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

Abstract

This invention provides a positive photosensitive composition with high weather resistance, high flexural strength, and high long-term reliability when the cured product is used in an organic EL display device. The positive photosensitive composition of this invention comprises: (A) a copolymer having structural units represented by formula (1) and formula (2), and having phenolic hydroxyl groups in the structure (referred to as "(A) copolymer"), (B) a quinone diazide compound, and (C) a solvent, wherein the content of the structural units represented by formula (1) in the copolymer (A) is 1 to 50 mol% relative to 100 mol% of all structural units contained in the copolymer (A). (In formula (1), R...) 1 It is an organic group with 1 to 20 carbon atoms. In formula (2), R 2 It is an organic group having 1 to 20 hydrogen or carbon atoms. In multiple formulas (1) and (2), R... 1 and R 2 They can be the same or different.

Description

Technical Field

[0001] This invention relates to positive photosensitive compositions, copolymers, cured products, electronic components, display devices, and information terminals. Background Technology

[0002] Organic electroluminescent (EL) displays are gaining attention as the next generation of flat panel displays in fields such as smartphones, tablets, and televisions. Compared to traditional liquid crystal displays, EL displays offer wider viewing angles and higher contrast ratios, and can also be made thinner and more flexible, thus warranting active research and development.

[0003] In the case of organic EL display devices, in addition to a planarization layer that serves as a base insulating layer that flattens the bumps caused by wiring formed on the substrate, there is also a pixel separation layer that serves as an insulating layer that separates each light-emitting pixel, such as red, blue, and green. These two layers are usually formed by photolithography.

[0004] It is known that the pixel segmentation layer and planarization layer significantly affect the long-term reliability of organic EL display devices. As materials for forming the planarization layer and pixel segmentation layer, compositions with positive or negative photosensitivity can be cited. For example, Patent Document 1 discloses a photosensitive composition containing polyimide resin, a polyimide precursor, a polybenzoxazole precursor, or a polysiloxane resin. Furthermore, it is disclosed that by setting the anhydride groups in the pixel segmentation layer formed using these materials to a specific range, pixel shrinkage is less likely to occur, and the pixel luminous area ratio can be highly maintained, thereby obtaining 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 structurally have bendable portions and / or portions fixed in a bent state, where bending stress is applied to the planarization layer and pixel segmentation layer. In flexible organic EL display devices including such bent portions, high bending resistance is required for the materials used in the planarization layer and pixel segmentation layer. Therefore, there is a strong desire to develop photosensitive compositions that can be patterned with high sensitivity and produce curing films with high bending resistance.

[0006] As materials for these planarization layers and pixel segmentation layers, photosensitive compositions containing resins composed of repeating units derived from vinyl-based monofunctional monomers have been investigated with the aim of developing economically viable organic EL display devices. Generally, vinyl-based monofunctional monomers are low in cost and can be polymerized easily in low-cost organic solvents; therefore, resins composed of repeating units derived from vinyl-based monofunctional monomers are economically advantageous. Furthermore, in cases where defects such as misalignment between the substrate and the exposure mask occur during manufacturing, the film can be easily removed by dissolving it in solvents or alkaline developers before the curing process, allowing for the reuse of the substrate after electrode formation, which is economically beneficial. Therefore, positive photosensitivity is of interest.

[0007] As a composition containing a resin composed of repeating units derived from vinyl-based monofunctional monomers and possessing positive photosensitivity, for example, Patent Document 2 discloses a positive photosensitivity composition for forming an interlayer insulating film of a liquid crystal display. Patent Document 2 discloses a positive photosensitivity composition containing a methacrylate copolymer as a resin having repeating units comprising a benzotriazole backbone and a phenolic backbone.

[0008] Existing technical documents Patent documents Patent Document 1: International Publication No. 2016 / 143740 Patent Document 2: Japanese Patent Application Publication No. 2023-23224 Summary of the Invention

[0009] The problem that the invention aims to solve However, regarding the technology of Patent Document 2, although a positive photosensitive composition containing a methacrylate copolymer having repeating units comprising a benzotriazole backbone and a phenol backbone as a resin is disclosed, the following issues have been identified: the flexural strength of the cured film of the aforementioned photosensitive composition and the long-term reliability when the cured film is used in an organic EL display device are insufficient. The present invention was made in view of such deficiencies of the prior art, and its object is to provide a positive photosensitive composition with high weather resistance, high flexural strength, and high long-term reliability when the cured material is used in an organic EL display device.

[0010] Methods for solving problems The present invention adopts the following structure.

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

[0012] [Chemical Formula 1] (In equation (1), R) 1 It is an organic group with 1 to 20 carbon atoms. In formula (2), R 2 It is an organic group with 1 to 20 hydrogen or carbon atoms. In multiple formulas (1) and (2), R... 1 and R 2 They can be the same or different. [2] The positive photosensitive composition as described in [1] above, wherein R in formula (1) 1 It is an organic group containing 5 to 20 carbon atoms in an alicyclic structure.

[0013] [3] The positive photosensitive composition as described in [1] or [2] above, wherein R in formula (2) 2 It may be an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 15 carbon atoms, or a hydrogen atom, which may contain ester or ether bonds.

[0014] [4] The positive photosensitive composition as described in any one of [1] to [3] above, wherein R in formula (2) 2 The group represented by formula (3) is a group.

[0015] [Chemical Formula 2] (In equation (3), R) 3 R is an alkylene group having 1 to 12 carbon atoms, which may contain ester or ether bonds. 4 It is a hydroxyl, carboxyl, cyclic ether, or a group containing an alicyclic structure with 5 to 15 carbon atoms, R 3 and R 4 (The total number of carbon atoms is less than 20.) [5] The positive photosensitive composition as described in [4] above, wherein, relative to 100 mol% of all structural units contained in copolymer (A), R in formula (3) 3 It is an alkylene group with 4 to 12 carbon atoms that may contain ester or ether bonds and R 4The content of the structural unit represented by formula (2) which is a cyclic ether group is 1 to 50 mol.

[0016] [6] The positive photosensitive composition as described in any one of [1] to [5] above, wherein R in formula (1) 1 The group represented by formula (4) is a group.

[0017] [Chemical Formula 3] (In equation (4), R) 5 and R 6 R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 7 R represents an alkyl group with 1 to 5 carbon atoms. a and b represent integers from 0 to 5. In multiple forms of formula (4), R... 5 ~R 7 They can be the same or different. [7] The positive photosensitive composition as described in any one of [1] to [6] above, wherein the (A) copolymer has a structural unit comprising a cyclic ether group.

[0018] [8] The positive photosensitive composition as described in any one of [1] to [7] above, wherein the (A) copolymer has a structural unit represented by formula (5), and the structural unit represented by formula (5) contained in the (A) copolymer is 1 to 40 mol% relative to 100 mol% of all structural units contained in the (A) copolymer.

[0019] [Chemical Formula 4] (In equation (5), R) 8 It is an organic group with 1 to 20 hydrogen or carbon atoms. In formula (5), R exists in multiple forms. 8 They can be the same or different. [9] The positive photosensitive composition as described in any one of [1] to [8] above, wherein the weight-average molecular weight of the (A) copolymer is 5,000 or more and 100,000 or less.

[0020]

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

[0021] [Chemical Formula 5] (In equation (1), R) 1 It is an organic group with 1 to 20 carbon atoms. In formula (2), R 2 It is an organic group with 1 to 20 hydrogen or carbon atoms. In multiple formulas (1) and (2), R... 1 and R 2 They can be the same or different.

[11] The copolymer as described in

[10] above, wherein R in formula (1) 1 The group represented by formula (4) is a group.

[0022] [Chemical Formula 6] (In equation (4), R) 5 and R 6 R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 7 R represents an alkyl group with 1 to 5 carbon atoms. a and b represent integers from 0 to 5. In multiple forms of formula (4), R... 5 ~R 7 They can be the same or different.

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

[0023]

[13] An electronic component having the solidified material described in

[12] above.

[0024]

[14] A display device having the solidified material described in

[12] above.

[0025]

[15] An information terminal having the display device described in

[14] above.

[0026] Invention Effects According to the present invention, a positive photosensitive composition with high weather resistance, high flexural strength, and high long-term reliability when the cured product is used in an organic EL display device can be obtained. Attached Figure Description

[0027] [ Figure 1 [This is a cross-sectional view of a TFT substrate in an organic EL display device, which is a specific example of an embodiment of the present invention.]

[0028] [ Figure 2 [This refers to the manufacturing process of an organic EL display device, including the formation process of a pixel segmentation layer, in all evaluable embodiments and comparative examples.] Detailed Implementation

[0029] The following describes in detail the methods for implementing the present invention. However, the present invention is not limited to the following embodiments and can be implemented with various modifications depending on the purpose and application. The numerical range indicated by "~" refers to the range of values ​​recorded before and after "~" as the lower limit and upper limit.

[0030] (Positive photosensitive composition) The positive photosensitive composition according to the embodiments of the present invention contains (A) a copolymer, (B) a quinone diazide compound, and (C) a solvent.

[0031] [(A) copolymer] The (A) copolymer used in the positive photosensitive composition of the present invention, the (A) copolymer used in the present invention is a copolymer having structural units represented by formula (1) and structural units represented by formula (2), and having phenolic hydroxyl groups in the structure.

[0032] [Chemical Formula 7] In equation (1), R 1 It is an organic group with 1 to 20 carbon atoms. In formula (2), R 2 It is an organic group with 1 to 20 hydrogen or carbon atoms. In multiple formulas (1) and (2), R... 1 and R 2 They can be the same or different.

[0033] In R 1 and R 2 In this context, an organic group with 1 to 20 carbon atoms refers to a group having 1 to 20 carbon atoms that may contain heteroatoms such as oxygen, sulfur, and nitrogen atoms. Examples include alkyl groups with straight-chain, branched, or cyclic structures that may have substituents, aryl groups that may have substituents, heteroaryl groups that may have substituents, aralkyl groups that may have substituents, and heteroarylalkyl groups that may have substituents.

[0034] Examples of substituents include hydroxyl, alkoxy, carboxyl, amino, and epoxy groups.

[0035] In equation (1), R 1 Preferably, the organic group comprises an alicyclic structure with 5 to 20 carbon atoms. By having an alicyclic structure, it is possible to suppress the reduction in film thickness of unexposed areas caused by development, and to suppress the absorption of UV light, which is a cause of long-term reliability degradation when the cured material is used in an organic EL display device.

[0036] Furthermore, considering the need to further improve the long-term reliability of using cured materials in organic EL display devices, R in equation (1) 1More preferably, it is a group represented by formula (4).

[0037] [Chemical Formula 8] In equation (4), R 5 and R 6 R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 7 This indicates an alkyl group with 1 to 5 carbon atoms. a and b represent integers from 0 to 5. It should be noted that in R... 6 R 7 When there are more than two, these R 6 R 7 Each can be the same or different. In multiple equations (4), R... 5 ~R 7 They can be the same or different.

[0038] Specific examples of monomers representing structural units as expressed in 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-cyclohexanediethanol monovinyl ether, triethylene glycol monovinyl ether, tricyclodecane vinyl ether, etc. It should be noted that these vinyl ethers can be used alone or in combination of two or more.

[0039] Among these vinyl ethers, vinyl ethers with an alicyclic structure are preferred from the perspective of suppressing the reduction in film thickness of unexposed areas caused by development and improving 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-cyclohexanediethanol monovinyl ether, and tricyclodecane vinyl ether. Among these, 1,4-cyclohexanediethanol monovinyl ether is further preferred from the perspective of further improving the solubility of the coated film in alkaline developing solution and its adhesion to the substrate, and from the perspective of improving the heat resistance, weather resistance, bending resistance, and long-term reliability of the thermocured film by crosslinking with (A) copolymer or other additives via hydrogen bonding, etc. On the other hand, cyclohexyl vinyl ether is preferred from the viewpoint of maintaining the solubility of the exposed areas in alkaline developing solution and suppressing the reduction in film thickness of unexposed areas.

[0040] The content of the structural unit represented by formula (1) in copolymer (A) is 1 to 50 mol% relative to 100 mol% of all structural units contained in copolymer (A). By making the content of the structural unit represented by formula (1) 1 mol% or more, the weather resistance, bending resistance, and long-term reliability of the cured product when used in organic EL display devices can be improved. The content of the structural unit represented by formula (1) is more preferably 5 mol% or more relative to 100 mol% of all structural units contained in copolymer (A), and even more preferably 10 mol% or more. On the other hand, by making the content of the structural unit represented by formula (1) 50 mol% or less, the copolymerization 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 relative to 100 mol% of all structural units contained in copolymer (A), and even more preferably 35 mol% or less.

[0041] Preferably, R in equation (2) is preferred. 2 It is a structural unit that may contain alkyl groups with 1 to 12 carbon atoms, alicyclic alkyl groups with 5 to 15 carbon atoms, or hydrogen atoms, which may contain ester or ether bonds.

[0042] R 2 The structural unit with hydrogen atoms is derived from acrylic acid, and is obtained by containing R in copolymer (A). 2 The structural units are hydrogen atoms, which improves solubility in alkaline developing solutions. R is relative to 100 mol% of all structural units contained in copolymer (A). 2 The total content of the structural units consisting of hydrogen atoms and the structural units derived from methacrylic acid (described later) is preferably 1 to 30 mol%, more preferably 5 to 20 mol%.

[0043] Regarding R 2 The structural unit is derived from acrylate, and may contain alkyl groups of 1 to 12 carbon atoms or alicyclic alkyl groups of 5 to 15 carbon atoms, which may include ester or ether bonds. From the perspective of suppressing film thickness reduction in unexposed areas due to development and improving long-term reliability when using the cured material in organic EL display devices, it is preferable to have R... 2 It is a structural unit of alicyclic alkyl groups with 5 to 15 carbon atoms.

[0044] In equation (2), R is preferred. 2 The group represented by formula (3) is a group.

[0045] [Chemical Formula 9] In equation (3), R 3R is an alkylene group having 1 to 12 carbon atoms, which may contain ester or ether bonds. 4 It is a hydroxyl, carboxyl, cyclic ether, or a group containing an alicyclic structure with 5 to 15 carbon atoms, R 3 and R 4 The total number of carbon atoms is less than 20.

[0046] In R 4 Among them, specific examples of groups containing alicyclic structures with 5 to 15 carbon atoms include cyclohexyl, epoxycyclohexyl, hydroxymethylcyclohexyl, isobornyl, dicyclopentyl, adamantyl, etc.

[0047] In equation (2), through R 2 The group represented by formula (3) can improve the bending resistance of the cured product.

[0048] More preferably, R in the aforementioned formula (3) is relative to 100 mol% of all structural units contained in copolymer (A). 3 It is an alkylene group with 4 to 12 carbon atoms that may contain ester or ether bonds and R 4 The content of the cyclic ether group structural unit is 1 to 50 mol%. By making the aforementioned structural unit 1 mol% or more, the flexural strength of the cured product can be further improved. In addition, by making the aforementioned structural unit 50 mol% or less, the reduction in long-term reliability when using the cured product in an organic EL display device can be suppressed. The content of the aforementioned structural unit is more preferably 5 to 40 mol% relative to 100 mol% of all structural units contained in copolymer (A).

[0049] Specific examples of monomers representing structural units as defined in formula (2) include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-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, 2-(2-ethoxyethoxy)ethyl acrylate, 2-ethylhexyl-diethylene glycol acrylate, methoxydipropylene glycol acrylate, 1-methylcyclopentyl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, isobornyl acrylate, dicyclopentyl acrylate, adamantane-1-yl acrylate, 2-methyladamantane-2-yl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene. 4-Hydroxybutyl acrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, methyl (3,4-epoxycyclohexyl) acrylate, ethyl (3,4-epoxycyclohexyl) acrylate, methyl (3-methyloxetane-3-yl) acrylate, methyl (3-ethyloxetane-3-yl) acrylate, tetrahydrofurfuryl acrylate, 1,4-cyclohexanediol monoacrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalic acid Dimethyl methacrylate, 1-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-phthalic acid, α-acryloyloxy-γ-butyrolactone, β-hydroxy-γ-butyrolactone acrylate, etc. It should be noted that these monomers can be used alone or in combination of two or more.

[0050] (A) The copolymer has phenolic hydroxyl groups in its structure. Here, "in its structure" refers to the copolymer (A). The phenolic hydroxyl groups may be included in formula (1) and / or formula (2), or they may be included in other structural units. By having phenolic hydroxyl groups in the copolymer (A), the solubility of the coated film in alkaline developing solution and its adhesion to the substrate can be improved.

[0051] As structural units containing phenolic hydroxyl groups, examples include structural units represented by formulas (6) and (7).

[0052] [Chemical Formula 10] In equation (6), R 9 R represents a hydrogen atom or a methyl group. 10R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 11 This indicates an alkyl group with 1 to 5 carbon atoms. Additionally, c represents an integer from 0 to 4, and d represents an integer from 1 to 5. It should be noted that in R... 11 When there are more than two, these R 11 They can be the same or different.

[0053] In equation (7), R 12 R represents a hydrogen atom or a methyl group. 13 This indicates an alkyl group with 1 to 5 carbon atoms. Additionally, 'e' represents an integer from 0 to 4, and 'f' represents an integer from 1 to 5. It should be noted that in R... 13 When there are more than two, these R 13 They can be the same or different.

[0054] Specific examples of monomers representing structural units represented by formula (6) include 4-hydroxyphenyl methacrylate, methyl methacrylate (4-hydroxyphenyl) methacrylate, ethyl methacrylate (4-hydroxyphenyl) methacrylate, propyl methacrylate (4-hydroxyphenyl) methacrylate, etc.

[0055] Specific examples of monomers representing structural units 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, 4-isopropenylphenol, etc.

[0056] It should be noted that these monomers can be used individually or in combination of two or more.

[0057] In the copolymerization method described later, from the viewpoint of reducing the residual monomers after copolymerization, the structural unit containing phenolic hydroxyl groups is preferably the structural unit represented by formula (6). On the other hand, from the viewpoint of suppressing heat generation during copolymerization, the structural unit containing phenolic hydroxyl groups is preferably the structural unit represented by formula (7).

[0058] The content of structural units containing phenolic hydroxyl groups is preferably 1 to 40 mol% relative to 100 mol% of all structural units contained in copolymer (A), and more preferably 5 to 30 mol%.

[0059] (A) The copolymer preferably has structural units containing cyclic ether groups. The cyclic ether groups may be included in formula (1) and / or formula (2), or in other structural units. By having cyclic ether groups in the (A) copolymer, a robust film is formed by crosslinking with the (A) copolymer or other additives, which can suppress gas escape, a cause of long-term reliability degradation when the cured product is used in an organic EL display device. Furthermore, the heat resistance and chemical resistance of the cured product can be further improved.

[0060] As a cyclic ether group, from the perspective of improving crosslinking, epoxy group and oxetyl group are preferred, and epoxy group is more preferred.

[0061] The content of structural units containing cyclic ether groups is preferably 1 to 60 mol% relative to 100 mol% of all structural units contained in copolymer (A), and more preferably 10 to 50 mol%.

[0062] (A) The copolymer preferably has the structural unit represented by formula (5).

[0063] [Chemical Formula 11] In equation (5), R 8 It is an organic group having 1 to 20 hydrogen or carbon atoms. In formula (5) where multiple groups exist, R 8 They can be the same or different.

[0064] (A) The copolymer, by having the structural unit represented by formula (5), can moderately suppress the reduction of film thickness in the unexposed portion caused by development.

[0065] R 8 The structural unit with hydrogen atoms is derived from methacrylic acid, and is obtained by containing R in copolymer (A). 8 The structural unit is composed of hydrogen atoms, which improves solubility in alkaline developing solutions. R is relative to 100 mol% of all structural units contained in copolymer (A). 8 The total content of the structural units consisting of hydrogen atoms and the aforementioned structural units derived from acrylic acid is preferably 1 to 30 mol%, more preferably 5 to 20 mol%.

[0066] In R 8 In this context, an organic group with 1 to 20 carbon atoms refers to a group having 1 to 20 carbon atoms that may contain heteroatoms such as oxygen, sulfur, and nitrogen atoms. Examples include alkyl groups with straight-chain, branched, or cyclic structures that may have substituents, aryl groups that may have substituents, heteroaryl groups that may have substituents, aralkyl groups that may have substituents, and heteroarylalkyl groups that may have substituents.

[0067] Examples of substituents include hydroxyl, alkoxy, carboxyl, amino, and epoxy groups.

[0068] In equation (5), R is preferred. 8 The group represented by formula (8) is a group.

[0069] [Chemical Formula 12] In equation (8), R 14 R is an alkylene group having 1 to 12 carbon atoms, which may contain ester or ether bonds. 15 It is a hydroxyl, carboxyl, cyclic ether, or a group containing an alicyclic structure with 5 to 15 carbon atoms, R 14 and R 15 The total number of carbon atoms is less than 20.

[0070] In R 15 Specific examples of groups containing alicyclic structures with 5 to 15 carbon atoms are the same as those mentioned above for R. 4 The same applies to specific examples of groups containing alicyclic structures with 5 to 15 carbon atoms. R 15 Preferably, it is epoxy-based, oxocyclobutane-based, or epoxycyclohexyl-based. From the perspective of improving the long-term reliability and flexural strength when the cured product is used in an organic EL display device, epoxycyclohexyl-based is preferred.

[0071] Specific examples of monomers representing structural units as defined in formula (5) include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, and 2-methoxyethyl methacrylate. 3-Methoxypropyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-ethylhexyl-diethylene glycol methacrylate, methoxydipropylene glycol methacrylate, 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, adamantane-1-yl methacrylate, 2-methyladamantane-2-yl methacrylate, 2-hydroxyethyl methacrylate, methylpropionic acid 2-Hydroxypropyl methacrylate, 4-Hydroxybutyl methacrylate, glycidyl methacrylate, 4-Hydroxybutyl methacrylate glycidyl ether, methyl methacrylate (3,4-epoxycyclohexyl), ethyl methacrylate (3,4-epoxycyclohexyl), methyl methacrylate (3-methyloxetane-3-yl), methyl methacrylate (3-ethyloxetane-3-yl), tetrahydrofurfuryl methacrylate, 1,4-cyclohexanediethanol monomethacrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxy Ethyl hexahydrophthalic acid, 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-phthalic acid, α-methacryloyloxy-γ-butyrolactone, β-hydroxy-γ-butyrolactone methacrylate, etc. It should be noted that these monomers can be used alone or in combination of two or more.

[0072] The structural unit represented by formula (5) in copolymer (A) is preferably 1 to 40 mol% relative to 100 mol% of all structural units contained in copolymer (A). By making the structural unit represented by formula (5) 1 mol% or more, the reduction in film thickness of unexposed areas caused by development can be moderately controlled, resulting in a good pattern. In addition, by making the structural unit represented by formula (5) 40 mol% or less, the generation of residues during development can be suppressed, and the escape gas caused by depolymerization, which is a cause of long-term reliability reduction when the cured material is used in an organic EL display device, can be suppressed. 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 copolymer (A).

[0073] Regarding copolymer (A), any monomers can be further copolymerized as needed. Specifically, examples 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 itaconic acid, monoethyl itaconic acid, dimethyl itaconic acid, and citronellol. Acids, dimethyl citrate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, N-(2-hydroxyethyl)maleimide, N-tert-butylmaleimide, 2-maleiminoacetic acid, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.

[0074] As a method for synthesizing copolymer (A), known methods such as free radical polymerization, living free radical polymerization, and living anionic polymerization can be applied. From an economic point of view, free radical polymerization is preferred.

[0075] As a free radical polymerization method, for example, the following method can be used: a monomer of structural unit represented by formula (1), a monomer of structural unit represented by formula (2), and a monomer having a phenolic hydroxyl group (in this case, the monomer having a phenolic hydroxyl group can be represented by formula (1) or formula (2)) are dissolved in an organic solvent, and stirred for 1 to 50 hours under a nitrogen atmosphere / liquid temperature of 50 to 120°C in the presence of a thermal free radical polymerization initiator until the desired weight-average molecular weight (Mw) is reached. The reaction is then stopped by cooling, and the product is obtained in the form of a resin solution. In terms of heating temperature and heating time, it is preferable to set them with reference to the 10-hour half-life temperature of the thermal free radical polymerization initiator used.

[0076] Examples of azo-based thermal free radical polymerization initiators include AIBN, AIBN-HP, V-65, V-65HP, VR-110, V-40, azobisisobutyronitrile, and V-601 as dimethyl 2,2'-azobis(isobutyrate) (all manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.). The amount of thermal free radical polymerization initiator added is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the monomers. Low-cost solvents such as isopropanol, diacetone alcohol, ethylene glycol monotert-butyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, and ethyl lactate can be used as organic solvents.

[0077] Depending on the requirements, chain transfer agents such as tert-dodecyl mercaptan and α-methylstyrene dimer can also be used as molecular weight distribution modifiers.

[0078] In this invention, the weight-average molecular weight refers to the value converted to polystyrene by gel permeation chromatography (GPC). From the viewpoint of coatability, the weight-average molecular weight of copolymer (A) is preferably 1,000 or more, more preferably 5,000 or more. From the viewpoint of curability of the coating film, it is further preferably 10,000 or more. On the other hand, as an upper limit, from the viewpoint of coatability, it is preferably 300,000 or less, more preferably 100,000 or less. From the viewpoint of improving solubility in alkaline developing solutions and suppressing the formation of residues, it is further preferably 50,000 or less.

[0079] [(B) Quinone diazide compound] The positive photosensitive composition of the present invention contains (B) a quinone diazide compound. Examples of quinone diazide compounds include compounds obtained by ester bonding of quinone diazide sulfonic acid to a polyhydroxy compound, compounds obtained by sulfonamide bonding of quinone diazide sulfonic acid to a polyamino compound, and compounds obtained by ester bonding and / or sulfonamide bonding of quinone diazide sulfonic acid to a polyhydroxy-polyamino compound. Preferably, at least 50 mol% of all functional groups in these polyhydroxy-polyamino compounds are replaced by quinone diazide sulfonic acid.

[0080] As a quinone diazide structure, either naphthoquinone diazide-5-sulfonyl or naphthoquinone diazide-4-sulfonyl is preferred. The compound may contain naphthoquinone diazide sulfonate compounds having both naphthoquinone diazide-4-sulfonyl and naphthoquinone diazide-5-sulfonyl groups in the same molecule, or it may contain both naphthoquinone diazide-4-sulfonate and naphthoquinone diazide-5-sulfonate compounds. The naphthoquinone diazide-4-sulfonate compound exhibits absorption in the i-line region of a mercury lamp, making it suitable for i-line exposure. The absorption of the naphthoquinone diazide-5-sulfonate compound extends to the g-line region of a mercury lamp, making it suitable for g-line exposure.

[0081] The naphthoquinone diazide-4-sulfonate compound and naphthoquinone diazide-5-sulfonate compound are preferably selected according to the exposure wavelength. From the viewpoint of increasing sensitivity, it is preferable to include naphthoquinone diazide-4-sulfonate compound. On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention described later is used as a planarization layer and / or pixel segmentation layer for an organic EL display device, it is preferable to include naphthoquinone diazide-5-sulfonate compound.

[0082] The aforementioned quinone diazide compounds can be synthesized from compounds with phenolic hydroxyl groups and quinone diazide sulfonic acid compounds through any esterification reaction. Using these quinone diazide compounds further improves resolution, sensitivity, and film retention.

[0083] In this invention, regarding the content of the (B)quinone diazide compound, from the viewpoint of maximizing sensitivity, it 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 of the solid components in 100 parts by mass of the positive photosensitive composition excluding the solvent. Here, "solid components" refers to the components in the positive photosensitive composition excluding the solvent. Furthermore, as an upper limit, it 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. By having the content of the (B)quinone diazide compound at or above the lower limit, it is easier to form a dissolution contrast between the exposed and unexposed areas. On the other hand, by having the content of the (B)quinone diazide compound at or below the upper limit, compatibility with the (A) copolymer can be improved, and whitening of the coating film, precipitation during solvent removal, and coloring caused by the decomposition of the (B)quinone diazide compound during thermal curing can be suppressed. In addition, long-term reliability can be improved by reducing the gas escape caused by the decomposition of (B) quinone diazide compounds when the cured material is made into the planarization layer and / or pixel segmentation layer of the organic EL display device.

[0084] [(C) Solvent] Examples of 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-tert-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, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monoethyl ... Ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene 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; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethyl lactate; 2 ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Acrylates, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, and N,N-dimethylisobutylamide; and 3-methyl-2-oxazolidinone, etc. It may contain two or more of these.

[0085] The solvent content is not particularly limited, but it is preferably 100 to 3000 parts by mass relative to 100 parts by mass of the solid component of the positive photosensitive composition excluding the solvent, and more preferably 150 to 2000 parts by mass. Furthermore, the proportion of solvents with a boiling point of 180°C or higher in the total solvent volume is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By setting the proportion of solvents with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of gas released after thermosetting can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0086] [(D) Thermal crosslinking agent] The positive photosensitive composition of the present invention may further contain a (D) thermal crosslinking agent. The (D) thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups such as alkoxymethyl, hydroxymethyl, epoxy, or oxetyl. By containing a (D) thermal crosslinking agent and crosslinking it with the (A) copolymer or other additives, the heat resistance, chemical resistance, and flexural strength of the thermocured film can be improved.

[0087] Preferred examples of compounds having at least two alkoxymethyl or hydroxymethyl 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, and TML-pp-BPF. TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOMTPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0088] Preferred examples of compounds having at least two epoxy groups include “EPOLIGHT” (registered trademark) 40E, “EPOLIGHT” 100E, “EPOLIGHT” 200E, “EPOLIGHT” 400E, “EPOLIGHT” 70P, “EPOLIGHT” 200P, “EPOLIGHT” 400P, “EPOLIGHT” 1500NP, “EPOLIGHT” 80MF, “EPOLIGHT” 4000, “EPOLIGHT” 3002 (all trade names, manufactured by Kyoei Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” EX-214L, “Denacol” EX-216L, and “Denacol” EX-850L (all trade names, manufactured by Nagase ChemteX). Corporation), GAN, GOT (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), "Epikote" (registered trademark) 828, "Epikote" 1002, "Epikote" 1750, "Epikote" 1007, YX8100-BH30, E1256, E4250, E4275 (the above are trade names, manufactured by JapanEpoxy Resin Co., Ltd.), "EPICLON" (registered trademark) EXA-9583, HP4032 (the above are trade names, manufactured by DIC Co., Ltd.), VG3101 (trade name, manufactured by Mitsui Chemicals Co., Ltd.), "TEPIC" (registered trademark) S, "TEPIC" G, "TEPIC" P (the above are trade names, manufactured by Nissan Chemical Industries, Ltd.), "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 Toto Kasei Co., Ltd.), EPPN502H, NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), "EPICLON" N695, HP7200 (all trade names, manufactured by DIC Co., Ltd.), etc.

[0089] Preferred examples of compounds having at least two oxocyclic butyl groups include, for example, "ETERNACOLL" (registered trademark) EHO, "ETERNACOLL" OXBP, "ETERNACOLL" OXTP, "ETERNACOLL" OXMA (these are trade names, manufactured by Ube Industries, Ltd.), and oxocyclic butanol Novolac.

[0090] (D) Two or more thermal crosslinking agents may be combined.

[0091] Regarding the content of the (D) thermal crosslinking agent, it is preferably 1 part by mass to 30 parts by mass out of 100 parts by mass of the solid components of the positive photosensitive composition excluding the solvent. If the content of the (D) thermal crosslinking agent is 1 part by mass or more, the chemical resistance and flexural strength of the cured product can be further improved. In addition, if the content of the (D) thermal crosslinking agent is 30 parts by mass or less, the amount of gas escaping 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 photosensitive composition is also excellent.

[0092] UV absorber The positive photosensitive composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the resolution of the positive photosensitive composition and the long-term reliability of the cured organic EL display device can be further improved. As an ultraviolet absorber, benzotriazole compounds, benzophenone compounds, and triazine compounds are preferred from the perspectives of transparency and non-coloring properties.

[0093] Examples of benzotriazole compounds include 2-(2H-benzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-tert-amylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole, and RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

[0094] In the case that these ultraviolet absorbers are polymeric compounds with unsaturated double bonds, they can also be mixed as monomers during the synthesis of (A) copolymers to copolymerize them.

[0095] [Sealing Improver] The positive photosensitive composition of the present invention may contain a binding modifier.

[0096] Examples of adhesion modifiers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and other silane coupling agents, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with silicon compounds containing alkoxy groups. Two or more of these may be included. By including adhesion modifiers, adhesion to substrates such as silicon wafers, ITO, SiO2, and silicon nitride can be improved during the development of photosensitive resin films. Furthermore, resistance to oxygen plasma and UV ozone treatments used for cleaning can be improved.

[0097] Regarding the content of the sealing modifier, it is preferably 0.1 to 10 parts by mass or more of the solid components of the positive photosensitive composition excluding the solvent, out of 100 parts by mass.

[0098] [Antioxidants] The positive photosensitive composition of the present invention may further contain antioxidants. By containing antioxidants, yellowing of the pixel segmentation layer and planarization layer can sometimes be prevented, resulting in higher transparency. For example, compounds represented by formula (9) and compounds represented by formula (10) can be cited.

[0099] [Chemical Formula 13] Regarding the content of antioxidants, it is preferably 0.1 to 10 parts by weight or more of the solid components of the positive photosensitive composition excluding the solvent, out of 100 parts by weight.

[0100] [surfactant] The positive photosensitive composition of the present invention may contain a surfactant for the purpose of improving wettability with a substrate or improving the uniformity of resin film thickness as needed.

[0101] Surfactants can be commercially available compounds. Specifically, examples of silicone-based surfactants include Dow Corning Toray Co., Ltd.'s SH, SD, and ST series; BYK-Chemie Japan Co., Ltd.'s BYK series; Shin-Etsu Chemical Co., Ltd.'s KP series; Nippon Oil Co., Ltd.'s Disfoam series; and Momentive Performance Materials Japan LLC.'s TSF series. Examples of fluorinated surfactants include DIC Co., Ltd.'s "Megafac" (registered trademark) series; 3M Japan Co., Ltd.'s Fluorad series; Asahi Glass Co., Ltd.'s "Surflon" (registered trademark) series and "AsahiGuard" (registered trademark) series; Mitsubishi Materials Electronic Chemicals Co., Ltd.'s EF series; and OMNOVA Solutions. Examples of surfactants derived from acrylic and / or methacrylic polymers include the PolyFox series from Kyoeisha Chemical Co., Ltd., and the "DISPARLON" (registered trademark) series from Kusumoto Chemical Co., Ltd.

[0102] Regarding the content of surfactant, it is preferably 0.001 parts by mass or less than 1 part by mass of the solid components of the positive photosensitive composition excluding solvent, out of 100 parts by mass. By setting it within the above range, the wettability with the substrate and the uniformity of the resin film thickness can be improved without generating defects such as bubbles or pinholes.

[0103] [particle] The positive photosensitive composition of the present invention may further contain particles. Due to the robust structure of the introduced particles, a strong film is formed, which can suppress excessive reflow of the pattern during thermosetting and control the pattern shape. Inorganic and organic particles are preferred as particles. Examples of inorganic particles include alumina, silica, magnesium oxide, ferrite, zirconium oxide, titanium oxide, barium titanate, hafnium oxide, talc, etc. Examples of organic particles include (meth)acrylic acid, (meth)acrylic acid derivatives, styrene, vinyl acetate, acrylonitrile, polymers of olefins, copolymers thereof, polyesters, polyamides, latex, polyurethanes, phenolic resins, melamine resins, polyethersulfone resins, silicone resins, cellulose, fluoropolymers, poly(fluoromethyl methacrylate), etc.

[0104] From the perspective of maintaining flexural strength, the particle content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, in 100 parts by mass of the solid component of the positive photosensitive composition excluding the solvent. On the other hand, from the perspective of suppressing excessive reflow, the particle content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, in 100 parts by mass of the solid component of the positive photosensitive composition excluding the solvent.

[0105] (Copolymer) In the copolymer of the present invention, the content of the structural unit represented by formula (1) in copolymer (A) is 1 to 50 mol% relative to 100 mol% of all structural units contained in copolymer (A).

[0106] Regarding copolymer (A), as described above. Relative to 100 mol% of all structural units contained in copolymer (A), the content of the structural unit represented by formula (1) in copolymer (A) is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, it is preferably 40 mol% or less, more preferably 35 mol% or less. From the viewpoint of further improving the long-term reliability of the display device of the present invention, particularly the organic EL display device, equipped with the cured product of the present invention, R in formula (1) 1 More preferably, it is a group represented by formula (4).

[0107] The copolymers of the present invention can be suitably used in the positive photosensitive compositions of the present invention. Furthermore, they can improve the weather resistance and flexural strength of the cured products of the present invention. Moreover, in the case of display devices of the present invention, particularly organic EL display devices, incorporating the cured products of the present invention, long-term reliability can be improved.

[0108] With regard to the copolymers of the present invention, compositions, particularly positive photosensitive compositions, can be prepared by further mixing with (D) thermal crosslinking agents, ultraviolet absorbers, adhesion modifiers, antioxidants, surfactants, particles, photopolymerization initiators, etc.

[0109] (cured material) 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 manufacturing the cured product using the composition according to embodiments of the present invention will be described. This method includes: a step of forming a coating film of the composition; a step of exposing and developing the coating film; and a step of heating the developed film.

[0110] First, the positive photosensitive composition according to the embodiments of the present invention is coated onto a substrate using known methods such as spin coating, dipping, or slit coating, and then pre-baked using a heating device such as a heating plate or oven. The pre-baking is performed at a temperature of 50–150°C for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1–15 μm.

[0111] After pre-baking, UV-Vis exposure equipment such as stepper, mirror projection mask aligner (MPA), and parallel light mask aligner (PLA) is used to expose the mask at 10–4000 J / m through the desired mask. 2 Approximately (based on exposure at a wavelength of 365nm).

[0112] After exposure, the exposed portion is dissolved by development, resulting in a positive pattern. As a development method, immersion in the developing solution for 5 seconds to 10 minutes is preferred, using methods such as spraying, dipping, or rotary immersion. Known alkaline developing solutions can be used as the developing solution. Specific examples include aqueous solutions of one or more of the following: alkali metal hydroxides, carbonates, phosphates, silicates, borates, etc.; amines such as 2-diethylaminoethanol, monoethanolamine, diethanolamine, etc.; and quaternary ammonium salts such as tetramethylammonium hydroxide, choline, etc.

[0113] After development, it is preferable to rinse with water, and then dry and bake in the range of 50 to 150°C.

[0114] Subsequently, bleaching exposure is preferred. Bleaching exposure photodecomposes unreacted quinone diazide compounds remaining in the film, further improving the film's light transparency. As a bleaching exposure method, a UV-Vis exposure machine such as a PLA is used to expose the entire surface at 100–20000 J / m². 2 Approximately (based on exposure at a wavelength of 365nm).

[0115] Then, the film is heated (cured) for about 30 seconds to 10 hours using heating devices such as heating plates and ovens within a temperature range of 100°C to 500°C, preferably 150°C to 400°C, in order to obtain a cured film.

[0116] (Electronic components) The electronic components of the present invention comprise the cured product of the present invention. Specifically, this refers not only to semiconductor devices, semiconductor elements themselves, or devices connected to a substrate, or devices connecting semiconductor elements to each other or substrates to each other, but also to the entirety of a device capable of functioning by utilizing the characteristics of semiconductor elements, including electro-optical devices, semiconductor circuit boards, and electronic components comprising them. The cured product of the present invention is suitable for use in semiconductor electronic components and semiconductor devices having electrodes, metal wiring, interlayer insulating layers, and / or surface protective layers on a substrate, and for interlayer insulating layers and / or surface protective layers in semiconductor devices.

[0117] (Display device) The display device of the present invention includes the cured product of the present invention. Specifically, examples include display devices comprising a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode, such as LCD (liquid crystal display), ECD (electrochromic display), ELD (electroluminescent display), organic EL, and other display devices. Hereinafter, an organic EL display device will be described as an example.

[0118] The cured material of the present invention can be suitably used as a planarization layer and / or pixel segmentation 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 fragile to gaseous components and moisture, and exposure to these conditions can cause a decrease in luminous brightness and pixel shrinkage. Here, pixel shrinkage refers to a decrease in luminous brightness or failure to illuminate from the pixel end. By including the cured material of the present invention as a planarization layer and / or pixel segmentation layer in an organic EL display device, long-term reliability can be improved. In particular, since the pixel segmentation layer is adjacent to the organic light-emitting material, it has a greater impact on long-term reliability than the planarization layer. To obtain an organic EL display device with high long-term reliability, it is preferable to include the cured material of the present invention at least in the pixel segmentation layer.

[0119] The display device of the present invention preferably has at least a portion of the cured portion that is a bendable portion and / or a portion fixed in a bendable state. By using the cured portion from which the positive photosensitive composition of the present invention is cured, an organic EL display device with excellent bend resistance can be obtained. The display device of the present invention can be bent at any suitable portion. For example, the organic EL display device can be bent in the center like a folding display device, and from the viewpoint of maximizing design and display image, it can also be bent at the ends. Furthermore, the organic EL display device can be bent along its long side or along its short side. Depending on the application, it is acceptable as long as a specific portion of the organic EL display device is bendable (e.g., a portion or all of the four corners can be bent diagonally).

[0120] A cross-sectional view of the TFT (Thin-film transistor) substrate in an organic EL display device is shown in the figure. Figure 1 .

[0121] On the surface of substrate 6, bottom-gate or top-gate TFTs 1 are arranged in a matrix, and a TFT insulating layer 3 is formed to cover the TFTs 1 and the wiring 2 connected to the TFTs 1. Examples of TFTs 1 include those formed from oxide semiconductors such as In-Ga-Zn-O (IGZO), Ga-Zn-Sn, and low-temperature polycrystalline silicon (LTPS). Further, a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and contact holes 7 are provided in the planarization layer 4 to open the wiring 2. The contact holes 7 can be, for example, circular openings. On the surface of the planarization layer 4, a first electrode 5 is patterned and connected to the wiring 2. A pixel segmentation layer 8 is disposed on the surface of the first electrode 5 such that a portion of the surface of the first electrode 5 is exposed, and a spacer layer 9 is disposed on a portion of the surface of the pixel segmentation layer 8. The pixel segmentation layer 8 has an opening, and a light-emitting pixel 10 containing organic EL light-emitting material is formed in the opening. A second electrode 11 is disposed to cover the pixel segmentation layer 8, the spacer layer 9, and the light-emitting pixel 10. The shape of the opening in the pixel segmentation layer 8 is not particularly limited; it can be square, rectangular, circular, or elliptical.

[0122] The size and shape of the light-emitting pixel 10 are determined by the size and shape of the opening in the pixel segmentation layer 8. The area of ​​each light-emitting pixel is, for example, 50–30,000 μm. 2 .

[0123] If a voltage is applied to the light-emitting pixel section after the TFT substrate formed from the above stacked structure is sealed under vacuum, it can be driven in the form of an organic EL display device, and light emitted from the light-emitting pixel section can be obtained.

[0124] The display device of the present invention can be a bottom-emitting organic EL display device in which the light emitted from the light-emitting pixel 10 is extracted through the substrate 6 to the substrate side, or it can be a top-emitting organic EL display device in which the light is extracted through the second electrode 11 to the opposite side of the substrate 6, without particular limitation. In order to suppress external light reflection and improve visual recognition, 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, 40-60%.

[0125] Examples of substrates 6 include glass substrates such as OA-10G, OA-11 (trade names, manufactured by Nippon Electric Glass Co., Ltd.), and AN-100 (trade name, manufactured by Asahi Glass Co., Ltd.).

[0126] (Information Terminal) The information terminal of the present invention is an information terminal having the display device of the present invention, such as an electronic device used as a display, for example, personal computers, smartphones, tablets, smartwatches, smart glasses, smart home appliances, etc.

[0127] Example The present invention will be further illustrated by the following embodiments, but the present invention is not limited to these embodiments.

[0128] (Determination of weight-average molecular weight) The weight-average molecular weight (Mw) was determined using the following method. The weight-average molecular weight of the polymer was calculated using GPC (Waters 996 detector, development solvent: tetrahydrofuran) via polystyrene conversion.

[0129] (Evaluation of residual film rate, residue and pattern cross-sectional shape in the unexposed area) The rotation speed was adjusted so that the thickness of the final cured film (hereinafter referred to as the cured film) was 2.0 μm. The positive photosensitive compositions obtained in each example and comparative example were spin-coated onto a 4-inch silicon wafer using a spin coater (Mikasa Co., Ltd. "1H-360S") to obtain a coating. Further, a pre-baked film was prepared by heating the substrate at 90°C for 3 minutes using a heating plate (Dainippon Screen Mfg. Co., Ltd. "SCW-636"). The prepared film was then subjected to a laser beam test using a PLA (Canon Co., Ltd. "PLA-501F") with an ultra-high pressure mercury lamp as the light source, through a grayscale mask used for sensitivity measurement, at a speed of 500 mJ / cm². 2 After exposure to the specified exposure level, the film was subjected to a 60-second immersion development using a 2.38 wt% tetramethylammonium hydroxide aqueous solution in an automatic developing apparatus (TAKI Sangyo Co., Ltd. "AD-1200"), followed by a 30-second rinse with pure water. Next, the developed film was heated at 250°C under a nitrogen atmosphere for 1 hour in a high-temperature inert gas oven (Koyo Thermo Systems Co., Ltd. "INH-9CD-S") to obtain a cured film. It should be noted that the film thickness was measured using an optical interferometer (Dainippon ScreenMfg. Co., Ltd. "Lambda Ace STM-602"), and the average value at three points within the plane was rounded to the nearest decimal place as the film thickness.

[0130] The residual film percentage of the unexposed portion after development is calculated using the following formula.

[0131] Unexposed film residual rate (%) = Unexposed film thickness after development ÷ Film thickness after pre-baking × 100 Regarding the residual film rate of the unexposed area, it was evaluated in the following 6 stages, with AA and A to C being set as qualified.

[0132] AA: The residual film rate in the unexposed section is over 95%.

[0133] A: The residual film rate of the unexposed section is above 90% and less than 95%.

[0134] B: The residual film rate of the unexposed section is above 85% and less than 90%.

[0135] C: The residual film rate of the unexposed area is above 80% and less than 85%.

[0136] D: The residual film rate in the unexposed area is less than 80%.

[0137] -: Unable to calculate the residual film rate of the unexposed portion.

[0138] The degree of residue formation was observed using an optical microscope on the obtained cured film. Regarding the area of ​​residue presence in the openings, for an exposure dose of 300 mJ / cm²... 2 A 20μm line and spacing pattern was exposed in the semi-transparent portion. The area of ​​the opening (St) and the area occupied by the residue in the opening (Sc) were calculated using Sc / St×100 (%). This value was calculated for 10 randomly selected line and spacing patterns, and the average of these values ​​was rounded to the first decimal place as the area of ​​residue in the opening. The pattern was evaluated in 5 stages according to the following criteria, with A to C being considered acceptable.

[0139] A: No residue was observed in the opening.

[0140] B: Residue was observed in the opening, and its area was less than 5%.

[0141] C: The area of ​​residue in the opening is more than 5% and less than 20%.

[0142] D: The area of ​​residue in the opening is more than 20%.

[0143] -: Unable to form a pattern.

[0144] The cross-sectional shape of the pattern on the cured film was observed using a field emission scanning electron microscope (S-4800; manufactured by Hitachi High-Technologies Corporation). The cross-sectional shape was observed at an exposure dose of 300 mJ / cm². 2 The cross-section of the 20μm line and spacing pattern in the semi-transparent part was observed, and the cone angle of the cross-section was measured.

[0145] (Determination of the minimum required exposure) On the surface of an alkali-free glass substrate with a length of 150 mm and a width of 150 mm, a silver alloy (an alloy formed of 99.00% by mass silver and 1.00% by mass copper) is deposited over the entire surface by sputtering. Further, an ITO (indium tin oxide) film is deposited over the entire surface by sputtering, resulting in a glass substrate with a silver alloy film / ITO film covering the entire surface of the alkali-free glass substrate.

[0146] The rotation speed was adjusted so that the final thickness of the pixel segmentation layer was 1.5 μm and the maximum thickness of the layer after the pixel segmentation layer and the spacer layer were stacked was 3.0 μm. The positive photosensitive compositions obtained in each embodiment and comparative example were coated onto the ITO surface of a glass substrate containing a silver alloy film / ITO film using a spin coater to obtain a coating. Further, the coating was pre-baked at 90°C for 3 minutes under atmospheric pressure using a heating plate to obtain a pre-baked film. Next, using a double-sided aligned single-sided exposure apparatus, and with a positive halftone exposure mask (designed as follows: 100 square, 100-square, 100-square-width, fully transparent portions arranged in a 100 μm x 100 μm square, with the exposure in the fully transparent portions set to 100%, the exposure in the masked portions set to 0%, and the exposure in the semi-transparent portions set to 30%), the exposure was maintained at 30–200 mJ / cm². 2 Within the range of the i-line reference, at every 10 mJ / cm 2 The exposure amount is changed in stages within the plane of the pre-baked film. Pattern exposure is performed on the pre-baked film using a mixed g, h, i line of an ultra-high pressure mercury lamp, resulting in an exposed film with exposed, half-exposed, and unexposed areas within the plane. It should be noted that pattern exposure is performed by bringing a positive halftone exposure mask into contact with the surface of the pre-baked film.

[0147] Next, as a developing process, an automatic developing apparatus (Takizawa Sangyo Co., Ltd. "AD-1200") and a 2.38% by mass tetramethylammonium hydroxide aqueous solution as an alkaline developing solution were used for development by immersion spinning. It should be noted that the developing time was set to a time within the range of 0.4 to 0.7 μm for film loss. 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 pre-baked film. Further, after rinsing with pure water by spraying for 30 seconds, the substrate was idled at 200 rpm for 30 seconds to dry it, resulting in a developed film substrate with the developed film.

[0148] Next, as a curing process, the developing film is heated for 1 hour in a nitrogen atmosphere at 250°C using a high-temperature inert gas oven to obtain a substrate for measuring the minimum exposure required to form a patterned cured film.

[0149] The patterned cured film was observed using an FPD inspection microscope (Olympus Corporation "MX-61L"). In each exposure region, the minimum necessary exposure (mJ / cm²) was determined by the following conditions: the average opening width of the 10 openings corresponding to the half-exposed portions of the aforementioned exposed film was within the range of 100 ± 1 μm; the thickness of the pixel segmentation layer was 1.5 μm; and the maximum thickness of the portion after the pixel segmentation layer and the spacer layer were stacked was 3.0 μm. 2 (i-line reference).

[0150] (Long-term reliability evaluation of organic EL display devices) Next, a planarization layer, a pixel segmentation layer, and a spacer layer formed from a cured film of a positive-type photosensitive composition are formed using the following method, and an organic EL display device having these layers is further fabricated. The fabrication process of an organic EL display device including the formation steps of the planarization layer, pixel segmentation layer, and spacer layer is shown below. Figure 2 .

[0151] An alkali-free glass substrate with a length of 100mm and a width of 100mm ( Figure 2 On the surface of the substrate (12), a spin coater was used to coat the positive photosensitive compositions obtained in each example and comparative example with a spin coater at a speed adjusted so that the thickness of the planarization layer obtained after the curing process was 2.0 μm, thus obtaining a coating film. Further, the coating film was pre-baked at 90°C for 3 minutes under atmospheric pressure using a heating plate to obtain a pre-baked film. Using a double-sided alignment single-sided exposure apparatus, the pre-baked film was pattern-exposed through a positive exposure mask at the minimum necessary exposure amount determined by the aforementioned method to obtain an exposed film. Next, the film was UV-exposed through a photomask, developed with a 2.38% (w / w) tetramethylammonium hydroxide aqueous solution to dissolve unwanted portions, and rinsed with pure water. The developed film was heated in a high-temperature inert gas oven at 250°C under a nitrogen atmosphere for 1 hour to obtain a planarization layer with a vertical length of 30 mm and a horizontal width of 30 mm formed in the center of the substrate. Figure 2A planarization layer (13) is formed on the substrate. A silver alloy (an alloy of 99% by mass silver and 1% by mass copper) is sputtered to form a patterned film. Using an alkali-soluble Novolac-based positive resist, the film is immersed in a silver alloy etching solution SEA-1 at 30°C to obtain a patterned silver alloy film with a thickness of 50 nm. Further, an ITO film is sputtered to form a patterned film. Using an alkali-soluble Novolac-based positive resist, the film is immersed in a 5% by mass oxalic acid aqueous solution at 50°C for 5 minutes, rinsed with deionized water for 2 minutes, dried with a forced-air fan, and the resist is peeled off to obtain a patterned ITO film with a thickness of 10 nm. Through the above processes, a first electrode (forming a stacked pattern of silver alloy film / ITO film) is obtained on the surface of an alkali-free glass substrate. Figure 2 The first electrode (14) forms the substrate.

[0152] Using a spin coater, the rotation speed was adjusted so that the thickness of the pixel segmentation layer obtained after the curing process was 1.5 μm, and the total thickness of the pixel segmentation layer and the spacer layer was 3.0 μm. The positive photosensitive composition was coated onto the entire surface of the first electrode forming substrate to obtain a coating. Further, using a heating plate, the coating was pre-baked at 90°C for 3 minutes under atmospheric pressure to obtain a pre-baked film. Using a double-sided aligned single-sided exposure apparatus, the pre-baked film was patterned and exposed through a positive halftone exposure mask (designed as follows: 100 square, 100 μm square, transverse and longitudinal sections, with 100% exposure in the fully transparent sections, 0% exposure in the masked sections, and 30% exposure in the semi-transparent sections). The necessary minimum exposure amount determined by the aforementioned method was used to obtain an exposed film. It should be noted that the patterning exposure was performed by bringing the positive halftone exposure mask into contact with the surface of the pre-baked film. Next, using the same method as when evaluating the necessary minimum exposure, development was performed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution to dissolve the unwanted portions, followed by rinsing with pure water. The developed film was heated in a high-temperature inert gas oven at 250°C for 1 hour under a nitrogen atmosphere, resulting in a pixel dividing layer with 100 openings arranged in a 30mm longitudinal / 30mm transverse region in the center of the first electrode forming substrate, and a spacer layer with a thickness of 1.5μm on a portion of the surface of the pixel dividing layer. Figure 2 A pixel segmentation layer / spacer layer is formed on the substrate (15).

[0153] Next, in order to form an organic EL layer containing a light-emitting layer at the opening of the pixel segmentation layer by vacuum evaporation ( Figure 2 The value is 16), and the vacuum degree is 1×10. -3Under evaporation conditions below Pa, the pixel segmentation layer / spacer layer forming substrate is rotated relative to the evaporation source. First, a compound (HT-1) is deposited with a thickness of 10 nm as a hole injection layer, and a compound (HT-2) is deposited with a thickness of 50 nm as a hole transport layer.

[0154] Next, on the light-emitting layer, a compound (GH-1) as the host material and a compound (GD-1) as the dopant material were deposited at a thickness of 40 nm. Then, a compound (ET-1) as the electron transport material and a compound (LiQ) were stacked at a volume ratio of 1:1 at a thickness of 40 nm.

[0155] [Chemical Formula 14] Next, after depositing a 2 nm layer of compound (LiQ), a silver / magnesium alloy (volume ratio 10:1) is deposited to a thickness of 150 nm to form the second electrode. Figure 2 (17). Next, under a low humidity / nitrogen atmosphere, an epoxy resin adhesive was used to bond the cover glass plate for sealing. Then, a circular polarizing plate (Edmund Optics "CP42HECIRCULAR POLARIZER") was further bonded to the light-emitting side to obtain the organic EL display device. It should be noted that the layers constituting the organic EL layer are very thin, and high measurement accuracy cannot be obtained with a stylus-type film thickness measuring device. Therefore, a crystal oscillating film thickness monitor suitable for films smaller than 100 nm was used for individual measurements. The average value at three points within the plane was rounded to the nearest decimal place as the film thickness.

[0156] The fabricated organic EL display device was placed with the emitting side facing upwards on a heating plate with a surface temperature maintained at 85°C, and driven by direct current (10mA / cm²). 2 This causes it to emit light. To maintain the luminous state of the organic EL display device, it is continuously irradiated with an illuminance of 3.0 W / cm² at a wavelength of 420 nm, using a xenon lamp that simulates sunlight and contains near-ultraviolet light. 2The light was applied. 1500 hours after the start of illumination, the circular polarizer was removed, and the pixel luminous area ratio (%) of the organic EL display device was evaluated. Here, the luminous surface refers to the light-extracting side of the area where the luminous pixels are arranged. Regarding the pixel luminous area ratio of the organic EL display device, for the 20 luminous pixel sections located in the center of the luminous surface, the image was magnified 100 times on a monitor, and the pixel luminous area ratio (%) of each pixel was measured. The average value was rounded to the nearest decimal place. The smaller the area of ​​the non-luminous portion within the luminous pixel section, the higher the pixel luminous area ratio can be maintained, and the better the organic EL display device. Evaluation was conducted based on the following criteria, with AA and A to C being considered acceptable.

[0157] AA: The pixel luminous area ratio of organic EL display devices is over 95%.

[0158] A: The pixel luminous area ratio of organic EL display devices is above 90% and less than 95%.

[0159] B: The pixel luminous area ratio of an organic EL display device is 85% or more and less than 90%.

[0160] C: The pixel luminous area ratio of an organic EL display device is 80% or more and less than 85%.

[0161] D: The pixel luminous area ratio of an organic EL display device is less than 80%.

[0162] -: The pixel luminous area ratio of the organic EL display device cannot be calculated.

[0163] (Evaluation of bending resistance) The positive photosensitive compositions obtained in the various examples and comparative examples were spin-coated onto a 20 μm thick polyimide film substrate at an arbitrary rotation speed. As a drying step, the substrate was pre-baked on a heating plate at 90°C for 3 minutes to obtain a pre-baked film. Next, using an automatic developing apparatus (Takizawa Sangyo Co., Ltd. "AD-1200"), the substrate was immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 30 seconds, followed by rinsing with pure water for 30 seconds. The developed substrate with the film was then heated in a high-temperature inert gas oven at 250°C under a nitrogen atmosphere for 1 hour to obtain a cured film with a thickness of 4.0 μm.

[0164] Next, ten sheets of polyimide film substrate with cured film, each 50mm x 10mm in size, were cut. Then, with the cured film side facing outwards, the polyimide film substrate was bent along a 25mm longitudinal line with a radius of curvature ranging from 0.05 to 1.00mm, and held for 30 seconds. After 30 seconds, the bent polyimide film substrate was opened, and the bent portion along the 25mm longitudinal line on the surface of the cured film was observed using an FPD inspection microscope to evaluate the appearance changes on the surface of the cured film. The bending test was conducted within a radius of curvature ranging from 0.05 to 1.00mm, and the minimum radius of curvature at which the cured film peeled off from the polyimide film substrate without causing cracks or other appearance changes on the surface of the cured film was recorded. The minimum radius of curvature was evaluated according to the following five stages, with AA and A through C being considered acceptable.

[0165] AA: Minimum radius of curvature is less than 0.10 mm.

[0166] A: The minimum radius of curvature is greater than 0.10mm and less than 0.20mm.

[0167] B: The minimum radius of curvature is greater than 0.20mm and less than 0.40mm.

[0168] C: The minimum radius of curvature is greater than 0.40 mm and less than 0.60 mm.

[0169] D: Minimum radius of curvature is 0.60 mm or more.

[0170] -: No rating available.

[0171] (Materials used in the examples and comparative examples) (Synthetic Example 1) Synthesis of copolymer (A-1) In a 500 ml three-necked 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, Ltd.), 3.44 g (0.040 mol) of methyl acrylate (Tokyo Chemical Industries, Ltd.), 2.88 g (0.040 mol) of acrylic acid (Tokyo Chemical Industries, Ltd.), 12.01 g (0.060 mol) of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Shin-Mitsubishi Corporation), and methyl methacrylate (3,4-epoxycyclohexyl) (Cyclomer, manufactured by Daicel Corporation) were prepared. 15.70 g (0.080 mol) of "M100" and 1.80 g of 2,2'-azobis(2,4-dimethylpentanonitrile) ("V-65" manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) as polymerization initiator were completely dissolved in 89.81 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). After the inside of the flask was under a nitrogen atmosphere, it was immersed in an oil bath at 70°C and reacted for 5 hours to obtain a resin solution. The obtained resin solution was diluted with PGMEA to adjust the solid content to 35.00% by mass to obtain a copolymer (A-1) solution. The weight average molecular weight of copolymer (A-1) was 28,000.

[0172] (Synthetic Example 2) Synthesis of copolymer (A-2) The methyl acrylate (0.040 mol) was replaced with cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), the methyl methacrylate (3,4-epoxycyclohexyl) (0.080 mol) was replaced with glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.080 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-2) solution.

[0173] (Synthetic Example 3) Synthesis of copolymer (A-3) Acrylic acid (0.040 mol) was replaced with methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), methyl acrylate (0.040 mol) was replaced with methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.040 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-3) solution.

[0174] (Synthetic Example 4) Synthesis of copolymer (A-4) The 4-hydroxybutyl acrylate glycidyl ether (0.060 mol) was replaced with 4-hydroxybutyl acrylate (Shinryo Corporation "4HBA") (0.060 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-4) solution.

[0175] (Synthetic Example 5) Synthesis of copolymer (A-5) The methyl methacrylate (3,4-epoxycyclohexyl) (0.080 mol) was replaced with cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.080 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 4 to obtain a copolymer (A-5) solution.

[0176] (Synthetic Example 6) Synthesis of copolymer (A-6) The 4-hydroxybutyl acrylate glycidyl ether (0.060 mol) was replaced with glycidyl methacrylate (0.060 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-6) solution.

[0177] (Synthetic Example 7) Synthesis of copolymer (A-7) Instead of using 4-hydroxybutyl acrylate, the amounts of methyl acrylate, polymerization initiator, and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 5 to obtain a copolymer (A-7) solution.

[0178] (Synthetic Example 8) Synthesis of copolymer (A-8) Methyl acrylate was replaced with a compound represented by formula (11) (manufactured by Otsuka Chemical Co., Ltd.) which is used as an ultraviolet absorber. The amounts of each monomer, polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-8) solution.

[0179] [Chemical Formula 15] (Synthetic Example 9) Synthesis of copolymer (A-9) The polymerization initiator and the amount of PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 4 to obtain a copolymer (A-9) solution.

[0180] (Synthetic Example 10) Synthesis of copolymer (A-10) 4-hydroxyphenyl methacrylate was replaced with 4-isopropenylphenol (Mitsui Chemicals Co., Ltd.), methyl acrylate was replaced with cyclohexyl acrylate, and the amounts of each monomer, polymerization initiator, and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a copolymer (A-10) solution.

[0181] (Synthetic Example 11) Synthesis of copolymer (A-11) Cyclohexyl vinyl ether (0.060 mol) was replaced with n-butyl vinyl ether ("NBVE" manufactured by Nippon Carbide Industries, Ltd.) (0.060 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 10 to obtain a copolymer (A-11) solution.

[0182] (Synthetic Example 12) Synthesis of copolymer (A-12) Cyclohexyl vinyl ether (0.060 mol) was replaced with 1,4-cyclohexanediethanol monovinyl ether (CHMVE manufactured by Nippon Carbide Industries, Ltd.) (0.060 mol), and the amounts of polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 10 to obtain a copolymer (A-12) solution.

[0183] (Synthetic Example 13) Synthesis of copolymer (A-13) Methyl methacrylate (3,4-epoxycyclohexyl) was not used. The amounts of each monomer, polymerization initiator, and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 10 to obtain a copolymer (A-13) solution.

[0184] (Synthetic Example 14) Synthesis of copolymer (a-1) Without using 4-hydroxyphenyl methacrylate and cyclohexyl acrylate, the amounts of each monomer, polymerization initiator, and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 2 to obtain a copolymer (a-1) solution.

[0185] (Synthetic Example 15) Synthesis of copolymer (a-2) Acrylic acid, cyclohexyl acrylate and cyclohexyl vinyl ether were replaced with methacrylic acid, methyl methacrylate and glycidyl methacrylate, respectively. The amounts of each monomer, polymerization initiator and PGMEA were changed as described in Table 1. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 10 to obtain copolymer (a-2) solution.

[0186] No precipitation occurred; all were homogeneous and transparent solutions. The weight-average molecular weight (Mw) of each copolymer is shown in Table 1.

[0187] (Synthesis Example 1) copolymer (A-1) to (Synthesis Example 13) copolymer (A-13) are (A) copolymers in this invention, and are copolymers of this invention.

[0188] (Synthesis Example 14) Copolymer (a-1) is copolymer (A) of the present invention, but is not a copolymer of the present invention.

[0189] (Synthesis Example 15) Copolymer (a-2) is not copolymer (A) of the present invention, nor is it a copolymer of the present invention.

[0190] [Table 1-1] [Table 1-2] [(B) Quinone diazide compound] (Synthetic Example 16) Synthesis of quinone diazide 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 naphthoquinone diazide-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and allowed to reach room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to the mixture without raising the temperature above 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain a quinone diazide compound (B-1) with the following structure.

[0191] [Chemical Formula 16] [(D) Thermal crosslinking agent] (D-1) "ETERNACOLL" (registered trademark) OXBP (manufactured by Ube Industries, Ltd.) [Sealing Improver] 3-Epoxypropoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBM-403 (trade name)", hereinafter "KBM-403") [Antioxidants] Hindered phenolic antioxidant "Irganox" 1010 (registered trademark, manufactured by BASF Japan Co., Ltd., hereinafter referred to as "Irganox1010") [surfactant] Polyacrylate surfactant BYK-352 (manufactured by BYK-Chemie Japan Co., Ltd.) [particle] Zirconia nanoparticles ZR-010 (manufactured by Solar Co., Ltd., hereinafter referred to as "ZR-010") (Example 1) Under yellow light, a positive photosensitive composition was prepared by adding 14.26 g of copolymer (A-1) solution, 0.59 g of quinone diazide compound (B-1), 0.29 g of thermal crosslinking agent (D-1), 0.06 g of Irganox 1010 as an antioxidant, 0.06 g of KBM-403 as a adhesion modifier, and 0.09 g of BYK-352 as a surfactant to 14.65 g of a mixed solvent (a mixed solvent of PGMEA and diethylene glycol ethyl methyl ether) as a 10% by mass PGMEA solution, and stirring. The proportions of each raw material are shown in Table 2. Using the obtained positive photosensitive composition, the evaluation results of unexposed film residue, residue, pattern cross-sectional shape, long-term reliability of the organic EL display device, and bending resistance are shown in Table 2, as described above.

[0192] (Examples 2-13) The copolymer (A-1) solution was changed to (A-2) to (A-13), and otherwise positive photosensitive compositions were prepared using the same method as in Example 1 and evaluated. The evaluation results are shown in Table 2.

[0193] (Examples 14-17) The amount of (B) quinone diazide compound was varied as described in Table 2. Otherwise, a positive photosensitive composition was prepared using the same method as in Example 2 and evaluated. The evaluation results are shown in Table 2.

[0194] (Example 18) Under yellow light, a positive photosensitive composition was prepared by adding 10.91 g of copolymer (A-2) solution, 0.59 g of quinone diazide compound (B-1), 0.29 g of thermal crosslinking agent (D-1), 0.06 g of Irganox 1010 as an antioxidant, 0.06 g of KBM-403 as a adhesion modifier, 0.09 g of BYK-352 as a surfactant (10% by mass PGMEA solution), and 3.92 g of zirconium oxide nanoparticles ZR-010 (30% by mass methyl ethyl ketone solution) to 14.09 g of a mixed solvent (a mixture of PGMEA and diethylene glycol ethyl methyl ether). The composition was then stirred and evaluated using the same method as in Example 1. The evaluation results are shown in Table 2.

[0195] (Comparative Example 1) The copolymer (A-1) solution was changed to (a-1), but otherwise, a positive photosensitive composition was prepared using the same method as in Example 1 and evaluated. Because the film completely dissolves immediately upon development, it was impossible to evaluate the unexposed film residue rate, residue, pattern cross-sectional shape, long-term reliability of the organic EL display device, and flexural strength. The evaluation results are shown in Table 2.

[0196] (Comparative Example 2) The copolymer (A-1) solution was changed to (a-2), and otherwise, a positive photosensitive composition was prepared using the same method as in Example 1 and evaluated. The evaluation results are shown in Table 2.

[0197] (Comparative Example 3) Without using (B)quinone diazide compounds, a positive photosensitive composition was prepared using the same method as in Example 2 and evaluated. Evaluations of unexposed area residual film rate, residue, pattern cross-sectional shape, and flexural strength were not possible because the film completely dissolved during development. In the evaluation of the long-term reliability of the organic EL display device, the pixel luminous area ratio could not be calculated because the exposed area did not dissolve and a pattern could not be obtained. The evaluation results are shown in Table 2.

[0198] [Table 2-1] [Table 2-2] Explanation of reference numerals in the attached figures 1: TFT 2: Wiring 3: TFT insulating layer 4: Planarization layer 5: First electrode 6: Substrate 7: Contact hole 8: Pixel segmentation layer 9: Spacer layer 10: Illuminated pixels 11: Second electrode 12: Alkali-free glass substrate 13: Planarization layer 14: First electrode 15: Pixel segmentation layer and spacer layer 16: Organic EL layer 17: Second electrode

Claims

1. A positive photosensitive composition comprising: (A) a copolymer having structural units represented by formula (1) and formula (2) and having phenolic hydroxyl groups in the structure (hereinafter referred to as "(A) copolymer"); (B) a quinone diazide compound; and (C) a solvent, wherein the content of the structural units represented by formula (1) in the copolymer is 1 to 50 mol% relative to 100 mol% of all structural units contained in the copolymer. [Chemical Formula 1] In equation (1), R 1 It is an organic group with 1 to 20 carbon atoms; in formula (2), R 2 It is an organic group having 1 to 20 hydrogen or carbon atoms; in multiple formulas (1) and (2), R 1 and R 2 They can be the same or different.

2. The positive photosensitive composition as claimed in claim 1, wherein, R in equation (1) 1 It is an organic group containing 5 to 20 carbon atoms in an alicyclic structure.

3. The positive photosensitive composition as claimed in claim 1, wherein, R in equation (2) 2 It may be an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 15 carbon atoms, or a hydrogen atom, which may contain ester or ether bonds.

4. The positive photosensitive composition of claim 1, wherein, R in equation (2) 2 For the group represented by formula (3), [Chemical Formula 2] In equation (3), R 3 R is an alkylene group having 1 to 12 carbon atoms, which may contain ester or ether bonds. 4 It is a hydroxyl, carboxyl, cyclic ether, or a group containing an alicyclic structure with 5 to 15 carbon atoms, R 3 and R 4 The total number of carbon atoms is less than 20.

5. The positive photosensitive composition as claimed in claim 4, wherein, Relative to 100 mol% of all structural units contained in copolymer (A), R in formula (3) 3 It is an alkylene group with 4 to 12 carbon atoms that may contain ester or ether bonds and R 4 The content of the structural unit represented by formula (2) which is a cyclic ether group is 1 to 50 mol.

6. The positive photosensitive composition of claim 1, wherein, R in equation (1) 1 For the group represented by formula (4), [Chemical Formula 3] In equation (4), R 5 and R 6 R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 7 R represents an alkyl group with 1 to 5 carbon atoms; a and b represent integers from 0 to 5; in multiple formulas (4), R 5 ~R 7 They can be the same or different.

7. The positive photosensitive composition of claim 1, wherein, The copolymer (A) has structural units comprising cyclic ether groups.

8. The positive photosensitive composition of claim 1, wherein, The copolymer (A) has structural units represented by formula (5), and the structural units represented by formula (5) contained in copolymer (A) are 1 to 40 mol% relative to 100 mol% of all structural units contained in copolymer (A). [Chemical Formula 4] In equation (5), R 8 It is an organic group with 1 to 20 hydrogen or carbon atoms; in multiple formulations (5), R 8 They can be the same or different.

9. The positive photosensitive composition of claim 1, wherein, The weight-average molecular weight of the copolymer (A) is between 5,000 and 100,000.

10. A copolymer having structural units represented by formula (1) and formula (2) and having phenolic hydroxyl groups in the structure (referred to as "(A) copolymer"), wherein the content of the structural units represented by formula (1) in copolymer (A) is 1 to 50 mol% relative to 100 mol% of all structural units contained in copolymer (A). [Chemical Formula 5] In equation (1), R 1 It is an organic group with 1 to 20 carbon atoms; in formula (2), R 2 It is an organic group having 1 to 20 hydrogen or carbon atoms; in multiple formulas (1) and (2), R 1 and R 2 They can be the same or different.

11. The copolymer of claim 10, wherein, R in equation (1) 1 For the group represented by formula (4), [Chemical Formula 6] In equation (4), R 5 and R 6 R represents a single bond or an alkylene group having 1 to 5 carbon atoms. 7 R represents an alkyl group with 1 to 5 carbon atoms; a and b represent integers from 0 to 5; in multiple formulas (4), R 5 ~R 7 They can 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 material as described in claim 12.

14. A display device comprising the cured material as claimed in claim 12.

15. An information terminal having the display device of claim 14.

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