamide-imide include reacting trimellitic anhydride with an aromatic diisocyanate in a solvent, and dehydrating and ring-closing the polyamide-imide precursor obtained by the aforementioned methods in a solvent. Examples of dehydration and ring-closing methods include chemical treatment using acids or alkalis, and heat treatment.

[0108] As a polymerization solvent, there are no particular limitations, and it may contain alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate, and isobutyl acetate, ketones such as methyl isobutyl ketone and methyl propyl ketone, alcohols such as butanol and isobutanol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and propylene glycol monomethyl ether. Ester, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolinone, N,N-dimethylpropenylurea, δ-valerolactone, 2-phenoxyethanol, 2-pyrrolidone, 2-methyl-1,3-propanediol, diethylene glycol butyl ether, triacetin, butyl benzoate, cyclohexylbenzene, dicyclohexane, o-nitrosoanisole, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, N-(2-hydroxyethyl)-2-pyrrolidone, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N,N',N'-tetramethylurea, 3-methyl-2-oxazolidinone, etc.

[0109] The content of alkali-soluble resin (a) is preferably 40% to 90% by mass in 100% by mass of the solid component of the resin composition. By setting the content of alkali-soluble resin (a) within this range, the heat resistance of the resin composition can be maintained and the light-shielding properties of the cured film can be improved.

[0110] <Photosensitive Compound (c)>

[0111] The resin composition of the present invention may further comprise a photosensitive compound (c).

[0112] When the resin composition of the present invention contains a photosensitive compound (c), from the viewpoint of increasing sensitivity, the content of the photosensitive compound (c) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the alkali-soluble resin (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used to form a planarization layer and / or insulating layer for an organic EL display device, it is preferably 100 parts by mass or less.

[0113] As a photosensitive compound (c), it may contain photoacid generators (c1), photopolymerization initiators (c2), etc. Photoacid generators (c1) are compounds that produce acids through light irradiation, while photopolymerization initiators (c2) are compounds that undergo bond cleavage and / or reactions through exposure to generate free radicals.

[0114] By including a photoacid-generating agent (c1), acid is generated in the light-irradiated area, increasing the solubility of the light-irradiated area in an alkaline aqueous solution, thus obtaining a positive raised pattern that dissolves in the light-irradiated area. Alternatively, by including a photoacid-generating agent (c1) and an epoxy compound or thermal crosslinking agent (described later), the acid generated in the light-irradiated area promotes the crosslinking reaction of the epoxy compound and the thermal crosslinking agent, thus obtaining a negative raised pattern that does not dissolve in the light-irradiated area. On the other hand, by including a photopolymerization initiator (c2) and a free radical polymerizable compound (described later), free radical polymerization occurs in the light-irradiated area, thus obtaining a negative raised pattern that does not dissolve in the light-irradiated area. From the viewpoint that fine patterns can be formed when the cured product of the present invention is used to form the planarization layer and / or insulating layer of an organic EL display device, the photosensitive compound (c) preferably includes a photoacid-generating agent (c1) that can obtain a positive raised pattern.

[0115] As a photoacid generator (c1), for example, it may contain quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc. The resin composition of the present invention preferably contains two or more photoacid generators (c1), and with two or more photoacid generators (c1), a photosensitive resin composition with higher sensitivity can be obtained. From the viewpoint of long-term reliability when the cured product of the present invention is used to form a planarization layer and / or insulating layer for an organic EL display device, the photoacid generator (c1) is particularly preferably a quinone diazide compound.

[0116] As quinone diazide compounds, they can be compounds formed by ester bonding of sulfonic acid of diazidoquinone with a polyhydroxy compound, compounds formed by sulfonamide bonding of sulfonic acid of diazidoquinone with a polyamino compound, and compounds formed by ester bonding and / or sulfonamide bonding of sulfonic acid of diazidoquinone with a polyhydroxy polyamino compound, etc.

[0117] As a diazidoquinone, either diazidonaphthoquinone-5-sulfonyl or diazidonaphthoquinone-4-sulfonyl is preferred. It may contain a diazidonaphthoquinone sulfonate compound having both diazidonaphthoquinone-4-sulfonyl and diazidonaphthoquinone-5-sulfonyl groups in the same molecule, or it may contain both diazidonaphthoquinone-4-sulfonate and diazidonaphthoquinone-5-sulfonate compounds. The diazidonaphthoquinone-4-sulfonate compound exhibits absorption in the i-line region of the mercury lamp, making it suitable for i-line exposure. The absorption of the diazidonaphthoquinone-5-sulfonate compound extends to the g-line region of the mercury lamp, making it suitable for g-line exposure.

[0118] The diazidonaphthoquinone-4-sulfonate compound and the diazidonaphthoquinone-5-sulfonate compound are preferably selected according to the wavelength of exposure, but from the viewpoint of increasing sensitivity, the diazidonaphthoquinone-4-sulfonate compound is preferred.

[0119] The aforementioned quinone diazide compounds can be synthesized from compounds with phenolic hydroxyl groups and diazidoquinone sulfonic acid compounds through any esterification reaction. By using these quinone diazide compounds, resolution, sensitivity, and residual film yield are further improved.

[0120] In this invention, among the photoacid generators (C1), sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferred as they moderately stabilize the acid components generated through exposure. Sulfonium salts are particularly preferred. Sensitizers may also be included as needed.

[0121] When the above-described resin composition contains a photoacid generator (Cl), from the viewpoint of increasing sensitivity, the content of the photoacid generator (Cl) is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more, relative to 100 parts by mass of the alkali-soluble resin (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used to form a planarization layer and / or insulating layer for an organic EL display device, it is preferably 100 parts by mass or less.

[0122] As the photopolymerization initiator (c2), for example, it may contain benzoyl ketal photopolymerization initiators, α-hydroxy ketone photopolymerization initiators, α-amino ketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, acridine photopolymerization initiators, titanium ceramsite photopolymerization initiators, benzophenone photopolymerization initiators, acetophenone photopolymerization initiators, aromatic keto ester photopolymerization initiators, benzoate ester photopolymerization initiators, etc. The resin composition of the present invention may contain two or more photopolymerization initiators (c2). From the viewpoint of further improving sensitivity, the photopolymerization initiator (c2) is further preferably an α-amino ketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or an oxime ester photopolymerization initiator.

[0123] As an α-aminoketone-based photopolymerization initiator, it may contain, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butane-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole, etc.

[0124] As an acylphosphine oxide-based photopolymerization initiator, it may contain, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc.

[0125] As an oxime ester-based photopolymerization initiator, it may contain, for example, 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyl) oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxacyclopentan-4-yl)methyloxy]benzoyl]-9H-carbazole-3-yl]acetone-1-(O-acetyl) oxime, or 1-(9-ethyl-6-nitro-9H-carbazole-3-yl)-1-[2-methyl-4-(1-methoxypropane-2-yloxy)phenyl]acetone-1-(O-acetyl) oxime, etc.

[0126] In this invention, when a photopolymerization initiator (c2) is included, from the viewpoint of increasing sensitivity, the content of the photopolymerization initiator (c2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to a total of 100 parts by mass of the alkali-soluble resin (a) and the free radical polymerizable compound described later. On the other hand, from the viewpoint of further improving resolution and reducing cone angle, it is preferably 50 parts by mass or less.

[0127] <Coloring agent (d)>

[0128] The resin composition of the present invention may also contain a colorant (d) other than the thallium compound (b). By containing the colorant (d), light-shielding properties are imparted, that is, light of wavelengths that the colorant (d) can absorb is blocked from light transmitted through the film of the resin composition or light reflected from the film of the resin composition. By imparting light-shielding properties, when the cured product of the present invention described later is used as a planarization layer and / or insulating layer for an organic EL display device, degradation, malfunction, leakage current, etc., caused by light intrusion into the TFT can be prevented. In addition, the suppression of external light reflection from wiring and TFT, and the contrast between the light-emitting area and the non-light-emitting area can be improved.

[0129] As a colorant (d), a dye (d1) and / or a pigment (d2) is preferably used. The colorant (d) preferably contains at least one, for example, preferably one dye or organic pigment, or two or more dyes or pigments, or one or more dyes and one or more pigments.

[0130] From the viewpoint of solvent solubility, dye (d1) is preferred as the colorant (d) in this invention. Furthermore, from the viewpoints of increased sensitivity and reduced residue, ionic dye (d10) that forms ion pairs of organic ions (hereinafter sometimes referred to as ionic dye (d10)) is preferred as dye (d1). On the other hand, from the viewpoint of suppressing the fading of the colorant during the heat treatment process of the resin composition of this invention, described later, pigment (d2) is preferred.

[0131] The resin composition of the present invention preferably contains a colorant (d-2) having a maximum absorption wavelength in the range of 350-800 nm, above 490 nm and below 580 nm. Specifically, it preferably contains: a dye (d1-2) having a maximum absorption wavelength in the range of 350-800 nm, above 490 nm and below 580 nm; and / or a pigment (d2-2) having a maximum absorption wavelength in the range of 350-800 nm, above 490 nm and below 580 nm. Hereinafter, they are sometimes simply referred to as component (d-2), component (d1-2), and component (d2-2), respectively.

[0132] In this invention, from the viewpoints of storage stability, fading during curing, and light irradiation, the (d1-2) component preferably contains a dye that is soluble in the organic solvent that dissolves the alkali-soluble resin (a) and is compatible with the resin, and a dye with high heat resistance and lightfastness. The (d1-2) component has a maximum absorption wavelength anywhere in the range of 350–800 nm, and above 490 nm but less than 580 nm; therefore, for example, it may contain red dyes, purple dyes, etc. As for the type of dye, for example, it may contain oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, or direct dyes.

[0133] Examples of dye backbone structures include anthraquinone, azo, phthalocyanine, methine, oxazine, quinoline, triarylmethane, and xanthones, but these are not limited to. Among these, anthraquinone, azo, methine, triarylmethane, and xanthones are preferred from the viewpoint of solubility and heat resistance in organic solvents. Furthermore, xanthones are further preferred from the viewpoint of processability when the xanthon compound (b) of the present invention is formulated into a resin composition. Additionally, each of the above-mentioned dyes can be used individually or in the form of metal-containing complex salts. Specifically, dyes that have a maximum absorption wavelength in the range of 350–800 nm, between 490 nm and 580 nm, can be obtained from the following sources: Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Industry Co., Ltd.), Orasol, Orracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, Acidol dye (manufactured by BASF Co., Ltd.), Kayaset, Kayakalan dye (manufactured by Nippon Kayaku Co., Ltd.), Valifafast Colors dye (manufactured by Orient Chemical Industries Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dye (manufactured by Clariant Japan KK), Aizen Spilon dye (manufactured by Hodogaya Chemical Industry Co., Ltd.), functional pigments (manufactured by Yamada Chemical Industry Co., Ltd.), PlastColor dye, Oil Color dye (manufactured by Arimoto Chemical Industry Co., Ltd.), etc., but are not limited to these. These dyes can be used alone or in mixtures.

[0134] In this invention, from the viewpoint of fading during curing and light irradiation, component (d-2) is preferably a pigment with high heat resistance and light resistance.

[0135] Specific examples of organic pigments are shown using their dye index (CI) numbers. Examples of red pigments include Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254. Examples of purple pigments include Pigment Violet 19, 23, 29, 32, 33, 36, 37, and 38. Pigments other than these may also be included.

[0136] The content of component (d-2) is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of alkali-soluble resin (a), more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass. By setting the content of component (d-2) to 0.1 parts by mass or more, it is possible to absorb light of the corresponding wavelength. In addition, by setting it to 300 parts by mass or less, it is possible to maintain the adhesion strength between the photosensitive coloring resin film and the substrate, the heat resistance of the film after heat treatment, the mechanical properties, and the absorption of light of the corresponding wavelength.

[0137] In this invention, the organic pigment used as component (d2-2) may contain organic pigments that have undergone surface treatments such as rosin treatment, acidic group treatment, or basic group treatment as needed. Additionally, a dispersant may be included, depending on the circumstances. The dispersant may contain surfactants such as cationic, anionic, nonionic, amphoteric, silicone-based, or fluorinated surfactants.

[0138] Furthermore, in the resin composition of the present invention, the colorant (d) may contain a colorant (d-1) having a maximum absorption wavelength in the range of 350-800 nm, above 400 nm and below 490 nm. Specifically, it may contain: a dye (d1-1) having a maximum absorption wavelength in the range of 350-800 nm, above 400 nm and below 490 nm; and / or a pigment (d2-1) having a maximum absorption wavelength in the range of 350-800 nm, above 400 nm and below 490 nm. Hereinafter, they will sometimes be referred to as component (d-1), component (d1-1), and component (d2-1), respectively.

[0139] In this invention, from the viewpoint of storage stability, fading during curing, and light irradiation, the dye (d1-1) used as component (d-1) is preferably a dye that is soluble in the organic solvent that dissolves the alkali-soluble resin (a) and is compatible with the resin, and has high heat resistance and lightfastness. Component (d1-1) has maximum absorption at any point in the wavelength range of 400 nm or higher and less than 490 nm; therefore, examples include, for example, yellow dyes and orange dyes. Examples of dye types include, for example, oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, or direct dyes.

[0140] Examples of dye backbone structures include anthraquinone, azo, phthalocyanine, methine, oxazine, quinoline, triarylmethane, and xanthones, but these are not limited to. Among these, anthraquinone, azo, methine, triarylmethane, and xanthones are preferred from the viewpoint of solubility and heat resistance in organic solvents. Furthermore, the aforementioned dyes can be used individually or as metal-containing complex salts. Specifically, dyes that have a maximum absorption wavelength in the range of 350–800 nm, or above 400 nm and below 490 nm, can be obtained from the following sources: Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Industry Co., Ltd.), Orasol, Orracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, Acidol dye (manufactured by BASF Co., Ltd.), Kayaset, Kayakalan dye (manufactured by Nippon Kayaku Co., Ltd.), Valifafast Colors dye (manufactured by Orient Chemical Industries Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dye (manufactured by Clariant Japan KK), Aizen Spilon dye (manufactured by Hodogaya Chemical Industry Co., Ltd.), functional pigments (manufactured by Yamada Chemical Industry Co., Ltd.), PlastColor dye, Oil Color dye (manufactured by Arimoto Chemical Industry Co., Ltd.), etc., but are not limited to these. These dyes can be used alone or in mixtures.

[0141] In this invention, from the viewpoint of fading during curing and light irradiation, the pigment (d2-1) used as component (d-1) is preferably a pigment with high heat resistance and light resistance.

[0142] Specific examples of organic pigments are shown using the Dye Index (CI) number. Examples of yellow pigments include Pigment Yellow 83, 117, 129, 138, 139, 150, and 180. Examples of orange pigments include Pigment Orange 38, 43, 64, 71, and 72. Pigments other than these may also be included.

[0143] The content of component (d-1) is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of alkali-soluble resin (a), more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass. By setting the content of component (d-1) to 0.1 parts by mass or more, light of the corresponding wavelength can be absorbed. In addition, by setting it to 300 parts by mass or less, the adhesion strength between the photosensitive coloring resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties can be maintained, and light of the corresponding wavelength can be absorbed.

[0144] In this invention, the organic pigment used as the (d2-1) component can be an organic pigment that has undergone surface treatments such as rosin treatment, acidic group treatment, or basic group treatment as required. Additionally, it can be used with a dispersant, depending on the situation. Examples of dispersants include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorinated surfactants.

[0145] In the resin composition of the present invention, the colorant (d) may contain a colorant (d-3) having a maximum absorption wavelength in the range of 350-800 nm and 580 nm or more but less than 800 nm. Specifically, it may contain: a dye (d1-3) having a maximum absorption wavelength in the range of 350-800 nm and 580 nm or more but less than 800 nm; and / or a pigment (d2-3) having a maximum absorption wavelength in the range of 350-800 nm and 580 nm or more but less than 800 nm. Hereinafter, they will sometimes be referred to as component (d-3), component (d1-3), and component (d2-3), respectively.

[0146] In this invention, from the viewpoint of storage stability, fading during curing, and light irradiation, the dye (d1-3) used as component (d-3) is preferably a dye that is soluble in the organic solvent that dissolves the alkali-soluble resin (a) and is compatible with the resin, and has high heat resistance and lightfastness. Component (d1-3) has a maximum absorption wavelength at any point in the range of 350 to 800 nm, and between 580 nm and 800 nm; therefore, examples include blue dyes and green dyes.

[0147] Examples of dye types include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, and direct dyes.

[0148] Examples of dye backbone structures include anthraquinone, azo, phthalocyanine, methine, oxazine, quinoline, and triarylmethane dyes, but these are not limited to. Among these, anthraquinone, azo, methine, and triarylmethane dyes are preferred from the viewpoint of solubility and heat resistance in organic solvents. Furthermore, each of the above dyes can be used individually or as a metal-containing complex salt. Specifically, dyes that have a maximum absorption wavelength in the range of 350–800 nm and between 580 nm and 800 nm can be obtained from the following sources: Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Industry Co., Ltd.), Orasol, Orracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, Acidol dye (manufactured by BASF Co., Ltd.), Kayaset, Kayakalan dye (manufactured by Nippon Kayaku Co., Ltd.), Valifafast Colors dye (manufactured by Orient Chemical Industries Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dye (manufactured by Clariant Japan KK), Aizen Spilon dye (manufactured by Hodogaya Chemical Industry Co., Ltd.), functional pigments (manufactured by Yamada Chemical Industry Co., Ltd.), Plast Color dye, OilColor dye (manufactured by Arimoto Chemical Industry Co., Ltd.), etc., but are not limited to these. These dyes can be used alone or in mixtures.

[0149] In this invention, from the viewpoint of fading during curing and light irradiation, the pigment (d2-3) used as component (d-3) is preferably a pigment with high heat resistance and light resistance.

[0150] Specific examples of organic pigments are shown using their dye index (CI) numbers. Examples of blue pigments include Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 22, 60, 64, etc. Examples of green pigments include Pigment Green 7, 10, 36, 47, 58, etc. Pigments other than these may also be included.

[0151] The content of component (d-3) is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of alkali-soluble resin (a), more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass. By setting the content of component (d-3) to 0.1 parts by mass or more, it is possible to absorb light of the corresponding wavelength. In addition, by setting it to 300 parts by mass or less, it is possible to maintain the adhesion strength between the photosensitive coloring resin film and the substrate, the heat resistance of the film after heat treatment, the mechanical properties, and the absorption of light of the corresponding wavelength.

[0152] In this invention, the organic pigment used as component (d2-3) can be an organic pigment that has undergone surface treatments such as rosin treatment, acidic group treatment, or basic group treatment as required. Additionally, it can be used with a dispersant, depending on the situation. Examples of dispersants include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorinated surfactants.

[0153] Furthermore, in this invention, by using the xaton compound (b), component (d-2), component (d-1), and / or the thermochromic compound described later, as well as component (d-3) as needed, the visible light transmittance of the cured material can be reduced, making it black. Regarding the optical density (hereinafter, sometimes referred to as OD value) per 1 μm film thickness of the cured material obtained by curing the resin composition containing the xaton compound (b) of this invention, an OD value of 0.5 or more is preferred, and more preferably 0.7 or more is preferred. If the OD value is within the above range, the light-shielding properties of the cured material can be improved. Therefore, in display devices such as organic EL display devices or liquid crystal display devices, the visibility of electrode wiring and external light reflection can be further reduced, and the contrast during image display can be improved. On the other hand, from the viewpoint of improving the sensitivity during exposure when preparing the resin composition containing the photosensitive compound described later, an OD value of 1.5 or less is preferred.

[0154] <Ionic dyes (d10) and organic anions>

[0155] The resin composition of the present invention preferably contains a xanthene compound (b1) in which n is 1 and Z is an organic anion in formula (1) (hereinafter sometimes referred to as xanthene compound (b1)), and an ionic dye (d10) that forms an ion pair between organic ions, and the aforementioned organic anion is one kind. Here, the ionic dye that forms an ion pair between organic ions means an ionic dye formed by each organic anion and organic cation, and a compound that is electrically neutral as a whole with an anion site and a cation site in the monomer, such as the xanthene compound where n is 0 in formula (1), is not regarded as an organic anion. In addition, here, the so-called organic anion being one kind means that the organic anion in the xanthene compound (b1) is the same as the organic anion constituting the ionic dye (d10). When the resin composition of the present invention contains the xanthene compound (b1) and the ionic dye (d10), and the respective organic anion parts are different from each other, the number of types of organic anions contained in the resin composition becomes two or more. In this case, since there are multiple organic anions and organic cations in the resin composition, the following problem occurs: the increase of foreign matters during cryogenic storage due to the ion exchange between ionic dyes, and the storage stability deteriorates. On the other hand, when the xanthene compound (b1) and the ionic dye (d10) are contained, by making the number of types of organic anions contained in the resin composition of the present invention one kind, the storage stability during cryogenic storage is improved. It is inferred that this is because, by limiting the types of organic anions for the xanthene compound (b1) and the ionic dye (d10), even if the organic cation parts are different from each other, the ion exchange between ionic dyes is suppressed in the resin composition.

[0156] The ionic dye (d10) that forms an ion pair between organic ions in the present invention refers to a salt-forming compound (Japanese: 造塩化合物) formed by the organic anion part of an acid dye and the organic cation part of a non-dye, a salt-forming compound formed by the organic cation part of a basic dye and the organic anion part of a non-dye, or a salt-forming compound formed by the organic anion part of an acid dye and the organic cation part of a basic dye.

[0157] The salt-forming compound formed by the organic cation part of a basic dye and the organic anion part of a non-dye can be manufactured by using a basic dye as a raw material and replacing the counter anion with an organic anion of a non-dye by a known method. The salt-forming compound formed by the organic anion part of an acid dye and the organic cation part of a non-dye can be manufactured by using an acid dye as a raw material and replacing the counter cation with an organic cation of a non-dye by a known method. The salt-forming compound formed by the organic anion part of an acid dye and the organic cation part of a basic dye can be manufactured by using an acid dye and a basic dye as raw materials and replacing them with their respective counter ions by a known method.

[0158] Acid dyes, which are the raw materials for ionic dyes (d10), are compounds that have acidic substituents such as sulfonyl or carboxyl groups in their molecules, or are anionic water-soluble dyes that are salts of these compounds. It should be noted that acid dyes include dyes that have acidic substituents such as sulfonyl or carboxyl groups and are classified as direct dyes.

[0159] Examples of acid dyes include: CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26. 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; CI Acid Brown 2, 4, 13, 248; CI Acid Violet 11, 56, 58; CI Acid Blue 92 Azo acid dyes such as CI Acid Yellow 2, 3, 5, etc.; Quinoline acid dyes such as CI Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289, etc.; Xanthan acid dyes such as CI Acid Red 82, 92; CI Acid Violet 41, 42, 43; CI Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127, 1, 129, 145, 167, 230; Anthraquinone acid dyes such as CI Acid Green 25, 27; CI Acid Violet 49; CI Acid Blue 7, 9, 22, 83, 90; CI Acid Green 9, 50; Triarylmethane acid dyes such as CI Food Green 3; Phthalocyanine acid dyes such as CI Acid Blue 249; Indigo acid dyes such as CI Acid Blue 74. In terms of heat resistance, acid dyes preferably contain xanthan acid dyes. Xanthan acid dyes are more preferably containing rhodamine acid dyes such as CI Acid Red 50, 52, and 289.

[0160] Examples of non-dye organic cationic portions that can be used as raw materials for ionic dyes (d10) include ammonium ions [N(R)4]. + Phosphorus ions [P(R)4] + Imine ion [(R)2-N=C(R)2] + Arsunium ion [As(R)4] + Antimonyonium ions [Sb(R)4] + Oxonium ions [O(R)3] + Sulfonium ions [S(R)3] +Selenium ions [Se(R)3] + stannonium ion [Sn(R)3] + Iodonium ions [I(R)2] + Diazoonium ion [RN] + [≡N] etc. From the viewpoint of insulation properties when a cured product formed from the resin composition of the present invention is applied, ammonium ions [N(R)4] are preferred. + Phosphorus ions [P(R)4] + Imine ion [(R)2-N=C(R)2] + It should be noted that each R in the ionic formula is an independent hydrocarbon group with 1 to 20 carbon atoms, which may have substituents or heteroatoms in the carbon chain. From the viewpoint of improving sensitivity by increasing the proportion of the coloring component per molecule and reducing the amount of ionic dye added, the molecular weight of the non-dye organic cationic portion is preferably 1000 or less, preferably 700 or less, and more preferably 300 or less. The lower limit of the molecular weight of the non-dye organic cationic portion is not particularly limited, but it is preferably 1 or more, and more preferably 100 or more.

[0161] Basic dyes that become raw materials for ionic dyes (d10) are compounds or their salts that have basic groups such as amino and imino in their molecules and form cationic dyes in aqueous solutions.

[0162] Examples of basic dyes include: CI Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46:1, 82; CI Basic Orange 2, 24, 25; CI Basic Violet 18; CI Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; CI Basic Brown 1; CI Basic Blue 41, 54, 64, 66, 67, 129, etc. (azo basic dyes); CI Basic Red 1, 2; CI Basic Violet 10, 11, etc. (xanthine basic dyes); CI Basic Yellow 11. 13, 21, 23, 28; CI Basic Orange 21; CI Basic Red 13, 14; CI Basic Violet 16, 39; etc., basic dyes of the methine family; CI Basic Blue 22, 35, 45, 47, etc., basic dyes of the anthraquinone family; CI Basic Violet 1, 2, 3, 4, 13, 14, 23; CI Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24, 26; CI Basic Green 1, 4, etc., basic dyes of the triarylmethane family and basic dyes of the xanthones family with the structures shown below.

[0163] [Chemical Formula 9]

[0164]

[0165] R 25 R 27 and R 29 ~R 31 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may have substituents, R 26 and R 28 Each can be independently represented by an alkyl group having 1 to 10 hydrogen or carbon atoms.

[0166] Regarding basic dyes, from the perspective of improving the blackness of the cured film, basic dyes containing saxon or triarylmethane are preferred, while from the perspective of high heat resistance, acid dyes containing saxon are preferred.

[0167] In addition to aliphatic or aromatic sulfonate ions and aliphatic or aromatic carboxylate ions, the non-dye organic anionic portion that can be used as a raw material for ionic dyes (d10) can also include sulfonamide anions [(RSO2)2N]. - , borate anion (BR4) - From the viewpoint of suppressing the deterioration of the electrodes and light-emitting layer of the organic EL display device when the cured product formed by the resin composition of the present invention is applied, the anionic compound is preferably an aliphatic or aromatic sulfonate ion or an aliphatic or aromatic carboxylate ion. Furthermore, from the viewpoint of increasing sensitivity and reducing residue, aliphatic or aromatic sulfonate ions are preferred. It should be noted that each R in the ionic formula is independently a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents or heteroatoms in the carbon chain. From the viewpoint of improving sensitivity by increasing the proportion of coloring component per molecule and reducing the amount of ionic dye added, the molecular weight of the non-dye organic anionic portion is preferably 1000 or less, preferably 700 or less, and more preferably 300 or less. The lower limit of the molecular weight of the non-dye anionic portion is not particularly limited, but is preferably 1 or more, and more preferably 100 or more.

[0168] From the viewpoint of high heat resistance, the organic anionic portion and / or organic cationic portion of the ionic dye (d10) preferably has a saxon backbone. Examples of organic anions having a saxon backbone include the aforementioned saxon-based acid dyes, and examples of organic cationic dyes having a saxon backbone include the aforementioned saxon-based basic dyes.

[0169] From the viewpoint of increasing alkali solubility and improving sensitivity during development, ionic dyes (d10) preferably have acidic groups. For example, acidic groups can be carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonate groups, etc., with sulfonic acid groups and sulfonate groups being particularly preferred.

[0170] When used in combination with xaton compound (b), from the viewpoint of improving the light-blocking properties of visible light, the ionic dye (d10) preferably contains a colorant (d10-2) that has the maximum absorption wavelength in the range of 350 to 800 nm, above 490 nm and below 580 nm.

[0171] Salt compounds obtained through ion exchange of acidic and basic dyes can be manufactured using known methods. For example, by preparing aqueous solutions of acidic and basic dyes separately and slowly mixing them while stirring, a salt compound formed from the organic anionic portion of the acidic dye and the organic cationic portion of the basic dye is generated as a precipitate. This salt compound can be recovered by filtration. The obtained salt compound is preferably dried at around 60–70°C.

[0172] Relative to 100 parts by weight of the alkali-soluble resin (a), the total content of the ionic dye (d10) in the resin composition of the present invention is preferably 0.1 parts by weight or more to 300 parts by weight, more preferably 0.2 parts by weight or more to 200 parts by weight, and particularly preferably 1 part by weight or more to 200 parts by weight. By setting the content of the ionic dye (b) to 0.1 parts by weight or more, light of the corresponding wavelength can be absorbed. In addition, by setting it to 300 parts by weight or less, the adhesion strength between the photosensitive coloring resin film and the substrate, the heat resistance of the film after heat treatment, the mechanical properties, and the absorption of light of the corresponding wavelength can be maintained.

[0173] <Thermochromic Compounds>

[0174] The resin composition of the present invention may contain a thermochromic compound. The thermochromic compound is a thermochromic compound that develops color by heat treatment and has maximum absorption in the range of 350 nm to 700 nm, more preferably a thermochromic compound that develops color by heat treatment and has maximum absorption in the range of 350 nm to 500 nm.

[0175] In this invention, the thermochromic compound is preferably a compound that develops color at a temperature higher than 120°C, and more preferably a thermochromic compound that develops color at a temperature higher than 180°C. The higher the color development temperature of the thermochromic compound, the better its heat resistance under high-temperature conditions. In addition, it is less likely to fade due to prolonged exposure to ultraviolet and visible light, and it has excellent lightfastness.

[0176] In this invention, the thermochromic compound can be a conventional thermosensitive pigment or pressure-sensitive pigment, or other compounds. Examples of thermochromic compounds include compounds that exhibit color development due to changes in their chemical structure and charge state caused by the action of acidic groups coexisting in the system during heat treatment, or compounds that exhibit color development due to thermal oxidation reactions caused by the presence of oxygen in the air. The thermochromic compound of this invention exhibits maximum absorption at no point in the range of 350 nm to 700 nm before heat treatment, thus differing from the colorant (d). For example, it is believed that the hydrogen atom of the methine group in a thermochromic compound with a triarylmethane skeleton is removed during heat treatment, resulting in the formation of a quinone structure from one aryl group, thereby causing color development. On the other hand, the colorant material (d) with a triarylmethane skeleton already possesses a quinone structure before heat treatment, thus differing from the thermochromic compound of this invention.

[0177] The skeletal structure of thermochromic compounds can contain triarylmethane, diarylmethane, fluorane, diester, phthalide, xanthanene, rhodamine lactone, fluorene, phenothiazine, phenothiazine, spiropyran, etc. Among them, the triarylmethane skeleton is preferred due to its high thermochromic temperature and excellent heat resistance.

[0178] Specific examples of the triarylmethane skeleton may include 2,4',4”-trihydroxytrimethylbenzene, 4,4',4”-trihydroxytrimethylbenzene, 4,4'-[(4-hydroxyphenyl)methylene]bis(aniline), 4,4'-[(4-aminophenyl)methylene]bisphenol, 4,4'-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol], 4,4'-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4- [bis(4-hydroxyphenyl)methyl]-2-methoxyphenol, 4,4'-[(2-hydroxyphenyl)methylene]bis[2-methylphenol], 4,4'-[(4-hydroxyphenyl)methylene]bis[2-methylphenol], 4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol, 4,4'-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol], 2,2'-[(4-hydroxyphenyl)methylene]bis[3,5-dimethyl] [4,4'-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol], 4,4'-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4,4'-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4'-[(4-hydroxyphenyl)methylene] Examples of hydroxyl compounds include bis[2-cyclohexyl-5-methylphenol], 4,4'-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol], 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol], and 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol]. These compounds can be used alone or in combination. It should be noted that, for hydroxyl-containing compounds with a triarylmethane skeleton, the compound can be ester-bonded with the sulfonic acid of diazidonaphthoquinone to be used as a quinone diazido compound.

[0179] In this invention, the content of the thermochromic compound is preferably 5 to 80 parts by mass relative to 100 parts by mass of the alkali-soluble resin (a), and particularly preferably 10 to 60 parts by mass. When the content of the thermochromic compound is 5 parts by mass or more, the transmittance of the cured material in the ultraviolet-visible region can be reduced. Furthermore, when it is 80 parts by mass or less, the heat resistance and strength of the cured material can be maintained, and the water absorption rate can be reduced.

[0180] <Free radical polymeric compounds>

[0181] The resin composition of the present invention may contain a free radical polymerizable compound. In particular, when the above-mentioned resin composition contains a photopolymerization initiator (c2), it is essential to contain a free radical polymerizable compound. A free radical polymerizable compound refers to a compound having multiple olefinic unsaturated double bonds in its molecule. During exposure, the free radical polymerizable compound undergoes free radical polymerization using free radicals generated by the aforementioned photopolymerization initiator (c2), and the light-irradiated area remains insoluble, thereby obtaining a negative pattern. Furthermore, by containing a free radical polymerizable compound, photocuring of the light-irradiated area is promoted, further improving sensitivity. Additionally, the crosslinking density increases after thermosetting, thus increasing the hardness of the cured product.

[0182] As a free radical polymerizable compound, a compound having (meth)acrylic acid groups that readily undergoes free radical polymerization is preferred. From the viewpoint of improved sensitivity during exposure and increased hardness of the cured product, a compound having two or more (meth)acrylic acid groups within the molecule is more preferred. As for the double bond equivalent of the free radical polymerizable compound, from the viewpoint of improved sensitivity during exposure and increased hardness of the cured product, 80 to 400 g / mol is preferred.

[0183] As a free radical polymerizable compound, it may contain, for example, trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(3-(methyl)]acrylate, etc. Acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloyloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene or their acid-modified, ethylene oxide-modified, propylene oxide-modified, etc.

[0184] From the viewpoint of further improving sensitivity and reducing cone angle, the content of the free radical polymerizable compound is preferably 15% by mass or more, more preferably 30% by mass or more, out of a total of 100% by mass of the alkali-soluble resin (a) and the free radical polymerizable compound. On the other hand, from the viewpoint of further improving the heat resistance of the cured product and reducing cone angle, it is preferably 65% ​​by mass or less, more preferably 50% by mass or less, out of a total of 100% by mass of the alkali-soluble resin (a) and the free radical polymerizable compound.

[0185] <Thermal Crosslinking Agent>

[0186] The resin composition of the present invention may contain a thermal crosslinking agent. A thermal crosslinking agent is a compound having at least two thermally reactive functional groups such as alkoxymethyl, hydroxymethyl, epoxy, or oxetyl in its molecule. By containing a thermal crosslinking agent, crosslinking occurs between the thermal crosslinking agent and the alkali-soluble resin (a), or between the thermal crosslinking agents themselves, thereby improving the heat resistance, chemical resistance, and flexural strength of the cured product after thermosetting.

[0187] Preferred examples of compounds having at least two alkoxymethyl or hydroxymethyl groups may include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp- BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc.

[0188] As a preferred example of a compound having at least two epoxy groups, it may contain "EPOLIGHT" (registered trademark) 40E, "EPOLIGHT" 100E, "EPOLIGHT" 200E, "EPOLIGHT" 400E, "EPOLIGHT" 70P, "EPOLIGHT" 200P, "EPOLIGHT" 400P, "EPOLIGHT" 1500NP, "EPOLIGHT" 80MF, "EPOLIGHT" 4000, "EPOLIGHT" 3002 (all manufactured by Kyoei Chemical Co., Ltd.), "DENACOL" (registered trademark) EX-212L, "DENACOL" EX-214L, "DENACOL" EX-216L, "DENACOL" EX-850L (all manufactured by Nagase). Chemtex (manufactured by Chemtex Co., Ltd.), GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), "Epikote" (registered trademark) 828, "Epikote" 1002, "Epikote" 1750, "Epikote" 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy). Resin Co., Ltd., “EPICLON” (registered trademark) EXA-9583, HP4032 (all manufactured by DIC Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals Co., Ltd.), “TEPIC” (registered trademark) S, “TEPIC” G, “TEPIC” P (all manufactured by Nissan Chemical Industry Co., Ltd.), “DENACOL” EX-321L (manufactured by Nagase Chemtex Co., Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), “Epotohto” (registered trademark) YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), “EPICLON” (registered trademark) N695, HP7200 (all manufactured by DIC Co., Ltd.), etc.

[0189] As a compound having at least two oxocyclic butyl groups, it may contain, for example, ETERNACOLL EHO, ETERNACOLL OXBP, ETERNACOLL OXTP, ETERNACOLL OXMA (all manufactured by Ube Industries, Ltd.), oxocyclic butanol Novolac, etc.

[0190] It can be combined to contain two or more thermal crosslinking agents.

[0191] When a thermal crosslinking agent is present, its content is preferably 1% to 30% by mass out of 100% by mass of the total resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1% by mass or more, the chemical resistance and flexural strength of the cured product can be further improved. Furthermore, if the content of the thermal crosslinking agent is 30% by mass or less, the amount of gas escaping from the cured product can be further reduced, further improving the long-term reliability of the organic EL display device, and the storage stability of the resin composition is also excellent.

[0192] Solvent

[0193] The resin composition of the present invention may contain a solvent. By containing a solvent, it is possible to produce a varnish-like state, which improves coatability.

[0194] As a solvent, it can contain polar aprotic solvents such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ... Ethers such as n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, dioxane, etc.; acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, etc.; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, etc.; ethyl 2-hydroxy-2-methylpropionic acid. Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, ethyl hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate The solvent may contain esters, such as butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone, etc. Two or more of these solvents may be present.

[0195] The solvent content is not particularly limited, but is preferably 100 to 3000 parts by mass relative to 100 parts by mass of the total resin composition excluding the solvent, and more preferably 150 to 2000 parts by mass. Furthermore, the proportion of solvents with a boiling point of 180°C or higher in 100% by mass of the total solvent is preferably 20% by mass or less, and more preferably 10% by mass or less. By keeping the proportion of solvents with a boiling point of 180°C or higher at 20% by mass or less, the amount of gas released after thermosetting can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0196] <Sealing Modifier>

[0197] The resin composition of the present invention may contain adhesion modifiers. As adhesion modifiers, they may include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds. Two or more of these may be included. By containing these adhesion modifiers, the adhesion to substrates such as silicon wafers, indium tin oxide (ITO), SiO2, and silicon nitride can be improved during resin film development. Furthermore, resistance to oxygen plasma and UV ozone treatment used in cleaning processes can be improved. The content of the sealing modifier is preferably 0.01 to 10% by mass in 100% by mass of the total resin composition excluding the solvent.

[0198] <surfactants>

[0199] The resin composition of the present invention may contain surfactants. By containing surfactants, wettability with the substrate can be improved. As surfactants, for example, fluorinated surfactants such as the SH series, SD series, and ST series of Dow Corning Toray Co., Ltd., the BYK series of BYK Chemie Japan Co., Ltd., the KP series of Shin-Etsu Chemical Industry Co., Ltd., the DISFOAM series of Nippon Oil Co., Ltd., the MEGAFACE series of DIC Co., Ltd., the Fluorad series of Sumitomo 3M Co., Ltd., the Surflon series of Asahi Glass Co., Ltd., the Asahiguard series of Asahi Glass Co., Ltd., the PolyFox series of OMNOVA Solutions Inc., acrylic and / or methacrylic surfactants such as the POLYFLOW series of Kyoeisha Chemical Co., Ltd., and the DISPARLON series of Kusunomoto Chemical Co., Ltd. may be contained.

[0200] When surfactant is present, its content is preferably 0.001 to 1% by mass in 100% by mass of the total resin composition excluding solvent.

[0201] <Inorganic particles>

[0202] The resin composition of the present invention may contain inorganic particles. Preferred examples of inorganic particles include, for instance, silicon dioxide, titanium dioxide, barium titanate, aluminum oxide, talc, etc. The primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0203] The content of inorganic particles is preferably 5 to 90% by mass in 100% of the total amount of the resin composition excluding the solvent.

[0204] <All chlorine atoms, all bromine atoms>

[0205] Regarding the resin composition of the present invention, the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is preferably 150 ppm or less, more preferably 100 ppm or less, and even more preferably 2 ppm or less (which is the detection limit of combustion ion chromatography) relative to the total mass of the solid components of the resin composition. Here, the total mass of the solid components of the resin composition refers to the mass after removing the mass of the solvent from the total mass of the resin composition. The lower limit of the total mass of all chlorine atoms and all bromine atoms is 0 ppm, and anything below the detection limit of combustion ion chromatography is considered to be 0 ppm.

[0206] By ensuring that the total amount of all chlorine atoms and all bromine atoms contained in the resin composition is less than 150 ppm relative to the solid components of the resin composition, it is possible to suppress the deterioration of the electrodes and light-emitting layers of organic EL display devices having cured products obtained by curing the resin composition, thereby improving long-term reliability.

[0207] <Method for manufacturing resin composition>

[0208] Next, a method for manufacturing the resin composition of the present invention will be described. For example, a thallium compound (b), an alkali-soluble resin (a), and, as needed, a photosensitive compound (c), a colorant (d), a thermochromic compound, a free radical polymerizable compound, a thermocrosslinking agent, a solvent, a bonding modifier, a surfactant, inorganic particles, etc., can be dissolved to obtain the resin composition of the present invention.

[0209] Examples of dissolution methods include stirring and heating. When heating is used, it is preferable to set the heating temperature within a range that does not impair the properties of the resin composition, typically between room temperature and 80°C. Furthermore, the order in which the components are dissolved is not particularly limited; for example, a method of dissolving compounds with low solubility sequentially can be used. Additionally, for components such as surfactants and certain adhesion modifiers that are prone to generating bubbles during stirring, other components can be dissolved first and then added last, thereby preventing poor dissolution of other components due to bubble formation.

[0210] The resulting resin composition is preferably filtered using a filter to remove dirt and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, and 0.02 μm. Examples of filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Polyethylene and nylon are preferred.

[0211] <Methods for manufacturing solidified products>

[0212] The method for manufacturing the cured product of the present invention is as follows, which includes: a step of forming a resin film on a substrate by forming a resin composition containing a photosensitive compound (c) in the resin composition of the present invention; a step of exposing the resin film; a step of developing the exposed resin film; and a step of heat-treating the developed resin film.

[0213] The process of forming a resin film on a substrate using a resin composition comprising the photosensitive compound (c) of the resin composition of the present invention is described. In the present invention, the resin film can be obtained by coating a resin composition comprising the photosensitive compound (c) of the resin composition of the present invention onto a substrate, obtaining a coated film of the resin composition, and then drying it.

[0214] Methods for coating the resin composition of the present invention include, for example, spin coating, slot coating, dip coating, spray coating, and printing. Among these, slot coating is preferred from the perspective of being able to use a small amount of coating liquid and reducing costs. The amount of coating liquid required by slot coating is, for example, about 1 / 5 to 1 / 10 compared to spin coating. As for the slot nozzle used in coating, for example, slot nozzles from various manufacturers can be selected, such as the "Linearcoater" manufactured by Dainippon Screen Mfg.Co.,Ltd., the "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TSCoater" manufactured by Toray Engineering Co., Ltd., the "Tabel Coater" manufactured by Chugai Furnace Industry Co., Ltd., the "CS series" and "CL series" manufactured by Tokyo Electron Co., Ltd., the "Inline type slot coating machine" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC series" manufactured by Hirata Kiko Co., Ltd. The coating speed is typically in the range of 10 mm / s to 400 mm / s. The film thickness varies depending on the concentration of solid components and viscosity of the resin composition, and is usually coated with a film thickness of 0.1 to 10 μm after drying, preferably 0.3 to 5 μm.

[0215] Before coating, the substrate of the coating resin composition can be pretreated using the aforementioned adhesion modifier. Examples of pretreatment methods include treating the substrate surface with a solution obtained by dissolving 0.5–20% by mass of the adhesion modifier in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. Examples of substrate surface treatment methods include spin coating, stencil coating, rod coating, dip coating, spray coating, and steam treatment.

[0216] After coating, perform vacuum drying as needed.

[0217] While the vacuum drying rate depends on factors such as the vacuum chamber volume, vacuum pump capacity, and piping diameter between the chamber and pump, it is preferably set to conditions where the vacuum chamber is reduced to 40 Pa after 60 seconds in the uncoated substrate state. Typical vacuum drying times are generally between 30 and 100 seconds, and the ultimate pressure within the vacuum chamber at the end of vacuum drying is typically below 100 Pa in the coated substrate state. By maintaining an ultimate pressure below 100 Pa, a drying state with reduced stickiness on the coated film surface can be achieved, thereby suppressing surface contamination and particle generation during subsequent substrate handling.

[0218] After coating or vacuum drying, the coated film is usually heated and dried. This process is also called pre-baking. Drying is performed using a heating plate, oven, infrared radiation, etc. When using a heating plate, the coated film is held directly on the plate and heated, or it is held on a clamp such as a fixing pin mounted on the plate and heated. The heating time is preferably from 1 minute to several hours. The heating temperature varies depending on the type and purpose of the coated film, but from the viewpoint of promoting solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0219] Next, the process of exposing the above-mentioned resin film will be described.

[0220] A resin film containing a photosensitive compound (c) can form a pattern. For example, the resin film can be exposed by irradiating it with chemical rays through a photomask having the desired pattern, and then developed to form the desired pattern.

[0221] In the process of exposing the resin film, the photomask used for exposure is preferably a halftone photomask having a light-transmitting portion, a light-blocking portion, and a semi-transparent portion. By using a halftone photomask for exposure, a pattern with a height difference shape can be formed after development. It should be noted that when using a positive resin film, in the pattern with a height difference shape, the area formed by the light-blocking portion corresponds to a thick film portion, and the area formed by the halftone exposure portion irradiated with active chemical rays through the semi-transparent portion corresponds to a thin film portion. When the transmittance of the light-transmitting portion in the halftone photomask is set to 100%, the transmittance of the semi-transparent portion is preferably 5% or more, more preferably 10% or more. If the transmittance of the semi-transparent portion is within the aforementioned range, a clear height difference between the thick film portion and the thin film portion can be formed. On the other hand, the transmittance of the semi-transparent portion is preferably 30% or less, more preferably 25% or less, more preferably 20% or less, and most preferably 15% or less. If the transmittance of the semi-transparent portion is within the aforementioned range, the film thickness of the thin film portion can be made thicker, and even in the case of forming a black cured material with low light density under visible light per 1 μm film thickness, the overall light density of the film can be improved.

[0222] Examples of chemical rays used in exposure include ultraviolet light, visible light, electron beams, and X-rays. In this invention, the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp are preferably used. When positive photosensitivity is present, the exposed portion dissolves in the developer. When negative photosensitivity is present, the exposed portion solidifies and becomes insoluble in the developer.

[0223] Next, the process of developing the exposed resin film will be explained.

[0224] After exposure, in the case of a positive image, the exposed areas are removed with a developer; in the case of a negative image, the unexposed areas are removed with a developer, thereby forming the desired pattern. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. Alternatively, one or more of the following can be added to these alkaline aqueous solutions: polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of development methods include spraying, immersion, soaking, and ultrasonic methods.

[0225] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropanol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate can be added to the distilled water for rinsing.

[0226] Next, the process of heat-treating the developed resin film will be explained.

[0227] After development, the developed resin film is heated to obtain a cured product.

[0228] From the viewpoint of further reducing the amount of gas escape generated by the cured product, the heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher. On the other hand, from the viewpoint of improving the film toughness of the cured product, the temperature is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature can be increased in stages or continuously. From the viewpoint of further reducing the amount of gas escape, the heat treatment time is preferably 30 minutes or higher. In addition, from the viewpoint of improving the film toughness of the cured product, the time is preferably 3 hours or less. For example, the following methods can be cited: a method of heat treatment at 150°C and 250°C for 30 minutes each; a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours; and so on.

[0229] <Cured product>

[0230] The first aspect of the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. By heat-treating the resin composition of the present invention, components with low heat resistance can be removed, thereby further improving heat resistance and chemical resistance. In particular, when the resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer thereof with a polyimide, heat treatment forms an imide ring or an oxazole ring, thereby further improving heat resistance and chemical resistance.

[0231] Furthermore, in this invention, by using thallium compound (b), component (d-2), component (d-1), and / or a thermochromic compound, as well as component (d-3) if necessary, the light-shielding property of visible light can be improved, thereby obtaining a black cured product. From the viewpoint of further reducing the amount of gas emitted from the cured product, the heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher. On the other hand, from the viewpoint of improving the film toughness of the cured product, the temperature is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature can be increased in stages or continuously. From the viewpoint of further reducing the amount of gas emitted, the heat treatment time is preferably 30 minutes or higher. Furthermore, from the viewpoint of improving the film toughness of the cured product, the time is preferably 3 hours or less. For example, methods such as heat treatment at 150°C and 250°C for 30 minutes each; heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours; and so on.

[0232] In addition, the second aspect of the cured product of the present invention is a cured product containing the thallium compound (b') represented by formula (2) (hereinafter, sometimes referred to as the cured product of the second aspect).

[0233] [Chemical Formula 10]

[0234]

[0235] In equation (2), A 1 ~A 4 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms that may have electron-donating substituents. Among them, A... 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that may have electron-donating substituents has an electron-donating substituent. R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. --SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 A monovalent hydrocarbon group with 1 to 20 carbon atoms. R 5 Represents hydrogen atom, -SO3H, -SO3 - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 R 6 ~R 10 Each of the following groups independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. Among them, the thallium compound (b') represented by formula (2) is an electrically neutral or cationic compound.

[0236] By including the thallium compound (b') represented by formula (2) in the cured product, the light-shielding properties of the cured product under visible light can be improved. From the viewpoint of improving the overall light-shielding properties under visible light, the cured product of the second embodiment preferably also includes a colorant (d) other than that of formula (2), and more preferably includes a colorant (d-2) that has the maximum absorption wavelength at any point in the range of 350 to 800 nm, above 490 nm and below 580 nm.

[0237] Other preferred embodiments of the xaton compound (b') represented by formula (2) are the same as those of the xaton compound (b) represented by formula (1).

[0238] <Examples of applications of resin compositions and cured products>

[0239] Resin compositions and cured products containing the pyrithione compound (b) of the present invention are suitable for use as surface protective layers for semiconductor devices, interlayer insulating layers, insulating layers for organic electroluminescence (EL) elements, planarization layers for thin film transistor (TFT) substrates used in display devices employing organic EL elements, wiring protective insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and planarization layers for various display devices and solid-state imaging devices. For example, they are suitable as surface protective layers and interlayer insulating layers for MRAM with low heat resistance, polymer ferroelectric RAM (PFRAM) and phase change RAM (PCRAM, Ovonics Unified Memory (OUM)) which are expected to be next-generation memories. Additionally, they can also be used as insulating layers for display devices comprising a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode, such as LCDs, ECDs, ELDs, and display devices using organic electroluminescent elements (organic electroluminescent devices). The following explanation will take organic EL display devices, semiconductor devices, and semiconductor electronic components as examples.

[0240] Organic EL Display Device

[0241] The organic EL display device of the present invention is an organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, wherein the planarization layer and / or the insulating layer have the cured product of the present invention. It should be noted that the substrate is part of the organic EL display device.

[0242] In the case of the organic EL display device of the present invention, it is preferable that the aforementioned insulating layer has the cured product of the present invention, and the optical density under visible light per 1 μm film thickness of the aforementioned insulating layer is 0.5 to 1.5. If the OD value is 0.5 or higher, the light-shielding property can be improved by utilizing the cured product. Therefore, in display devices such as organic EL display devices or liquid crystal display devices, the visibility of electrode wiring and external light reflection can be further reduced, and the contrast during image display can be improved. In addition, if the OD value is 1.5 or lower, the sensitivity during exposure when preparing the resin composition containing the photosensitive compound can be improved.

[0243] When the aforementioned insulating layer is a black film, the thickness of the insulating layer is preferably 1.0 to 5.0 μm, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. By making the black insulating layer within the aforementioned range, even a black film with low visible light density per 1 μm film thickness can improve the overall optical density of the film, thereby enhancing the effect of reducing external light reflection.

[0244] Taking an active matrix display device as an example, a TFT and wiring located on the side of the TFT and connected to the TFT are provided on a substrate such as glass or various plastics. A planarization layer is provided on the planarization layer in a manner that covers unevenness, and a display element is further disposed on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. In particular, in recent years, the flexibility of organic EL display devices has become mainstream, so the aforementioned organic EL display device with a resin film on a substrate having a driving circuit is preferred. If the cured product obtained by curing the resin composition of the present invention is used as the insulating layer and planarization layer of such a flexible display device, the bending resistance is excellent, so it is particularly preferred. From the viewpoint of improving the adhesion to the cured product obtained by curing the resin composition of the present invention, polyimide is particularly preferred as the resin film.

[0245] To improve the effect of reducing external light reflection, the organic EL display device of the present invention preferably also includes a color filter with a black matrix. The black matrix preferably contains resins such as epoxy resins, acrylic resins, urethane resins, polyester resins, polyimide resins, polyolefin resins, or siloxane resins.

[0246] The black matrix contains a colorant. As a colorant, it may contain, for example, black organic pigments, mixed organic pigments, or black inorganic pigments. As a black organic pigment, it may contain, for example, carbon black, perylene black, aniline black, or benzofuranone pigments. As a mixed organic pigment, it may contain, for example, mixed organic pigments that approximate blackness by mixing two or more pigments such as red, blue, green, purple, yellow, magenta, and / or cyan. As a black inorganic pigment, it may contain, for example, graphite; particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitrides, titanium carbides, and their composite particles with metals such as silver, which have high opacity, are preferred.

[0247] The OD value of the black matrix is ​​preferably 1.5 or higher, more preferably 2.5 or higher, and even more preferably 4.5 or higher.

[0248] Figure 1The diagram shows a cross-sectional view of an example TFT substrate. On substrate 6, bottom-gate or top-gate TFTs (thin-film transistors) 1 are arranged in rows and columns, and a TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2, which connects to the TFTs 1, is also provided on the TFT insulating layer 3. Furthermore, a planarization layer 4 is provided on the TFT insulating layer 3 to embed the wiring 2. Contact holes 7, reaching the wiring 2, are provided in the planarization layer 4. Then, ITO (transparent electrode) 5 is formed on the planarization layer 4 through the contact holes 7, connecting to the wiring 2. Here, ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is then formed to cover the periphery of the ITO 5. The organic EL element can be a top-emitting type that emits light from the side opposite to substrate 6, or a bottom-emitting type that extracts light from the side of substrate 6. As described above, an active matrix type organic EL display device can be obtained, in which TFTs 1 for driving each organic EL element are connected to it.

[0249] The TFT insulating layer 3, planarization layer 4, and / or insulating layer 8 can be formed as described above by the following steps: a step of forming a resin film formed from the resin composition of the present invention; a step of exposing the aforementioned resin film; a step of developing the exposed resin film; and a step of heat-treating the developed resin film. An organic EL display device can be obtained by a manufacturing method having these steps.

[0250] Display devices other than organic EL display devices>

[0251] The display device of the present invention comprises at least metal wiring, the cured material of the present invention, and a plurality of light-emitting elements. The display device is configured such that each light-emitting element has a pair of electrode terminals on one side, the pair of electrode terminals are connected to a plurality of metal wirings extending in the cured material, and the plurality of metal wirings are electrically insulated by the cured material. The display device of the present invention refers to a display device other than an organic EL display device.

[0252] Regarding the aforementioned display device, Figure 2 This will be illustrated as an example of a method.

[0253] exist Figure 2 In the display device 11, a plurality of light-emitting elements 12 are disposed on the opposing substrate 15, and a cured material 13 is disposed on the light-emitting elements 12. The term "on the light-emitting element" refers not only to the surface of the light-emitting element, but also to any part located above the supporting substrate and the light-emitting element. Figure 2The illustrated configuration shows a structure in which multiple cured layers 13 are further stacked on top of a cured layer 13 arranged in contact with at least a portion of the light-emitting element 12, resulting in a total of three layers. However, the cured layer 13 can also be a single layer. The light-emitting element 12 has a pair of electrode terminals 16 on the side opposite to the surface in contact with the opposing substrate 15, and each electrode terminal 16 is connected to a metal wiring 14 extending in the cured layer 13. It should be noted that if the multiple metal wirings 14 extending in the cured layer 13 are covered by the cured layer 13, the cured layer 13 also functions as an insulating layer, thus forming a configuration that maintains electrical insulation. The configuration that maintains electrical insulation for the metal wiring means that the portion of the metal wiring requiring electrical insulation is covered by a cured layer obtained by curing a resin composition containing an alkali-soluble resin (a). In addition, in this invention, the state in which the insulating layer has electrical insulation means that the volume resistivity of the insulating layer is 10 Ω·cm. 12 The light-emitting element 12 is in a state of Ω·cm or higher. Furthermore, the light-emitting element 12 is electrically connected to a driving element 18 attached to a light-emitting element driving substrate 17 located opposite the opposing substrate 15 via metal wirings 14, 14c, enabling control of the light emission of the light-emitting element 12. Additionally, the light-emitting element driving substrate 17 is electrically connected to the metal wirings 14 via, for example, solder bumps 20. Furthermore, to prevent the diffusion of metal from the metal wirings 14, a barrier metal 19 can be provided.

[0254] The aforementioned cured material 13 is preferably black, and the OD value under visible light for each 1 μm film thickness of the insulating layer is 0.5 to 1.5. If the OD value is 0.5 or higher, the light-shielding property can be improved by using the cured material. Therefore, in display devices such as organic EL display devices or liquid crystal display devices, the visibility of electrode wiring and external light reflection can be further reduced, and the contrast during image display can be improved. In addition, if the OD value is 1.5 or lower, the sensitivity during exposure when preparing the resin composition containing the photosensitive compound can be improved.

[0255] Example

[0256] The present invention will now be described by way of examples, but the present invention is not limited to these examples. It should be noted that the evaluations in the examples were performed using the following methods.

[0257] (1) Evaluation of the maximum absorption wavelength of xaton compound (b) in the range of 350–800 nm

[0258] On a 5 cm square glass substrate, varnish A containing a resin composition of xabutane compound (b) and varnish B containing a resin composition of xabutane compound (b) obtained in each example and comparative example were spin-coated to a film thickness of 1.5 μm after heat treatment (curing). The coatings were then pre-baked at 120°C for 120 seconds to obtain pre-baked films A and B. The transmission spectra of the pre-baked films A and B in the wavelength range of 300 nm to 800 nm were measured using a MultiSpec-1500 UV-Vis spectrophotometer (manufactured by Shimadzu Corporation). Next, the transmission spectrum of prebaked film B is converted into absorbance and then subtracted from the transmission spectrum of prebaked film A to obtain the transmission spectrum of xaton compound (b). In the range of 350-800 nm, if the maximum absorption wavelength is above 600 nm, it is identified as "A"; if the maximum absorption wavelength is above 580 nm and below 600 nm, it is identified as "B"; and if the maximum absorption wavelength is below 580 nm, it is identified as "C".

[0259] (2) Evaluation of the heat resistance of xaton compound (b)

[0260] The pre-baked film A and pre-baked film B, obtained in the same manner as in (1), were cut into two pieces. The first piece was left untreated. For the second piece, an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) was used to heat-treat the second piece at 230°C in an atmospheric atmosphere for 1 hour to produce the corresponding cured products A and B. Then, the transmission spectra of the pre-baked film and the cured product at wavelengths of 300 nm to 800 nm were measured in the same manner as in (1). The transmission spectra of the corresponding pre-baked film B and cured film B were converted into absorbance and then subtracted from the transmission spectra of the pre-baked film A and the cured film A to obtain the transmission spectra of the pre-baked film and the cured film from compound (b). Based on the transmission spectra of the pre-baked and cured films from xaton compound (b), the absorbance at the maximum absorption wavelength was calculated, and the absorbance change rate (absorbance of the cured product from xaton compound (b) / absorbance of the pre-baked film from xaton compound (b)) (%) was calculated. If the absorbance change rate was ≥90%, it was classified as "A"; if it was ≥75% but <90%, it was classified as "B"; and if it was <75%, it was classified as "C".

[0261] (3) Evaluation of the sensitivity of the resin composition

[0262] Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Co., Ltd.), varnishes obtained from the various examples and comparative examples were spin-coated onto an 8-inch silicon wafer, and baked at 120°C for 2 minutes to prepare a pre-baked film with a thickness of 4.0 μm. It should be noted that the film thickness was measured using a stylus profilometer (P-15; manufactured by KLA Corporation). Then, using an NSR-2005i9C i-line stepper (manufactured by Nikon Corporation), through a mask with a pattern of 10 μm apertures, exposure was performed at a rate of 50–300 mJ / cm². 2 Within the range, at every 5 mJ / cm 2 Exposure is performed. After exposure, the aforementioned ACT-8 developing apparatus is used to develop the film using a 2.38% by mass tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Industry Co., Ltd.) until the film loss in the non-exposed areas reaches 0.5 μm. Then, the film is rinsed with distilled water and spun dry to obtain the pattern.

[0263] The obtained pattern was observed at 20x magnification using an FPD microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the holes was measured. The minimum exposure required for the opening diameter of the contact holes to reach 10 μm was determined and used as the sensitivity. The sensitivity was less than 120 mJ / cm². 2 In this case, it is judged as "A", with a sensitivity of 120mJ / cm 2 Above and below 150 mJ / cm 2 In this case, it is judged as "B", with a sensitivity of 150mJ / m 2 In the above cases, the judgment is "C".

[0264] (4) Evaluation of OD value per 1 μm of resin composition

[0265] On a 5 cm square glass substrate, a varnish obtained from each example and comparative example was spin-coated to a thickness of 2.0 μm after heat treatment (curing). The varnish was then pre-baked at 120°C for 120 seconds to create a pre-baked film. Then, a cured film was prepared by curing at 230°C for 60 minutes in an atmospheric atmosphere using a Koyo Thermo Systems Co., Ltd. INH-9CD-S high-temperature cleanroom oven. It should be noted that the thickness of the cured film was measured using a stylus profilometer (P-15; KLA). For the cured film obtained as described above, the OD value was measured using a densitometer (361T; X-Rite). The obtained OD value was divided by the thickness of the cured film to obtain the OD value per 1 μm (OD value per 1 μm = OD value / thickness of cured film). If the OD value per 1 μm is 0.70 or higher, it is classified as "A"; if it is less than 0.70 but greater than 0.50, it is classified as "B"; and if it is less than 0.50, it is classified as "C".

[0266] (5) Evaluation of the change in OD value of the resin composition due to repeated curing

[0267] The cured film obtained in (4) was cured again using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. at 230°C for 60 minutes in an atmospheric atmosphere, resulting in a cured film that underwent two curing cycles. The film thickness and OD value of the cured film were measured in the same manner as in (4). The OD value was divided by the film thickness to calculate the OD value per 1 μm after repeated curing. If the change in OD value due to repeated curing was less than 0.05, it was classified as "A"; if it was less than 0.10 but greater than 0.05, it was classified as "B"; and if it was greater than 0.10, it was classified as "C". In (4), if the OD value was less than 0.50, it was classified as "C" even if the change in OD value was less than 0.10.

[0268] (6) Evaluation of the cryopreservation stability of the resin composition

[0269] Using a Tokyo Electron Coating and Development System "CLEAN TRACK ACT-12", varnishes that had been filtered and stored at -18°C for 60 days were coated onto a 12-inch Si wafer. The wafers were then dried at 100°C for 3 minutes using a hot plate to obtain a photosensitive resin film with a thickness of 1000 nm. The obtained photosensitive resin film was then inspected using a TOPCON Wafer Surface Inspection System "WM-10" to count foreign objects larger than 0.27 μm. The measurement area was set to approximately 201 cm², extending from the center of the wafer to the inner edge of a circle with a radius of 8 cm. 2 Calculate the value per 1cm 2 Foreign matter count (defect density) in the coating. The defect density per substrate is less than 1.00 defects / cm². 2 In this case, it is judged as "A", with a value of 1.00 pieces / cm. 2 More than or less than 3.00 pieces / cm 2 In this case, it is judged as "B", with 3.00 pieces / cm. 2 In the above cases, the judgment is "C".

[0270] (7) Analysis of xanthones (b') in TOF-SIMS-based cured films

[0271] After cleaning the surface of the cured film using etch ions, TOF-SIMS analysis was performed. The TOF-SIMS apparatus and measurement conditions used in the analysis are described below.

[0272] Device: TOF.SIMS5 manufactured by ION-TOF Company

[0273] Primary ion: Bi3 ++

[0274] Acceleration voltage of primary ions: 30kV

[0275] Primary ion current: 0.1 pA

[0276] Etching ions: Ar gas cluster ions

[0277] Etching ion acceleration voltage: 5.0kV

[0278] Measurement range: 200μm×200μm.

[0279] Synthesis Example 1: Synthesis of a diamine compound (α) containing a hydroxyl group

[0280] 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to -15 °C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise. After the addition was complete, the reaction was carried out at -15 °C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50 °C.

[0281] 30g of the solid was placed in a 300mL stainless steel autoclave and dispersed in 250mL of methyl cellosolve. 2g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was considered complete when the balloon stopped deflating. After the reaction, the palladium compound acting as a catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a diamine compound (α) containing a hydroxyl group, as shown in the following formula.

[0282] [Chemical Formula 11]

[0283]

[0284] Synthesis Example 2: Synthesis of quinone diazide compound (c-1)

[0285] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of diazidonaphthoquinone-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the solution was brought to room temperature. 15.18 g of triethylamine, mixed with 50 g of 1,4-dioxane, was added dropwise without raising the temperature above 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain the quinone diazide compound represented by the following formula (c-1).

[0286] [Chemical Formula 12]

[0287]

[0288] Synthesis Example 3: Synthesis of Alkali-soluble Resin (a-1)

[0289] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of 1-methyl-2-pyrrolidone (hereinafter, sometimes referred to as NMP). 45.35 g (0.075 mol) of the hydroxyl-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were added together with 50 g of NMP, and the reaction was carried out at 40 °C for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol (hereinafter referred to as MAP) as a capping agent was added together with 5 g of NMP, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of NMP was added. After addition, the solution was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using a vacuum dryer at 80°C for 24 hours to obtain the polyimide precursor (a-1) used as an alkali-soluble resin.

[0290] Synthesis Example 4: Synthesis of xaton compound (b-1)

[0291] In the following reaction formula [1], a mixture of 20.26 g (0.05 mol) of the compound represented by (β), 120 g of ethylene glycol, and 20.58 g (0.15 mol) of 4-ethoxyaniline was heated and stirred at 120 °C for 18 hours. After the reaction was completed, the reaction solution was cooled to room temperature and then added dropwise to 450 g of 17.5% hydrochloric acid at 0–10 °C, and stirred for 1 hour. Then, the precipitate was filtered off, washed with pure water at 80 °C, and dried at 60 °C for 24 hours to obtain a xanthonium compound (b-1-1) in which two aryl groups are substituted at the nitrogen atom.

[0292] Next, a mixture of 24.27 g (0.04 mol) of the obtained compound (b-1-1), 150 g of 1-methyl-2-pyrrolidone, 1.3 g of copper powder, 8.3 g of potassium carbonate, and 19.84 g (0.08 mol) of 4-iodophenethyl ether was heated and stirred at 150 °C for 12 hours. After the reaction was complete, the reaction solution was filtered to remove insoluble matter, and the reaction solution was added dropwise to 540 g of 17.5% hydrochloric acid at 0–10 °C, and stirred for 1 hour. Then, the precipitate was filtered off and dried at 60 °C for 24 hours to obtain the xanthonium compound (b-1) with three aryl groups substituted at the nitrogen atom. The obtained compound was confirmed as the target compound by LC-MS analysis using LC-MS 2020 (manufactured by Shimadzu Corporation).

[0293] LC-MS (ESI, posi): m / z 727[M+H] +

[0294] [Chemical Formula 13]

[0295] [II

[0296]

[0297] Synthesis Example 5: Synthesis of compound (b-2)

[0298] In the following reaction formula [2], a mixture of 18.46 g (0.05 mol) of the compound represented by (γ), 120 g of sulfolane, 13.63 g of zinc chloride, and 20.58 g (0.15 mol) of 4-ethoxyaniline was heated and stirred at 170 °C for 8 hours. After the reaction was completed, the reaction solution was cooled to room temperature and then added dropwise to 450 g of 17.5% hydrochloric acid at 0–10 °C and stirred for 1 hour. Then, the precipitate was filtered off, added to 500 g of 5% sodium carbonate aqueous solution and stirred for 1 hour. After filtration, the precipitate was washed with pure water and dried at 60 °C for 24 hours to obtain a xanthonium compound (b-2-1) in which two aryl groups were substituted at the nitrogen atom.

[0299] Next, a mixture of 22.83 g (0.04 mol) of the obtained compound (b-2-1), 150 g of 1-methyl-2-pyrrolidone, 1.3 g of copper powder, 8.3 g of potassium carbonate, and 19.84 g (0.08 mol) of 4-iodophenethyl ether was heated and stirred at 150 °C for 12 hours. After the reaction was complete, the reaction solution was filtered to remove insoluble matter, and the reaction solution was added dropwise to 450 g of 17.5% hydrochloric acid at 0–10 °C, and stirred for 1 hour. Then, the precipitate was filtered off and dried at 60 °C for 24 hours to obtain the xanthonium compound (b-2) with four aryl groups substituted at the nitrogen atom. The obtained compound was confirmed as the target compound by LC-MS analysis using LC-MS 2020 (manufactured by Shimadzu Corporation).

[0300] LC-MS (ESI, posi): m / z 811[M+H] +

[0301] [Chemical Formula 14] [2]

[0303] Synthesis Example 6: Synthesis of compound (b-3)

[0304] In the following reaction formula [3], 1.69 g (0.01 mol) of phosphoryl chloride was added dropwise to a mixture of 8.10 g (0.01 mol) of xanthonium compound (b-2) obtained in Synthesis Example 5, 2.54 g (0.015 mol) of diphenylamine, 10.11 g (0.1 mol) of triethylamine and 150 g of 1,2-dichloroethane at room temperature, and the mixture was heated and stirred at 85 °C for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature and then added to 300 g of pure water and extracted with 100 g of chloroform. The organic layer was washed with 150 g of 4 mol / L hydrochloric acid and 150 g of pure water, and the solvent was removed by distillation to obtain xanthonium compound (b-3) formed by amidation of xanthonium compound (b-2). The obtained compound was confirmed to be the target compound by LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation).

[0305] LC-MS (ESI, posi): m / z 963[M+H] +

[0306] [Chemical Formula 15] [3]

[0308]

[0309] Synthesis Example 7: Synthesis of xaton compound (b-4)

[0310] In the following reaction formula [5], a mixture of 22.83 g (0.04 mol) of compound (b-2-1) obtained in the same manner as in Synthesis Example 5, 150 g of 1-methyl-2-pyrrolidone, 1.3 g of copper powder, 8.3 g of potassium carbonate, and 17.43 g (0.08 mol) of 3-iodotoluene was heated and stirred at 150 °C for 12 hours. After the reaction was completed, the reaction solution was filtered to remove insoluble matter, and the reaction solution was added dropwise to 450 g of 17.5% hydrochloric acid at 0–10 °C and stirred for 1 hour. Then, the precipitate was filtered off and dried at 60 °C for 24 hours to obtain a xanthonium compound in which four aryl groups were substituted at the nitrogen atom. At room temperature, 1.69 g (0.01 mol) of phosphoryl chloride was added dropwise to a mixture of 7.51 g (0.01 mol) of the obtained xanthone compound, 2.54 g (0.015 mol) of diphenylamine, 10.11 g (0.1 mol) of triethylamine, and 150 g of 1,2-dichloroethane. The mixture was heated and stirred at 85 °C for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature and then added to 300 g of pure water. The solution was extracted with 100 g of chloroform. The organic layer was washed with 150 g of 4 mol / L hydrochloric acid and 150 g of pure water, and the solvent was removed by distillation to obtain the amidated xanthone compound (b-4). The obtained compound was confirmed as the target compound by LC-MS analysis using a 2020 LC-MS instrument (manufactured by Shimadzu Corporation).

[0311] LC-MS (ESI, posi): m / z 903[M+H] +

[0312] [Chemical Formula 16]

[0313]

[0314] Synthesis Example 8: Synthesis of compound (b-5)

[0315] In the following reaction formula [6], 9.39 g (0.01 mol) of compound (b-4) obtained in the same manner as in Synthesis Example 7 was dissolved in 150 g of N,N-dimethylformamide (DMF), and 2.91 g (0.015 mol) of sodium p-toluenesulfonate was added. The mixture was heated and stirred at 40 °C for 3 hours. After the reaction solution was cooled to room temperature, it was injected into 1000 g of pure water. The precipitated crystals were filtered off, washed with water, and dried at 60 °C for 24 hours to obtain the xatonium compound (b-5) obtained by exchanging the counterion of (b-4). The obtained compound was confirmed to be the target compound by LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation).

[0316] LC-MS (ESI, posi): m / z 903[M+H]+

[0317] LC-MS(ESI, nega): m / z 171[M] -

[0318] [Chemical Formula 17] [6]

[0320]

[0321] Synthesis Example 9: Synthesis of compound (b-6)

[0322] In the following reaction formula [7], 2.91 g (0.015 mol) of sodium p-toluenesulfonate was replaced with 5.23 g (0.015 mol) of sodium laurylbenzenesulfonate. Otherwise, the same procedure as in Synthesis Example 8 was followed to obtain the xaton compound (b-6) obtained by exchanging the counterion of (b-4).

[0323] The obtained compound was analyzed by LC-MS 2020 (manufactured by Shimadzu Corporation) and confirmed to be the target compound.

[0324] LC-MS (ESI, posi): m / z 903[M+H] +

[0325] LC-MS (ESI, nega): m / z 325[M]-

[0326] [Chemical Formula 18] [7]

[0328]

[0329] Synthesis Example 10: Synthesis of compound (b-7)

[0330] In the following reaction formula [8], 2.54 g (0.015 mol) of diphenylamine was replaced with 1.28 g (0.015 mol) of piperidine, and the process was otherwise performed in the same manner as in Synthesis Example 7 to obtain the amidated xaton compound (b-7).

[0331] The obtained compound was analyzed by LC-MS 2020 (manufactured by Shimadzu Corporation) and confirmed to be the target compound.

[0332] LC-MS (ESI, posi): m / z 819[M+H] +

[0333] [Chemical Formula 19]

[0334]

[0335] Synthesis Example 11: Synthesis of xaton compound (b-8)

[0336] In the following reaction formula

[10] , 2.91 g (0.015 mol) of sodium p-toluenesulfonate was replaced with 2.58 g (0.015 mol) of sodium trifluoromethanesulfonate. Otherwise, the same procedure as in Synthesis Example 5 was followed to obtain the xaton compound (b-8) obtained by exchanging the counterion of (b-4).

[0337] The obtained compound was identified as the target compound by LC-MS analysis using an LC-MS2020 (manufactured by Shimadzu Corporation).

[0338] LC-MS (ESI, posi): m / z 903[M+H] +

[0339] LC-MS (ESI, nega): m / z 149[M]-

[0340] [Chemical Formula 20]

[10]

[0342]

[0343] Synthesis Example 12: Synthesis of xaton compound (b-9)

[0344] In the following reaction formula

[11] , 2.91 g (0.015 mol) of sodium p-toluenesulfonate was replaced with 5.13 g (0.015 mol) of sodium tetraphenylborate. Otherwise, the same procedure as in Synthesis Example 8 was followed to obtain the xaton compound (b-9) obtained by exchanging the counterion of (b-4).

[0345] The obtained compound was identified as the target compound by LC-MS analysis using an LC-MS2020 (manufactured by Shimadzu Corporation).

[0346] LC-MS (ESI, posi): m / z 903[M+H] +

[0347] LC-MS (ESI, nega): m / z 319[M]-

[0348] [Chemical Formula 21]

[11]

[0350]

[0351] Synthesis Example 13: Synthesis of xaton compound (b-10)

[0352] In the following reaction formula

[12] , 2.91 g (0.015 mol) of sodium p-toluenesulfonate was replaced with 4.78 g (0.015 mol) of potassium bis(trifluoromethanesulfonyl)imide. Otherwise, the same procedure as in Synthesis Example 8 was followed to obtain the xaton compound (b-10) obtained by exchanging the counterion of (b-4).

[0353] The obtained compound was identified as the target compound by LC-MS analysis using an LC-MS2020 (manufactured by Shimadzu Corporation).

[0354] LC-MS (ESI, posi): m / z 903[M+H] +

[0355] LC-MS (ESI, nega): m / z 280[M]-

[0356] [Chemical Formula 22]

[12]

[0358]

[0359] Synthesis Example 11: Synthesis of xaton compound (b-11)

[0360] In the following reaction formula

[13] , 20.58 g (0.15 mol) of 4-ethoxyaniline was replaced with 16.07 g (0.15 mol) of p-toluidine, and the same procedure was followed as in Synthesis Example 5 to obtain a xanthonium compound (b-11-1) in which four aryl groups were substituted at the nitrogen atom. Next, 8.10 g (0.01 mol) of xanthonium compound (b-2) was replaced with 6.90 g (0.01 mol) of the obtained xanthonium compound (b-11-1), and the same procedure was followed as in Synthesis Example 6 to obtain a xanthonium compound (b-11) formed by amidation of xanthonium compound (b-11-1).

[0361] The obtained compound was identified as the target compound by LC-MS analysis using an LC-MS2020 (manufactured by Shimadzu Corporation).

[0362] LC-MS (ESI, posi): m / z 842[M+H] +

[0363] [Chemical Formula 23]

[13]

[0365]

[0366] Comparative Synthesis Example 1: Synthesis of Xanthon Compound (1)

[0367] In the following reaction formula [4], a mixture of 20.26 g (0.05 mol) of the compound represented by (β), 120 g of 2-propanol, and 7.3 g (0.06 mol) of 2,6-dimethylaniline was heated and stirred at 80 °C for 15 hours. After the reaction was completed, the reaction solution was cooled to room temperature and then added dropwise to 450 g of 17.5% hydrochloric acid. The mixture was stirred at room temperature for 1 hour. The precipitate was then filtered, washed with pure water at 80 °C, and dried at 60 °C for 24 hours to obtain a xatonne compound in which one aryl group was substituted at the nitrogen atom.

[0368] Next, a mixture of 19.60 g (0.04 mol) of the obtained xanthonium compound, 100 g of ethylene glycol, and 8.57 g (0.08 mol) of o-toluidine was heated and stirred at 120 °C for 18 hours. After the reaction was complete, the reaction solution was cooled to room temperature and then added dropwise to 400 g of 17.5% hydrochloric acid. The mixture was stirred at room temperature for 1 hour. The precipitate was then filtered off, washed with pure water at 80 °C, and dried at 60 °C for 24 hours to obtain a xanthonium compound with two aryl groups substituted at the nitrogen atom.

[0369] Next, a mixture of 19.62 g (0.035 mol) of the obtained xanthonium compound, 130 g of 1-methyl-2-pyrrolidone, 7.8 g of potassium carbonate, and 14.9 g (0.105 mol) of iodomethane was stirred at 80 °C for 2 hours. After the reaction was complete, the reaction solution was cooled to room temperature and then added dropwise to 540 g of 17.5% hydrochloric acid at 0–10 °C, and stirred for 1 hour. The precipitate was then filtered and dried at 60 °C for 24 hours to obtain xanthonium compound (1). The obtained compound was confirmed as the target compound by LC-MS analysis using LC-MS 2020 (manufactured by Shimadzu Corporation).

[0370] LC-MS (ESI, posi): m / z 589[M+H] +

[0371] [Chemical Formula 24] [4]

[0373]

[0374] Comparative Synthesis Example 2: Synthesis of Xanthon Compound (2)

[0375] In the following reaction formula [9], 20.58 g (0.15 mol) of 4-ethoxyaniline was replaced with g (0.015 mol) of aniline. Otherwise, the same procedure as in Synthesis Example 5 was followed to obtain a xaton compound in which two aryl groups without electron-donating substituents were substituted on the nitrogen atom.

[0376] Next, 22.83 g (0.04 mol) of (b-2-1) was replaced with 19.30 g (0.04 mol) of the xaton compound in which the two aryl groups without electron-donating substituents were substituted at the nitrogen atom, and 19.84 g (0.08 mol) of 4-iodophenethyl ether was replaced with 16.32 g (0.08 mol) of iodobenzene. Otherwise, the same procedure as in Synthesis Example 5 was followed to obtain a xaton compound (2) in which the four aryl groups without electron-donating substituents were substituted at the nitrogen atom.

[0377] LC-MS (ESI, posi): m / z 635[M+H] +

[0378] [Chemical Formula 25] [91

[0380]

[0381] The names of the compounds used in each example and comparative example are shown below. It should be noted that the colorant (d) was synthesized using a known method, and the transmission spectrum of the GBL solution at wavelengths from 300 nm to 800 nm was measured using a MultiSpec-1500 UV-Vis spectrophotometer (manufactured by Shimadzu Corporation), thereby calculating the maximum absorption wavelength. The maximum absorption wavelength of compound (d10-2-1) is 534 nm, and the maximum absorption wavelength of compound (d10-2-2) is 536 nm.

[0382] e-1: 4,4',4”-Trihydroxytrimethylbenzene (thermally chromogenic compound)

[0383] GBL: γ-Butyrolactone

[0384] EL: Ethyl lactate

[0385] PGME: Propylene Glycol Monomethyl Ether

[0386] [Chemical Formula 26]

[0387]

[0388] Example 1

[0389] 7.0 g of polyimide precursor (a-1) and 0.5 g of xanthonium compound (b-1) were added to 20 g of GBL to obtain varnish A1, a resin composition containing xanthonium compound (b). Separately, 7.0 g of polyimide precursor (a-1) was added to 20 g of GBL to obtain varnish B1, a resin composition not containing xanthonium compound (b). Using the obtained varnishes A1 and B1, the maximum absorption wavelength (350–800 nm) and the heat resistance of the dyes were evaluated as described above.

[0390] Examples 2-11, Comparative Examples 1-3

[0391] As described in Table 1, the alkali-soluble resin (a), xaton compound (b), and solvent were changed, except that the procedure was the same as in Example 1, to obtain varnish A containing the resin composition of xaton compound (b) and varnish B containing the resin composition of xaton compound (b). Using the obtained varnishes A and B, the maximum absorption wavelength of 350–800 nm and the heat resistance of the dye were evaluated as described above.

[0392] Example 12

[0393] 10.0 g of polyimide precursor (a-1), 2.0 g of xanthones compound (b), 2.0 g of photosensitive compound (c-1), 1.0 g of (d10-2-2), and 2.0 g of (e-1) were dissolved in 10 g of GBL, 20 g of EL, and 70 g of PGME. The solution was then filtered using a 0.2 μm polytetrafluoroethylene filter to obtain varnish AA of the positive photosensitive resin composition. The sensitivity, OD value, and change in OD value of the obtained varnish were evaluated as described above.

[0394] Examples 13-23, Comparative Examples 3-5

[0395] As described in Table 2, the alkali-soluble resin (a), thiamethoxam compound (b), photosensitive compound (c), coloring material (d), other additives, and solvents were changed, except that the procedure was the same as in Example 12, to obtain a varnish of the positive photosensitive resin composition. The obtained varnish was used to evaluate the sensitivity, OD value, and the amount of change in OD value as described above.

[0396] Examples 24-25

[0397] The varnishes using the positive photosensitive resin compositions described in Table 2 were evaluated for freeze-drying stability as described above.

[0398] Example 26

[0399] Using the cured film of the resin composition AE obtained in Example 16, the analysis of the thallium compound (b') in the TOF-SIMS-based cured film was performed as described above. The results confirmed that the concentration down to m / z 902 ( 902 C 62 H 52 The molecular ion of N3O4 was confirmed. Based on this result, it was confirmed that the cured film of the resin composition AE contains the cationic portion of the thallium compound (b-5).

[0400] The composition and evaluation results of each embodiment and comparative example are shown in Tables 1 to 4.

[0401] [Table 1]

[0402] [Table 1]

[0403]

[0404] [Table 2]

[0405]

[0406] [Table 3]

[0407] [Table 3]

[0408]

[0409] [Table 4]

[0410] [Table 4]

[0411]

[0412] Explanation of reference numerals in the attached figures

[0413] 1: TFT (Thin Film Transistor)

[0414] 2: Wiring

[0415] 3: TFT insulating layer

[0416] 4: Planarization layer

[0417] 5: ITO (Transparent Electrode)

[0418] 6: Substrate

[0419] 7: Contact hole

[0420] 8: Insulation layer

[0421] 11: Display device

[0422] 12: Light-emitting element

[0423] 13: Cured product

[0424] 14, 14c: Metal wiring

[0425] 15: Opposite substrate

[0426] 16: Electrode terminals

[0427] 17: Light-emitting element driving substrate

[0428] 18: Driving element

[0429] 19: Blocking metal

[0430] 20: Solder bump

Claims

1. Compound (b) represented by formula (1), [Chemical Formula 1] In equation (1), A 1 ~A 4 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may have electron-donating substituents; wherein, A 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents has an electron-donating substituent; R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 Or a monovalent hydrocarbon group with 1 to 20 carbon atoms; R 5 Indicates -SO3H, -SO3 - -SO3NR 6 R 7 or -CONR 9 R 10 ;R 6 ~R 10 Each of the following groups independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms; Z represents an anionic compound, and n represents 0 or 1; wherein, the thallium compound (b) represented by formula (1) is an electrically neutral compound as a whole; the electron-donating substituent is selected from alkyl, alkoxy, aryloxy, hydroxy, amino, and alkylamino.

2. The xaton compound (b) as described in claim 1, wherein, The substituent constant σ according to the Hammett rule for electron-donating substituents. p The value is below -0.

20.

3. The xaton compound (b) as described in claim 1 or 2, wherein, In the above formula (1), n ​​is 0.

4. The xaton compound (b) as described in claim 1 or 2, wherein, In the formula (1), n ​​is 1 and Z is an aliphatic or aromatic sulfonate ion.

5. A resin composition comprising the thiamethoxam compound (b) of claim 1 and an alkali-soluble resin (a).

6. The resin composition of claim 5, further comprising a photosensitive compound (c).

7. The resin composition of claim 6, wherein, The photosensitive compound (c) contains a quinone diazide compound.

8. The resin composition of claim 5, further comprising a colorant (d-2) having a maximum absorption wavelength at any point in the range of 350-800 nm, above 490 nm and below 580 nm.

9. The resin composition of claim 5, comprising a thallium compound (b1) in which n is 1 and Z is an organic anion in formula (1), and an ionic dye (d10) forming an ion pair of organic ions, wherein the organic anion is one.

10. The resin composition of claim 5, wherein, The alkali-soluble resin (a) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, polyamide-imide precursor and copolymers thereof.

11. The resin composition of claim 5, wherein, The total mass of all chlorine atoms and all bromine atoms contained in the resin composition is less than 150 ppm relative to the total mass of the solid components of the resin composition.

12. A cured product obtained by curing the resin composition of claim 5.

13. A solidified compound containing a thallium compound (b') represented by formula (2). [Chemical Formula 2] In equation (2), A 1 ~A 4 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may have electron-donating substituents; wherein, A 1 ~A 4 At least three of the aryl groups are aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents, and at least one of the aryl groups with 6 to 10 carbon atoms that can have electron-donating substituents has an electron-donating substituent; R 1 ~R 4 Each independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, -SO3H, and -SO3. - -SO3NR 6 R 7 -COOH, -COO - -COOR 8 -CONR 9 R 10 Or a monovalent hydrocarbon group with 1 to 20 carbon atoms; R 5 Indicates -SO3H, -SO3 - -SO3NR 6 R 7 or -CONR 9 R 10 ;R 6 ~R 10 Each of the following groups independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms; wherein the thallium compound (b') represented by formula (2) is an electrically neutral or cationic compound; the electron-donating substituent is selected from alkyl, alkoxy, aryloxy, hydroxy, amino, and alkylamino groups.

14. A method for manufacturing a cured material, comprising: The process of forming a resin film on a substrate using the resin composition of claim 6; The process of exposing the resin film; The process of developing an exposed resin film; and the process of heat-treating the developed resin film.

15. The method for manufacturing a cured product as described in claim 14, wherein, In the process of exposing the resin film, the photomask used during exposure is a halftone photomask having a light-transmitting part, a light-blocking part, and a semi-transmitting part, and the transmittance of the semi-transmitting part is 5% to 30% when the transmittance of the light-transmitting part is set to 100%.

16. An organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, wherein the planarization layer and / or the insulating layer has the cured material as described in claim 12 or 13.

17. The organic EL display device as claimed in claim 16, wherein, The insulating layer has the cured material, and the optical density under visible light is 0.5~1.5 per 1 μm film thickness of the insulating layer.

18. The organic EL display device of claim 16, further comprising a color filter having a black matrix.

19. A display device having at least metal wiring, a cured material as described in claim 12 or 13, and a plurality of light-emitting elements, the display device being configured such that: each light-emitting element has a pair of electrode terminals on any side, the pair of electrode terminals being connected to a plurality of metal wirings extending in the cured material, the plurality of metal wirings being electrically insulated by the cured material.

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