Polymers, polymer solutions, photosensitive resin compositions, and cured products

Abstract

The present invention provides a polymer that is not subject to PFAS regulations, yet possesses water-repellent and liquid-repellent properties, as well as high heat resistance. [Solution] A polymer comprising a structural unit represented by formula (NB), a structural unit having a siloxane bond, and a maleimide-based structural unit. TIFF2026168856000027.tif58153 In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently either a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

Description

[Technical Field]

[0001] The present invention relates to a polymer, a polymer solution containing the polymer, a photosensitive resin composition containing the polymer solution, and a cured product of the photosensitive resin composition. [Background technology]

[0002] In the field of advanced devices such as semiconductor elements and display panels, a method has been proposed in which a photosensitive material film is processed into a fine pattern using photolithography technology, and a functional film is uniformly coated onto that fine pattern. In particular, from the viewpoint of waterproofing and wettability control, there is a need for a method to impart water-repellent or liquid-repellent properties to a part of the component, and a method has been proposed to form a fine pattern with water-repellent or liquid-repellent properties using photolithography technology.

[0003] A common method for imparting water-repellent and liquid-repellent properties to patterns is to coat the fine patterns with fluorine-based water-repellent and liquid-repellent agents containing long-chain perfluoroalkyl groups, such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, long-chain perfluoroalkyl group-containing compounds used as water-repellent and liquid-repellent agents are poorly biodegradable and highly bioaccumulative, raising concerns about their impact on the environment and human health, leading to a global movement to regulate their use. For these reasons, the development of alternatives to long-chain perfluoroalkyl group-containing compounds is being widely pursued. Perfluoropolyether group-containing compounds are attracting attention as alternatives to long-chain perfluoroalkyl group-containing compounds. These compounds exhibit relatively low biopersistence and environmental accumulation, and high water repellency. Furthermore, from the perspective of ease of use, compounds with hydrolyzable silanes at the reactive end are primarily used. However, fluorine-containing silane-based water-repellent agents do not react sufficiently with the substrate when simply applied and heated, resulting in insufficient durability. To address these challenges, Patent Document 1 proposes a method for increasing the reactivity between the substrate and the film by forming a film of a perfluoropolyether group-containing silane-based water repellent that has been hydrolyzed in the presence of a catalyst and water.

[0004] Regarding the use of fluoropolymers in electronic devices, the technology described in Patent Document 2 can be cited. Patent Document 2 describes a technology for using a polymer containing norbornene-type repeats having hydrocarbyl groups or maleimide groups, and norbornene-type repeating units having perhalocarbyl groups, as an intermediate layer material for electronic devices. Patent Document 2 aims to improve the thermal stability and reduce the dielectric constant of the film-forming polymer by introducing repeating units derived from norbornene monomers having pentafluorophenyl groups. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-174508 [Patent Document 2] Patent Publication No. 5932793 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, when the water-repellent agent described in Patent Document 1 was formed on a substrate to create a pattern, the resulting pattern did not exhibit sufficient water repellency, and there was room for improvement in terms of the pattern's heat resistance. In addition, substances having perfluorinated methyl groups (-CF3) or perfluorinated methylene groups (-CF2-) are classified as PFAS, and in recent years, regulations on PFAS-classified substances have been progressing due to concerns about biopersistence and environmental accumulation, and the polymer described in Patent Document 1 also falls under the category of PFAS. Furthermore, the polymer described in Patent Document 2 has maleimide pendant groups, which sometimes prevented sufficient liquid repellency from being obtained. [Means for solving the problem]

[0007] The inventors of the present invention have discovered that by adjusting the constituent components of the polymer used in the photosensitive resin composition, it is possible to create a fluorine-free polymer that is therefore PFAS-free, while the polymer itself possesses water-repellent and liquid-repellent properties, as well as excellent heat resistance, leading to the present invention.

[0008] The present invention provides the following polymers, polymer solutions, photosensitive resin compositions, and cured products. [1] A structural unit represented by formula (NB), Structural units having siloxane bonds, Structural units represented by formula (MI), A polymer containing, [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. a1 is 0, 1, or 2. [ka] In the formula (MI), R 31 This is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 32 and R 33 Each of these is an independent polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms. [2] [1] The polymer described above, The structural unit having a siloxane bond includes at least one structural unit selected from structural units represented by formula (SI-1), formula (SI-2), and formula (SI-3), [ka] In formula (SI-1), R aeach independently represents an alkyl group having 1 to 30 carbon atoms, R a ' each independently represents a divalent organic group having 1 to 30 carbon atoms, m represents an integer of 1 or more, n represents an integer of 1 or more,

Chemical Formula

Chemical Formula

Chemical Formula

[10] A polymer described in any of [1] to [6], Including a photosensitive agent, Photosensitive resin composition. A cured product formed from the photosensitive resin composition described in

[11]

[10] . [Effects of the Invention]

[0009] The present invention provides a polymer that is PFAS-free, yet whose cured product has water-repellent and liquid-repellent properties, as well as high heat resistance, and a photosensitive resin composition containing the polymer. [Brief explanation of the drawing]

[0010] [Figure 1] This diagram schematically illustrates the manufacturing method of organic EL elements using the printing method. [Figure 2] This diagram schematically illustrates the manufacturing method of organic EL elements using the printing method, and schematically shows a portion of the cross-section in Figure 1. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described below. In this specification, the notation "a~b" in descriptions of numerical ranges means "a or more and b or less" unless otherwise specified. For example, "5~90%" means "5% or more and 90% or less".

[0012] In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0013] [Polymer P] The polymer of the present invention (hereinafter referred to as "polymer P") will now be described. Unless otherwise specified, structural units or compounds represented by the same structural formula have a common definition across all embodiments, and the same applies to preferred embodiments.

[0014] The polymer P according to this embodiment is The structural unit represented by formula (NB), Structural units having siloxane bonds, It includes a structural unit represented by formula (MI).

[0015] [ka]

[0016] In formula (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. a1 is 0, 1, or 2.

[0017] [ka]

[0018] In the formula (MI), R 31 This is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 32 and R 33Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0019] The polymer P in this embodiment contains structural units derived from a cyclic olefin represented by formula (NB). These structural units are chemically robust. Therefore, polymer P containing these structural units exhibits minimal weight loss and stability when subjected to heat treatment. As a result, the cured product of a photosensitive resin composition containing such polymer P has high heat resistance.

[0020] In the structural unit represented by the above formula (NB) that constitutes polymer P, R 1 ~R 4 Organic groups having 1 to 30 carbon atoms that can constitute these groups include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

[0021] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0022] Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. Examples of alkynyl groups include the ethynyl group. Examples of alkylidene groups include methylidene groups and ethylidene groups. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

[0023] Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0024] Note, R 1 ~R 4 Organic groups having 1 to 30 carbon atoms that can constitute this may contain at least one atom selected from O, N, S, P, and Si in their structure.

[0025] R 1 ~R 4 This is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0026] In the structural unit represented by formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0027] The proportion of the structural unit represented by formula (NB) among all structural units constituting polymer P is preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and even more preferably 40 to 60 mol%.

[0028] The polymer P of this embodiment contains structural units having siloxane bonds. By possessing structural units having siloxane bonds, polymer P exhibits high water and liquid repellency. In polymer P of this embodiment, the structural units having siloxane bonds are introduced into the molecular chain of polymer P by covalent bonds. Thus, because polymer P itself possesses siloxane bonds, polymer P exhibits improved water and liquid repellency compared to a sea-island structure mixture in which a silicone-containing compound is dispersed in a polymer consisting of formulas (NB) and (MI). Because of its liquid repellency, such polymer P can suppress the mixing of liquid materials such as inks, making it suitable for use as a partition or coating material for organic electroluminescent elements. Furthermore, by containing structural units having siloxane bonds, polymer P has a low refractive index of 1.50 or less. Therefore, polymer P can be suitably used as a coating material applied to optical components such as lenses and display elements for the purpose of anti-reflection and anti-fouling.

[0029] The polymer P of this embodiment contains a structural unit represented by formula (MI). The structural unit represented by formula (MI) is a structural unit derived from a maleimide monomer. By containing the structural unit represented by formula (MI), polymer P has high heat resistance and excellent solvent (PGMEA) solubility, as well as alkali solubility and heat discoloration resistance. Due to its excellent PGMEA solubility, polymer P can be suitably used as a resist material, coating material, and ink material.

[0030] In the structural unit represented by the above formula (MI) that can constitute polymer P, R 31 R is a hydrogen atom or an organic group having 1 to 30 carbon atoms. 32 and R 33 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. In the structural unit represented by formula (MI), R 32 and R 33Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 32 and R 33 It is preferable that it be a hydrogen atom. R in equation (MI) 31 Organic groups having 1 to 30 carbon atoms that can constitute this include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups. 31 Preferably, it is a hydrocarbon group having 1 to 25 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably a hydrocarbon group having 1 to 15 carbon atoms.

[0031] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0032] Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. Examples of alkynyl groups include the ethynyl group. Examples of alkylidene groups include methylidene groups and ethylidene groups. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

[0033] Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0034] R in the structural unit represented by formula (MI) 31 Preferred elements include hydrogen atoms, alkyl groups, cycloalkyl groups, aryl groups, or aralkyl groups. Note, R 31 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, R 31 As an organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected.

[0035] The proportion of structural units represented by formula (MI) in the total structural units constituting polymer P is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and even more preferably 20 to 70 mol%. By setting the proportion of structural units represented by formula (MI) in polymer P within the above range, the heat resistance can be adjusted to a desired degree.

[0036] In one embodiment, polymer P may include at least one structural unit selected from structural units represented by formulas (SI-1), (SI-2), and (SI-3) as structural units having siloxane bonds.

[0037] [ka]

[0038] In formula (SI-1), R a Each of these is independently an alkyl group having 1 to 30 carbon atoms. R a Each of these is independently a divalent organic group having 1 to 30 carbon atoms. m represents an integer greater than or equal to 1. n represents an integer greater than or equal to 1.

[0039] [ka]

[0040] In formula (SI-2), R b Each of these is independently an alkyl group having 1 to 30 carbon atoms. R b Each of these is independently a divalent organic group having 1 to 30 carbon atoms. n represents an integer greater than or equal to 1.

[0041] [ka]

[0042] In formula (SI-3), R c Each of these is independently an alkyl group having 1 to 30 carbon atoms. R c ' is a divalent organic group having 1 to 30 carbon atoms, R c '' is an organic group having 1 to 30 carbon atoms, R c1 is a hydrogen atom or a methyl group, n represents an integer greater than or equal to 1.

[0043] R in the group represented by formula (SI-1) a Each of these is an alkyl group having 1 to 30 carbon atoms. aThe number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0044] R in the group represented by formula (SI-1) a’ Each of these is independently a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. a’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.

[0045] In the base represented by formula (SI-1), m represents an integer of 1 or more, preferably 1 to 500, more preferably 10 to 250, and more preferably 20 to 200. In the base represented by formula (SI-1), n ​​represents an integer of 1 or more, preferably 1 to 30, more preferably 2 to 20, and more preferably 3 to 10.

[0046] The group represented by formula (SI-1) is, for example, a group derived from a polysiloxane compound to which one thiol group (-SH) has been introduced (which may be referred to herein as "monovalent mercaptosilicone").

[0047] When polymer P contains a group represented by formula (SI-1), the proportion of the group represented by formula (SI-1) in the total structural units of polymer P is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0048] R in the group represented by formula (SI-2) b Each of these is an alkyl group having 1 to 30 carbon atoms. bThe number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0049] R in the group represented by formula (SI-2) b’ R is a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. b’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. In the base represented by formula (SI-2), n represents an integer of 1 or more, preferably 1 to 500, more preferably 10 to 250, and more preferably 20 to 200.

[0050] The group represented by formula (SI-2) is, for example, a group derived from a polysiloxane compound to which two thiol groups (-SH) have been introduced (which may be referred to herein as a "divalent mercaptosilicone").

[0051] When polymer P contains a group represented by formula (SI-2), the proportion of the group represented by formula (SI-2) in the total structural units of polymer P is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0052] R in the structural unit represented by formula (SI-3) c Each of these is an alkyl group having 1 to 30 carbon atoms. c The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. R in the structural unit represented by formula (SI-3)c1 This is either a hydrogen atom or a methyl group.

[0053] R in the structural unit represented by formula (SI-3) c’ R is a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. c’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.

[0054] R in the structural unit represented by formula (SI-3) c’’ R is an organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. c’’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.

[0055] In the structural unit represented by formula (SI-3), n represents an integer of 1 or more, preferably 1 to 500, more preferably 10 to 250, and more preferably 20 to 200.

[0056] The structural unit represented by formula (SI-3) is, for example, a structural unit derived from a polysiloxane compound to which one (meth)acrylic group has been introduced (which may be referred to herein as "(meth)acrylic silicone").

[0057] When polymer P contains structural units represented by formula (SI-3), the proportion of groups represented by formula (SI-3) in the total structural units of polymer P is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0058] In one embodiment, polymer P may contain structural units derived from maleic anhydride represented by formula (MA).

[0059] [ka]

[0060] The structural unit derived from maleic anhydride, represented by formula (MA), undergoes ring-opening in an alkaline developer to produce two carboxyl groups (the structural unit represented by formula (3) below). Therefore, polymer P containing this structural unit exhibits excellent developability. A photosensitive resin composition containing such polymer P may exhibit excellent developability when subjected to a photolithography method using an alkaline aqueous solution as the developer. When polymer P contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) in the total structural units of polymer P is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0061] [ka]

[0062] The content (ratio) of each structural unit contained in polymer P depends on the amount (moles) of raw materials used in the synthesis of the polymer, the amount of raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence of peaks in the 1C-NMR spectrum and their peak areas.

[0063] The weight-average molecular weight Mw of polymer P is, for example, 2,000 to 100,000. Preferably, the weight-average molecular weight Mw of polymer P is 3,000 to 75,000, more preferably 4,000 to 50,000. The heat resistance of polymer P can be adjusted by appropriately adjusting the weight-average molecular weight. Furthermore, the polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P in this embodiment is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 8.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P can be made homogeneous, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0064] The glass transition temperature of polymer P is preferably 50 to 250°C, and more preferably 70 to 230°C. Polymer P has a relatively high glass transition temperature due to containing structural units represented by formula (NB) and structural units represented by formula (MI). This is advantageous in the manufacturing of liquid crystal display devices and solid-state image sensors because it allows for the stable existence of patterns formed on the substrate. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0065] The silicon content in polymer P is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, and even more preferably 4 to 25% by mass. By adjusting the silicon content within this range, polymer P with excellent water repellency and liquid repellency can be obtained. Furthermore, by setting the silicon content within the above range, polymer P can be designed to have a low refractive index. The refractive index of polymer P is, for example, 1.30 to 1.50, preferably 1.40 to 1.50, more preferably 1.41 to 1.49, and particularly more preferably 1.42 to 1.48. Polymer P having a refractive index within the above range can be used in applications requiring low refractive index, such as anti-reflective coatings for display elements and optical components.

[0066] In this specification, the silicon content of polymer P is: 1 It can be calculated by 1H-NMR measurement. Furthermore, in this specification, the refractive index of polymer P is a value calculated by extrapolation from the refractive index of polymer P solutions of different concentrations measured at 25°C.

[0067] (Method for manufacturing polymer P) Polymer P can be manufactured (synthesized) by any method. Typically, polymer P can be manufactured using either step Ia or step Ib below, depending on the structure of the desired polymer.

[0068] (Step Ia) When producing polymer P ("polymer Pa") which consists of a structural unit represented by formula (NB), a structural unit having a siloxane bond, and a structural unit represented by formula (MI), wherein the structural unit having a siloxane bond is one of the structural units represented by formulas (SI-1) to (SI-3), a monomer composition ("monomer composition a") containing a monomer represented by formula (NBm), one of a silicone-containing compound (SI-m) represented by formula (SI-1-m), formula (SI-2-m), or formula (SI-3-m), and a maleimide represented by formula (MIm) is polymerized (addition polymerization).

[0069] (Step Ib) When producing polymer P (referred to as "polymer Pb") which consists of a structural unit represented by formula (NB), a structural unit having a siloxane bond, a structural unit represented by formula (MI), and a structural unit represented by formula (MA), wherein the structural unit having a siloxane bond is one of the structural units represented by formulas (SI-1) to (SI-3), a monomer composition (referred to as "monomer composition b") containing a monomer represented by formula (NBm), one of a silicone-containing compound (SI-m) represented by formula (SI-1-m), formula (SI-2-m), or formula (SI-3-m), a maleimide monomer represented by formula (MIm), and maleic anhydride, polymerize (addition polymerization).

[0070] Here, in equation (NBm), R 1 , R 2 , R 3 and R 4 Furthermore, the definition of a1 is the same as that of equation (NB). In equation (SI-1-m), R a , R a The definitions of ', m, and n are equivalent to those in equation (SI-1). In equation (SI-2-m), R b , R b The definitions of ', and n are equivalent to those in equation (SI-2). In equation (SI-3-m), R c , R c ', R c''оR c1 The definitions of , and n are equivalent to those in equation (SI-3). Also, R in equation (MIm) 31 ~R 33 The definition is the same as that in formula (MI).

[0071] (Monomer represented by formula (NBm)) [ka]

[0072] Examples of monomers represented by formula (NBm) include norbornene, bicyclo[2.2.1]-hepto-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic acid anhydride. During polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more types.

[0073] (Compound represented by formula (SI-1-m)) [ka]

[0074] The silicone-containing compound represented by formula (SI-1-m) is a monovalent mercaptosilicone, and commercially available examples include "KF-2001" and "KF-2004" manufactured by Shin-Etsu Chemical Co., Ltd.

[0075] (Compound represented by formula (SI-2-m)) [ka]

[0076] The silicone-containing compound represented by formula (SI-2-m) is a divalent mercaptosilicone, and commercially available examples include "X-22-167B" and "X-22-167C" manufactured by Shin-Etsu Chemical Co., Ltd.

[0077] (Compound represented by formula (SI-3-m)) [ka]

[0078] The compound represented by formula (SI-3-m) is (meth)acrylic silicone. Commercially available products include, for example, Shin-Etsu Chemical Co., Ltd.'s products "X-22-174ASX", "X-22-174B", "KF-2012", "X-22-2426", and "X-22-1404", and JNC Corporation's products "FM-0711", "FM-0721", and "FM-0725".

[0079] (Monomer represented by formula (MIm)) [ka]

[0080] In step Ia or step Ib, the polymerization method is not limited, but radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding polymerization initiators, one type may be used, or two or more types may be used in combination.

[0081] For the polymerization reaction, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used as solvents. The polymerization solvent may be a single solvent or a mixture of solvents.

[0082] In step Ia or step Ib, the synthesis of polymer Pa or polymer Pb is carried out by dissolving each raw material monomer and polymerization initiator in a solvent, charging them into a reaction vessel, and then heating to allow addition polymerization to proceed. The heating temperature is, for example, 50-80°C, and the heating time is, for example, 5-20 hours.

[0083] In step Ia, the molar ratio of the monomer represented by formula (NBm) to the monomer represented by formula (MIm) when charging into the reaction vessel is preferably (NBm):(MIm) = 0.5:1 to 1:0.5, and from the viewpoint of molecular structure control, it is more preferable to use an amount such that (NBm):(MIm) = 0.5:0.8 to 0.7:0.5. Furthermore, the molar ratio of the silicone-containing compound (SI-m) represented by any of formulas (SI-1-m), (SI-2-m), or (SI-3-m) to formula (NBm) is preferably (SI-m):(NBm) = 1:100 to 40:100.

[0084] In step Ib, when charging the reaction vessel, the molar ratio of the monomer represented by formula (NBm), the monomer represented by formula (MIm), and maleic anhydride (MAN) is preferably such that (NBm):(MAN+MIm)=0.5:1 to 1:0.5, and is particularly preferable from the viewpoint of controlling the molecular structure of the polymer if (NBm):(MAN+MIm)=0.5:0.8 to 0.7:0.5. Furthermore, the molar ratio of the silicone-containing compound (SI-m) represented by any of formulas (SI-1-m), (SI-2-m), or (SI-3-m) to formula (NBm) is preferably such that (SI-m):(NBm)=1:100 to 40:100.

[0085] By step Ia or step Ib described above, the polymer P (polymer Pa or polymer Pb) of this embodiment can be obtained. The polymer P may be any of the following: random copolymer, alternating copolymer, block copolymer, periodic copolymer, etc.

[0086] Furthermore, after the synthesis of polymer P, a step may be performed to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized polymer P and low molecular weight components is concentrated as needed, and then mixed with an organic solvent such as tetrahydrofuran (THF) or methyl ethyl ketone (MEK) to obtain a solution. This solution is then mixed with a poor solvent such as methanol, 2-propanol, or 1-butanol to precipitate the monomers. The precipitate is filtered, and if necessary, further washed with a poor solvent such as heptane, and then dried to increase the purity of polymer P.

[0087] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. The polymer solution of this embodiment may also contain a silicone compound along with the polymer P.

[0088] (Silicone compounds) The silicone compound that may be included in the polymer solution of this embodiment may be an unreacted silicone compound used in step Ia or step Ib in the production of polymer P, or it may be one that has been added separately.

[0089] Examples of silicone compounds that can be incorporated into polymer solutions include, but are not limited to, monovalent mercaptosilicone represented by the above formula (SI-1-m), divalent mercaptosilicone represented by the above formula (SI-2-m), and (meth)acrylicsilicone represented by the above formula (SI-3-m).

[0090] In the polymer solution of this embodiment, if a silicone compound is added separately from the unreacted silicone compound used in the production of polymer P, the amount added may be such that the peak area derived from the silicone compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P.

[0091] [Production of polymer solutions] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material in the photosensitive resin composition described below.

[0092] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the polymer P described above and a photosensitive agent. That is, the photosensitive resin composition of this embodiment comprises the polymer solution of this embodiment described above and a photosensitive agent. Each component is described below.

[0093] (Photosensitive agent) Examples of photosensitive agents used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators. Known compounds can be used as photoradical polymerization initiators, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1 Alkylphenone compounds such as -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl Benzoin compounds such as benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], etanone, Examples include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of polymer P.

[0094] The photosensitive resin composition of this embodiment, by containing the above-mentioned components, has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method.

[0095] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a coloring agent. The inclusion of a coloring agent makes it suitable for use as a material for forming color filters in liquid crystal displays and solid-state image sensors. Various pigments or dyes can be used as the coloring agent. Organic pigments and inorganic pigments can be used as pigments.

[0096] Organic pigments that can be used include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, and dye lake pigments.

[0097] Inorganic pigments that can be used include white and extender pigments (titanium dioxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (lead yellow, cadmium-based pigments, chrome vermilion, nickel titanium, chromium titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luminescent pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0098] As dyes, for example, known dyes described in Japanese Patent Publication No. 2003-270428, Japanese Patent Publication No. Hei 9-171108, Japanese Patent Publication No. 2008-50599, etc., can be used. If the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one type of coloring agent or two or more types.

[0099] Colorants (especially pigments) can be of an appropriate average particle size depending on the purpose and application. In particular, when transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while in other cases, such as in paints where opacity is required, a larger average particle size of 0.5 μm or more is preferred.

[0100] Depending on the purpose and application, the colorants may undergo surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, or wax coating.

[0101] If the photosensitive resin composition contains a colorant, the amount can be set appropriately depending on the purpose and application, but in order to balance the color concentration and the dispersion stability of the colorant, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total nonvolatile components (components excluding solvents) of the photosensitive resin composition.

[0102] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0103] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when applied to a substrate to obtain a resin film, allowing for the creation of a coating film of uniform thickness. Furthermore, it prevents residue and pattern lifting during the development of the coating film.

[0104] Nonionic surfactants are compounds containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or compounds with a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant that includes a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorine-based silicone-based surfactants include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 from DIC Corporation, and Novec FC4430 and FC4432 from Sumitomo 3M Co., Ltd., while an example of a silicone-based surfactant is Shin-Etsu Chemical Co., Ltd. Examples include, but are not limited to, the following models manufactured by ): KF-6017, KF-6028, KF-6038, KF-6028P, KF-6011, PKF-6017P, KF-6106, KF-6104, KF-6180, KF-6105, KF-6048, KF-6015, KF-6011P, KF-6043, KF-578, KF-6012, KF-6115, KF-6004, etc. When using a surfactant, the amount of surfactant to be blended is preferably 0.01 to 50% by weight, particularly preferably 0.05 to 40% by weight, and most preferably 0.1 to 40% by weight, per 100 parts by weight of resin.

[0105] (solvent) Photosensitive resin compositions typically contain a solvent. Organic solvents are preferred as the solvent. Specifically, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0106] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutylcarbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof. The amount of solvent used is not particularly limited, but it is used in such an amount that the concentration of nonvolatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0107] (Light-blocking agent) The resin composition of this embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or it may contain two or more types.

[0108] When a photosensitive resin composition contains a light-shielding agent, the amount can be set appropriately depending on the purpose and application, but in order to balance light-shielding performance and dispersion stability of the light-shielding agent, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total non-volatile components (components excluding solvents) of the photosensitive resin composition.

[0109] (Crosslinking agent) The photosensitive resin composition of this embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking polymer P (i.e., chemically bonding with polymer P) through the action of activated chemical species generated from the photopolymerization initiator. The crosslinking agent may not only chemically bond with the polymer, but may also react with other crosslinking agents to form bonds.

[0110] The crosslinking agent is preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the polymers mentioned above). Using a crosslinking agent having the same type of crosslinkable group (polymerizable double bond) as the polymer is preferable in terms of uniform curability and further improvement of sensitivity. There is no particular upper limit to the number of functionalities (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0111] Specifically, the crosslinking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene Polyfunctional (meth)acrylates such as oxide-added ditrimethylolpropanetetra(meth)acrylate, ethylene oxide-added pentaerythritoltetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropanetri(meth)acrylate, propylene oxide-added ditrimethylolpropanetetra(meth)acrylate, propylene oxide-added pentaerythritoltetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropanetri(meth)acrylate, ε-caprolactone-added ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone-added pentaerythritoltetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexanyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexanyl ether; Vinyl ether group-containing (meth)acrylic acid esters such as (meth)acrylate 2-vinyloxyethyl, (meth)acrylate 3-vinyloxypropyl, (meth)acrylate 1-methyl-2-vinyloxyethyl, (meth)acrylate 2-vinyloxypropyl, (meth)acrylate 4-vinyloxybutyl, (meth)acrylate 4-vinyloxycyclohexyl, (meth)acrylate 5-vinyloxypentyl, (meth)acrylate 6-vinyloxyhexyl, (meth)acrylate 4-vinyloxymethylcyclohexylmethyl, (meth)acrylate p-vinyloxymethylphenylmethyl, (meth)acrylate 2-(vinyloxyethoxy)ethyl, (meth)acrylate 2-(vinyloxyethoxyethoxyethoxy)ethyl; Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; Allyl group-containing (meth)acrylic acid esters, such as (meth)acrylic acid allyl; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate; Polyfunctional allyl group-containing isocyanurates, such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; Examples include:

[0112] Among these, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0113] When a photosensitive resin composition contains a crosslinking agent, the composition may contain only one type of crosslinking agent or two or more types. When a photosensitive resin composition contains a crosslinking agent, the amount can be appropriately set according to the purpose and application. As an example, the amount of crosslinking agent can usually be about 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, per 100 parts by mass of photosensitive resin.

[0114] (Other additives) Depending on the purpose and required properties, the photosensitive resin composition may also contain components such as fillers, binder resins other than the polymers mentioned above, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, oscillating agents, oscillating aids, silane coupling agents, and polyvalent phenol compounds.

[0115] The photosensitive resin composition of this embodiment can be designed as either a negative or positive type by appropriately adjusting the type of photosensitive agent and the reactivity of the crosslinking agent, but since the polymer has (meth)acryloyl groups, use in the negative type is preferred.

[0116] [Application] A patterned film can be obtained by forming a film using the above-described photosensitive resin composition, and then exposing and developing the film to form a pattern. This film can be used as a partition for organic electroluminescent (EL) elements.

[0117] Furthermore, the above-mentioned photosensitive resin composition is useful as an insulating layer for electronic devices, a water-repellent and oil-repellent agent, a mold release agent, a composition for forming liquid-repellent films such as display pixels, biochips, and microchemical chips, an antifouling coating agent, a hard coat agent, an imprint resin composition, and a composition for optical materials such as lens arrays. Furthermore, the polymer of this embodiment may be used alone for any application, or it may be prepared as a non-photosensitive composition mixed with any component and applied to any application. Because the polymer of this embodiment contains a silicone structure, it is believed to exhibit not only water repellency and liquid repellency, but also antifouling, mold release properties, lubricity, stress reduction, and refractive index reduction. In other words, in addition to the above applications, it can be applied to technical fields where these properties are required.

[0118] A method for manufacturing an organic electroluminescent element using the photosensitive resin composition of this embodiment is: A film formation step of forming a photosensitive resin film on a substrate using the above-mentioned photosensitive resin composition, The photosensitive resin film is subjected to a pattern exposure process, A developing step in which the exposed photosensitive resin film is developed to obtain a partition, The printing process involves printing an ink (material solution) in which organic materials are dissolved or dispersed in an organic solvent onto a region on the substrate enclosed by partitions obtained in the developing process. Includes. The above printing process is preferably carried out by an inkjet method.

[0119] The partitions manufactured using the photosensitive resin composition of this embodiment retain sufficient water and liquid repellency even after development. Therefore, mixing of material liquids (inks) between adjacent pixels can be suppressed during the manufacturing of organic EL elements. This can lead to improved performance and yield of the organic EL element.

[0120] This section describes each step in the manufacturing process of organic EL elements.

[0121] ·Film formation process The substrates used here are not particularly limited and include, for example, glass substrates, plastic substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates. When manufacturing organic EL elements, glass substrates are typically used. The substrate may be an unprocessed substrate or a substrate with electrodes or elements formed on its surface. It may also be surface-treated to improve adhesion.

[0122] The method for forming a photosensitive resin film using a photosensitive resin composition is not particularly limited. For example, it can be done by rotary coating using a spinner, spray coating using a spray coater, bar coating, dipping, printing, roll coating, inkjet method, etc. The photosensitive resin composition coated on the substrate is typically dried by heat treatment using a hot plate, hot air, oven, etc. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. The heating time is usually 30 to 600 seconds, preferably 30 to 300 seconds.

[0123] The thickness of the photosensitive resin film is not particularly limited and can be adjusted as appropriate depending on the pattern to be ultimately obtained. The thickness of the photosensitive resin film is usually 0.5 to 10 μm, preferably 1 to 5 μm. The thickness can be adjusted by changing the solvent content in the photosensitive resin composition, the coating method, and the coating conditions.

[0124] • Exposure process Exposure is performed by irradiating the photosensitive resin film with active light, such as through a suitable photomask. Examples of active light include X-rays, electron beams, ultraviolet light, and visible light. In terms of wavelength, light in the range of 200 to 500 nm is preferred. In terms of pattern resolution and handling ease, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, with the i-line being particularly preferred. Alternatively, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, mirror projection, or stepper is preferred. The amount of light used for exposure can be adjusted as appropriate depending on the amount of photosensitive agent in the photosensitive resin film, for example, 100-500 mJ / cm². 2 It is to that extent.

[0125] Furthermore, if necessary, the photosensitive resin film may be heated again after exposure (post-exposure baking). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.

[0126] ·Development process A partition can be formed by developing an exposed photosensitive resin film with a suitable developer.

[0127] In the development process, development can be carried out using a suitable developer solution and methods such as immersion, paddle, or spray. Development dissolves and removes the exposed areas (in the case of positive type) or unexposed areas (in the case of negative type) of the photosensitive resin film, resulting in the formation of a partition structure.

[0128] The type of developer that can be used is not particularly limited. For example, alkaline aqueous solutions and organic solvents can be used. Examples of specific alkaline aqueous solutions include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. The developing solution may contain, for example, water-soluble organic solvents such as methanol or ethanol, or surfactants.

[0129] In this embodiment, it is preferable to use an aqueous solution of tetramethylammonium hydroxide as the developer. The concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

[0130] Through the above process, partitions can be formed on the substrate, or more specifically, regions (openings) surrounded by partitions can be provided on the substrate.

[0131] Furthermore, additional processing may be performed after development and before the printing process. For example, after developing, washing with a rinsing solution may be performed. Examples of rinsing solutions include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used individually or in combination of two or more. The partition wall may also be heated and hardened. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and more preferably 200 to 250°C. The heating time is not particularly limited, but is, for example, in the range of 15 to 300 minutes. This heat treatment can be carried out using a hot plate, an oven, or a heating oven with a temperature programmable. The atmospheric gas used during the heat treatment may be air, or an inert gas such as nitrogen or argon. Heating may also be carried out under reduced pressure.

[0132] • Printing process (explained with reference to Figures 1 and 2) In the development process, an ink (material solution 4), in which an organic material is dissolved or dispersed in an organic solvent, is injected into a region (opening 3) on the substrate surrounded by partitions. Typically, pixels 5 can then be formed by drying the organic solvent in the ink (material solution 4).

[0133] The method for injecting the ink (material liquid 4) is preferably an inkjet method. For example, while moving the inkjet head 10, as shown in Figure 1, relative to the substrate 1, a predetermined amount of three types of ink (material liquid 4) corresponding to the RGB three colors is injected into a predetermined opening 3. In other words, inkjet printing is performed on the opening 3 using the ink (material liquid 4).

[0134] The ink (material liquid 4) is not particularly limited, but is typically a polymer material and / or low molecular weight material capable of forming an organic light-emitting layer, dissolved or dispersed in an organic solvent. Examples of organic solvents used here include anisole and cyclohexylbenzene, but other organic solvents can also be used.

[0135] Examples of "polymer materials capable of forming an organic light-emitting layer" include polyphenylene vinylene and its derivatives, polyacetylene and its derivatives, polyphenylene and its derivatives, polyparaphenylene ethylene and its derivatives, poly-3-hexylthiophene and its derivatives, polyfluorene and its derivatives, and the like.

[0136] Examples of "low molecular weight materials capable of forming an organic light-emitting layer" include combinations of dopant materials and host materials. Examples of dopant materials include BCzVBi (4,7-diphenyl-1,10-phenanthroline), coumarin, rubrene, and DCJTB ([2-tert-butyl-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo[ij]quinoridine-9-yl)vinyl]-4H-pyran-4-ylidene]malononitrile). Examples of host materials include DPVBi (4,4'-bis(2,2-diphenylethenyl)biphenyl) and Alq3 (tris(8-quinolinolato)aluminum).

[0137] The materials for the ink (material liquid 4) are appropriately selected from the above materials and other known materials so as to produce the desired RGB colors.

[0138] The ink (material liquid 4) printed (injected) into the opening 3 can be dried, for example, by an oven or hot air drying.

[0139] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope of achieving the objectives of the present invention are included. [Examples]

[0140] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0141] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride NB:2-Norbornen • PhMI:N-phenylmaleimide • CMI:N-cyclohexylmaleimide ·KF-2001: Side-chain monovalent mercaptosilicone (manufactured by Shin-Etsu Chemical Co., Ltd.) (Formula (SI-1-m) (wherein R a =CH 3、 R a (A compound represented by '=CH2) ·X-22-174ASX, KF-2012: Single-ended monovalent methacrylate silicone (manufactured by Shin-Etsu Chemical Co., Ltd.) (Formula (SI-3-m) (wherein R c =CH 3、 R c '=CH 2、 R c Compounds represented as ''=CH3) MIBK: Methyl isobutyl ketone (4-methyl-2-pentanone) • MEK: Methyl ethyl ketone • V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., azo polymerization initiator)

[0142] <Synthesis of Polymer P> (Comparative Example 1) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 2-norbornene (NB, 47.08 g, 0.500 mol), N-cyclohexylmaleimide (CMI, 89.6 g, 0.500 mol), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 298.63 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. Next, MEK (227.81 g) was added, and the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (2773.7 g). The obtained white solid was further washed with methanol (2773.7 g), and this process was repeated twice. The mixture was then vacuum-dried at 80°C to obtain 125.6 g of polymer P1, which comprises structural units derived from 2-norbornene and structural units derived from N-cyclohexylmaleimide. The obtained polymer P1 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 5,400, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.86.

[0143] (Comparative Example 2) To a reaction vessel equipped with a stirrer, a condenser tube and a dropping funnel, maleic anhydride (49.03 g, 0.500 mol), 2-norbornene (47.08 g, 0.500 mol), KF-2001 (48.03 g, 0.0253 mol in terms of the mercapto group equivalent regarded as the molecular weight), dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol) and methyl ethyl ketone (MEK, 102.52 g) were added, and the mixture was stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, the system was heated, and further reacted at 70°C for 18 hours. Then, after adding MEK (213.57 g), the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to methanol (1922.1 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1922.1 g), then the operation of further washing the obtained white solid with heptane (1922.1 g) was performed twice, and vacuum drying was performed at a temperature of 80°C, to obtain 88.7 g of Polymer P2 having a structural unit derived from 2-norbornene, a structural unit derived from maleic anhydride, and a structural unit derived from KF-2001. As a result of measuring the obtained Polymer P2 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 10,400, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 3.15. Further, the obtained Polymer P2 was 1 measured using H-NMR, and the silicon (Si) content of Polymer P2 was 7.4 wt%. Further, the sulfur content in the obtained Polymer P2 was confirmed by elemental analysis using flask combustion and ion chromatography, and the sulfur content in Polymer P2 was 0.50 wt%. For Polymer P2, 13 C-NMR analysis was performed, and in addition to the peak derived from the C of the maleic anhydride ester at 170 to 174 ppm, a peak derived from the C bonded to Si at -2 ppm to 4 ppm, and a peak derived from R in formula (SI-1) at 16 to 17 ppm a It was confirmed that a peak derived from any one of the C's of ' appeared. 13 13C-NMR analysis and elemental analysis results confirmed that mercaptosilicone was introduced into polymer P2.

[0144] (Comparative Example 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (34.58 g, 0.367 mol), KF-2012 (35.71 g, 0.0078 mol calculated by considering the methacrylic group equivalent as molecular weight), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 3.45 g, 0.015 mol), and methyl ethyl ketone (MEK, 145.60 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. Next, MEK (81.82 g) was added, and the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (1189.5 g). The obtained white solid was further washed with methanol (1189.5 g), and the resulting white solid was washed again with heptane (1189.5 g) twice. By vacuum drying at a temperature of 80°C, 55.5 g of polymer P3, which comprises structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from KF-2012, was obtained. The obtained polymer P3 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 9,100, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.68. Furthermore, the obtained polymer P3 was used 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 12.0 wt%.

[0145] (Example 1) To a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 2-norbornene (47.08 g, 0.500 mol), N-cyclohexylmaleimide (CMI, 89.61 g, 0.500 mol), KF-2001 (68.40 g, 0.0360 mol in terms of the mercapto group equivalent taken as the molecular weight), dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol) and methyl ethyl ketone (MEK, 230.23 g) were added, and the mixture was stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the system was heated and further allowed to react at 70°C for 18 hours. Then, after adding MEK (227.81 g), the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to methanol (2733.7 g) to precipitate a white solid. The operation of further washing the obtained white solid with methanol (2733.7 g) was performed twice, followed by vacuum drying at 80°C, to obtain 174.3 g of Polymer P4 comprising a structural unit derived from 2-norbornene, a structural unit derived from N-cyclohexylmaleimide, and a structural unit derived from KF-2001. As a result of measuring the obtained Polymer P4 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 11,900, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 3.07. Further, the obtained Polymer P4 was 1 measured using H-NMR, and the silicon (Si) content of Polymer P4 was 14.4 wt%. Furthermore, the sulfur content in the obtained polymer was confirmed by elemental analysis through flask combustion and ion chromatography, and it was verified that elemental sulfur was present in the polymer. For Polymer P4, 13 C-NMR analysis was performed, and in addition to the peak derived from the C of the maleic anhydride ester at 170 to 174 ppm and the peak derived from the C of the cyclohexylmaleimide ester at 174 to 180 ppm, the peak derived from the C bonded to Si at -2 ppm to 4 ppm, and the peak derived from any C of R in formula (SI-1) at 16 to 17 ppm a ' were confirmed to appear. 13 1C-NMR analysis and elemental analysis results confirmed that a maleimide skeleton and mercaptosilicone were introduced into polymer P4.

[0146] (Example 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 2-norbornene (47.08 g, 0.500 mol), N-phenylmaleimide (PhMI, 86.58 g, 0.500 mol), KF-2001 (66.88 g, 0.0352 mol calculated by considering the mercapto group equivalent as molecular weight), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 224.68 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. Next, MEK (222.76 g) was added, and the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (2673.1 g). The obtained white solid was further washed twice with methanol (2673.1 g) and vacuum-dried at 80°C to obtain 178.2 g of polymer P5, which comprises structural units derived from 2-norbornene, N-phenylmaleimide, and KF-2001. The obtained polymer P5 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 12,000, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.08. Furthermore, the obtained polymer P5 was used 1 Measurements using 1H-NMR revealed that the silicon (Si) content of polymer P5 was 15.3 wt%. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur elements in the polymer was confirmed. Polymer P5 13¹¹C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of N-phenylmaleimide at 125 ppm to 140 ppm, peaks originating from the carbon atoms of the ester of N-phenylmaleimide at 174 to 180 ppm, as well as peaks originating from the carbon atoms bonded to Si at -2 ppm to 4 ppm, and R atoms in formula (SI-1) at 16 to 17 ppm. a We confirmed the appearance of a peak originating from one of the C's. 13 1C-NMR analysis and elemental analysis results confirmed that a maleimide skeleton and mercaptosilicone were introduced into polymer P5.

[0147] (Example 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 2-norbornene (34.29 g, 0.364 mol), N-phenylmaleimide (PhMI, 64.94 g, 0.375 mol), KF-2012 (49.61 g, 0.0108 mol calculated by considering the methacrylic group equivalent as molecular weight), 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 3.45 g, 0.015 mol), and methyl ethyl ketone (MEK, 208.37 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (1488.4 g). The obtained white solid was further washed twice with methanol (1488.4 g) and vacuum-dried at 80°C to obtain 110.2 g of polymer P6, which comprises structural units derived from 2-norbornene, N-phenylmaleimide, and KF-2012. The obtained polymer P6 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 10,100, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.82. Furthermore, the obtained polymer P6 1Measurements using 1H-NMR revealed that the silicon (Si) content of polymer P6 was 13.3 wt%. Polymer P6 13 ¹¹C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of N-phenylmaleimide at 125 ppm to 140 ppm, peaks originating from the carbon atoms of the ester of N-phenylmaleimide at 174 to 180 ppm, peaks originating from the carbon atoms bonded to Si at -2 ppm to 4 ppm, and R atoms in equation (SI-3) around 13 ppm and 18 ppm. c1 The C (the C of the CH3 in the methacryloyl group) and the R in formula (SI-3) c ', R c A peak originating from one of the C groups appeared, and the peak originating from the -CH2=C C group of the methacryloyl group of the raw material methacrylic silicone (KF-2012) around 123 ppm disappeared, confirming that the maleimide skeleton and methacrylic silicone were introduced into polymer P6.

[0148] (Example 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (24.52 g, 0.250 mol), 2-norbornene (47.08 g, 0.500 mol), N-phenylmaleimide (PhMI, 43.29 g, 0.250 mol), KF-2001 (57.48 g, 0.0303 mol calculated by considering the mercapto group equivalent as molecular weight), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 126.46 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. Next, MEK (102.12 g) was added, and the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (1148.8 g). The obtained white solid was washed twice with methanol (1148.8 g) and then vacuum-dried at 80°C to obtain 85.6 g of polymer P7, which comprises structural units derived from 2-norbornene, maleic anhydride, N-phenylmaleimide, and KF-2001. The obtained polymer P7 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 10,400, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.97. Furthermore, the obtained polymer P7 was used 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 13.1 wt%. The amount of sulfur in the obtained polymer P7 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur in polymer P7 was confirmed. Polymer P7 13¹¹C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of N-phenylmaleimide at 125 ppm–140 ppm, peaks originating from the carbon atoms of the maleic anhydride ester at 170–174 ppm, peaks originating from the carbon atoms of the N-phenylmaleimide ester at 174–180 ppm, as well as peaks originating from the carbon atoms bonded to Si at -2 ppm–4 ppm, and R atoms in formula (SI-1) at 16–17 ppm. a We confirmed the appearance of a peak originating from one of the C's. 13 1C-NMR analysis and elemental analysis results confirmed that a maleimide skeleton and mercaptosilicone were introduced into polymer P7.

[0149] (Example 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 2-norbornene (47.08 g, 0.500 mol), N-cyclohexylmaleimide (CMI, 89.61 g, 0.500 mol), KF-2001 (136.71 g, 0.0720 mol calculated by considering the mercapto group equivalent as molecular weight), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 253.05 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. Next, MEK (136.69 g) was added, and the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (2733.7 g). The obtained white solid was washed twice with methanol (2733.7 g), and then vacuum-dried at 80°C to obtain 167.8 g of polymer P8, which comprises structural units derived from 2-norbornene, N-cyclohexylmaleimide, and KF-2001. The obtained polymer P8 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 15,100, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.72. Furthermore, the obtained polymer P8 was used 1 Measurements using 1H-NMR revealed that the silicon (Si) content of polymer P8 was 19.3 wt%. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur elements in the polymer was confirmed. Polymer P8 13 ¹¹C-NMR analysis revealed peaks originating from the carbon of maleic anhydride esters at 170–174 ppm, peaks originating from the carbon of cyclohexylmaleimide esters at 174–180 ppm, peaks originating from carbon bonded to Si at -2 ppm–4 ppm, and R in formula (SI-1) at 16–17 ppm. a We confirmed the appearance of a peak originating from one of the C's. 13 13C-NMR analysis and elemental analysis results confirmed that a maleimide skeleton and mercaptosilicone were introduced into polymer P8.

[0150] (Example 6) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 2-norbornene (34.13 g, 0.363 mol), N-cyclohexylmaleimide (CMI, 89.61 g, 0.500 mol), X-22-174ASX (123.75 g, 0.1375 mol calculated by considering the methacrylic group equivalent as molecular weight), 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 355.25 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 18 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (2474.9 g). The obtained white solid was further washed twice with methanol (2474.9 g) and vacuum-dried at 80°C to obtain 126.2 g of polymer P9, which comprises structural units derived from 2-norbornene, N-cyclohexylmaleimide, and X-22-174ASX. The obtained polymer P9 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 37,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 5.55. Furthermore, the obtained polymer P9 was used 1 Measurements using 1H-NMR revealed that the silicon (Si) content of polymer P9 was 16.6 wt%. Polymer P9 13 ¹¹C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of N-phenylmaleimide at 125 ppm to 140 ppm, peaks originating from the carbon atoms of the ester of N-phenylmaleimide at 174 to 180 ppm, peaks originating from the carbon atoms bonded to Si at -2 ppm to 4 ppm, and R atoms in equation (SI-3) around 13 ppm and 18 ppm. c1 The C (the C of the CH3 in the methacryloyl group) and the R in formula (SI-3) c ', R cA peak derived from any of the above C atoms appeared, and it was confirmed that the peak derived from the C of -CH2=C of the methacryloyl group in the raw material methacrylic silicone (X-22-174ASX) near 123 ppm disappeared, confirming that the maleimide skeleton and methacrylic silicone were introduced into Polymer P9.

[0151] Table 1 below shows the types of monomers used for the synthesis of Polymer P, the charged ratio of monomers, the charged amount of the silicone compound, as well as the weight average molecular weight (Mw), polydispersity (Mw / Mn), and silicon (Si) content of the raw material polymer.

[0152]

Table 1

[0153] <Evaluation of Physical Properties of Polymer P> The following physical properties were evaluated for the Polymer P of the above Examples and Comparative Examples.

[0154] (Water Repellency and Liquid Repellency of Polymer P) In Comparative Examples 1 to 3 and Examples 1 to 6, the obtained Polymer P was dissolved in 2-heptanone to prepare a solution with a solid content concentration of 30 mass%, which was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film with a thickness of about 1.0 μm (±0.2 μm). Using a contact angle meter (Automatic Contact Angle Meter DM-501 manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of this thin film with water and the contact angle with PGMEA were measured. At this time, the prepared droplet volume was 2 μL, the observation time was set to 10 seconds after droplet landing, and the average value of 5 measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°).

[0155] Next, the thin film after the contact angle measurement was heated and cured at 230°C for 60 minutes to obtain a cured film. The contact angle of the obtained cured film was measured in the same manner as described above. The results are shown in Table 2.

[0156] As for the contact angle with water, a value of 90° or more can be regarded as indicating good water repellency, 100° or more as indicating better water repellency, and 105° or more as indicating particularly excellent water repellency. As for the contact angle with PGMEA, a value of 7° or more can be regarded as indicating good liquid repellency, 10° or more as indicating better liquid repellency, and 15° or more as indicating particularly excellent liquid repellency.

[0157] (Heat Resistance of Polymer P) The heat resistance of Polymer P was evaluated using the 20% weight loss temperature (Td20) as an indicator. The measurement method is as follows. In Comparative Examples 1 to 3 and Examples 1 to 6, 1 mg of Polymer P was set in a thermogravimetric-differential thermal analyzer (STA7200RV, manufactured by Hitachi High-Tech Science Corporation). This was heated from 35°C to 500°C at a heating rate of 10°C / min under an air atmosphere. At this time, the temperature (Td20) at which a 20% thermogravimetric loss occurs relative to the weight of the set polymer was read. The results are shown in Table 2. When Td20 is 370°C or higher, the heat resistance is good; when it is 380°C or higher, the heat resistance is better; when it is 390°C or higher, the heat resistance is particularly better; and when it is 400°C or higher, the heat resistance can be regarded as particularly excellent.

[0158] (Refractive Index of Polymer P) The refractive index of Polymer P was measured by the following method. First, the polymers obtained in Comparative Examples 1 to 3 and Examples 1 to 6 were dissolved in MEK to prepare solutions with solid content concentrations of 20.0%, 10.0%, 5.0%, and 2.5%. The refractive index at 589 nm was measured for the prepared polymer solutions and MEK alone containing no polymer using a refractometer (RA-600, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). For each polymer, the refractive index was plotted against the solid content concentration, and in the approximate curve obtained by linearly approximating the resulting plot, the refractive index at a solid content concentration of 100% was calculated as the refractive index at 589 nm. The results are shown in Table 2. A refractive index of 1.50 or less can be considered low, 1.48 or less can be considered even lower, 1.46 or less can be considered particularly low, and 1.45 or less can be considered even particularly low.

[0159] (Solubility of polymer P in PGMEA) The solubility of polymer P in PGMEA was evaluated by the following method. First, the polymers obtained in Comparative Examples 1-3 and Examples 1-6 were dissolved in PGMEA to prepare solutions with solid content concentrations of 30.0% and 10.0%. The solubility of the prepared polymer solutions was evaluated according to the following criteria. The results are shown in Table 2. A: It is a clear solution with a solid content of 30.0%, containing no insoluble matter and no turbidity. B: At a solid content concentration of 30.0%, there are insoluble particles and turbidity, but at a solid content concentration of 10.0%, it is a clear solution with neither insoluble particles nor turbidity. C: Solids content is 10.0%, and there is insoluble matter and turbidity.

[0160] (PFAS-eligible polymer P) Table 2 shows the PFAS classification of polymer P in each example and comparative example. "PFAS classified" indicates that polymer P is derived from a monomer classified as PFAS, and "PFAS not classified" indicates that polymer P is derived from a monomer not classified as PFAS.

[0161] [Table 2]

[0162] Comparative Example 1, polymer P1, which does not contain a silicone structure, was not subject to PFAS regulations, but it exhibited low water repellency and liquid repellency. Polymers P4 to P9 of Examples 1 to 6, which have a silicone structure and a structure represented by formula (MI), were not PFAS-compliant, but they exhibited high water repellency and liquid repellency, good heat resistance, a low refractive index, and excellent PGMEA solubility. In particular, polymers P4-P6, P8, and P9 of Examples 1-3, 5, and 6, which do not contain the structural unit represented by formula (MA), exhibited particularly excellent PGMEA solubility. [Explanation of symbols]

[0163] 1 circuit board 2 Bulkhead 2a Top surface (top surface of the partition) 3 Opening 4 Material liquid 5 pixels 5R, 5G, 5B pixels 10 inkjet heads

Claims

1. A structural unit represented by formula (NB), Structural units having siloxane bonds, Structural units represented by formula (MI), A polymer containing, 【Chemistry 1】 In formula (NB), R １ , R ２ , R ３ and R ４ Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. a １ is 0, 1, or 2, 【Chemistry 2】 In the formula (MI), R ３１ This is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ３２ and R ３３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

2. The polymer according to claim 1, The structural unit having a siloxane bond includes at least one structural unit selected from the structural units represented by formula (SI-1), formula (SI-2), and formula (SI-3), 【Transformation 3】 In formula (SI-1), R ａ are each independently an alkyl group having 1 to 30 carbon atoms, R ａ Each of these is independently a divalent organic group having 1 to 30 carbon atoms. m represents an integer greater than or equal to 1, n represents an integer greater than or equal to 1, 【Chemistry 4】 In formula (SI-2), R ｂ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｂ Each of these is independently a divalent organic group having 1 to 30 carbon atoms. n represents an integer greater than or equal to 1, 【Transformation 5】 In formula (SI-3), R ｃ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｃ ' is a divalent organic group having 1 to 30 carbon atoms, R ｃ '' is an organic group having 1 to 30 carbon atoms, R ｃ１ is a hydrogen atom or a methyl group, n is a polymer representing an integer greater than or equal to 1.

3. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (MA). 【Transformation 6】

4. The polymer according to claim 1, A polymer having a weight-average molecular weight of 2,000 or more and 100,000 or less.

5. The polymer according to claim 1, A polymer having a silicon content of 1% by mass or more and 35% by mass or less.

6. The polymer according to claim 1, A polymer having a refractive index of 1.30 or more and 1.50 or less.

7. A polymer solution comprising the polymer described in any one of claims 1 to 6.

8. The polymer solution according to claim 7, A polymer solution further containing a silicone compound.

9. The polymer solution according to claim 7, A polymer solution used to form partitions or coatings for organic electroluminescent elements.

10. A polymer according to any one of claims 1 to 6, Including a photosensitive agent, Photosensitive resin composition.

11. A cured product formed from the photosensitive resin composition described in claim 10.

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