Positive photosensitive composition, copolymer, cured product, electronic component, display device, and information terminal

Abstract

The present invention provides a positive photosensitive composition, a cured product of which has high weather resistance and bending tolerance and has high long-term reliability when used in an organic EL display device. A positive photosensitive composition according to the present invention comprises: (A) a copolymer (referred to as copolymer (A)) which has a structural unit represented by formula (1) and a structural unit represented by formula (2), and which has a phenolic hydroxyl group in the structure thereof; (B) a quinone diazide compound; and (C) a solvent, wherein the content of the structural unit represented by formula (1) in the copolymer (A) is 1-50 mol% with respect to 100 mol% of all structural units contained in the copolymer (A). (In formula (1), R1 is a C1-20 organic group. In formula (2), R2 is a hydrogen atom or a C1-20 organic group. In the plurality of formulae (1) and (2), R1 and R2 may be the same or different.)

Description

Positive photosensitive compositions, copolymers, cured products, electronic components, display devices and information terminals

[0001] The present invention relates to a positive-working photosensitive composition, a copolymer, a cured product, an electronic component, a display device, and an information terminal.

[0002] Organic electroluminescence (EL) display devices are attracting attention as next-generation flat panel displays in fields such as smartphones, tablet PCs, and televisions. Compared to conventional liquid crystal display devices, organic EL display devices have a wider viewing angle and higher contrast, and can also be made thinner and more flexible, so research and development into these devices is currently underway.

[0003] An organic EL display device typically comprises a planarizing layer, which is an underlying insulating layer that has the function of planarizing the protruding steps resulting from wiring formed on a substrate, as well as a pixel dividing layer, which is an insulating layer that has the function of separating each light-emitting pixel, such as red, blue, or green, and both layers are generally formed by photolithography.

[0004] It is known that pixel division layers and planarization layers significantly affect the long-term reliability of organic EL display devices. Materials for forming the planarization layer and pixel division layer include compositions with positive or negative photosensitivity. For example, Patent Document 1 discloses a photosensitive composition containing a polyimide resin, a polyimide precursor, a polybenzoxazole precursor, or a polysiloxane resin. It also discloses that by controlling the amount of acid anhydride groups in a pixel division layer formed using these materials within a specific range, pixel shrinkage is less likely to occur and a high pixel light-emitting area ratio can be maintained, resulting in an organic EL display device with excellent long-term reliability.

[0005] In recent years, the development of flexible organic EL display devices formed on resin film substrates has been actively pursued. Flexible organic EL display devices have structurally bendable portions and / or portions fixed in a bent state, and bending stress is applied to the planarizing layer and pixel dividing layer at these bent portions. In flexible organic EL display devices including such bent portions, high bending resistance is required for the materials for the planarizing layer and the pixel dividing layer. For these reasons, there is a strong demand for the development of photosensitive compositions that can be patterned with high sensitivity and can produce cured films with high bending resistance.

[0006] As materials for these planarization layers and pixel division layers, photosensitive compositions containing resins composed of repeating units derived from vinyl monofunctional monomers have been investigated with the aim of developing economically advantageous organic EL display devices. Generally, vinyl monofunctional monomers are low cost and can be polymerized by a simple method in low-cost organic solvents, making the cost of resins composed of repeating units derived from vinyl monofunctional monomers economically advantageous. In particular, positive-tone photosensitivity has attracted attention because, for example, in the event of a malfunction during the manufacturing process, such as misalignment between the substrate and the exposure mask, the film can be easily removed by dissolving in a solvent or alkaline developer before the curing step, thereby enabling the substrate to be reused at least after the formation of electrodes, which is economically advantageous.

[0007] As a composition containing a resin composed of repeating units derived from a vinyl monofunctional monomer and having positive photosensitivity, for example, a positive photosensitive composition for forming an interlayer insulating film of a liquid crystal display is disclosed in Patent Document 2. Patent Document 2 discloses a positive photosensitive composition containing a methacrylate ester copolymer having repeating units containing a benzotriazole skeleton and a phenol skeleton as the resin.

[0008] International Publication No. 2016 / 143740 Japanese Patent Application Laid-Open No. 2023-23224

[0009] However, while Patent Document 2 discloses a positive-type photosensitive composition containing a methacrylate ester copolymer having a repeating unit containing a benzotriazole skeleton and a phenol skeleton as a resin, it has been found that the bending resistance of a cured film of the photosensitive composition and the long-term reliability when the cured film is used in an organic EL display device are insufficient. The present invention has been made in view of the shortcomings of the prior art, and an object of the present invention is to provide a positive-type photosensitive composition that provides a cured product with high weather resistance and bending resistance, and that provides high long-term reliability when the cured product is used in an organic EL display device.

[0010] The present invention has the following configuration.

[0011] [1] A positive-working photosensitive composition comprising (A) a copolymer (hereinafter referred to as "(A) copolymer") having a structural unit represented by formula (1) and a structural unit represented by formula (2) and having a phenolic hydroxyl group in its structure, (B) a quinone diazide compound, and (C) a solvent, wherein the content of the structural unit represented by formula (1) contained in the (A) copolymer is 1 to 50 mol % relative to 100 mol % of all structural units contained in the (A) copolymer.

[0012]

[0013] (In formula (1), R １ is an organic group having 1 to 20 carbon atoms. ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. In formula (1) and formula (2) where multiple R １ and R ２ may be the same or different. [2] R in the formula (1) １ is an organic group having 5 to 20 carbon atoms and containing an alicyclic structure.

[0014] [3] R in the formula (2) ２ is an alkyl group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, an alicyclic alkyl group having 5 to 15 carbon atoms, or a hydrogen atom.

[0015] [4] R in the formula (2)２ is a group represented by formula (3).

[0016]

[0017] (In formula (3), R ３ is an alkylene group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ is a group containing a hydroxy group, a carboxy group, a cyclic ether group, or an alicyclic structure having 5 to 15 carbon atoms, and R ３ and R ４ The total number of carbon atoms in R in the formula (3) is 20 or less. ３ is an alkylene group having 4 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ is a cyclic ether group, is 1 to 50 mol % relative to 100 mol % of all structural units contained in the copolymer (A).

[0018] [6] R in the formula (1) １ is a group represented by formula (4).

[0019]

[0020] (In formula (4), R ５ and R ６ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ７ represents an alkyl group having 1 to 5 carbon atoms. a and b represent integers of 0 to 5. In formula (4) where multiple R ５ ~R ７ may be the same or different.) [7] The positive photosensitive composition according to any one of [1] to [6] above, wherein the copolymer (A) has a structural unit containing a cyclic ether group.

[0021] [8] The positive photosensitive composition according to any one of [1] to [7] above, wherein the copolymer (A) has a structural unit represented by formula (5), and the structural unit represented by formula (5) contained in the copolymer (A) accounts for 1 to 40 mol % relative to 100 mol % of all structural units contained in the copolymer (A).

[0022]

[0023] (In formula (5), R ８ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. ８ may be the same or different.) [9] The positive photosensitive composition according to any one of [1] to [8] above, wherein the weight average molecular weight of the copolymer (A) is 5,000 or more and 100,000 or less.

[10] A copolymer (referred to as "copolymer (A)") having a structural unit represented by formula (1) and a structural unit represented by formula (2) and having a phenolic hydroxyl group in the structure, wherein the content of the structural unit represented by formula (1) contained in copolymer (A) is 1 to 50 mol % relative to 100 mol % of all structural units contained in copolymer (A).

[0024]

[0025] (In formula (1), R １ is an organic group having 1 to 20 carbon atoms. ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. In formula (1) and formula (2) where multiple R １ and R ２ may be the same or different.

[11] R in the formula (1) １ is a group represented by formula (4).

[0026]

[0027] (In formula (4), R ５ and R ６ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ７ represents an alkyl group having 1 to 5 carbon atoms. a and b represent integers of 0 to 5. In formula (4) where multiple R５ ~R ７ may be the same or different.)

[12] A cured product obtained by curing the positive photosensitive composition according to any one of [1] to [9] above.

[0028]

[13] An electronic component comprising the cured product according to

[12] above.

[0029]

[14] A display device comprising the cured product according to

[12] above.

[0030]

[15] An information terminal having the display device according to

[14] .

[0031] According to the present invention, a positive photosensitive composition can be obtained which provides a cured product with high weather resistance and bending resistance, and which exhibits high long-term reliability when used in an organic EL display device.

[0032] 1 is a cross-sectional view of a TFT substrate in an organic EL display device that can be given as a specific example of an embodiment of the present invention. 2 is a diagram illustrating a manufacturing process of an organic EL display device, including a step of forming a pixel dividing layer, in all examples and comparative examples that could be evaluated.

[0033] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be carried out with various modifications depending on the purpose and application. A numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits.

[0034] (Positive Photosensitive Composition) The positive photosensitive composition according to an embodiment of the present invention contains (A) a copolymer, (B) a quinone diazide compound, and (C) a solvent.

[0035] [Copolymer (A)] The copolymer (A) used in the positive photosensitive composition of the present invention and the copolymer (A) used in the copolymer of the present invention are copolymers having a structural unit represented by formula (1) and a structural unit represented by formula (2) and having a phenolic hydroxyl group in the structure.

[0036]

[0037] In formula (1), R １is an organic group having 1 to 20 carbon atoms. ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. In formula (1) and formula (2) where multiple R １ and R ２ may be the same or different.

[0038] R 1 and R ２ In the above, the organic group having 1 to 20 carbon atoms means a group having 1 to 20 carbon atoms which may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples thereof include an alkyl group having a linear, branched, or cyclic structure which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an aralkyl group which may have a substituent, and a heteroaralkyl group which may have a substituent.

[0039] Examples of the substituent include a hydroxy group, an alkoxy group, a carboxy group, an amino group, and an epoxy group.

[0040] In formula (1), R １ is preferably an organic group containing an alicyclic structure and having 5 to 20 carbon atoms. The presence of an alicyclic structure can suppress a decrease in film thickness in unexposed areas due to development, and can also suppress absorption of UV light, which can cause a decrease in long-term reliability when a cured product is used in an organic EL display device.

[0041] In addition, in order to further improve the long-term reliability when the cured product is used in an organic EL display device, １ is more preferably a group represented by formula (4).

[0042]

[0043] In formula (4), R ５ and R ６ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ７ represents an alkyl group having 1 to 5 carbon atoms. a and b represent integers of 0 to 5. ６ , R ７ When there are two or more R ６ , R ７may be the same or different. ５ ~R ７ may be the same or different.

[0044] Specific examples of monomers constituting the structural unit represented by formula (1) include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, tricyclodecane vinyl ether, etc. These vinyl ethers may be used alone or in combination of two or more.

[0045] Among these vinyl ethers, vinyl ethers having an alicyclic structure are preferably used because they can suppress the film thickness reduction in unexposed areas due to development and improve the long-term reliability when the cured product is used in an organic EL display device. Specific examples of more preferred monomers include cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, and tricyclodecane vinyl ether. Of these, 1,4-cyclohexanedimethanol monovinyl ether is even more preferred in terms of further improving the solubility of the coating film in alkaline developers and adhesion to substrates, and in terms of crosslinking with the (A) copolymer or other additives via hydrogen bonding or the like to improve the heat resistance, weather resistance, and bending resistance of the film after thermal curing, as well as the long-term reliability when the cured product is used in an organic EL display device. Meanwhile, cyclohexyl vinyl ether is preferred from the perspective of suppressing the film thickness reduction in unexposed areas while maintaining the solubility of the exposed areas in alkaline developers.

[0046] The content of the structural unit represented by formula (1) in the copolymer (A) is 1 to 50 mol %, based on 100 mol % of all structural units contained in the copolymer (A). By ensuring that the content of the structural unit represented by formula (1) is 1 mol % or more, the weather resistance and bending resistance of the cured product, as well as the long-term reliability when the cured product is used in an organic EL display device, can be improved. The content of the structural unit represented by formula (1) is more preferably 5 mol % or more, and even more preferably 10 mol % or more, based on 100 mol % of all structural units contained in the copolymer (A). On the other hand, by ensuring that the content of the structural unit represented by formula (1) is 50 mol % or less, the copolymerizability with the structural unit represented by formula (2) and other structural units can be improved. The content of the structural unit represented by formula (1) is more preferably 40 mol % or less, and even more preferably 35 mol % or less, based on 100 mol % of all structural units contained in the copolymer (A).

[0047] In formula (2), R ２ Preferably, the alkyl group has a structural unit which is an alkyl group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, an alicyclic alkyl group having 5 to 15 carbon atoms, or a hydrogen atom.

[0048] R ２ The structural unit in which R is a hydrogen atom is a structural unit derived from acrylic acid, and in the copolymer (A), R ２ By containing a structural unit in which R is a hydrogen atom, the solubility in an alkaline developer can be increased. ２ is a hydrogen atom and the structural unit derived from methacrylic acid described below is preferably 1 to 30 mol %, and more preferably 5 to 20 mol %, relative to 100 mol % of all structural units contained in the copolymer (A).

[0049] R ２ The structural unit in which R is an alkyl group having 1 to 12 carbon atoms, which may contain an ester bond or an ether bond, or an alicyclic alkyl group having 5 to 15 carbon atoms, is a structural unit derived from an acrylic acid ester. Among these, R is preferred because it can suppress the film thickness reduction in the unexposed area due to development and improve the long-term reliability when the cured product is used in an organic EL display device.２ is preferably an alicyclic alkyl group having 5 to 15 carbon atoms.

[0050] In formula (2), R ２ is preferably a group represented by formula (3).

[0051]

[0052] In formula (3), R ３ is an alkylene group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ is a group containing a hydroxy group, a carboxy group, a cyclic ether group, or an alicyclic structure having 5 to 15 carbon atoms, and R ３ and R ４ The total number of carbon atoms is 20 or less.

[0053] R ４ In the formula (I), specific examples of the group containing an alicyclic structure having 5 to 15 carbon atoms include a cyclohexyl group, an epoxycyclohexyl group, a hydroxymethylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and an adamantyl group.

[0054] In formula (2), R ２ When the group represented by formula (3) is a group represented by formula (3), the bending resistance of the cured product can be improved.

[0055] Among them, R in the formula (3) ３ is an alkylene group having 4 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ However, it is more preferable that the content of the structural unit that is a cyclic ether group is 1 to 50 mol % relative to 100 mol % of all structural units contained in the copolymer (A). By making the structural unit 1 mol % or more, the bending resistance of the cured product can be further improved. Furthermore, by making the structural unit 50 mol % or less, it is possible to suppress a decrease in long-term reliability when the cured product is used in an organic EL display device. It is more preferable that the content of the structural unit is 5 to 40 mol % relative to 100 mol % of all structural units contained in the copolymer (A).

[0056] Specific examples of monomers constituting the structural unit represented by formula (2) include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, s-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, dodecyl acrylate, octadecyl acrylate, 2-methoxyethyl acrylate, 3-methoxypropyl acrylate, acrylic acid ... 2-(2-ethoxyethoxy)ethyl acrylate, 2-ethylhexyl-diglycol acrylate, methoxydipropylene glycol acrylate, 1-methylcyclopentyl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, adamantan-1-yl acrylate, 2-methyladamantan-2-yl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid 4-Hydroxybutyl, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, (3,4-epoxycyclohexyl)methyl acrylate, (3,4-epoxycyclohexyl)ethyl acrylate, (3-methyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl acrylate, tetrahydrofurfuryl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 1-acryloyloxyethyl acrylate, Examples of suitable acrylates include acryloyloxy-3-hydroxyadamantane, phenoxyethyl acrylate, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, 6-(4-hydroxyphenoxy)hexyl acrylate, 4-hydroxyphenyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalate, α-acryloxy-γ-butyrolactone, and β-hydroxy-γ-butyrolactone acrylate.These monomers may be used alone or in combination of two or more.

[0057] The (A) copolymer has a phenolic hydroxyl group in its structure. Here, "in its structure" means in the (A) copolymer. The phenolic hydroxyl group may be contained in formula (1) and / or formula (2), or may be contained in another structural unit. The presence of a phenolic hydroxyl group in the (A) copolymer can improve the solubility of the coating film in an alkaline developer and the adhesion to a substrate.

[0058] Examples of the structural unit containing a phenolic hydroxyl group include structural units represented by formula (6) and formula (7).

[0059]

[0060] In formula (6), R ９ represents a hydrogen atom or a methyl group, R １０ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R １１ represents an alkyl group having 1 to 5 carbon atoms, c represents an integer of 0 to 4, and d represents an integer of 1 to 5. １１ When there are two or more R １１ may be the same or different.

[0061] In formula (7), R １２ represents a hydrogen atom or a methyl group, R １３ represents an alkyl group having 1 to 5 carbon atoms, e represents an integer of 0 to 4, and f represents an integer of 1 to 5. １３ When there are two or more R １３ may be the same or different.

[0062] Specific examples of the monomer that constitutes the structural unit represented by formula (6) include 4-hydroxyphenyl methacrylate, (4-hydroxyphenyl)methyl methacrylate, (4-hydroxyphenyl)ethyl methacrylate, and (4-hydroxyphenyl)propyl methacrylate.

[0063] Specific examples of the monomer constituting the structural unit represented by formula (7) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,4-dihydroxystyrene, 2,6-dihydroxystyrene, 2,4,6-trihydroxystyrene, 2,3,4,5-tetrahydroxystyrene, pentahydroxystyrene, 2-isopropenylphenol, 3-isopropenylphenol, and 4-isopropenylphenol.

[0064] These monomers may be used alone or in combination of two or more.

[0065] In the copolymerization method described below, from the viewpoint of reducing residual monomers after copolymerization, the structural unit containing a phenolic hydroxyl group is preferably a structural unit represented by formula (6). On the other hand, from the viewpoint of suppressing heat generation during copolymerization, the structural unit containing a phenolic hydroxyl group is preferably a structural unit represented by formula (7).

[0066] The content of the structural unit containing a phenolic hydroxyl group is preferably 1 to 40 mol %, more preferably 5 to 30 mol %, relative to 100 mol % of all structural units contained in the copolymer (A).

[0067] The (A) copolymer preferably has a structural unit containing a cyclic ether group. The cyclic ether group may be contained in formula (1) and / or formula (2), or may be contained in another structural unit. The presence of a cyclic ether group in the (A) copolymer allows crosslinking with the (A) copolymer or other additives to form a strong film, thereby suppressing outgassing, which can cause a decrease in long-term reliability when the cured product is used in an organic EL display device. In addition, the heat resistance and chemical resistance of the cured product can be further improved.

[0068] As the cyclic ether group, an epoxy group or an oxetane group is preferred in terms of improving crosslinkability, and an epoxy group is more preferred.

[0069] The content of the structural unit containing a cyclic ether group is preferably 1 to 60 mol %, and more preferably 10 to 50 mol %, relative to 100 mol % of all structural units contained in the copolymer (A).

[0070] The copolymer (A) preferably has a structural unit represented by formula (5).

[0071]

[0072] In formula (5), R ８ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. ８ may be the same or different.

[0073] When the copolymer (A) has a structural unit represented by formula (5), it is possible to appropriately suppress a decrease in film thickness in the unexposed areas due to development.

[0074] R ８ The structural unit in which R is a hydrogen atom is a structural unit derived from methacrylic acid, and in (A) copolymer, R ８ By containing a structural unit in which R is a hydrogen atom, the solubility in an alkaline developer can be increased. ８ is a hydrogen atom and the structural units derived from acrylic acid are contained in the copolymer (A). The total content of these structural units is preferably 1 to 30 mol %, and more preferably 5 to 20 mol %, relative to 100 mol % of all structural units contained in the copolymer (A).

[0075] R ８ In the above, the organic group having 1 to 20 carbon atoms means a group having 1 to 20 carbon atoms which may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples thereof include an alkyl group having a linear, branched, or cyclic structure which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an aralkyl group which may have a substituent, and a heteroaralkyl group which may have a substituent.

[0076] Examples of the substituent include a hydroxy group, an alkoxy group, a carboxy group, an amino group, and an epoxy group.

[0077] In formula (5), R ８ is preferably a group represented by formula (8).

[0078]

[0079] In formula (8), R １４ is an alkylene group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, and R １５ is a group containing a hydroxy group, a carboxy group, a cyclic ether group, or an alicyclic structure having 5 to 15 carbon atoms, and R １４ and R １５ The total number of carbon atoms is 20 or less.

[0080] R １５ In the above, specific examples of the group containing an alicyclic structure having 5 to 15 carbon atoms are the above-mentioned R ４ The specific examples of the group containing an alicyclic structure having 5 to 15 carbon atoms are the same as those in R １５ is preferably an epoxy group, an oxetane group, or an epoxycyclohexyl group, and is preferably an epoxycyclohexyl group in order to improve the long-term reliability and bending resistance when the cured product is used in an organic EL display device.

[0081] Specific examples of monomers constituting the structural unit represented by formula (5) include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxypropyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-ethylhexyl-diglycol methacrylate, methoxydipropylene glycol methacrylate, 1-methylcyclopentyl methacrylate, methacrylate, Cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, adamantan-1-yl methacrylate, 2-methyladamantan-2-yl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, (3,4-epoxycyclohexyl)methyl methacrylate, (3,4-epoxycyclohexyl)ethyl methacrylate, (3-methyloxetan-3-yl)methyl methacrylate, (3-ethyloxetan-3-yl)methyl methacrylate, tetrahydrofurfuryl methacrylate, 1,Examples of the monomers include 4-cyclohexanedimethanol monomethacrylate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalate, 1-methacryloyloxy-3-hydroxyadamantane, phenoxyethyl methacrylate, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl methacrylate, 6-(4-hydroxyphenoxy)hexyl methacrylate, 4-hydroxyphenyl methacrylate, phenoxydiethylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxyethyl phthalate, α-methacryloxy-γ-butyrolactone, and β-hydroxy-γ-butyrolactone methacrylate. These monomers may be used alone or in combination of two or more.

[0082] The structural unit represented by formula (5) contained in the copolymer (A) is preferably 1 to 40 mol % relative to 100 mol % of all structural units contained in the copolymer (A). By controlling the structural unit represented by formula (5) to 1 mol % or more, it is possible to appropriately control the film thickness reduction in unexposed areas due to development, thereby obtaining a good pattern. Furthermore, by controlling the structural unit represented by formula (5) to 40 mol % or less, it is possible to suppress the generation of residues during development and to suppress outgassing due to depolymerization, which can cause a decrease in long-term reliability when the cured product is used in an organic EL display device. The content of the structural unit represented by formula (5) is more preferably 10 to 35 mol % relative to 100 mol % of all structural units contained in the copolymer (A).

[0083] The copolymer (A) can further contain any desired monomer copolymerized therewith, if necessary. Specific examples thereof include crotonic acid, methyl crotonate, ethyl crotonate, maleic acid, monomethyl maleate, monoethyl maleate, dimethyl maleate, diethyl maleate, monocyclohexyl maleate, fumaric acid, monomethyl fumarate, monoethyl fumarate, dimethyl fumarate, diethyl fumarate, monocyclohexyl fumarate, itaconic acid, monomethyl itaconate, monoethyl itaconate, dimethyl itaconate, citraconic acid, dimethyl citraconic acid, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, N-(2-hydroxyethyl)maleimide, N-t-butylmaleimide, 2-maleimidoacetic acid, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0084] The copolymer (A) can be synthesized by known methods such as free radical polymerization, living radical polymerization, and living anionic polymerization. From the viewpoint of economical advantages, it is preferable to employ the free radical polymerization method.

[0085] Examples of free radical polymerization methods include dissolving a monomer constituting a structural unit represented by formula (1), a monomer constituting a structural unit represented by formula (2), and a monomer having a phenolic hydroxyl group (in this case, the monomer having a phenolic hydroxyl group may be represented by formula (1) or formula (2)) in an organic solvent, stirring in the presence of a thermal radical polymerization initiator at a liquid temperature of 50 to 120°C for 1 to 50 hours under a nitrogen atmosphere until the desired weight average molecular weight (Mw) is reached, and then cooling to terminate the reaction, thereby obtaining a resin solution. The heating temperature and heating time are preferably set with reference to the 10-hour half-life temperature of the thermal radical polymerization initiator used.

[0086] Examples of the thermal radical polymerization initiator include azo-based thermal radical polymerization initiators such as AIBN, AIBN-HP, V-65, V-65HP, VR-110, V-40, azobisisobutyronitrile, and V-601, which is 2,2'-azobis(isobutyrate) dimethyl (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The amount of the thermal radical polymerization initiator added is preferably 0.5 to 10 parts by mass per 100 parts by mass of the total monomers. Examples of the organic solvent that can be used include low-cost solvents such as isopropyl alcohol, diacetone alcohol, ethylene glycol mono-t-butyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, and ethyl lactate.

[0087] If necessary, a chain transfer agent such as t-dodecanethiol or α-methylstyrene dimer may be used as a molecular weight distribution regulator.

[0088] The weight-average molecular weight in the present invention refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. The weight-average molecular weight of the (A) copolymer is preferably 1,000 or more, more preferably 5,000 or more, from the viewpoint of coatability. From the viewpoint of curability of the coating film, it is even more preferably 10,000 or more. On the other hand, the upper limit is preferably 300,000 or less, more preferably 100,000 or less, from the viewpoint of coatability. From the viewpoint of improving solubility in an alkaline developer and suppressing the generation of residues, it is even more preferably 50,000 or less.

[0089] [(B) Quinone Diazide Compound] The positive photosensitive composition of the present invention contains (B) a quinone diazide compound. Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, those in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, and those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond. It is preferred that 50 mol % or more of the total functional groups of these polyhydroxy compounds or polyamino compounds be substituted with the sulfonic acid of quinone diazide.

[0090] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. A naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure.

[0091] It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure, but from the viewpoint of increasing sensitivity, it is preferable to contain a 4-naphthoquinone diazide sulfonyl ester compound. On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention, which will be described later, is used as a planarizing layer and / or pixel dividing layer of an organic EL display device, a 5-naphthoquinone diazide sulfonyl ester compound is preferred.

[0092] The quinone diazide compound can be synthesized by any esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. The use of such a quinone diazide compound further improves resolution, sensitivity, and film retention.

[0093] In the present invention, from the viewpoint of achieving high sensitivity, the content of the (B) quinone diazide compound is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent. The solid content here refers to the components in the positive photosensitive composition excluding the solvent. The upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. When the content of the (B) quinone diazide compound is equal to or greater than the lower limit, a dissolution contrast between exposed and unexposed areas is easily achieved. On the other hand, when the content of the (B) quinone diazide compound is equal to or less than the upper limit, compatibility with the (A) copolymer is improved, and whitening of the coating film, precipitation during solvent removal, and coloration due to decomposition of the (B) quinone diazide compound during thermal curing can be suppressed. Furthermore, when the cured product is used as a planarizing layer and / or pixel dividing layer in an organic EL display device, outgassing due to decomposition of the quinone diazide compound (B) can be reduced, thereby improving long-term reliability.

[0094] [Solvent (C)] Examples of the solvent (C) include 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, ethylene glycol mono-t-butyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol ethyl methyl 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 ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol Ethers such as glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. acetate, propylene glycol monoethyl ether acetate, esters such as ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate,Other esters such as i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; 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-dimethylpropanamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone. Two or more of these may be contained.

[0095] The content of the solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the solid content of the positive-type photosensitive composition excluding the solvent. Furthermore, the proportion of the solvent having a boiling point of 180°C or higher relative to the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of the solvent having a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0096] [(D) Thermal Crosslinking Agent] The positive-type photosensitive composition of the present invention may further contain (D) a thermal crosslinking agent. The (D) thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. The inclusion of the (D) thermal crosslinking agent crosslinks with the (A) copolymer or other additives, thereby improving the heat resistance, chemical resistance, and bending resistance of the film after thermal curing.

[0097] Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups 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- Examples of such copolymers include 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, and HMOMTPHAP (all of which are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, and "NIKALAC" MX-750LM (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0098] Preferred examples of compounds having at least two epoxy groups include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, "Epolite" 400P, "Epolite" 1500NP, "Epolite" 80MF, "Epolite" 4000, and "Epolite" 3002 (all of which are "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (all trade names, manufactured by Nagase ChemteX Corporation), GAN, GOT (all trade names, manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" (registered trademark) Picoat" 1007, YX8100-BH30, E1256, E4250, E4275 (all trade names, manufactured by Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, HP4032 (all trade names, manufactured by DIC Corporation), VG3101 (trade name, manufactured by Mitsui Chemicals, Inc.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (all trade names, manufactured by Nissan Chemical Industries, Ltd.) Examples of such a surfactant include "Denacol" EX-321L (trade name, manufactured by Nagase ChemteX Corporation), "Denacol" EX-321L (trade name, manufactured by Nagase ChemteX Corporation), NC6000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), and "Epiclon" N695, HP7200 (all trade names, manufactured by DIC Corporation).

[0099] Preferred examples of compounds having at least two oxetanyl groups include, for example, "Ethanacol" (registered trademark) EHO, "Ethanacol" OXBP, "Ethanacol" OXTP, "Ethanacol" OXMA (all trade names, manufactured by Ube Industries, Ltd.), oxetanized phenol novolac, etc.

[0100] (D) The thermal crosslinking agent may be contained in combination of two or more kinds.

[0101] The content of the (D) thermal crosslinking agent is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the solids content of the positive-type photosensitive composition excluding the solvent. When the content of the (D) thermal crosslinking agent is 1 part by mass or more, the chemical resistance and bending resistance of the cured product can be further improved. Furthermore, when the content of the (D) thermal crosslinking agent is 30 parts by mass or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the positive-type photosensitive composition can also be excellent.

[0102] [UV absorber] The positive photosensitive composition of the present invention may contain an UV absorber. By containing an UV absorber, the resolution of the positive photosensitive composition and the long-term reliability of the organic EL display device of the cured product can be further improved. As the UV absorber, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used in terms of transparency and non-coloring properties.

[0103] Examples of benzotriazole compounds include 2-(2H-benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-t-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, and RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

[0104] When these ultraviolet absorbers are polymerizable compounds having an unsaturated double bond, they may be mixed as a monomer during synthesis of the copolymer (A) and copolymerized.

[0105] [Adhesion Improver] The positive photosensitive composition of the present invention may contain an adhesion improver.

[0106] Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing an adhesion improver, when developing a photosensitive resin film, for example, it is possible to improve adhesion to silicon wafers, ITO, SiO ２ The adhesiveness to the base substrate such as silicon nitride can be improved. Furthermore, the resistance to oxygen plasma and UV ozone treatments used for cleaning can be improved.

[0107] The content of the adhesion improver is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent.

[0108] [Antioxidant] The positive photosensitive composition of the present invention may further contain an antioxidant. By containing an antioxidant, yellowing of the pixel dividing layer and the planarizing layer can be prevented, and higher transparency can be obtained. For example, a compound represented by formula (9) or a compound represented by formula (10) can be mentioned.

[0109]

[0110] The content of the antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent.

[0111] [Surfactant] The positive photosensitive composition of the present invention may contain a surfactant, if necessary, for the purposes of improving the wettability with the substrate and improving the thickness uniformity of the resin film.

[0112] The surfactant may be a commercially available compound. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., the BYK series from BYK Japan K.K., the KP series from Shin-Etsu Chemical Co., Ltd., the Disfoam series from NOF Corporation, and the TSF series from Momentive Performance Materials Japan LLC. Specific examples of fluorine-based surfactants include the Megafac (registered trademark) series from DIC Corporation, the Fluorad series from 3M Japan Ltd., the Surflon (registered trademark) series and Asahi Guard (registered trademark) series from Asahi Glass Co., Ltd., the EF series from Mitsubishi Materials Electronic Chemicals Co., Ltd., and the Polyfox series from Omnova Solutions. Specific examples of surfactants made from acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon (registered trademark) series from Kusumoto Chemicals Co., Ltd.

[0113] The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less per 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent. By setting the content within the above range, it is possible to improve the wettability with the substrate and the thickness uniformity of the resin film without causing problems such as bubbles or pinholes.

[0114] [Particles] The positive photosensitive composition of the present invention may further contain particles. The introduction of the robust structure of the particles results in a strong film, which suppresses excessive reflow of the pattern during thermal curing and allows for control of the pattern shape. Preferred examples of the particles include inorganic particles and organic particles. Examples of inorganic particles include alumina, silica, magnesia, ferrite, aluminum oxide, zirconium oxide, titanium oxide, barium titanate, hafnium oxide, and talc. Examples of organic particles include polymers of (meth)acrylic acid, (meth)acrylic acid derivatives, styrene, vinyl acetate, acrylonitrile, and olefins, copolymers thereof, polyesters, polyamides, latexes, polyurethanes, phenolic resins, melamine resins, polyethersulfone resins, silicone resins, cellulose, fluororesins, and poly(fluoromethyl methacrylate).

[0115] In order to maintain bending resistance, the particle content is preferably 90 parts by mass or less, and more preferably 70 parts by mass or less, based on 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent. On the other hand, in order to suppress excessive reflow, the particle content is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the solid content of the positive photosensitive composition excluding the solvent.

[0116] (Copolymer) In the copolymer of the present invention, the content of the structural unit represented by formula (1) contained in copolymer (A) is 1 to 50 mol % relative to 100 mol % of all structural units contained in copolymer (A).

[0117] The copolymer (A) is as described above. The content of the structural unit represented by formula (1) contained in the copolymer (A) is preferably 5 mol % or more, more preferably 10 mol % or more, based on 100 mol % of all structural units contained in the copolymer (A). On the other hand, it is preferably 40 mol % or less, more preferably 35 mol % or less. In order to further improve the long-term reliability of the display device of the present invention, particularly an organic EL display device, which includes the cured product of the present invention, it is preferable that R in formula (1) １ is more preferably a group represented by formula (4).

[0118] The copolymer of the present invention is preferably used in the positive-type photosensitive composition of the present invention. It can also improve the weather resistance and bending resistance of the cured product of the present invention. Furthermore, when the copolymer of the present invention is used in the display device of the present invention, particularly an organic EL display device, which includes the cured product of the present invention, it can improve long-term reliability.

[0119] The copolymer of the present invention can be further mixed with (D) a thermal crosslinking agent, an ultraviolet absorber, an adhesion improver, an antioxidant, a surfactant, particles, a photopolymerization initiator, etc. to form a composition, particularly a positive-type photosensitive composition.

[0120] (Cured Product) The cured product of the present invention is a cured product obtained by curing the positive photosensitive composition of the present invention. A method for producing a cured product using a composition according to an embodiment of the present invention will now be described. This method includes the steps of forming a coating film of the composition, exposing and developing the coating film, and heating the developed film.

[0121] First, the positive photosensitive composition according to the embodiment of the present invention is applied onto a base substrate by a known method such as spinning, dipping, or slitting, and then prebaked using a heating device such as a hot plate or oven. Prebaking is carried out at a temperature in the range of 50 to 150° C. for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 μm.

[0122] After pre-baking, a UV-visible exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA) is used to expose the film to 10 to 4000 J / m ２ The desired exposure amount (equivalent to an exposure amount at a wavelength of 365 nm) is then exposed through a desired mask.

[0123] After exposure, the exposed areas are dissolved by development, resulting in a positive pattern. A preferred development method involves immersion in a developer for 5 seconds to 10 minutes by showering, dipping, puddling, or other methods. Known alkaline developers can be used as the developer. Specific examples include aqueous solutions containing one or more of inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and choline.

[0124] After development, it is preferable to rinse with water, and then dry bake at a temperature in the range of 50 to 150°C.

[0125] It is preferable to carry out bleaching exposure after that. By carrying out bleaching exposure, unreacted quinone diazide compounds remaining in the film are photodecomposed, and the optical transparency of the film is further improved. As a method of bleaching exposure, an ultraviolet-visible exposure machine such as PLA is used, and 100 to 20,000 J / m２ The entire surface is exposed to about 1000 nm of light (equivalent to an exposure dose at a wavelength of 365 nm).

[0126] The film is then heated (cured) for approximately 30 seconds to 10 hours at a temperature in the range of 100°C to 500°C, preferably 150°C to 400°C, using a heating device such as a hot plate or oven, to obtain a film-like cured product.

[0127] (Electronic Components) The electronic components of the present invention comprise the cured product of the present invention. Specifically, the term refers not only to semiconductor devices, semiconductor elements themselves, or those connected to a substrate, or those connected to semiconductor elements or substrates, but also to devices in general that can function by utilizing the properties of semiconductor elements, such as electro-optical devices, semiconductor circuit boards, and electronic components including these. The cured product of the present invention can be suitably used for the interlayer insulating layer and / or surface protective layer in semiconductor electronic components and semiconductor devices having electrodes, metal wiring, an interlayer insulating layer, and / or a surface protective layer on a substrate.

[0128] (Display Device) The display device of the present invention comprises the cured product of the present invention. Specifically, the display device includes a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), or an organic EL display. Hereinafter, an organic EL display device will be described as an example.

[0129] The cured product of the present invention can be suitably used as a planarization layer and / or pixel division layer in 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. Organic light-emitting materials are generally susceptible to gas components and moisture, and exposure to these can cause a decrease in luminance and pixel shrinkage. Here, pixel shrinkage refers to a phenomenon in which luminance decreases or pixels stop lighting from the edge of a pixel. Incorporating the cured product of the present invention as a planarization layer and / or pixel division layer in an organic EL display device can improve long-term reliability. In particular, since the pixel division layer is adjacent to the organic light-emitting material, it has a greater impact on long-term reliability than the planarization layer. Therefore, in order to obtain an organic EL display device with high long-term reliability, it is preferable to include the cured product of the present invention in at least the pixel division layer.

[0130] The display device of the present invention preferably has at least a bendable portion and / or a portion fixed in a bent state in a portion comprising the cured product. By using a cured product obtained by curing the positive photosensitive composition of the present invention, an organic EL display device with excellent bending resistance can be obtained. The display device of the present invention can be bent at any appropriate portion. For example, the organic EL display device may be bendable at the center like a foldable display device, or at the end from the perspective of ensuring design and maximizing the display screen. Furthermore, the organic EL display device may be bendable along its longitudinal direction or along its lateral direction. It is sufficient that a specific portion of the organic EL display device is bendable depending on the application (for example, some or all of the four corners can be bent diagonally).

[0131] FIG. 1 shows a cross-sectional view of a TFT (Thin-film transistor) substrate in an organic EL display device.

[0132] Bottom-gate or top-gate TFTs 1 are arranged in a matrix on the surface of a substrate 6, and a TFT insulating layer 3 is formed to cover the TFTs 1 and the wiring 2 connected to the TFTs 1. Examples of the TFTs 1 include TFTs made of oxide semiconductors such as In—Ga—Zn—O (IGZO) and Ga—Zn—Sn, or low-temperature polysilicon (LTPS). Furthermore, a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and contact holes 7 are formed in the planarization layer 4 to open the wiring 2. The contact holes 7 may be, for example, circular openings. First electrodes 5 are patterned on the surface of the planarization layer 4 and connected to the wiring 2. A pixel dividing layer 8 is disposed on the surface of the first electrodes 5, partially exposing the surfaces of the first electrodes 5, and a spacer layer 9 is disposed on a portion of the surface of the pixel dividing layer 8. An opening is provided in the pixel division layer 8, and a light-emitting pixel 10 containing an organic EL light-emitting material is formed in the opening, and a second electrode 11 is disposed so as to cover the pixel division layer 8, the spacer layer 9, and the light-emitting pixel 10. The shape of the opening in the pixel division layer 8 is not particularly limited, and may be a square, a rectangle, a perfect circle, or an ellipse.

[0133] The size and shape of the light-emitting pixel 10 are determined by the size and shape of the opening of the pixel dividing layer 8. The area per light-emitting pixel is, for example, 50 to 30,000 μm ２ is.

[0134] When a TFT substrate having the above-described laminated structure is sealed under vacuum and a voltage is applied to the light-emitting pixel portion, the display device can be driven as an organic EL display device, and light can be emitted from the light-emitting pixel portion.

[0135] The display device of the present invention is not particularly limited and may be a bottom-emission organic EL display device in which light emitted from the light-emitting pixels 10 is extracted to the substrate side through the substrate 6, or a top-emission organic EL display device in which light is extracted to the opposite side of the substrate 6 through the second electrode 11. In order to suppress reflection of external light and improve visibility, a polarizing plate may be further provided on the light extraction side. The light transmittance of the polarizing plate at a wavelength of 560 nm is, for example, 40 to 60%.

[0136] Examples of the substrate 6 include glass substrates such as OA-10G and OA-11 (trade names, manufactured by Nippon Electric Glass Co., Ltd.) and AN-100 (trade name, manufactured by Asahi Glass Co., Ltd.).

[0137] (Information Terminal) The information terminal of the present invention is an information terminal having the display device of the present invention, and is, for example, an electronic device used as a display, such as a personal computer, a smartphone, a tablet, a smart watch, smart glasses, or smart home appliances.

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0139] (Measurement of Weight Average Molecular Weight) The weight average molecular weight (Mw) was determined by the following method: The weight average molecular weight of the polymer was determined in terms of polystyrene by GPC (Waters 996 detector, developing solvent: tetrahydrofuran).

[0140] (Evaluation of Unexposed Area Remaining Film Ratio, Residue, and Pattern Cross-Sectional Shape) The positive photosensitive compositions obtained in each of the Examples and Comparative Examples were spin-coated onto a 4-inch silicon wafer using a spin coater ("1H-360S" manufactured by Mikasa Co., Ltd.) while adjusting the rotation speed so that the film thickness of the final cured product (hereinafter referred to as "cured film") would be 2.0 μm, to obtain a coating film. The substrate was then heated at 90°C for 3 minutes using a hot plate ("SCW-636" manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film. The produced film was then exposed to 500 mJ / cm using PLA ("PLA-501F" manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source through a grayscale mask for sensitivity measurement. ２After exposure at an exposure dose of 1000 kJ / cm, the film was paddle-developed for 60 seconds with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide using an automatic developing apparatus ("AD-1200" manufactured by Takizawa Sangyo Co., Ltd.) and rinsed with pure water for 30 seconds. The developed film was then heated at 250°C for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven ("INH-9CD-S" manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film. The film thickness was measured using an optical interference film thickness meter ("Lambda Ace STM602" manufactured by Dai Nippon Screen Mfg. Co., Ltd.), and the value obtained by rounding off the first decimal place of the average value of three points on the surface was used as the film thickness.

[0141] The remaining film ratio of the unexposed area after development was calculated according to the following formula: Unexposed area remaining film ratio (%) = Unexposed area film thickness after development ÷ Film thickness after pre-baking × 100 The remaining film ratio of the unexposed area was evaluated according to the following six levels, with AA and A to C being considered acceptable. AA: Unexposed area remaining film ratio is 95% or more. A: Unexposed area remaining film ratio is 90% or more but less than 95%. B: Unexposed area remaining film ratio is 85% or more but less than 90%. C: Unexposed area remaining film ratio is 80% or more but less than 85%. D: Unexposed area remaining film ratio is less than 80%. -: Unexposed area remaining film ratio cannot be calculated.

[0142] The resulting cured film was observed using an optical microscope to check for the degree of residue generation. The area of ​​residue present in the opening was measured at an exposure dose of 300 mJ / cm. ２ For a 20 μm line and space pattern exposed in a semi-transparent area, the area of ​​the openings was calculated from the area of ​​the openings (St) and the area occupied by the residue present in the openings (Sc) according to Sc / St × 100 (%). This was calculated for 10 randomly selected line and space patterns, and the number average value was rounded to one decimal place to determine the area of ​​residue present in the openings. Evaluation was made on a five-point scale based on the following criteria, with A to C being considered acceptable. A: No residue was observed in the openings. B: Residue was observed in the openings, and its presence area was less than 5%. C: The area of ​​residue present in the openings was 5% or more but less than 20%. D: The area of ​​residue present in the openings was 20% or more. -: A pattern could not be formed.

[0143] The cross-sectional shape of the pattern on the obtained cured film was observed using a field emission scanning electron microscope (S-4800; manufactured by Hitachi High-Technologies Corporation). ２ The cross section of the 20 μm line and space pattern exposed in the semi-transparent area was observed, and the taper angle of the cross section was measured.

[0144] (Measurement of Minimum Required Exposure Dose) A silver alloy film (an alloy consisting of 99.00 mass % silver and 1.00 mass % copper) was formed on the entire surface of an alkali-free glass substrate measuring 150 mm in length and 150 mm in width by a sputtering method. An ITO (indium-tin oxide) film was then formed on the entire surface by a sputtering method, thereby obtaining a glass substrate having a silver alloy film / ITO film on the entire surface of the alkali-free glass substrate.

[0145] The positive photosensitive compositions obtained in each Example and Comparative Example were applied to the ITO surface of a glass substrate having a silver alloy film / ITO film using a spin coater, adjusting the rotation speed so that the final pixel division layer would have a film thickness of 1.5 μm and the maximum film thickness of the portion where the pixel division layer and spacer layer were laminated would be 3.0 μm, to obtain a coating film. The coating film was then prebaked at 90°C for 3 minutes under atmospheric pressure using a hot plate to obtain a prebaked film. Next, using a double-sided alignment single-sided exposure device, the positive halftone exposure mask (a mask with an arrangement of 100 fully transparent portions, each 100 μm long and 100 μm wide, designed so that when the exposure amount in the fully transparent portions is 100% and the exposure amount in the shielding portions is 0%) was applied at 30 to 200 (mJ / cm) . ２ : i-line standard) within the range of 10 mJ / cm ２ The prebaked film was pattern-exposed to a mixture of g, h, and i rays from an ultra-high pressure mercury lamp, with the exposure dose being varied stepwise within the surface of the prebaked film for each exposure, to obtain an exposed film having exposed, semi-exposed, and unexposed areas within its surface. The pattern exposure was carried out by contacting a positive half-tone exposure mask with the surface of the prebaked film.

[0146] Next, in the development step, development was carried out by puddle method using an automatic developing apparatus ("AD-1200" manufactured by Takizawa Sangyo Co., Ltd.) and a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as an alkaline developer. The development time was set to the time until the film loss was in the range of 0.4 to 0.7 μm. The film loss here refers to the value obtained by subtracting the film thickness of the unexposed portion of the developed film from the film thickness of the prebaked film. Furthermore, after rinsing with pure water for 30 seconds by shower method, the substrate was dried by idling at 200 rpm for 30 seconds to obtain a developed film-formed substrate having a developed film.

[0147] Next, in the curing step, the developed film was heated in a high-temperature inert gas oven at 250° C. for 1 hour in a nitrogen atmosphere to obtain a substrate for measuring the minimum required exposure dose on which a patterned cured film was formed.

[0148] The patterned cured film was observed using an FPD inspection microscope (Olympus Corporation, "MX-61L"), and the exposure dose when the exposed film was collectively formed so that the average opening width of 10 openings in the portion corresponding to the half-exposed portion in the exposed film was within the range of 100±1 μm, the film thickness of the pixel dividing layer was 1.5 μm, and the maximum film thickness of the portion where the pixel dividing layer and the spacer layer were stacked was 3.0 μm was determined as the minimum required exposure dose (mJ / cm). ２ : i-ray standard).

[0149] (Long-term reliability evaluation of organic EL display device) Next, a planarizing layer, a pixel dividing layer, and a spacer layer each made of a cured film of a positive-type photosensitive composition were formed by the following method, and an organic EL display device having these layers was fabricated. The fabrication process for an organic EL display device, including the steps of forming the planarizing layer, the pixel dividing layer, and the spacer layer, is shown in Figure 2.

[0150] The positive-type photosensitive compositions obtained in each Example and Comparative Example were applied to the surface of a 100 mm long x 100 mm wide alkali-free glass substrate (12 in Figure 2) using a spin coater, adjusting the rotation speed so that the thickness of the planarizing layer obtained after the curing process would be 2.0 μm, to obtain a coating film. The coating film was then prebaked at 90°C under atmospheric pressure for 3 minutes using a hot plate to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the prebaked film was pattern-exposed using a positive exposure mask at the minimum required exposure dose measured by the above method to obtain an exposed film. This film was then UV-exposed through a photomask, developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and the unnecessary portions were dissolved, followed by rinsing with pure water. The resulting developed film was heated in a high-temperature inert gas oven at 250°C for 1 hour under a nitrogen atmosphere to obtain a planarizing layer-formed substrate with a 30 mm long x 30 mm wide planarizing layer (13 in Figure 2) formed in the center of the substrate. A silver alloy film (an alloy consisting of 99% by mass of silver and 1% by mass of copper) was formed over the entire surface by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was immersed in a silver alloy etching solution SEA-1 at a solution temperature of 30°C and etched to obtain a patterned silver alloy film with a thickness of 50 nm. Furthermore, an ITO film was formed over the entire surface by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was immersed in a 5% by mass aqueous oxalic acid solution at a solution temperature of 50°C for 5 minutes, shower-washed with deionized water for 2 minutes, dried with an air blower, and the resist was peeled off to obtain a patterned ITO film with a thickness of 10 nm. Through the above steps, a first electrode-forming substrate was obtained in which a first electrode (14 in FIG. 2 ) consisting of a laminated pattern of a silver alloy film / ITO film was formed on the surface of the alkali-free glass substrate.

[0151] The positive photosensitive composition was applied to the entire surface of the first electrode-forming substrate using a spin coater, adjusting the rotation speed so that the thickness of the pixel division layer obtained after the curing process was 1.5 μm and the total thickness of the pixel division layer and spacer layer was 3.0 μm, to obtain a coating film. The coating film was then prebaked at 90°C for 3 minutes at atmospheric pressure using a hot plate to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the prebaked film was pattern-exposed to the minimum required exposure dose determined by the above method through a positive halftone exposure mask (a mask with an arrangement of 100 fully transparent square portions, each 100 μm long and 100 μm wide, designed so that when the exposure dose in the fully transparent portions is 100% and the exposure dose in the shielding portions is 0%), to obtain an exposed film. The pattern exposure was performed by contacting the positive halftone exposure mask with the surface of the prebaked film. Next, using the same method as in the evaluation of the minimum required exposure dose, the developed film was developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide to dissolve unnecessary portions, and then rinsed with pure water. The resulting developed film was heated at 250°C for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven to obtain a pixel division layer / spacer layer-forming substrate having 100 openings arranged in an area of ​​30 mm length x 30 mm width at the center of the first electrode-forming substrate, a pixel division layer with a film thickness of 1.5 µm, and a spacer layer (15 in Figure 2) with a film thickness of 1.5 µm on a part of the surface of the pixel division layer.

[0152] Next, an organic EL layer (16 in FIG. 2) including a light-emitting layer is formed in the opening of the pixel dividing layer by vacuum deposition. －３ The pixel dividing layer / spacer layer-forming substrate was rotated relative to the evaporation source under evaporation conditions of 0.1 Pa or less, and first, compound (HT-1) was evaporated to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was evaporated to a thickness of 50 nm as a hole transport layer.

[0153] Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm, followed by deposition of compound (ET-1) as an electron transport material and compound (LiQ) at a volume ratio of 1:1 to a thickness of 40 nm.

[0154]

[0155] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor deposition of a silver / magnesium alloy (volume ratio 10:1) to a thickness of 150 nm to form a second electrode (17 in Figure 2). Next, under a low-humidity / nitrogen atmosphere, a cap-shaped glass plate was sealed by bonding it using an epoxy resin adhesive. A circular polarizer (CP42HE CIRCULAR POLARIZER manufactured by Edmund Optics) was then attached to the light-emitting surface side to obtain an organic EL display device. Since each layer constituting the organic EL layer is very thin and a stylus-type film thickness measurement device cannot achieve high measurement accuracy, each layer was measured using a quartz crystal oscillator film thickness monitor, which is suitable for thin films of less than 100 nm, and the film thickness was determined by rounding the average value of three points within the surface to the nearest tenth.

[0156] The fabricated organic EL display device was placed on a hot plate with the light-emitting surface facing up and the surface temperature maintained at 85°C, and was driven by a direct current (10 mA / cm ２ The light-emitting surface of the organic EL display device was kept in a luminous state, and the light was emitted from a xenon lamp as a light source, which was used as simulated sunlight containing near-ultraviolet rays, at a wavelength of 420 nm and an illuminance of 3.0 W / cm. ２The organic EL display device was continuously irradiated with light of 1000 ohms. 1,500 hours after the start of irradiation, the circular polarizer was removed and the pixel emission area ratio (%) of the organic EL display device was evaluated. The "emission surface" here refers to the surface on the light extraction side of the region where the light-emitting pixels are arranged. The pixel emission area ratio of the organic EL display device was calculated by measuring the pixel emission area ratio (%) for each pixel at 20 light-emitting pixel sections located in the center of the emission surface, enlarging the display at 100x magnification on a monitor, and rounding the average value to the nearest whole number. The smaller the area of ​​non-emitting portions in the light-emitting pixel sections and the higher the pixel emission area ratio maintained, the better the organic EL display device. Evaluation was based on the following criteria, with AA and A to C being deemed acceptable. AA: The pixel emission area ratio of the organic EL display device was 95% or more. A: The pixel emission area ratio of the organic EL display device was 90% or more but less than 95%. B: The pixel emission area ratio of the organic EL display device was 85% or more but less than 90%. C: The pixel light-emitting area ratio of the organic EL display device is 80% or more and less than 85%. D: The pixel light-emitting area ratio of the organic EL display device is less than 80%. -: The pixel light-emitting area ratio of the organic EL display device cannot be calculated.

[0157] (Bending Resistance Evaluation) The positive photosensitive compositions obtained in each Example and Comparative Example were applied to a 20 μm-thick polyimide film substrate by spin coating at an arbitrary rotation speed, and the substrate was prebaked for 3 minutes on a hot plate at 90°C as a drying step to obtain a prebaked film. Next, using an automatic developing apparatus ("AD-1200" manufactured by Takizawa Sangyo Co., Ltd.), the substrate was paddle-developed for 30 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then rinsed with pure water for 30 seconds. After development, the substrate with the film was heated in a high-temperature inert gas oven under a nitrogen atmosphere at 250°C for 1 hour to obtain a cured film with a thickness of 4.0 μm.

[0158] Next, 10 polyimide film substrates with a cured film were cut into pieces measuring 50 mm long x 10 mm wide. Next, with the cured film facing outward, the polyimide film substrate was folded along a 25 mm vertical line with a radius of curvature ranging from 0.05 to 1.00 mm and held in this state for 30 seconds. After 30 seconds, the folded polyimide film substrate was unfolded, and the bent portion of the cured film surface along the 25 mm vertical line was observed using an FPD inspection microscope to evaluate changes in the appearance of the cured film surface. The bending test was performed with a radius of curvature ranging from 0.05 to 1.00 mm, and the minimum radius of curvature at which no changes in appearance, such as peeling of the cured film from the polyimide film substrate or cracks on the cured film surface, were recorded. The minimum radius of curvature was evaluated on a 5-point scale, with AA and A to C being considered acceptable. AA: The minimum radius of curvature was less than 0.10 mm. A: The minimum curvature radius is 0.10 mm or more and less than 0.20 mm. B: The minimum curvature radius is 0.20 mm or more and less than 0.40 mm. C: The minimum curvature radius is 0.40 mm or more and less than 0.60 mm. D: The minimum curvature radius is 0.60 mm or more. -: Cannot be evaluated.

[0159] Materials Used in Examples and Comparative Examples Synthesis Example 1 Synthesis of Copolymer (A-1) In a 500 ml three-neck flask, 10.69 g (0.060 mol) of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Resonac Corporation), 15.14 g (0.120 mol) of cyclohexyl vinyl ether ("CHVE" manufactured by Nippon Carbide Industries Co., Ltd.), 3.44 g (0.040 mol) of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.88 g (0.040 mol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-hydroxybutyl acrylate glycidyl ether ( 12.01 g (0.060 mol) of (3,4-epoxycyclohexyl)methyl methacrylate ("4HBAGE" manufactured by Shinryo Corporation) and 15.70 g (0.080 mol) of (3,4-epoxycyclohexyl)methyl methacrylate ("Cyclomer M100" manufactured by Daicel Corporation), and 1.80 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator ("V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were completely dissolved in 89.81 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). After placing the flask under a nitrogen atmosphere, the flask was immersed in a 70 °C oil bath and reacted for 5 hours to obtain a resin solution. The obtained resin solution was diluted with PGMEA and adjusted to a solids content of 35.00 mass%, to obtain a copolymer (A-1) solution. The weight average molecular weight of copolymer (A-1) was 28,000.

[0160] Synthesis Example 2 Synthesis of Copolymer (A-2) Polymerization was carried out in the same manner as in Synthesis Example 1, except that methyl acrylate (0.040 mol) was changed to cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), (3,4-epoxycyclohexyl)methyl methacrylate (0.080 mol) was changed to glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.080 mol), and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-2) solution.

[0161] Synthesis Example 3 Synthesis of Copolymer (A-3) Polymerization was carried out in the same manner as in Synthesis Example 1, except that acrylic acid (0.040 mol) was changed to methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), methyl acrylate (0.040 mol) was changed to methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-3) solution.

[0162] Synthesis Example 4 Synthesis of Copolymer (A-4) Polymerization was carried out in the same manner as in Synthesis Example 1, except that 4-hydroxybutyl acrylate glycidyl ether (0.060 mol) was changed to 4-hydroxybutyl acrylate ("4HBA" manufactured by Shinryo Corporation) (0.060 mol) and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-4) solution.

[0163] Synthesis Example 5 Synthesis of Copolymer (A-5) Polymerization was carried out in the same manner as in Synthesis Example 4, except that (3,4-epoxycyclohexyl)methyl methacrylate (0.080 mol) was changed to cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.080 mol) and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-5) solution.

[0164] Synthesis Example 6 Synthesis of Copolymer (A-6) Polymerization was carried out in the same manner as in Synthesis Example 1, except that 4-hydroxybutyl acrylate glycidyl ether (0.060 mol) was changed to glycidyl methacrylate (0.060 mol) and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-6) solution.

[0165] Synthesis Example 7 Synthesis of Copolymer (A-7) Polymerization was carried out in the same manner as in Synthesis Example 5, except that 4-hydroxybutyl acrylate was not used and the blending amounts of methyl acrylate, the polymerization initiator, and PGMEA were changed as shown in Table 1, to obtain a copolymer (A-7) solution.

[0166] Synthesis Example 8 Synthesis of Copolymer (A-8) Polymerization was carried out in the same manner as in Synthesis Example 1, except that methyl acrylate was changed to a compound represented by formula (11) (manufactured by Otsuka Chemical Co., Ltd.) as the ultraviolet absorber, and the amounts of each monomer, polymerization initiator, and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-8) solution.

[0167]

[0168] Synthesis Example 9 Synthesis of Copolymer (A-9) Polymerization was carried out in the same manner as in Synthesis Example 4, except that the blending amounts of the polymerization initiator and PGMEA were changed as shown in Table 1, to obtain a copolymer (A-9) solution.

[0169] Synthesis Example 10 Synthesis of Copolymer (A-10) Polymerization was carried out in the same manner as in Synthesis Example 1, except that 4-hydroxyphenyl methacrylate was changed to 4-isopropenylphenol (manufactured by Mitsui Chemicals, Inc.), methyl acrylate was changed to cyclohexyl acrylate, and the amounts of each monomer, polymerization initiator, and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-10) solution.

[0170] Synthesis Example 11 Synthesis of Copolymer (A-11) Polymerization was carried out in the same manner as in Synthesis Example 10, except that cyclohexyl vinyl ether (0.060 mol) was changed to n-butyl vinyl ether ("NBVE" manufactured by Nippon Carbide Industries Co., Ltd.) (0.060 mol) and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-11) solution.

[0171] Synthesis Example 12 Synthesis of Copolymer (A-12) Polymerization was carried out in the same manner as in Synthesis Example 10, except that cyclohexyl vinyl ether (0.060 mol) was changed to 1,4-cyclohexanedimethanol monovinyl ether ("CHMVE" manufactured by Nippon Carbide Industries Co., Ltd.) (0.060 mol) and the amounts of the polymerization initiator and PGMEA added were changed as shown in Table 1, to obtain a copolymer (A-12) solution.

[0172] Synthesis Example 13 Synthesis of Copolymer (A-13) Polymerization was carried out in the same manner as in Synthesis Example 10, except that (3,4-epoxycyclohexyl)methyl methacrylate was not used and the amounts of each monomer, polymerization initiator, and PGMEA were changed as shown in Table 1, to obtain a copolymer (A-13) solution.

[0173] Synthesis Example 14 Synthesis of Copolymer (a-1) Polymerization was carried out in the same manner as in Synthesis Example 2, except that 4-hydroxyphenyl methacrylate and cyclohexyl acrylate were not used, and the amounts of each monomer, polymerization initiator, and PGMEA were changed as shown in Table 1, to obtain a copolymer (a-1) solution.

[0174] Synthesis Example 15 Synthesis of Copolymer (a-2) Polymerization was carried out in the same manner as in Synthesis Example 10, except that acrylic acid, cyclohexyl acrylate, and cyclohexyl vinyl ether were changed to methacrylic acid, methyl methacrylate, and glycidyl methacrylate, respectively, and the amounts of each monomer, polymerization initiator, and PGMEA added were changed as shown in Table 1, to obtain a copolymer (a-2) solution.

[0175] The weight average molecular weight (Mw) of each copolymer is shown in Table 1.

[0176] Copolymer (A-1) (Synthesis Example 1) to copolymer (A-13) (Synthesis Example 13) are copolymer (A) of the present invention, and are copolymers of the present invention.

[0177] (Synthesis Example 14) Copolymer (a-1) is the copolymer (A) of the present invention, but does not fall under the copolymer of the present invention.

[0178] (Synthesis Example 15) Copolymer (a-2) is not the copolymer (A) of the present invention, and does not fall under the copolymer of the present invention.

[0179]

[0180]

[0181] [(B) Quinonediazide Compound] (Synthesis Example 16) Synthesis of Quinonediazide Compound (B-1) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (B-1) having the following structure.

[0182]

[0183] [(D) Thermal Crosslinking Agent] (D-1) "Ethanacol" (registered trademark) OXBP (manufactured by Ube Industries, Ltd.) [Adhesion improver] 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403 (trade name)", hereinafter "KBM-403") [Antioxidant] Hindered phenol-based antioxidant "Irganox" (registered trademark) 1010 (manufactured by BASF Japan Ltd., hereinafter "Irganox 1010") [Surfactant] Polyacrylate-based surfactant BYK-352 (manufactured by BYK Japan KK) [Particles] Zirconia nanoparticles ZR-010 (manufactured by Solar Co., Ltd., hereinafter "ZR-010") (Example 1) Under yellow light, 14.26 g of the copolymer (A-1) solution, 0.59 g of the quinone diazide compound (B-1), 0.29 g of the thermal crosslinker (D-1), 0.06 g of Irganox 1010 as an antioxidant, 0.06 g of KBM-403 as an adhesion promoter, and 0.09 g of BYK-352 as a surfactant were added to 14.65 g of a mixed solvent (a mixed solvent of PGMEA and diethylene glycol ethyl methyl ether) and stirred to prepare a positive-tone photosensitive composition. The blending amounts of each raw material are shown in Table 2. The obtained positive-tone photosensitive composition was used to evaluate the unexposed portion remaining film ratio, residue, pattern cross-sectional shape, long-term reliability, and bending resistance of the organic EL display device, as described above, and the results are shown in Table 2.

[0184] (Examples 2 to 13) Positive photosensitive compositions were prepared and evaluated in the same manner as in Example 1, except that the copolymer (A-1) solution was changed to (A-2) to (A-13), respectively. The evaluation results are shown in Table 2.

[0185] (Examples 14 to 17) Positive photosensitive compositions were prepared and evaluated in the same manner as in Example 2, except that the blending amount of (B) the quinone diazide compound was changed as shown in Table 2. The evaluation results are shown in Table 2.

[0186] Example 18 Under yellow light, 10.91 g of copolymer (A-2) solution, 0.59 g of quinone diazide compound (B-1), 0.29 g of thermal crosslinker (D-1), 0.06 g of Irganox 1010 as an antioxidant, 0.06 g of KBM-403 as an adhesion promoter, 0.09 g of a 10% by weight solids PGMEA solution of BYK-352 as a surfactant, and 3.92 g of a 30% by weight solids methyl ethyl ketone solution of zirconia nanoparticles ZR-010 as particles were added to 14.09 g of a mixed solvent (a mixed solvent of PGMEA and diethylene glycol ethyl methyl ether), and the mixture was stirred to prepare a positive photosensitive composition, which was then evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0187] Comparative Example 1 A positive photosensitive composition was prepared and evaluated in the same manner as in Example 1, except that the copolymer (A-1) solution was changed to (a-1). Because the film immediately and completely dissolved during development, it was not possible to evaluate the unexposed portion remaining film ratio, residue, pattern cross-sectional shape, long-term reliability, and bending resistance of the organic EL display device. The evaluation results are shown in Table 2.

[0188] Comparative Example 2 A positive photosensitive composition was prepared and evaluated in the same manner as in Example 1, except that the copolymer (A-1) solution was changed to (a-2). The evaluation results are shown in Table 2.

[0189] (Comparative Example 3) A positive photosensitive composition was prepared and evaluated in the same manner as in Example 2, except that (B) quinone diazide compound was not used. Evaluations of the unexposed area remaining film ratio, residue, pattern cross-sectional shape, and bending resistance were not possible because the film was completely dissolved during development. In evaluation of the long-term reliability of the organic EL display device, the exposed area was not dissolved, making it impossible to obtain a pattern, and therefore the pixel luminescence area ratio could not be calculated. The evaluation results are shown in Table 2.

[0190]

[0191]

[0192] 1: TFT 2: Wiring 3: TFT insulating layer 4: Planarization layer 5: First electrode 6: Substrate 7: Contact hole 8: Pixel dividing layer 9: Spacer layer 10: Light-emitting pixel 11: Second electrode 12: Alkali-free glass substrate 13: Planarization layer 14: First electrode 15: Pixel dividing layer and spacer layer 16: Organic EL layer 17: Second electrode

Claims

1. A positive-type photosensitive composition comprising (A) a copolymer having a structural unit represented by formula (1) and a structural unit represented by formula (2) and having a phenolic hydroxyl group in its structure (hereinafter referred to as "(A) copolymer"), (B) a quinone diazide compound, and (C) a solvent, wherein the content of the structural unit represented by formula (1) contained in the (A) copolymer is 1 to 50 mol % relative to 100 mol % of all structural units contained in the (A) copolymer. (In formula (1), R １ is an organic group having 1 to 20 carbon atoms. ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. In formula (1) and formula (2) where multiple R １ and R ２ may be the same or different.) 2. R in the formula (1) １ 2. The positive photosensitive composition according to claim 1, wherein is an organic group having 5 to 20 carbon atoms and containing an alicyclic structure.

3. R ​​in the formula (2) ２ 2. The positive photosensitive composition according to claim 1, wherein is an alkyl group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, an alicyclic alkyl group having 5 to 15 carbon atoms, or a hydrogen atom.

4. R in the formula (2) ２ The positive photosensitive composition according to claim 1 , wherein is a group represented by formula (3): (In formula (3), R ３ is an alkylene group having 1 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ is a group containing a hydroxy group, a carboxy group, a cyclic ether group, or an alicyclic structure having 5 to 15 carbon atoms, and R ３ and R ４ The total number of carbon atoms is 20 or less.) 5. R in the formula (3) ３ is an alkylene group having 4 to 12 carbon atoms which may contain an ester bond or an ether bond, and R ４ is a cyclic ether group, is 1 to 50 mol % relative to 100 mol % of all structural units contained in the copolymer (A).

6. R in the formula (1) １ The positive photosensitive composition according to claim 1 , wherein is a group represented by formula (4): (In formula (4), R ５ and R ６ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ７ represents an alkyl group having 1 to 5 carbon atoms. a and b represent integers of 0 to 5. In formula (4) where multiple R ５ ~R ７ may be the same or different.) 7. The positive photosensitive composition according to claim 1, wherein the copolymer (A) has a structural unit containing a cyclic ether group.

8. The positive photosensitive composition according to claim 1, wherein the copolymer (A) has a structural unit represented by formula (5), and the structural unit represented by formula (5) contained in the copolymer (A) accounts for 1 to 40 mol % relative to 100 mol % of all structural units contained in the copolymer (A). (In formula (5), R ８ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. ８ may be the same or different.) 9. The positive photosensitive composition according to claim 1, wherein the weight average molecular weight of the copolymer (A) is 5,000 or more and 100,000 or less.

10. A copolymer (referred to as "copolymer (A)") having a structural unit represented by formula (1) and a structural unit represented by formula (2) and having a phenolic hydroxyl group in the structure, wherein the content of the structural unit represented by formula (1) contained in copolymer (A) is 1 to 50 mol % relative to 100 mol % of all structural units contained in copolymer (A). (In formula (1), R １ is an organic group having 1 to 20 carbon atoms. ２ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. In formula (1) and formula (2) where multiple R １ and R ２ may be the same or different.) 11. R in the formula (1) １ The copolymer according to claim 10 , wherein is a group represented by formula (4): (In formula (4), R ５ and R ６ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ７ represents an alkyl group having 1 to 5 carbon atoms. a and b represent integers of 0 to 5. In formula (4) where multiple R ５ ~R ７ may be the same or different.) 12. A cured product obtained by curing the positive photosensitive composition according to any one of claims 1 to 9.

13. An electronic component comprising the cured product according to claim 12.

14. A display device comprising the cured product according to claim 12.

15. An information terminal having the display device according to claim 14.

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