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. [Solution] A polymer comprising a structural unit represented by formula (NB), a structural unit derived from maleic anhydride, and a silicone-containing structural unit of a specific structure. TIFF2026047058000130.tif58153 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, 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 derived from maleic anhydride, including the structure represented by formula (1-4), A polymer comprising a silicone-containing structural unit having at least one structure selected from structures represented by formulas (SI-1) to (SI-3), [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] [ka] 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, [ka] In formula (SI-2), R bis, independently of each other, an alkyl group having 1 to 30 carbon atoms, R b ’ is, independently of each other, a divalent organic group having 1 to 30 carbon atoms, n represents an integer of 1 or more, [Chemical formula] In formula (SI-3), R c is, independently of each other, 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 of 1 or more, Polymer. [2] The polymer according to [1], The polymer further contains at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), [Chemical formula] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, [Chemical formula] In formula (1-3), R s is a group having one (meth)acryloyl group, Polymer. [3] The polymer according to [1] or [2], The polymer further contains a structural unit represented by formula (1-5), [Chemical formula] In formula (1-5), R 51 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, Polymer. A polymer according to any of [4] [1] to [3], The polymer further comprises a structural unit represented by formula (1-1), [ka] In formula (1-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom, or a substituted or unsubstituted alkylene group with 1 to 4 carbon atoms. A polymer in which Q is the alkyl group and X is the alkylene group, and Q and X may condense to form a cyclic group. A polymer according to any of [5] [1] to [4], The polymer further comprises a structural unit represented by formula (MA). [ka] A polymer according to any of [6] [1] to [5], The polymer further comprises a structural unit represented by formula (B1) or formula (B2), [ka] [ka] In equations (B1) and (B2), R d This is a group represented by formula (SI-4), formula (SI-5), or formula (SI-6), [ka] In formula (SI-4), R f Each of these is independently an alkyl group having 1 to 30 carbon atoms. R f 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, [ka] In formula (SI-5), R g Each of these is independently an alkyl group having 1 to 30 carbon atoms. R g ' is a divalent organic group having 1 to 30 carbon atoms, n represents an integer greater than or equal to 1, [ka] In formula (SI-6), R h Each of these is independently an alkyl group having 1 to 30 carbon atoms. R h Each of these is independently a divalent organic group having 1 to 30 carbon atoms. n is a polymer representing an integer greater than or equal to 1. [7] [2] The polymer described above, The polymer includes the structure represented by formula (1-2) above, R in equation (1-2) above p is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), [ka] In formula (1b), k is either 2 or 3. R represents a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X 1 X is a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -ZX- (where Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms), and there are multiple X groups. 1 They may be the same or different. X 1' represents a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group with 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 It is an organic group with 1 to 12 carbon atoms and a (k+1) valency. [ka] In formula (1c), k, R, X 1 and X 2 These are R, k, and X in equation (1b), respectively. 1 and X 2 This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X 1 They may be the same or different from each other. X 3 This is a single bond or a divalent organic group having 1 to 6 carbon atoms. X 4 and X 5 Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X 6 It is a divalent organic group having 1 to 6 carbon atoms. [ka] In formula (1d), n is an integer between 2 and 5. R is independently either a hydrogen atom or a methyl group. polymer. [8] [2] The polymer described above, The polymer includes the structure represented by the above formula (1-3), R in equation (1-3) above s This is a base represented by formula (2a), [ka] In formula (2a), X 10 A polymer in which R is a divalent organic group and R is either a hydrogen atom or a methyl group. A polymer according to any of [9] [1] to [8], The structural unit represented by formula (NB) includes the structural unit represented by formula (ES), [ka] In the formula (ES), R 31 , R 32 , R 33 and R 34 At least one of them is an alkyl ester-containing group represented by formula (es), R 31 , R 32 , R 33 and R 34 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a3 is 0, 1, or 2. -X 3 -C(=O)-OR 35 (es) In the formula (es), X 3 This is an alkylene group having 1 to 20 carbon atoms. R 35 It is a polymer consisting of alkyl groups with 1 to 3 carbon atoms. A polymer according to any of [1] to [9], The structural unit represented by formula (NB) includes the structural unit represented by formula (CA), [ka] In the formula (CA), R 41 , R 42 , R 43 and R 44 At least one of them is a carboxyl group-containing group represented by formula (ca), and R 41 , R 42 , R 43 and R 44 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a4 is 0, 1, or 2. -X 4 -C(=O)-OH (ca) In formula (ca), X 4 This is a polymer consisting of alkylene groups with 1 to 20 carbon atoms.

[11] A polymer according to any of [1] to

[10] , The structural unit represented by formula (NB) further comprises at least one structural unit represented by formula (NB-a), [ka] In equation (NB-a), R 51 , R 52 , R 53 and R 54 At least one of them is a linear, branched, or cyclic hydrocarbon group having 2 to 30 carbon atoms, a polyoxyalkyl group having 2 to 30 carbon atoms, and the following formula (5a): [ka] at least one group selected from, where in formula (5a), * represents a bond, R 51 , R 52 , R 53 and R 54 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a5 is a polymer where a5 is 0, 1, or 2.

[12] A polymer according to any of [1] to

[11] , The polymer further comprises a structural unit represented by formula (MI), [ka] In the formula (MI), R 61 This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 62 and R 63 Each of these is an independent polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms.

[13] A polymer according to any of [1] to

[12] , A polymer having a weight-average molecular weight of 2,000 or more and 50,000 or less.

[14] A polymer according to any of [1] to

[13] , A polymer having a silicon content of 1% by mass or more and 35% by mass or less.

[15] A polymer according to any of [1] to

[14] , A polymer having a refractive index of 1.30 or more and 1.50 or less.

[16] A polymer solution comprising any of the polymers described in [1] to

[15] .

[17]

[16] The polymer solution described above, A polymer solution further containing a silicone compound.

[18] A polymer solution as described in

[16] or

[17] , A polymer solution used to form partitions or coatings for organic electroluminescent elements.

[19] A polymer described in any of [1] to

[15] , Including a photosensitive agent, Photosensitive resin composition. A cured product formed from the photosensitive resin composition described in

[20]

[19] .

[21] A structural unit represented by formula (NB), The structural unit represented by formula (MA), A polymer comprising a silicone-containing structural unit having at least one structure selected from structures represented by formulas (SI-1) to (SI-3), [ka] 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] [ka] 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, [ka] 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, [ka] 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. polymer.

[22]

[21] The polymer described above, The structural unit represented by formula (NB) includes the structural unit represented by formula (ES), [ka] In the formula (ES), R 31 , R 32 , R 33 and R 34At least one of them is an alkyl ester-containing group represented by the formula (es), and R 31 、R 32 、R 33 and R 34 The rest are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a3 is 0, 1 or 2, -X 3 -C(=O)-O-R 35 (es) In the formula (es), X 3 is an alkylene group having 1 to 20 carbon atoms, R 35 is an alkyl group having 1 to 3 carbon atoms, a polymer. The polymer according to

[23] ,

[21] or

[22] , The structural unit represented by the formula (NB) includes the structural unit represented by the formula (CA),

Chemical formula

[24] ,

[21] to

[23] , The structural unit represented by the formula (NB) further includes at least one of the structural units represented by the formula (NB-a),

Chemical formula

[25]

[21] to

[24] , The polymer further comprises a structural unit represented by formula (MI), [ka] In the formula (MI), R 61 This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 62 and R 63 Each of these is an independent polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms. [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 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] In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" as used herein refers to a concept that encompasses both the acryloyl group represented by -C(=O)-CH=CH2 and the methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0014] [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 the same definitions across all embodiments, and the same applies to preferred embodiments.

[0015] <First Embodiment> (Polymer P(I)) The polymer of the present invention according to the first embodiment (hereinafter referred to as "polymer P(I)") is The structural unit represented by formula (NB), A structural unit derived from maleic anhydride, containing the structure represented by formula (1-4), and a silicone-containing structural unit, containing at least one structure selected from the structures represented by formula (SI-1) to formula (SI-3).

[0016]

Chemical formula

[0017] In formula (NB), R 1 、R 2 、R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2.

[0018]

Chemical formula

[0019]

Chemical formula

[0020] In formula (SI-1), R a are each independently an alkyl group having 1 to 30 carbon atoms, R a ’ are each independently 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.

[0021]

Chemical formula

[0022] In formula (SI-2), R b are each independently an alkyl group having 1 to 30 carbon atoms, R bEach of these is independently a divalent organic group having 1 to 30 carbon atoms. n represents an integer greater than or equal to 1.

[0023] [ka]

[0024] 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.

[0025] The polymer P(I) of this embodiment contains silicone-containing structural units represented by formulas (SI-1) to (SI-3). Due to the presence of silicone-containing groups, polymer P(I) possesses high water and liquid repellency. Because of its liquid repellency, polymer P(I) 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, due to the presence of silicone-containing groups, polymer P(I) has a low refractive index of 1.50 or less. Possessing water and liquid repellency, as well as a low refractive index, polymer P(I) is suitable for use as a coating material applied to optical components such as lenses and display elements for anti-reflective and anti-fouling purposes.

[0026] The polymer P(I) of this embodiment contains structural units derived from a cyclic olefin represented by formula (NB). The structural units represented by formula (NB) are chemically robust. Therefore, polymer P(I) containing these structural units exhibits little weight loss and is stable when subjected to heat treatment. As a result, the cured product of a photosensitive resin composition containing such polymer P(I) has high heat resistance.

[0027] In the structural unit represented by the above formula (NB) that constitutes polymer P(I), 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.

[0028] 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.

[0029] 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.

[0030] 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 the heterocyclic group include an epoxy group, an oxetanyl group, and the like.

[0031] In addition, the organic group having 1 to 30 carbon atoms that can form R 1 ~R 4 may contain at least one atom selected from O, N, S, P, and Si in its structure.

[0032] R 1 ~R 4 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0033] In the structural unit represented by the formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0034] The proportion of the structural unit represented by the formula (NB) in all the structural units constituting the polymer P(I) is preferably 20 to 85 mol%, more preferably 25 to 80 mol%, still more preferably 30 to 75 mol%.

[0035] The polymer P(I) of the present embodiment contains a structural unit represented by the formula (1-4).

[0036] By including a structural unit containing a carboxy group represented by the formula (1-4) in the polymer P(I), the acid value of the polymer P(I) can be designed to a relatively large value. As a result, the polymer P(I) has appropriate sensitivity and developability for patterning formation by photolithography. The structural unit represented by the formula (1-4) is, for example, a structural unit derived from maleic anhydride.

[0037] When the polymer P(I) contains a structural unit represented by the formula (1-4), the proportion of the structural unit represented by the formula (1-4) in all the structural units of the polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0038] In this embodiment, polymer P(I) includes a silicone-containing structural unit comprising at least one of the structures represented by formulas (SI-1) to (SI-3).

[0039] R in the group represented by formula (SI-1) that can constitute polymer P(I) a Each of these is an alkyl group having 1 to 30 carbon atoms. a 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.

[0040] 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.

[0041] 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.

[0042] 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").

[0043] When polymer P(I) 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(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0044] R in the group represented by formula (SI-2) that can constitute polymer P(I) b Each of these is an alkyl group having 1 to 30 carbon atoms. b 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.

[0045] 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.

[0046] 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").

[0047] When polymer P(I) 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(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0048] R in the structural unit represented by formula (SI-3) that can constitute polymer P(I)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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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").

[0053] When polymer P(I) 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(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0054] In one embodiment, polymer P(I) comprises structural units represented by formula (1-2) and / or structural units represented by formula (1-3).

[0055] [ka]

[0056] In formula (1-2), R p This is a group having two or more (meth)acryloyl groups.

[0057] [ka]

[0058] In formula (1-3), R s This is a group having one (meth)acryloyl group.

[0059] When polymer P(I) contains structural units comprising two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2), or structural units comprising one (meth)acryloyl group represented by formula (1-3), or a combination thereof, the photosensitive resin composition containing polymer P(I) exhibits excellent sensitivity when subjected to photolithography. This is thought to be because the (meth)acryloyl groups contained in the structural units represented by formula (1-2) or formula (1-3) promote the curing reaction (polymerization reaction).

[0060] In the structural unit represented by formula (1-2), R p R is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 9 (meth)acryloyl groups, and more preferably a group containing 3 to 6 (meth)acryloyl groups.p By optimizing the number of (meth)acryloyl groups contained in the polymer, the sensitivity of polymer P(I) containing it during exposure treatment can be further increased. Furthermore, it becomes easier to achieve a higher level of compatibility between the sensitivity and alkali solubility of polymer P(I).

[0061] R in equation (1-2) p Preferably, the group is represented by formula (1b), formula (1c), or formula (1d), and includes at least one selected from these. Having such a group tends to make it easier to obtain the various effects described above.

[0062] [ka]

[0063] In formula (1b), k is either 2 or 3. R represents a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X 1 X is a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -ZX- (where Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms), and there are multiple X groups. 1 They may be the same or different. X 1 ' represents a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group with 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 It is an organic group with 1 to 12 carbon atoms and a (k+1) valency. For R, a hydrogen atom is preferred due to further improvements in sensitivity (ease of polymerization), etc. k can be either 2 or 3, but it is preferably 3 from the standpoint of ease of obtaining raw materials and further improvement of sensitivity.

[0064] X 1 If the alkylene group has 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 If it is an alkylene group with 1 to 6 carbon atoms, then X 1 The group is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably a -CH2-(methylene group).

[0065] X 1 When the group is represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group X having 1 to 6 carbon atoms may be linear or branched. The alkylene group of X having 1 to 6 carbon atoms is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2-CH2-(ethylene group) or -CH2-CH(CH3)-.

[0066] X 1 If ' is an alkylene group having 1 to 6 carbon atoms, then the specific form is X 1 It is similar to that. X 1 If ' is a base represented by -X'-Z'-, the specific form of X' is the same as that of X above.

[0067] X 2 As an organic group with 1 to 12 carbon atoms and a (k+1) valency, any group obtained by removing (k+1) hydrogen atoms from any organic compound can be cited. Here, "any organic compound" refers to, for example, an organic compound with a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 This group is, for example, a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms) from which (k+1) hydrogen atoms have been removed. More preferably, it is a linear hydrocarbon having 1 to 3 carbon atoms from which (k+1) hydrogen atoms have been removed. The hydrocarbon here may contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. In another form, X 2The group may include a cyclic structure. Examples of groups including a cyclic structure include groups including an alicyclic structure and groups including a heterocyclic structure (for example, an isocyanuric acid structure).

[0068] [ka]

[0069] In formula (1c), k, R, X 1 and X 2 These are R, k, and X in equation (1b), respectively. 1 and X 2 This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X 1 They may be the same or different from each other. X 3 It is a divalent organic group having 1 to 6 carbon atoms. X 4 and X 5 Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X 6 It is a divalent organic group having 1 to 6 carbon atoms.

[0070] R, k, X 1 and X 2 The specific embodiments and preferred embodiments are the same as those described in formula (1b). X 3 and X 6 Examples of divalent organic groups having 1 to 6 carbon atoms include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon here may also contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of divalent organic groups having 1 to 6 carbon atoms include linear or branched alkylene groups. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0071] [ka]

[0072] In equation (1d), n is an integer between 2 and 5, preferably 2 or 3. The specific and preferred embodiments of R are the same as those described in equation (1b).

[0073] When polymer P(I) contains structural units represented by formula (1-2), the proportion of structural units represented by formula (1-2) in the total structural units of polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0074] In the structural units represented by formula (1-3) that can constitute polymer P(I), R S This group contains only one (meth)acryloyl group. In particular, in the design of typical photosensitive resin compositions, when curability is increased to increase sensitivity, curing tends to progress too much, resulting in poor developability. On the other hand, when developability is improved, curing tends to be insufficient. Therefore, it is preferable that polymer P(I) contains either or both of the structural units represented by formula (1-2) and / or formula (1-3), thereby achieving a good balance between sensitivity and developability.

[0075] R S This is a group represented, for example, by the following formula (2a).

[0076] [ka]

[0077] In equation (2a), X 10 X is a divalent organic group, and R is either a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10A preferred divalent organic group is, for example, an alkylene group. Some of the -CH2- groups in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but linear is more preferred.

[0078] X 10 The divalent organic group is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 Number of carbon atoms (X 10 By appropriately selecting the chain length, the structural unit represented by formula (2a) becomes more readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0079] X 10 The divalent organic group (e.g., alkylene group) may be substituted with any substituent. Examples of substituents include alkyl groups, aryl groups, alkoxy groups, and aryloxy groups. Also, X 10 The divalent organic group may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxyl groups, etc.

[0080] When polymer P(I) contains structural units represented by formulas (1-3), the proportion of structural units represented by formula (2) in the total structural units of polymer P(I) is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.

[0081] Furthermore, if polymer P(I) contains both structural units represented by formula (1-2) and structural units represented by formula (1-3), the total proportion of structural units represented by formula (1-2) and structural units represented by formula (1-3) in polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, and even more preferably 15 to 30 mol%, based on the total structural units constituting polymer P(I).

[0082] In one embodiment, polymer P(I) comprises at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2). Here, the structural unit represented by formula (1) is a structural unit derived from maleic anhydride composed of formulas (1-4) and (1-2), and the structural unit represented by formula (2) is a structural unit derived from maleic anhydride composed of formulas (1-4) and (1-3).

[0083] [ka]

[0084] [ka]

[0085] In equations (1) and (2), R p and R s This is equivalent to the one in equations (1-2) and (1-3) above.

[0086] When polymer P(I) contains structural units represented by formula (1), the proportion of structural units represented by formula (1) in the total structural units of polymer P(I) is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0087] When polymer P(I) contains structural units represented by formula (2), the proportion of structural units represented by formula (2) in the total structural units of polymer P(I) is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0088] In one embodiment, polymer P(I) includes structural units represented by formula (1-5).

[0089] [ka]

[0090] In formula (1-5), R 51These are linear, branched, or cyclic hydrocarbon groups having 1 to 10 carbon atoms. R 51 Examples of linear, branched, or cyclic hydrocarbon groups having 1 to 10 carbon atoms that can constitute this include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, and cycloalkyl groups.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] Polymer P(I) has high alkali solubility due to containing structural units represented by formula (1-5). As a result, a photosensitive resin composition containing polymer P(I) exhibits excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. When polymer P(I) contains structural units represented by formula (1-5), the proportion of structural units represented by formula (1-5) in the total structural units of polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0095] In one embodiment, polymer P(I) contains a structural unit derived from maleic anhydride represented by formula (4), which consists of a structure represented by formula (1-4) and a structure represented by formula (1-5).

[0096] [ka]

[0097] In formula (4), R 51 This is equivalent to the one in equation (1-5).

[0098] Polymer P(I) has high alkali solubility due to the inclusion of structural units represented by formula (5). As a result, photosensitive resin compositions containing polymer P(I) exhibit excellent developability when subjected to photolithography using an alkaline aqueous solution as the developer.

[0099] When polymer P(I) contains structural units represented by formula (5), the proportion of structural units represented by formula (5) in the total structural units of polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0100] In one embodiment, polymer P(I) includes a structural unit represented by formula (1-1).

[0101] [ka]

[0102] In the structural unit represented by formula (1-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom, or a substituted or unsubstituted C1-C6 alkyl group. Examples of this alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. Substituents for substituted C1-C6 alkyl groups include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups. X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of alkylene groups constituting X include methylene, ethylene, propylene, and butylene groups. Examples of substituents on a substituted alkylene group having 1 to 4 carbon atoms include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q and any carbon atom of the alkylene group of X may bond to form a ring. Examples of ring structures include a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, decalin ring, benzene ring, naphthalene ring, and the like. In formula (1-1), the embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or the embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group, is preferably used.

[0103] Preferably, X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following formula (1a), or X is an oxygen atom and Z is a (meth)acryloyl group.

[0104] [ka]

[0105] In formula (1a), R is either a hydrogen atom or a methyl group.

[0106] When polymer P(I) contains structural units represented by formula (1-1), the proportion of structural units represented by formula (1-1) in the total structural units of polymer P(I) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%.

[0107] When polymer P(I) contains both the structural unit of formula (1-1) and the structural unit of formula (1-4), polymer P(I) will have both a (meth)acryloyl group (the "-Z" group in formula (1-1)) and a carboxyl group represented by formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, polymer P(I) can be designed to have relatively large double bond equivalents and acid values ​​because the polymerizable group and carboxyl group are present within the same polymer molecule. In contrast, it is difficult to increase the content of both polymerizable groups and carboxyl groups in other resins such as (meth)acrylic resins. By having such a structure, polymer P(I) can achieve a high level of both sensitivity and developability.

[0108] Polymer P(I) may contain at least one of the structural units represented by formula (8) and the structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit consisting of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), and the structural unit of formula (9) is a structural unit consisting of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-3).

[0109] [ka]

[0110] [ka]

[0111] In equation (8), Q, X, and Z are equivalent to those in equation (1-1), and R p This is equivalent to the one in equation (1-2). In equation (9), Z, Q, and X are equivalent to those in equation (1-1), and R S This is equivalent to the one in equation (1-3).

[0112] When polymer P(I) contains structural units represented by formula (8), the proportion of structural units represented by formula (8) to the total structural units of polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. When polymer P(I) contains structural units represented by formula (9), the proportion of structural units represented by formula (9) in the total structural units of polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0113] Polymer P(I) may contain structural units derived from maleic anhydride represented by formula (MA).

[0114] [ka]

[0115] The structural unit derived from maleic anhydride, represented by formula (MA), undergoes ring-opening with an alkaline developer to produce two carboxyl groups (the structural unit represented by formula (3) below). Therefore, polymer P(I) containing this structural unit exhibits excellent developability. When polymer P(I) contains the structural unit represented by formula (MA), the amount of the structural unit represented by formula (MA) in the total structural units of polymer P(I) is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0116] [ka]

[0117] In one embodiment, polymer P(I) further comprises structural units represented by formula (B1) and / or formula (B2).

[0118] [ka]

[0119] [ka]

[0120] In equations (B1) and (B2), R d This is a group represented by formula (SI-4), formula (SI-5), or formula (SI-6).

[0121] [ka]

[0122] R in the group represented by formula (SI-4) f Each of these is an alkyl group having 1 to 30 carbon atoms. f 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.

[0123] R in the group represented by formula (SI-4) f’ Each of these is independently a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. f’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.

[0124] In the base represented by formula (SI-4), 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-4), n represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 3.

[0125] The group represented by formula (SI-4) is, for example, a group derived from the reaction of a structural unit derived from maleic anhydride represented by the above formula (MA) with a polysiloxane compound in which one amino group (-NH2) is introduced to the side chain of the polysiloxane (which may be referred to herein as "side-chain type aminosilicone").

[0126] [ka]

[0127] R in the group represented by formula (SI-5) g Each of these is an alkyl group having 1 to 30 carbon atoms. g 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.

[0128] R in the group represented by formula (SI-5) g’ R is a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. g’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. In the base represented by formula (SI-5), n represents an integer of 1 or more, preferably 1 to 500, more preferably 10 to 250, and more preferably 20 to 200.

[0129] The group represented by formula (SI-5) is, for example, a group derived from the reaction of a structural unit derived from maleic anhydride represented by the above formula (MA) with a polysiloxane compound in which one amino group (-NH2) is introduced to one end of the polysiloxane (which may be referred to herein as a "single-ended monoaminosilicone").

[0130] [ka]

[0131] R in the group represented by formula (SI-6) h Each of these is an alkyl group having 1 to 30 carbon atoms. h 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.

[0132] R in the group represented by formula (SI-6) h’ Each of these is independently a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. g’ The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. In the base represented by formula (SI-6), n represents an integer of 1 or more, preferably 1 to 500, more preferably 10 to 250, and more preferably 20 to 200.

[0133] The group represented by formula (SI-6) is, for example, a group derived from the reaction of a structural unit derived from maleic anhydride represented by the above formula (MA) with a polysiloxane compound in which two amino groups (-NH2) are introduced at both ends of the polysiloxane (which may be referred to herein as "double-ended diaminosilicone").

[0134] Polymer P(I) contains structural units represented by formula (B1) and / or formula (B2), and R d However, if the formula is (SI-4) (where n is 2 or greater) or (SI-6), polymer P(I) may have a structure in which polymer chains are crosslinked via multiple bonds of formula (SI-4) or (SI-6).

[0135] When polymer P(I) contains a group represented by formula (B1), the proportion of the group represented by formula (B1) in the total structural units of polymer P(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0136] When polymer P(I) contains a group represented by formula (B2), the proportion of the group represented by formula (B2) in the total structural units of polymer P(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0137] When polymer P(I) contains both structural units represented by formula (B1) and structural units represented by formula (B2), the total proportion of structural units represented by formula (B1) and structural units represented by formula (B2) in polymer P(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%, based on the total structural units constituting polymer P(I).

[0138] In one embodiment, polymer P(I) includes structural units represented by formula (ES) as structural units represented by formula (NB).

[0139] [ka]

[0140] In the formula (ES), R 31 , R 32 , R 33 and R 34 At least one of them is an alkyl ester-containing group represented by formula (es), R 31 , R 32 , R33 and R 34 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a3 is 0, 1, or 2. -X 3 -C(=O)-OR 35 (es) In equation (es), X 3 This is an alkylene group having 1 to 20 carbon atoms. R 35 These are alkyl groups having 1 to 3 carbon atoms.

[0141] The structural unit represented by formula (ES) is an alkyl ester group (-C(=O)-OR in formula (es)). 35 It has a cyclic olefin skeleton with ). The structural unit represented by formula (ES) is chemically robust due to the cyclic olefin skeleton. For this reason, polymer P(I) containing this as a structural unit exhibits little weight loss and is stable when subjected to heat treatment.

[0142] In the structural unit represented by the above formula (ES) that can constitute polymer P(I), a3 is 0, 1, or 2, preferably a3 is 0 or 1, and more preferably a3 is 0.

[0143] In the structural unit represented by the above formula (ES) that can constitute polymer P(I), R 31 , R 32 , R 33 and R 34 At least one of them is a base represented by formula (es), R 31 , R 32 , R 33 and R 34 The remaining elements are, independently, either hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. -X 3 -C(=O)-OR 35 (es) In the base represented by equation (es), X 3is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 14 carbon atoms, and more preferably an alkylene group having 3 to 10 carbon atoms. 3 The alkylene group is either linear or branched, and is preferably linear.

[0144] R in equation (es) 35 This is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group.

[0145] R in the structural unit represented by formula (ES) 31 , R 32 , R 33 or R 34 C1-C30 alkyl groups that can constitute the alkyl group include linear or branched alkyl groups having 1-30 carbon atoms. Specific examples of C1-C30 alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

[0146] In the structural unit represented by formula (ES), R other than the group represented by formula (es) 31 , R 32 , R 33 or R 34 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

[0147] In one embodiment, R 31 , R 32 , R 33 and R 34 At least one of them is a base represented by formula (es), and R in formula (es) 35 is an alkyl group having 1 to 3 carbon atoms, and R 31 , R 32 , R 33 and R 34 The remainder is a hydrogen atom. Preferably, R 31 , R 32 , R 33and R 34 One of the following is a base represented by formula (es), and R in formula (es) 35 is an alkyl group having 1 to 3 carbon atoms, and R 31 , R 32 , R 33 and R 34 The remaining three of these are hydrogen atoms. The structure of formula (ES) allows for improved film-forming properties of the resulting photosensitive resin composition containing polymer P(I), as well as improved water and liquid repellency of the cured film obtained by curing the photosensitive resin composition.

[0148] When polymer P(I) contains structural units represented by formula (ES), the proportion of structural units represented by formula (ES) among all structural units constituting polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and even more preferably 35 to 75 mol%.

[0149] In one embodiment, polymer P(I) includes structural units represented by formula (CA) as structural units represented by formula (NB).

[0150] [ka]

[0151] In the formula (CA), R 41 , R 42 , R 43 and R 44 At least one of them is a carboxyl group-containing group represented by formula (ca), and R 41 , R 42 , R 43 and R 44 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a4 is 0, 1, or 2. -X 4 -C(=O)-OH (ca) In equation (ca), X 4This is an alkylene group having 1 to 20 carbon atoms.

[0152] The structural unit represented by formula (CA) has a cyclic olefin skeleton with a carboxyl group (-C(=O)-OH in formula (ca)). The structural unit represented by formula (ES) is chemically robust due to its cyclic olefin skeleton. Therefore, polymer P(I) containing this as a structural unit exhibits little weight loss and is stable when subjected to heat treatment.

[0153] In the structural unit represented by the above formula (CA) that can constitute polymer P(I), a4 is 0, 1, or 2, preferably a4 is 0 or 1, and more preferably a4 is 0.

[0154] In the structural unit represented by the above formula (CA) that constitutes polymer P(I), R 41 , R 42 , R 43 and R 44 At least one of them is a group represented by formula (ca), and R 41 , R 42 , R 43 and R 44 The remaining elements are, independently, either hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. -X 4 -C(=O)-OH (ca) In the group represented by formula (ca), X 4 is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 14 carbon atoms, and more preferably an alkylene group having 3 to 10 carbon atoms. 4 The alkylene group is either linear or branched, and is preferably linear.

[0155] R in the structural unit represented by formula (CA) 41 , R 42 , R 43 or R 44C1-C30 alkyl groups that can constitute the alkyl group include linear or branched alkyl groups having 1-30 carbon atoms. Specific examples of C1-C30 alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

[0156] In the structural unit represented by formula (CA), R other than the group represented by formula (ca) 41 , R 42 , R 43 or R 44 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

[0157] In one embodiment, R 41 , R 42 , R 43 and R 44 At least one of them is a group represented by formula (ca), and R 41 , R 42 , R 43 and R 44 The remainder is a hydrogen atom. Preferably, R 41 , R 42 , R 43 and R 44 One of these is a group represented by formula (ca), and R 41 , R 42 , R 43 and R 44 The remaining three of these are hydrogen atoms. Having this structure in formula (CA) improves the film-forming properties of the resulting photosensitive resin composition containing polymer P(I), and also improves the water-repellent and liquid-repellent properties of the cured film obtained by curing the photosensitive resin composition.

[0158] When polymer P(I) contains structural units represented by formula (CA), the proportion of structural units represented by formula (CA) among all structural units constituting polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and even more preferably 35 to 75 mol%.

[0159] In one embodiment, polymer P(I) includes a structural unit represented by formula (NB-a) as a structural unit represented by formula (NB).

[0160] [ka]

[0161] In equation (NB-a), R 51 , R 52 , R 53 and R 54 At least one of them is a linear, branched, or cyclic hydrocarbon group having 2 to 30 carbon atoms, a polyoxyalkyl group having 2 to 30 carbon atoms, and the following formula (5a): [ka] at least one group selected from, where in formula (5a), * represents a bond, R 51 , R 52 , R 53 and R 54 The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a5 is 0, 1, or 2.

[0162] The structural unit represented by formula (NB-a) is chemically robust due to its cyclic olefin backbone. Therefore, polymer P(I) containing this structural unit exhibits minimal weight loss and is stable when subjected to heat treatment.

[0163] In the structural unit represented by the above formula (NB-a) that can constitute polymer P(I), a5 is 0, 1, or 2, preferably a5 is 0 or 1, and more preferably a5 is 0.

[0164] R in the structural unit represented by formula (NB-a) 51 , R 52 , R 53 or R 54 C1-C30 alkyl groups that can constitute the alkyl group include linear or branched alkyl groups having 1-30 carbon atoms. Specific examples of C1-C30 alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

[0165] In the structural unit represented by formula (NB-a), R other than the group represented by formula (5a) above 51 , R 52 , R 53 or R 54 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

[0166] In one embodiment, R 51 , R 52 , R 53 and R 54 At least one of the above formulas (5a) is R 51 , R 52 , R 53 and R 54 The remainder is a hydrogen atom. Preferably, R 51 , R 52 , R 53 and R 54 One of the above equations (5a) is R 51 , R 52 , R 53 and R 54The remaining three of these are hydrogen atoms. Having such a structure in formula (NB-a) improves the film-forming properties of the resulting photosensitive resin composition containing polymer P(I), and also improves the water-repellent and liquid-repellent properties of the cured film obtained by curing the photosensitive resin composition.

[0167] When polymer P(I) contains structural units represented by formula (NB-a), the proportion of structural units represented by formula (CA) among all structural units constituting polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and even more preferably 35 to 75 mol%.

[0168] In one embodiment, the polymer P(I) includes a structural unit represented by formula (MI).

[0169] [ka]

[0170] In the formula (MI), R 61 This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 62 and R 63 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. In the structural unit represented by (MI), R 61 R is a hydrogen atom or an organic group having 1 to 30 carbon atoms. 62 and R 63 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0171] In the structural unit represented by formula (MI), R 62 and R 63 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 62 and R 63 It is preferable that it be a hydrogen atom. R in equation (MI) 61Organic 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. 61 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] R in the structural unit represented by formula (MI) 61 Preferred elements include hydrogen atoms, alkyl groups, aryl groups, or aralkyl groups. R in the structural unit represented by formula (MI) 61 , R 62 and R 63 By selecting appropriately, in particular, R 61 By selecting R, the alkali solubility of the resulting polymer P(I) can be adjusted. For example, R 61 By using a hydrogen atom, the alkali solubility of the resulting polymer P(I) can be improved. 61 By using alkyl groups, cycloalkyl groups, or aryl groups, the alkali solubility of the resulting polymer P(I) can be suppressed. These substituents in the structural unit represented by formula (MI) can be selected according to the desired alkali solubility for the application of polymer P(I). Note, R 61 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 61 As an organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected.

[0176] When polymer P(I) contains structural units represented by formula (MI), the proportion of structural units represented by formula (MI) among all structural units constituting polymer P(I) is preferably 1 to 30 mol%, more preferably 1.5 to 28 mol%, and even more preferably 2 to 25 mol%. By setting the proportion of structural units represented by formula (MI) in polymer P(I) within the above range, the balance of sensitivity, alkali solubility, and heat discoloration resistance of polymer P(I) can be improved to a high level.

[0177] The content (ratio) of each structural unit contained in polymer P(I) 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.

[0178] The weight-average molecular weight Mw of polymer P(I) is, for example, 2,000 to 50,000. Preferably, the weight-average molecular weight Mw of polymer P(I) is 3,000 to 40,000, more preferably 4,000 to 30,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted. Furthermore, the degree of dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P(I) can be made homogenized, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0179] The glass transition temperature of polymer P(I) is preferably 30 to 250°C, more preferably 50 to 230°C. Polymer P(I) has a relatively high glass transition temperature due to the inclusion of structural units represented by formula (NB). This is advantageous in the manufacturing of liquid crystal displays and solid-state image sensors, as 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).

[0180] The acid value of polymer P(I) is 60 to 150 mg KOH / g, preferably 70 to 140 mg KOH / g. The double bond equivalent of polymer P1 is 100 to 900 g / mol, preferably 200 to 850 g / mol, more preferably 200 to 800 g / mol. By having an acid value of 60 mgKOH / g or higher for polymer P(I), good developability can be obtained. Furthermore, by having a double bond equivalent of 900 g / mol or less, the sensitivity of the photosensitive resin composition containing polymer P(I) can be increased.

[0181] Furthermore, if the acid value of polymer P(I) is too high, there is a concern that the exposed areas may dissolve easily during development with an alkaline developer, leading to an increased exposure amount required for photocuring or an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mg KOH / g. Furthermore, if the double bond equivalent of polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too high), unexposed or underexposed areas tend to be difficult to dissolve during development with an alkaline developer, and residual film tends to form during development. Also, if the double bond equivalent is too small, the molecular weight may increase excessively due to crosslinking, raising concerns about an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0182] The polymer P(I) of this embodiment, by having the above configuration, can have an alkali dissolution rate of 5 nm / s or more, preferably 100 nm / s or more, more preferably 300 nm / s or more, and particularly preferably 500 nm / s or more. The upper limit is not particularly limited, but for example it may be 3,000 nm / s or less. In this specification, the alkali dissolution rate is the value obtained when measured under the following conditions. (Method for measuring alkali dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, the obtained polymer solution is spin-coated onto a wafer, the PGMEA is dried, and a resin film with a thickness of 1 μm ± 0.2 is prepared by pre-baking at a temperature of 100°C for 2 minutes. This resin film, along with the wafer, is immersed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23°C. The immersed wafer is visually observed, and the time until the resin film dissolves and the interference pattern disappears, or the time until the resin film peels off, whichever is earlier, is measured. The alkali dissolution rate (nm / second) is calculated by dividing the film thickness before immersion (1 μm ± 0.2) by that time.

[0183] By adjusting the acid value and / or double bond equivalent of polymer P(I), it is possible to achieve an even higher level of balance between sensitivity and developability.

[0184] The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or other methods. For example, they can be determined by the following procedure (see the examples for more details). (1) Polymer 1 From the 1H-NMR chart, the area (integral value) of the peaks corresponding to hydrogen atoms of the carboxyl group and hydrogen atoms near polymerizable carbon-carbon double bonds is determined. (2) The area obtained in (1) is used to determine the amount of carboxyl groups and carbon-carbon double bonds from the area of ​​the peaks originating from the standard substance. (3) Convert the amount of carboxyl groups obtained in (2) to the acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) to the double bond equivalent (g / mol).

[0185] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P(I), particularly the number of polymerizable carbon-carbon double bonds in the (meth)acryloyl groups contained in the structural units represented by formula (1) or formula (2).

[0186] The silicon content in polymer P(I) is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass. By adjusting the silicon content within this range, polymer P(I) with excellent water repellency and liquid repellency can be obtained. Furthermore, polymer P(I) having a silicon content within the above range has a low refractive index of 1.50 or less. The refractive index of polymer P(I) 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(I) 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.

[0187] In this specification, the silicon content of polymer P(I) is as detailed in the examples. 1 It can be calculated by 1H-NMR measurement. Furthermore, in this specification, the refractive index of polymer P(I) is a value estimated from the refractive index of polymer P(I) solutions of different concentrations measured at 25°C.

[0188] (Method for producing polymer P(I)) Polymer P(I) can be manufactured (synthesized) by any method. Typically, polymer P(I) can be manufactured by the following steps aI, aII, and aIII. Step aI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA). Step aII: A step in which the raw material polymer obtained in step aI is reacted with a predetermined compound to open the ring of the structural unit of formula (MA) and obtain a polymer precursor. Step aIII: A step in which the polymer precursor obtained in step aII is reacted with an epoxy group-containing (meth)acrylic compound.

[0189] Based on the desired structure of polymer P(I), the conditions used in steps aI to aIII above can be adjusted. If polymer P(I) contains structural units represented by formula (1-2) and / or formula (1-3), the following step aII-i (ring opening of maleic anhydride-derived structural units by (meth)acrylate) is performed after step aI. Step aII-i: A step to prepare polymer P(I) (referred to as "polymer precursor (Ia)") which includes a structural unit of formula (MA) by reacting the raw material polymer obtained in Step aI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxyl group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to open the ring of the structural unit of formula (MA), thereby including the structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), and the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and optionally further including the structural unit represented by formula (MA). Here, the structural unit represented by equation (1) consists of the structural unit represented by equation (1-4) and the structural unit represented by equation (1-2), and the structural unit represented by equation (2) consists of the structural unit represented by equation (1-4) and the structural unit represented by equation (1-3).

[0190] If polymer P(I) contains structural units represented by formula (B1) and / or formula (B2), the following step aII-ii (ring opening of maleic anhydride-derived structural units by aminosilicone) is performed after step aI. Step aII-ii: A step in which the raw material polymer obtained in Step aI is reacted with an aminosilicone represented by formula (SI-4-m), formula (SI-5-m), or formula (SI-6-m), as detailed below, in the presence of a basic catalyst to open the ring of the structural unit of formula (MA) and obtain a polymer precursor (referred to as "polymer precursor (Ib)") containing the structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), the structural unit represented by formula (B1) and / or formula (B2), and the structural unit represented by formula (MA). Here, the structural units represented by formula (B1) and / or formula (B2) are structural units obtained by the reaction of the structural unit represented by formula (MA) in the raw material polymer with aminosilicone.

[0191] If polymer P(I) contains structural units represented by formula (1-5), the following step aII-iii (ring opening of maleic anhydride-derived structural units with alcohol) is performed after step aI or after step aII-ii. Step aII-iii: A step in which the raw material polymer obtained in step aI, or the polymer precursor (Ib) obtained in step aII-ii, is reacted with an alcohol represented by formula (AL) in the presence of a basic catalyst to open the ring of the structural unit of formula (MA) and obtain a polymer precursor containing the structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), the structural unit represented by formula (4), and the structural unit represented by formula (MA) (a precursor when going through the raw material polymer, referred to as "polymer precursor (Ic-i)"), or a polymer precursor containing the structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), the structural unit represented by formula (B1) and / or formula (B2), and the structural unit represented by formula (MA) (a precursor when going through polymer precursor (Ib), referred to as "polymer precursor (Ic-ii)"). Here, the structural unit represented by formula (4) has a structure consisting of structural units represented by formulas (1-5) and structural units represented by formulas (1-4), and is a structural unit obtained by the reaction of the structural unit represented by formula (MA) in the polymer precursor (Ia) with the alcohol represented by formula (AL). R 51 -OH (AL) In equation (AL), R 51 This refers to R in (1-5) above. 51 It is synonymous with [the above].

[0192] If polymer P(I) contains a structural unit represented by formula (1-1), the following step aIII-i is performed after step aII. Step aIII-i: A step to prepare polymer P(I) containing structural units represented by formula (NB), structural units represented by formula (1-1), and optionally further structural units represented by formula (MA), by reacting the first polymer precursor (Ia) obtained in step aII-i and the second polymer precursor (Ib) obtained in step aII-iii with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst.

[0193] The following describes each step. (Process aI) The step of preparing a raw material polymer containing a structural unit represented by formula (NB), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA) in step aI can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), any of the silicone-containing compounds (SI-m) represented by formula (SI-1-m), formula (SI-2-m), or formula (SI-3-m), and maleic anhydride represented by formula (MAm). 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). Also, 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).

[0194] Furthermore, if polymer P(I) contains structural units represented by formula (ES), formula (CA), and / or formula (NB-a), the monomers represented by formula (ESm), formula (CAm), and / or formula (NB-am) are used, respectively. The definitions of substituents for each monomer are the same as those for the corresponding structural units.

[0195] Furthermore, if polymer P(I) contains structural units represented by formula (MI), then the starting monomers represented by formula (MIm) are used. Here, the definition of substituents in formula (MIm) is the same as that in formula (MI).

[0196] (Monomer represented by formula (NBm)) [ka]

[0197] 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.

[0198] (Compound represented by formula (SI-1-m)) [ka]

[0199] 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.

[0200] (Compound represented by formula (SI-2-m)) [ka]

[0201] 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.

[0202] (Compound represented by formula (SI-3-m)) [ka]

[0203] 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".

[0204] (Monomer represented by formula (ESm)) [ka]

[0205] The monomer represented by formula (ESm) is available, for example, from Promelas, LLC. Furthermore, during polymerization, one monomer represented by formula (ESm) may be used, or two or more monomers may be used in combination.

[0206] (Monomer represented by formula (CAm)) [ka]

[0207] (Monomer represented by formula (NB-am)) [ka]

[0208] (Monomer represented by formula (MIm)) [ka]

[0209] While the polymerization method is not limited, 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.

[0210] 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.

[0211] The raw material polymer is synthesized by dissolving a monomer represented by formula (NBm), one of the silicone compounds represented by formulas (SI-1-m), (SI-2-m), or (SI-3-m), maleic anhydride, and a polymerization initiator in a solvent, charging the mixture into a reaction vessel, and then heating it to allow addition polymerization to proceed. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. When charging the reaction vessel, the molar ratio of the monomer represented by formula (NBm) to maleic anhydride (MAm) is preferably (NBm):(MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 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. Through this process, "raw material polymers" can be obtained. The raw material polymer may be any of the following: random copolymer, alternating copolymer, block copolymer, or periodic copolymer. Typically, it is a random copolymer or alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0212] Furthermore, after the synthesis of the raw material polymer, a step may be taken to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized raw material polymer 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. This precipitate is filtered, and if necessary, further washed with a poor solvent such as heptane, and then dried to increase the purity of the raw material polymer.

[0213] (Step aII-i) In step aII-i, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This reaction causes some of the structural units represented by formula (MA) in the raw material polymer to open rings, forming structural units represented by formula (1) and / or formula (2). A polymer precursor is obtained that contains structural units represented by formula (NB), as well as structural units represented by formula (1) and / or formula (2), and structural units represented by formula (MA). For convenience of explanation, the polymer precursor obtained here will be referred to as "polymer precursor (Ia)".

[0214] More specifically, first, a solution is prepared by dissolving the raw material polymer in a suitable organic solvent. As the organic solvent, single or mixed solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF) can be used, but are not limited to these; various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0215] To obtain a polymer precursor containing the structural unit represented by formula (NB), as well as both the structural unit represented by formula (1) and the structural unit represented by formula (2), a polyfunctional (meth)acrylic compound is then added to the above solution. A basic catalyst is then added. The solution is then properly mixed to obtain a homogeneous solution containing at least the structural unit of formula (NB) and the structural unit of formula (1) (step aII(1)).

[0216] Examples of polyfunctional (meth)acrylic compounds that can be used here include the compound represented by formula (1b-m), the compound represented by formula (1c-m), and the compound represented by formula (1d-m). k, R, and X in formula (1b-m) 1 , X 1 'and X 2The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in equation (1c) above. n and R in equation (1d-m) are the same as those in equation (1d) above.

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] Next, the polymer precursor obtained in step aII(1) is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor containing the structural unit of formula (NB), the structural unit of formula (1), and the structural unit of formula (2) (step aII(2)).

[0221] As a basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be used as appropriate. For example, amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds can be used as catalysts. The amount of basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of raw material polymer. Note that using an excess of basic catalyst may increase the amount of acid required for neutralization, potentially complicating the purification process.

[0222] By heating the above solution at a temperature of preferably 60-80°C for about 3-9 hours, ring-opening of the structural unit of formula (MA) and formation of the structural unit of formula (1) contained in the raw material polymer are achieved.

[0223] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process described above, ring-opening of the structural unit of formula (MA) contained in the raw material polymer and formation of the structural unit of formula (2) occur, and polymer P(I) having the structural unit represented by formula (2) is produced.

[0224] Due to steric hindrance and other factors, monofunctional (meth)acrylic compounds containing hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic compounds containing hydroxyl groups. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable not to add the monofunctional (meth)acrylic compound containing hydroxyl groups to the reaction system from the beginning, but rather to add it to the reaction system later. Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include compounds represented by the following formulas (2a-m). In equation (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0225] [ka]

[0226] Specific examples of compounds represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid.

[0227] To obtain a polymer precursor (Ia) containing a structural unit represented by formula (NB), and either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of steps aII(1) or aII(2) needs to be carried out after step aI.

[0228] (Step aII-ii) In step aII-ii, the raw material polymer obtained in step aI is reacted with an aminosilicone represented by formula (SI-4-m), formula (SI-5-m), or formula (SI-6-m) to open the ring of the structural unit of formula (MA), thereby generating a polymer precursor (Ib) containing the structural unit represented by formula (NB), one of the structural units represented by formulas (SI-1) to (SI-3), the structural unit represented by formula (B1) and / or formula (B2), and the structural unit represented by formula (MA).

[0229] Here, the definitions of substituents in formulas (SI-4-m), (SI-5-m), and (SI-6-m) are the same as those in formulas (SI-4), (SI-5), and (SI-6), respectively.

[0230] (Aminosilicone represented by formula (SI-4-m)) [ka]

[0231] The aminosilicone represented by formula (SI-4-m) is a side-chain type aminosilicone. Commercially available examples include Shin-Etsu Chemical's products such as "KF-868," "KF-865," "KF-859," "KF-860," "KF-880," "KF-8002," "KF-8021," "X-22-3939A," and "KF-877," Dow Toray's products such as the "DOWSIL(registered trademark) BY16" series, and Azmax's products such as the "AMS" series and "MCR-A series."

[0232] (Aminosilicone represented by formula (SI-5-m)) [ka]

[0233] The aminosilicone represented by formula (SI-5-m) is a single-ended monoaminosilicone, and commercially available products include, for example, Shin-Etsu Chemical Co., Ltd.'s products "X-22-9643", "X22-9644", and "X-22-9645".

[0234] (Aminosilicone represented by formula (SI-6-m)) [ka]

[0235] The aminosilicone represented by formula (SI-6-m) is a double-ended diaminosilicone. Commercially available examples include the "DOWSIL(registered trademark) BY16" series, "DOWSIL(registered trademark) FZ" series, and "DOWSIL(registered trademark) SF" series from Dow Toray, etc., "FM-3311", "FM-3321", "FM-3325", etc. from JNC Corporation, and "PAM-E", "KF-8010", "X22-161A", "X22-161B", "KF-8012", "KF-8008", "X-XX-1660B-3", and "X-22-9409", etc. from Shin-Etsu Chemical Co., Ltd.

[0236] (Step aII-iii) In steps aII-iii, the raw material polymer obtained in step aI, or the polymer precursor (Ib) obtained in step aII-ii, is reacted with an alcohol compound (AL) in the presence of an excess amount of the alcohol compound (AL) or a basic catalyst to produce a polymer precursor (Ic) containing the structural unit represented by formula (NB), the structural unit represented by formula (4), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA).

[0237] In steps aII-iii, an alcohol compound (AL) having a secondary or tertiary hydroxyl group is added to the reaction system containing the polymer precursor (Ia) obtained in step aII-i. By stirring this mixed solution, the polymer precursor (Ic) can be obtained. Examples of alcohol compounds (AL) include those represented by the following (AL): R 51 -OH (AL) In equation (AL), R 51 This is R in the above equation (1-5). 51 It is synonymous with [the above].

[0238] In step aII-iii, an alcohol compound represented by formula (AL) is added to the reaction system containing the polymer precursor (Ib) obtained in step aII-i. By stirring this mixed solution, the polymer precursor (Ic) can be obtained.

[0239] (Step aIII) In step aIII, the polymer precursor (Ia) obtained in step aII-i is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. This reaction causes the carboxyl groups (structural units (1-4)) of the structural units represented by formula (1) and / or formula (2) in the polymer precursor (Ia) to react with the epoxy groups of the epoxy group-containing (meth)acrylic compound to form the structural unit represented by formula (1-1). If the polymer precursor (Ia) obtained in step aII-i is used, step aIII-i produces polymer P(I) containing the structural unit represented by formula (NB), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (8) and / or the structural unit represented by formula (9). If some of the structural unit of formula (MA) remains ring-opened, polymer P(I) further contains the structural unit represented by formula (MA).

[0240] The reaction between the polymer precursor (Ia) and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst can be the one remaining in the reaction system obtained in step aII-i. Therefore, it is preferable to carry out step aIII by adding the epoxy group-containing (meth)acrylic compound in situ to the reaction mixture containing the polymer precursor obtained in step aII-i, without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor (Ia) obtained in step aII-i, or neutralizing the basic catalyst contained in the mixture.

[0241] Specifically, the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor (Ia) is heated, preferably at 60-80°C for about 1-9 hours. This reaction between the carboxyl groups (structural units (1-4)) of the polymer precursor (Ib) or (Ic) and the epoxy groups of the epoxy group-containing (meth)acrylic compound forms a structural unit represented by formula (1-1), thereby generating the target polymer P(I).

[0242] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate, and glycidyl acrylate, and one or more of these can be used.

[0243] The amount of epoxy group-containing (meth)acrylic compound added is preferably 0.1 to 3.0 moles per mole of carboxyl groups in the polymer precursor.

[0244] After step aIII, it is preferable to perform the following steps as appropriate to remove unwanted components other than the desired polymer P(I).

[0245] First, the reaction mixture containing polymer P(I) is diluted with an organic solvent, and then an acid (e.g., formic acid, citric acid, etc.) is added. The resulting reaction solution is then vigorously stirred in a separatory funnel for at least 3 minutes. After allowing it to stand for at least 30 minutes, the mixture separates into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of polymer P(I) is obtained.

[0246] After step aIII, the following steps may be carried out to purify the desired polymer P(I). First, an excess amount of toluene is added to the organic solution of polymer P(I) obtained in step aIII to reprecipitate polymer P(I). Then, the polymer powder obtained by reprecipitation is washed with toluene several more times (for example, twice). Furthermore, to remove acidic and basic catalysts, the obtained polymer powder is washed with deionized water several times (for example, three times). High-purity polymer P(I) of this embodiment can be obtained by drying the polymer powder, after washing with deionized water, at, for example, 30-60°C for 16 hours or more.

[0247] <Second Embodiment> The polymer of the present invention according to the first embodiment (hereinafter referred to as "polymer P(II)") is, The structural unit represented by formula (NB), The structural unit represented by formula (MA), A silicone-containing structural unit comprising at least one structure selected from structures represented by formulas (SI-1) to (SI-3), and a

[0248] [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.

[0249] [ka]

[0250] [ka]

[0251] 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.

[0252] [ka]

[0253] 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.

[0254] [ka]

[0255] 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.

[0256] Polymer P(II) is a raw material polymer used in the production of polymer P(I) in the first embodiment, and is the polymer obtained in steps aI and cI described above.

[0257] The weight-average molecular weight Mw of polymer P(II) is, for example, 2,000 to 30,000. Preferably, the weight-average molecular weight Mw of polymer P(II) is 2,500 to 20,000, and particularly preferably 3,000 to 15,000. By appropriately adjusting the weight-average molecular weight, it is possible to adjust the weight-average molecular weight of polymer P(I) obtained from polymer P(II), and as a result, the sensitivity and solubility of polymer P(I) in alkaline developers can be adjusted to a desired degree. Furthermore, the degree of dispersion of polymer P(II) (weight-average molecular weight Mw / number-average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0.

[0258] [Polymer solution] The polymer solution of this embodiment comprises the polymer P(I) and / or polymer P(II) described above. The polymer solution of this embodiment may also contain a silicone compound together with polymer P(I) and / or polymer P(II). This embodiment

[0259] (Silicone compounds) The silicone compound that may be included in the polymer solution of this embodiment may be the unreacted silicone compound used in steps aI and aII of the production of polymer P(I), or it may be one that has been added separately.

[0260] Examples of silicone compounds that can be incorporated into polymer solutions include, but are not limited to, monovalent mercaptosilicone represented by formula (SI-1-m), divalent mercaptosilicone represented by formula (SI-2-m), (meth)acrylicsilicone represented by formula (SI-3-m), side-chain aminosilicone represented by formula (SI-4-m), one-ended aminosilicone represented by formula (SI-5-m), and double-ended aminosilicone represented by formula (SI-6-m).

[0261] 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(I), 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(I).

[0262] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0263] Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyl lactone, N-methylpyrrolidone, and cyclohexanone. These may be used individually or in combination of two or more. The amount of organic 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.

[0264] [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.

[0265] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the polymer P(I) 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.

[0266] (Photosensitive agent) Examples of photosensitive agents used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators and acid generators. Known compounds can be used as photoradical polymerization initiators, for example, 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, 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(I). Known compounds can be used as acid generators. For example, specific examples include photosensitive diazoquinone compounds, onium salts (sulfonium salts, iodonium salts, etc.), sulfonic acid ester compounds, triazine compounds, oximesulfonate compounds, diazodisulfone compounds, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonate compounds, 2,6-bis(trichloromethyl)-1,3,5-triazine compounds, and dihydropyridine compounds. In particular, when the photosensitive resin composition is of the positive type (where the exposed area dissolves when developed with an alkaline developer after pattern exposure), it is preferable that the photosensitive agent contains a diazoquinone compound. Using a diazoquinone compound can improve sensitivity, resolution, and developability.

[0267] 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.

[0268] (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.

[0269] 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.

[0270] 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.).

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0276] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when applying it 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.

[0277] 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.

[0278] (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.

[0279] 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.

[0280] (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.

[0281] 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.

[0282] (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.

[0283] 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.

[0284] 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:

[0285] 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.

[0286] 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.

[0287] (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.

[0288] The photosensitive resin composition of this embodiment may be negative or positive. It can be designed to be either depending on the desired pattern shape. Typically, the photosensitive resin composition can be designed to be negative or positive by appropriately adjusting the type of photosensitive agent and the reactivity of the crosslinking agent.

[0289] [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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] This section describes each step in the manufacturing process of organic EL elements.

[0294] ·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.

[0295] 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.

[0296] 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.

[0297] • 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.

[0298] 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.

[0299] ·Development process A partition can be formed by developing an exposed photosensitive resin film with a suitable developer.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] • 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).

[0306] 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).

[0307] 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.

[0308] 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.

[0309] 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).

[0310] 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.

[0311] The ink (material liquid 4) printed (injected) into the opening 3 can be dried, for example, by an oven or hot air drying.

[0312] 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 that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0313] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0314] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride • PhMI:N-phenylmaleimide NB:2-Norbornen • C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (manufactured by Promelas, LLC) • DecNB: A compound represented by the following formula (DecNB). [ka] • MeOAcNB: A compound represented by the following formula (MeOAcNB). [ka] ·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) ·X-22-167C, X-22-167B: Bivalent mercaptosilicone (manufactured by Shin-Etsu Chemical Co., Ltd.) (Formula (SI-2-m) (wherein R b =CH 3、 R b (A compound represented by '=CH2) • KF-96-100cs: Unmodified silicone (manufactured by Shin-Etsu Chemical Co., Ltd.) HEMA:2-hydroxyethyl methacrylate 4-HBA: 4-hydroxybutyl acrylate • BuOH: 1-butanol • KF-868: Side-chain type aminosilicone (manufactured by Shin-Etsu Chemical Co., Ltd.) (Formula (SI-4-m) (wherein R f =CH 3、 R f (A compound represented by '=CH2) GMA: Glycidyl methacrylate • MEK: Methyl ethyl ketone • V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., azo polymerization initiator)

[0315] <Synthesis of raw material polymers> The raw material polymer was synthesized using the following method.

[0316] (Synthesis of raw material polymer 1) In a reaction vessel equipped with a stirrer and a condenser, maleic anhydride (588.36 g, 6.0 mol), 2-norbornene (564.90 g, 6.0 mol), and dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 55.26 g, 0.24 mol) were weighed and added. These were dissolved in a mixed solvent consisting of methyl ethyl ketone (1716.8 g) and toluene (188.3 g) to prepare a solution. To this solution, nitrogen was passed through for 30 minutes to remove oxygen, and then the mixture was heated at 65°C for 1.5 hours while stirring, and then heated at 80°C for 6 hours to polymerize maleic anhydride and 2-norbornene, thereby preparing a polymerization solution. The polymerization solution obtained above was added dropwise to methanol (14230.2 g) to precipitate a white solid. The obtained white solid was further washed with methanol (3557.5 g) and then vacuum-dried at 120°C to obtain 1027.2 g of polymer (raw material polymer 1) comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 7,200, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 1.83.

[0317] (Synthesis of raw material polymer 2) In a reaction vessel of appropriate size equipped with a stirrer and condenser, maleic anhydride (353.02 g, 3.6 mol), 2-norbornene (338.94 g, 3.6 mol), and dimethyl 2,2'-azobis(2-methylpropionate) (41.45 g, 0.180 mol) were weighed and placed. These were dissolved in a mixed solvent consisting of methyl ethyl ketone (578.98 g) and toluene (113.0 g) to prepare a solution. To this solution, nitrogen was passed through for 30 minutes to remove oxygen, and then the mixture was heated at 63°C for 9.5 hours while stirring to polymerize maleic anhydride and 2-norbornene, thereby preparing a polymerization solution. The polymerization solution obtained above was diluted with methyl ethyl ketone (712.92 g), and then precipitated as a white solid by dropping it into methanol (8519.9 g). The obtained white solid was vacuum-dried at 120°C to obtain 550.4 g of a polymer (raw material polymer 2) having structural units derived from 2-norbornene and structural units derived from maleic anhydride. GPC analysis of the obtained polymer revealed a weight-average molecular weight (Mw) of 11,600 and a polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) of 1.79.

[0318] (Synthesis of raw material polymer 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB, 381.01 g, 1.221 mol), maleic anhydride (MAN, 119.73 g, 1.221 mol), dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 30.14 g, 0.131 mol), and methyl ethyl ketone (MEK, 94.86 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the reaction was carried out at an internal temperature of 60°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 (2000.0 g). The obtained white solid was further washed with methanol (2000.0 g) and then vacuum-dried at 120°C to obtain 90.50 g of a polymer (raw material polymer 3) comprising structural units derived from C4F9NB and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 6,400, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 1.51. Furthermore, the obtained polymer 19 Measurements using 1F-NMR revealed that the fluorine content of the polymer was 39.9 wt%.

[0319] In addition, 19The conditions for F-NMR measurement are as follows: Approximately 100 mg of polymer and approximately 60 mg of (trifluoromethyl)benzene as an internal standard were weighed and dissolved in approximately 1 g of acetone-d6. This solution was then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 19 1F-NMR measurements were performed. From the integral ratio of the CF3 signals (-75 to -81 ppm, 3F) and CF2 signals (-100 to -130 ppm, 2F) of the polymer in the obtained spectral chart, and the CF3 signal (-63 ppm, 3F) of the internal standard, the amounts of CF3 (mol / g) and CF2 (mol / g) in the polymer were calculated. The fluorine content (wt%) in the polymer was calculated from the total amount of CF3 (mol / g) and CF2 (mol / g) calculated in the polymer.

[0320] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (35.31 g, 0.375 mol), and methyl ethyl ketone (MEK, 69.33 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the temperature was raised to 60°C. A solution of KF-2001 (14.25 g, 0.075 mol calculated by considering the mercapto group equivalent as molecular weight) and dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 3.45 g, 0.015 mol) dissolved in 69.33 g of MEK was added dropwise over 1 hour while maintaining the temperature at 60°C. The reaction was then continued at 60°C for 4 hours. After adding 47.55 g of MEK, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into methanol (1151.1 g). The obtained white solid was then washed with methanol (1151.1 g), and this process was repeated twice, followed by washing with heptane (1151.1 g). Vacuum drying at 80°C yielded 10.1 g of polymer (raw material polymer 4) containing structural units derived from 2-norbornene, maleic anhydride, and KF-2001. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 13,500, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.82. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 12.0 wt%. 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.

[0321] The elemental analysis method is as follows: - Test items Flask combustion and ion chromatography for the determination of total sulfur. - Test method Flask combustion ~ Ion chromatography (1) Completely combust approximately 50 mg of the sample in a sealed flask with oxygen replaced. (2) The generated gas is collected in the hydrogen peroxide absorption solution that has been added to the flask beforehand, and the volume is adjusted to 50 ml to be used as the test solution. (3) The sample solution and standard solution are introduced into an ion chromatograph, and the concentration of sulfate ions is determined by the calibration curve method to calculate the amount of sulfur contained in the sample. -Equipment used DIONEX ICS-3000 Ion Chromatograph

[0322] The method for measuring the silicon (Si) content of a polymer is as follows: Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in acetone-d6. This solution was then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1¹H-NMR measurements were performed. The amount of Si in the polymer (mol / g) was calculated from the integral ratio of the CH3 signal (-0.40-0.40 ppm, 3H) bonded to Si in the obtained spectral chart and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). The Si content (wt%) in the polymer was then calculated. In this calculation, all carbon atoms bonded to Si were treated as CH3.

[0323] (Synthesis of raw material polymer 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (35.31 g, 0.375 mol), and methyl ethyl ketone (MEK, 62.24 g) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated to an internal temperature of 60°C. A solution of KF-2001 (28.50 g, 0.015 mol calculated by considering the mercapto group equivalent as molecular weight) and dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 3.45 g, 0.015 mol) dissolved in MEK (62.24 g) was added dropwise over 1 hour while maintaining the internal temperature at 60°C. The reaction was then continued at 60°C for another 4 hours. Finally, MEK (16.64 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 (1341.1 g). The obtained white solid was then washed with methanol (1341.1 g), and this process was repeated twice, followed by vacuum drying at 80°C to obtain 20.1 g of polymer (raw material polymer 5) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from KF-2001. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 15,700, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.77. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 17.3 wt%. 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.

[0324] (Synthesis of raw material polymer 6) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (32.26 g, 0.342 mol), X-22-174ASX (29.16 g, 0.0324 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, 133.08 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 (1091.0 g). The obtained white solid was further washed with methanol (1091.0 g), and the resulting white solid was washed again with heptane (1091.0 g) twice. By vacuum drying at 80°C, 55.2 g of a polymer (raw material polymer 6) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-174ASX was obtained. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 9,800, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 1.93. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 10.3 wt%. Raw material polymer 6 13 ¹³C-NMR analysis revealed peaks originating from carbon bound to Si at -2 ppm to 4 ppm, and R in equation (SI-3) around 13 ppm and 18 ppm. c1The C (the C of the CH3 in the methacryloyl group) and the R in formula (SI-1) c ', R c A peak originating from one of the C atoms appeared, and the peak originating from the -CH2=C of the methacryloyl group of the raw material methacrylic silicone (X-22-174ASX) around 123 ppm disappeared, confirming that methacrylic silicone had been introduced into the raw material polymer 6.

[0325] In addition, 13 The conditions for 1C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding the measurement solvent to the weighed sample to adjust the concentration, and then pouring the specified amount into an NMR measurement sample tube. • Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR spectrometer ·Resonance frequency: 100.53MHz • Measurement nucleus: 13 C • Measurement method: BCM measurement (Bi-level CoMplete decoupling method) Pulse width: 11.8 μsec • Pulse repetition waiting time: 2s • Total number of times: 2048 ·Measurement temperature: room temperature • Measurement solvent: THF-d8 (deuterated tetrahydrofuran) • Sample concentration: 30% (w / v)

[0326] (Synthesis of raw material polymer 7) In a reaction vessel equipped with a stirrer, condenser, and 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 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, 102.52 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 (213.57 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 (1922.1 g). The obtained white solid was further washed with methanol (1922.1 g), and the resulting white solid was washed again with heptane (1922.1 g) twice. By vacuum drying at 80°C, 88.7 g of a polymer (raw material polymer 7) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from KF-2001 was obtained. The obtained polymer 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 3.15. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 7.4 wt%. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the sulfur content in the polymer was found to be 0.50 wt%. Raw material polymer 7 13 ¹¹C-NMR analysis revealed peaks originating from the carbon in the maleic anhydride ester at 170–174 ppm, as well as peaks originating from the carbon bonded to Si at -2 ppm–4 ppm, and R in equation (SI-1) at 16–17 ppm. a We confirmed the appearance of a peak originating from one of the C's. 13 Based on 1C-NMR analysis and elemental analysis results, it was confirmed that mercaptosilicone was introduced into the raw material polymer 7.

[0327] (Synthesis of raw material polymer 8) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), 2-norbornene (47.08 g, 0.500 mol), X-22-167C (48.03 g, 0.0209 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, 102.52 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 (213.57 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 (1922.1 g). The obtained white solid was further washed with methanol (1922.1 g), and the resulting white solid was washed again with heptane (1922.1 g) twice. By vacuum drying at 80°C, 79.0 g of a polymer (raw material polymer 8) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-167C was obtained. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 6,200, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.08. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 7.6 wt%. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the sulfur content in the polymer was found to be 0.37 wt%. Raw material polymer 8 13¹¹C-NMR analysis revealed peaks originating from the carbon of the maleic anhydride ester at 170–174 ppm, as well as peaks originating from the carbon bonded to Si at -2 ppm–4 ppm, and R in equation (SI-2) at 16–17 ppm. b We confirmed the appearance of a peak originating from one of the C's. 13 Based on 13C-NMR analysis and elemental analysis results, it was confirmed that mercaptosilicone was introduced into the raw material polymer 8.

[0328] (Synthesis of raw material polymer 9) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (31.72 g, 0.337 mol), X-22-174AX (34.26 g, 0.0381 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, 140.10 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 (1141.7 g). The obtained white solid was further washed with methanol (1141.7 g), and the resulting white solid was washed again with heptane (1141.7 g) twice. By vacuum drying at a temperature of 80°C, 47.2 g of a polymer (raw material polymer 9) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-174AX was obtained. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 6,200, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.08. Furthermore, the obtained polymer 1Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 10.7 wt%.

[0329] (Synthesis of raw material polymer 10) 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 a polymer (raw material polymer 10) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from KF-2012 was obtained. The obtained polymer 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. 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. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 12.0 wt%.

[0330] (Synthesis of raw material polymer 11) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), 2-norbornene (47.08 g, 0.500 mol), X-22-167B (48.03 g, 0.0282 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, 102.52 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 (213.57 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 (1922.1 g). The obtained white solid was further washed with methanol (1922.1 g), and the resulting white solid was washed again with heptane (1922.1 g) twice. By vacuum drying at 80°C, 88.4 g of a polymer (raw material polymer 11) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-167B was obtained. The obtained polymer 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 1.82. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 8.1 wt%.

[0331] (Synthesis of raw material polymer 12) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (28.48 g, 0.303 mol), X-22-174AX (65.27 g, 0.0725 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, 182.84 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 (36.24 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 (1450.3 g). The obtained white solid was further washed with methanol (1450.3 g), and then the obtained white solid was further washed with heptane (1450.3 g). By vacuum drying at a temperature of 80°C, 5.2 g of a polymer (raw material polymer 12) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-174ASX was obtained. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 13,300, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.75. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 15.3 wt%.

[0332] (Synthesis of raw material polymer 13) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), DecNB (117.20 g, 0.500 mol), KF-2001 (83.13 g, 0.0438 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, 207.79 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 (369.40 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 (3324.6 g). The obtained white solid was further washed with methanol (3324.6 g) and then vacuum-dried at 80°C to obtain 99.8 g of a polymer (raw material polymer 13) comprising structural units derived from DecNB, structural units derived from maleic anhydride, and structural units derived from KF-2001. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 13,900, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.84. 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. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 14.9 wt%.

[0333] (Synthesis of raw material polymer 14) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), MeOAcNB (83.11 g, 0.500 mol), KF-2001 (66.12 g, 0.0349 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, 164.19 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 (293.64 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 (2642.8 g). The obtained white solid was further washed with methanol (2642.8) and then vacuum-dried at 80°C to obtain 120.3 g of a polymer (raw material polymer 14) comprising structural units derived from MeOAcNB, structural units derived from maleic anhydride, and structural units derived from KF-2001. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 10,000, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.75. 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. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 16.5 wt%.

[0334] (Synthesis of raw material polymer 15) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), 2-norbornene (47.08 g, 0.500 mol), X-22-167B (144.16 g, 0.0848 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, 219.96 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 80°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 (1922.1 g). The obtained white solid was further washed with methanol (1922.1 g), and this process was repeated twice. The resulting white solid was then vacuum-dried at 80°C to obtain 150.2 g of a polymer (raw material polymer 15) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-167B. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,900, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 1.96. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 23.4 wt%.

[0335] (Synthesis of raw material polymer 16) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (25.53 g, 0.271 mol), X-22-174ASX (93.45 g, 0.1038 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, 221.67 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 80°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 (1557.6 g). The obtained white solid was further washed with methanol (1557.6 g), and this process was repeated twice. The resulting white solid was then vacuum-dried at 80°C to obtain 86.1 g of a polymer (raw material polymer 16) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-174ASX. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 13,400, while the polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) was 2.78. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 20.7 wt%.

[0336] (Synthesis of raw material polymer 17) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (18.09 g, 0.192 mol), X-22-174ASX (164.57 g, 0.1829 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, 319.66 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 80°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 (1557.6 g). The obtained white solid was further washed with methanol (1557.6 g), and this process was repeated twice. The resulting white solid was then vacuum-dried at 80°C to obtain 134.2 g of a polymer (raw material polymer 17) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from X-22-174ASX. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 22,400, with a polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) of 3.43. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 26.4 wt%.

[0337] (Synthesis of raw material polymer 18) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (36.77 g, 0.375 mol), 2-norbornene (31.14 g, 0.331 mol), KF-2012 (203.72 g, 0.0443 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. 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 (2716.3 g). The obtained white solid was further washed with methanol (2716.3 g), and this process was repeated twice. The resulting white solid was then vacuum-dried at 80°C to obtain 167.7 g of a polymer (raw material polymer 18) comprising structural units derived from 2-norbornene, structural units derived from maleic anhydride, and structural units derived from KF-2012. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 17,300, with a polydispersity ((weight-average molecular weight Mw) / (number-average molecular weight Mn)) of 3.40. 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. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 32.8 wt%.

[0338] (Synthesis of raw material polymer 19) 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 (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 (raw material polymer 19) containing structural units derived from 2-norbornene, maleic anhydride, N-phenylmaleimide, and KF-2001. The obtained polymer 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 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 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur elements in the polymer was confirmed. Raw material polymer 19 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 Based on 13C-NMR analysis and elemental analysis results, it was confirmed that a maleimide skeleton and mercaptosilicone were introduced into the raw material polymer 19.

[0339] Table 1 below shows the monomer species used in the synthesis of the raw material polymer, the monomer charge ratio, and the weight-average molecular weight (Mw), polydispersity (Mw / Mn), and silicon (Si) content of the raw material polymer.

[0340] [Table 1]

[0341] [Examples A1-A18, Comparative Examples A1-A3] The water repellency, liquid repellency, heat resistance, refractive index, and tackiness of the raw polymers in each example were measured as follows. The results are shown in Table 2-1.

[0342] (Water-repellent and liquid-repellent properties of the raw polymer alone) In Comparative Examples A1-A3, Examples A1-A11, and Examples A14-A18, the obtained raw material polymer was dissolved in 2-heptanone to prepare a solution with a solid content concentration of 30% by mass. This solution was then rotary coated onto 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 approximately 1.0 μm (±0.2 μm). In Examples A12 and A13, a mixture of the raw material polymer and the silicone compound shown in Table 2-1 was rotary coated onto 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 approximately 1.0 μm (±0.2 μm). The contact angles of this thin film with respect to water and with respect to PGMEA were measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). In this experiment, the volume of the prepared droplet was 2 μL, the observation time was 10 seconds after droplet placement, and the average of 5 measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°).

[0343] Next, the thin film, after contact angle measurement, was heated at 230°C for 60 minutes to cure it and 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 2-1.

[0344] A contact angle of 94° or higher with respect to water indicates good water repellency, 98° or higher indicates better water repellency, and 102° or higher indicates particularly excellent water repellency. A contact angle of 5° or higher with respect to PGMEA indicates good liquid repellency, 10° or higher indicates better liquid repellency, and 15° or higher indicates particularly excellent liquid repellency.

[0345] (Heat resistance of raw polymer) The heat resistance of the raw polymer was evaluated using the 5% weight loss temperature (Td5), 10% weight loss temperature (Td10), and 20% weight loss temperature (Td20) as indicators. The measurement method is as follows. In Comparative Examples A1-A3, Examples A1-A11, and Examples A14-A18, the raw polymer (1 mg) 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 in an air atmosphere at a heating rate of 10°C / min. During this process, the temperatures at which a 5% thermogravimetric loss occurred (Td5), a 10% thermogravimetric loss occurred (Td10), and a 20% thermogravimetric loss occurred (Td20) relative to the weight of the polymer were recorded. The results are shown in Table 2-1. If Td5 is 290°C or higher, the heat resistance is considered good; if it is 310°C or higher, the heat resistance is considered better; and if it is 330°C or higher, the heat resistance is considered particularly excellent. If Td10 is 310°C or higher, the heat resistance is considered good; if it is 320°C or higher, the heat resistance is considered better; and if it is 340°C or higher, the heat resistance is considered particularly excellent. If Td20 is 330°C or higher, the heat resistance is considered good; if it is 340°C or higher, the heat resistance is considered better; and if it is 365°C or higher, the heat resistance is considered particularly excellent.

[0346] (Potential for thick-film coating of raw polymers) The coating properties of the raw material polymer were evaluated in terms of workability when forming thick films with a thickness of 5 μm or more. In Comparative Examples A1-A3 and Examples A1-A18, the obtained raw material polymer was dissolved in 2-heptanone to prepare a solution with a solid content concentration of 30% by mass. This solution was then rotary coated onto 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 approximately 5.0 μm (±0.2 μm). The appearance of the obtained thin film was observed, and the thick-film coating capability was evaluated according to the following evaluation criteria. The results are shown in Table 2-1. A: The membrane has no visible abnormalities such as cracks or roughness. B: The membrane has cosmetic abnormalities such as cracks or roughness.

[0347] (PFAS compliance of raw material polymers) Furthermore, Table 2-1 shows the PFAS classification of the raw material polymers. "PFAS classified" indicates that the raw material polymer is derived from a monomer classified as PFAS, while "PFAS not classified" indicates that the raw material polymer is derived from a monomer not classified as PFAS.

[0348] (Refractive index of raw material polymer) The refractive index of the raw material polymers was measured using the following method. First, the raw material polymers obtained in Comparative Examples A1-A3 and Examples A1-A18 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 without polymers using a Kyoto Electronics Manufacturing Co., Ltd. refractometer (RA-600). For each polymer, the refractive index against solid content concentration was plotted, and the refractive index at 589 nm was calculated from the approximation curve obtained by linearly approximating the obtained plots, where the solid content concentration was 100%. The results are shown in Table 2-1. 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.

[0349] (Tackiness of the raw polymer) The tackiness of the raw polymer was evaluated using the following method. The presence or absence of tackiness in the raw material polymer is an indicator of whether the silicone compound used as the raw material compound was introduced into the molecule of the resulting raw material polymer, or whether it was not introduced into the raw material polymer and existed as a free compound. The silicone compound used as the raw material compound has high tackiness on its own. When the silicone compound is introduced into the molecular chain of the raw material polymer, the tackiness of the silicone compound disappears or is reduced, and the resulting raw material polymer has little to no tackiness. In Comparative Examples A1-A3, Examples A1-A11, and Examples A14-A18, the obtained raw material polymer was dissolved in 2-heptanone to prepare a solution with a solid content concentration of 30% by mass. This solution was then rotary coated onto a 3-inch silicon wafer to form a coating film of 2±0.2 μm after drying, and then dried at 100°C for 2 minutes to obtain the coating film. In Examples A12 to A13, a mixture of the raw material polymer and the silicone compound shown in Table 2-1 was rotary coated onto a 3-inch silicon wafer to form a coating film of 2 ± 0.2 μm after drying, and then dried at 100°C for 2 minutes to obtain the coated film. The tackiness of the obtained coating film was checked by touch. The results were evaluated in a sensory test using the following criteria. The sensory test method involved pressing an index finger onto the coating film for 3 seconds, and then lifting the finger straight up to evaluate the degree to which the coating film stuck to the finger. The results are shown in Table 2-1. A coating without tackiness is easier to handle. A: When you lift your finger, the coating does not stick to your finger. B: When you lift your finger, the coating film sticks to your finger, but it comes off immediately. C: When you release your finger, the coated film lifts slightly before separating.

[0350] [Table 2] [Table 3]

[0351] (Change in molecular weight due to curing of the raw polymer) In Examples A3, A4, and A5, the molecular weight changes of raw material polymers 6, 7, and 8 before and after curing were measured. First, the weight-average molecular weight of raw polymers 6, 7, and 8 was measured using GPC. The results are shown in Table 2-2 as "Mw before curing". Next, raw material polymers 6, 7, and 8 were rotary coated onto a 4-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 approximately 1.0 μm (±0.2 μm). Then, this wafer was heated at 230°C for 60 minutes to cure. After curing, THF (5 m) was dropped onto the coated film and allowed to stand for 15 minutes. After that, the THF on the wafer was filtered, and the weight-average molecular weight was measured using GPC. The results are shown in Table 2-2 as "Mw after curing".

[0352] [Table 4]

[0353] The raw material polymers 4-19 in the examples were PFAS-free and exhibited high water and liquid repellency. The raw polymers 6, 9, 12, 13, and 15-18 showed increased liquid repellency after curing treatment. The raw material polymers 4, 5, 7, 13, and 14, and the raw material polymers 15-18 with high Si content, into which side-chain mercaptosilicone (KF-2001) was introduced, showed improved flexibility and enabled thick film coating. The raw material polymers 4-19 in the examples all had high Td5, Td10, and Td20 values, and exhibited excellent heat resistance. The weight-average molecular weight Mw of raw polymers 6 and 7 increased after the curing treatment. The raw polymer 8 underwent a change in contact angle due to the curing treatment, but there was no change in its weight-average molecular weight.

[0354] <Synthesis of Polymer P> Using the above-mentioned raw material polymers, polymer P was prepared using the following method. Table 3 shows the components used in the synthesis example and the amount of each component used, converted to maleic anhydride (MA) equivalent. The following physical properties of the obtained polymer P were measured. The results are shown in Table 3. (Weight average molecular weight, polydispersity) The obtained polymer P was subjected to GPC measurements to determine its weight-average molecular weight and polydispersity. (Silicon content) The silicon (Si) content (wt%) of the obtained polymer P is, 1 The results were measured by 1H-NMR. (double bond equivalent) The double bond equivalent of polymer P was measured by the following method. Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1¹H-NMR measurements were performed. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from acryloyl groups (5.8-6.7 ppm, 3H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H) in the obtained spectral chart. The amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from methacryloyl groups (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). Here, the signal originating from methacryloyl groups at 6.0-6.1 ppm was minute and overlapped with the signal of acryloyl groups, so it was calculated as the signal of acryloyl groups. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and the double bond equivalent (g / mol) was calculated from the double bond amount. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer.

[0355] (Preparation Example 1) Polymer P1 was prepared by ring-opening the maleic anhydride-derived structural units (MA units) of raw material polymer 1 with a monofunctional (meth)acrylic compound (HEMA), and then reacting them with an epoxy group-containing (meth)acrylic compound (GMA). The details are described below. First, MEK (18.57g) was added to raw material polymer 1 (10.00g, equivalent to 0.052 moles of MA calculated from the amount of raw material polymer 1 used) to prepare a solution. Next, HEMA (4.23g, 0.035 mol) was added to this solution, followed by triethylamine (1.00g, 0.010 mol), and the mixture was reacted at 70°C for 6 hours. After that, GMA (2.22g, 0.016 mol) was added, and the mixture was reacted at 70°C for 4 hours. The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified using the following procedure. • The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of water. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, polymer P1 was obtained by ring-opening the maleic anhydride-derived structural units in the raw material polymer with HEMA, and then reacting them with GMA. GPC analysis of polymer P1 confirmed the disappearance of the peaks of the monofunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P1 did not contain any unreacted (meth)acrylic compounds or epoxy group-containing (meth)acrylic compounds. 1 1H-NMR measurements confirmed that polymer P1 has a structure in which the MA units of the raw material polymer are ring-opened with HEMA, and a structure in which GMA has reacted with it.

[0356] (Preparation Example 2) Polymer P2 was prepared by ring-opening the MA units of raw material polymer 2 with an excess amount of 1-butanol. Details are described below. First, 1-butanol (BuOH) (20.00g, 0.270 mol) was added to raw material polymer 2 (10.00g, 0.052 mol in MA equivalent, calculated from the amount of raw material polymer 2 used), and the mixture was reacted at 118°C for 16 hours to prepare the reaction solution. The resulting reaction mixture was subjected to solvent removal under reduced pressure at 50°C using a rotary evaporator. The solvent removal process was stopped when the solid content of the polymer solution was confirmed to be 35±2% by mass, as measured by a heat-drying moisture meter. Then, PGMEA was added to bring the solid content to 25% by mass, and the mixture was mixed until homogeneous. The same procedure was repeated two more times, removing the solvent under reduced pressure at 50°C, adjusting the solid content to 35±2% by mass as measured by a heat-drying moisture meter, and then adding PGMEA to bring the solid content to 25% by mass, mixing until homogeneous. Finally, the solvent was removed or PGMEA was added and stirred until homogeneous, resulting in a solid content of 30±3% by mass. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Based on the above, a resin composition 2 containing polymer P2 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 2 with 1-butanol. 13 1C-NMR measurements confirmed that polymer P2 has a structure in which the structural units (MA units) derived from maleic anhydride of the raw material polymer 2 are ring-opened with 1-butanol.

[0357] (Preparation Example 3) Polymer P3 was prepared by ring-opening the MA units of raw material polymer 3 with a monofunctional (meth)acrylic compound (4-HBA), and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are explained below. First, MEK (10.00g) was added to raw material polymer 3 (10.00g, equivalent to 0.024 moles of MA calculated from the amount of raw material polymer 3 used) to prepare a solution. Next, 4-HBA (2.19g, 0.015 mol) was added to this solution, followed by triethylamine (1.50g, 0.015 mol), and the mixture was reacted at 70°C for 6 hours. After that, GMA (1.03g, 0.007 mol) was added, and the mixture was reacted at 70°C for 4 hours. The prepared reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid and aqueous citric acid solutions. The polymer was then purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water, and this process was repeated twice. The resulting reaction product was vacuum-dried at 40°C for 12 hours. Based on the above, the structural units derived from maleic anhydride in the raw material polymer 3 were ring-opened with a monofunctional (meth)acrylic compound (4-HBA), and polymer P3 was obtained by reacting it with GMA to obtain 8.3 g of polymer P3. GPC analysis of polymer P3 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound. Also 131C-NMR measurements confirmed that polymer P3 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 3 is ring-opened with 4-HBA, and a structure in which GMA is introduced. Furthermore, the obtained polymer 19 Measurements using 1F-NMR revealed that the fluorine content of the polymer was 32 wt%.

[0358] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA units of raw material polymer 6 with a monofunctional (meth)acrylic compound (4-HBA), and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are explained below. First, MEK (20.00g) was added to raw material polymer 6 (10.00g, calculated as 0.052 moles of MA with a composition ratio of NB / MAN = 50 / 50) to prepare a solution. Next, 4-HBA (4.69g, 0.033 mol) was added to this solution, followed by triethylamine (1.50g, 0.015 mol), and the mixture was reacted at 70°C for 6 hours. After that, GMA (2.03g, 0.015 mol) was added, and the mixture was reacted at 70°C for 4 hours. After neutralization by adding formic acid aqueous solution to the prepared reaction solution, the polymer was purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water, and this process was repeated twice. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, the MA units of polymer 6 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 10.1 g of polymer P4. GPC analysis of polymer P4 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P4 did not contain any unreacted monofunctional (meth)acrylic compound. Also 131C-NMR measurements confirmed that polymer P4 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 6 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0359] (Preparation Example 5) Polymer P5 was prepared by ring-opening the MA units of raw material polymer 6 with side-chain aminosilicone (KF-868). Details are described below. First, a solution was prepared by adding tetrahydrofuran (100.00g) to raw material polymer 6 (10.00g, equivalent to 0.052 moles of MA calculated with a composition ratio of NB / MAN = 50 / 50). Next, a solution of KF-868 (2.50g, equivalent to 0.00028 moles calculated by considering the amino group equivalent as molecular weight) dissolved in tetrahydrofuran (12.50g) was added to this solution, and the mixture was reacted at 60°C for 6 hours. The polymer was reprecipitated from the prepared reaction solution with methanol (1000 g). The polymer powder obtained by reprecipitation was washed with methanol (1000 g) twice. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, 8.5 g of polymer P5 was obtained by ring-opening the maleic anhydride-derived structural units in raw material polymer 6 with side-chain type aminosilicone (KF-868). Also 13 1C-NMR measurements confirmed that polymer P5 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 6 is ring-opened with KF-868.

[0360] (Preparation Example 6) Except for using raw material polymer 7 (10.00 g, with an MA equivalent mole of 0.052 moles calculated with a composition ratio of NB / MAN = 50 / 50) instead of raw material polymer 6, the MA units of raw material polymer 7 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 10.4 g of polymer P6. Furthermore, GPC analysis of polymer P6 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P6 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P6 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 7 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0361] (Preparation Example 7) Except for using raw material polymer 7 (10.00 g, with an MA equivalent mole of 0.052 moles calculated with a composition ratio of NB / MAN = 50 / 50) instead of raw material polymer 2, the MA units of raw material polymer 7 were ring-opened with an excess amount of butanol to obtain a resin composition 7 containing polymer P7. 13 1C-NMR measurements confirmed that polymer P7 has a structure in which the maleic anhydride-derived structural unit (MA unit) of the raw material polymer 7 is ring-opened with 1-butanol.

[0362] (Preparation Example 8) Except for using raw material polymer 7 (10.00 g, with an MA equivalent mole of 0.052 calculated with a composition ratio of NB / MAN = 50 / 50) instead of raw material polymer 6, the MA units of raw material polymer 7 were ring-opened with side-chain aminosilicone (KF-868) to obtain 9.5 g of polymer P8. 13 1C-NMR measurements confirmed that polymer P8 has a structure in which the structural units (MA units) derived from maleic anhydride of the raw material polymer 7 are ring-opened with side-chain type aminosilicone (KF-868).

[0363] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA units of raw material polymer 7 with side-chain aminosilicone (KF-868), and then further ring-opening with butanol (BuOH). Details are explained below. First, a suspension was prepared by adding 1-butanol (BuOH) (40.00 g, 0.540 mol) to raw material polymer 7 (10.00 g, equivalent to 0.052 moles of MA calculated with a composition ratio of NB / MAN = 50 / 50). Next, to this suspension, moles of a solution of KF-868 (2.50 g, equivalent to 0.00028 mol when the amino group equivalent is considered as molecular weight) dissolved in BuOH) (10.00 g, 0.135) were added, and the mixture was reacted at 118°C for 4 hours to prepare a reaction solution. The resulting reaction mixture was subjected to solvent removal under reduced pressure at 50°C using a rotary evaporator. The solvent removal process was stopped when the solid content of the polymer solution was confirmed to be 35±2% by mass, as measured by a heat-drying moisture meter. Then, PGMEA was added to bring the solid content to 25% by mass, and the mixture was mixed until homogeneous. The same procedure was repeated two more times, removing the solvent under reduced pressure at 50°C, adjusting the solid content to 35±2% by mass as measured by a heat-drying moisture meter, and then adding PGMEA to bring the solid content to 25% by mass, mixing until homogeneous. Finally, the solvent was removed or PGMEA was added and stirred until homogeneous, resulting in a solid content of 30±3% by mass. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Based on the above, a resin composition 9 containing polymer P9 was obtained by ring-opening the structural units derived from maleic anhydride in the raw material polymer 7 with KF-868 and 1-butanol. GPC analysis of polymer P9 confirmed the disappearance of the 1-butanol peak. This confirmed that the obtained polymer P9 did not contain unreacted 1-butanol. Also 13 1C-NMR measurements confirmed that polymer P9 has a structure in which the structural units derived from maleic anhydride of the starting polymer 7 are ring-opened with KF-868 and BuOH.

[0364] (Preparation Example 10) Except for using raw material polymer 8 (10.00 g, with an MA equivalent mole of 0.052 calculated with a composition ratio of NB / MAN = 50 / 50) instead of raw material polymer 6, the MA units of raw material polymer 8 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 9.4 g of polymer P10. GPC analysis of polymer P10 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P10 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P10 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 8 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0365] (Preparation Example 11) Except for using raw material polymer 8 (10.00 g, with an MA equivalent mole of 0.052 moles calculated with a composition ratio of NB / MAN = 50 / 50) instead of raw material polymer 6, the MA units of raw material polymer 8 were ring-opened with side-chain aminosilicone (KF-868) to obtain polymer P11, in the same manner as in Preparation Example 5. 13 1C-NMR measurements confirmed that polymer P11 has a structure in which the structural units (MA units) derived from maleic anhydride of the raw material polymer 8 are ring-opened with side-chain type aminosilicone (KF-868).

[0366] (Preparation Example 12) Polymer P12 was prepared by ring-opening the MA units of raw material polymer 7 with a monofunctional (meth)acrylic compound. Details are described below. First, MEK (20.00g) was added to the raw material polymer 7 (10.00g, equivalent to 0.052 moles of MA calculated with a composition ratio of NB / MAN = 50 / 50) to prepare a solution. Next, 4-HBA (7.50g, 0.052 moles) was added to this solution, followed by triethylamine (1.50g, 0.015 moles), and the mixture was reacted at 70°C for 6 hours to prepare a reaction solution. After neutralization by adding formic acid aqueous solution to the prepared reaction solution, the polymer was purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water, and this process was repeated twice. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, 9.2 g of polymer P12 was obtained by ring-opening the maleic anhydride-derived structural units in raw material polymer 7 with 4-HBA. GPC analysis of polymer P12 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P12 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P12 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0367] (Preparation Example 13) Except for using raw material polymer 13 (10.00 g, with an MA equivalent mole of 0.030 moles calculated with a composition ratio of DecNB / MAN = 50 / 50) instead of raw material polymer 6, the MA units of raw material polymer 13 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 9.0 g of polymer P13. GPC analysis of polymer P13 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P14 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P14 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 13 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0368] (Preparation Example 14) Except for using raw material polymer 14 (10.00 g, with a composition ratio of MeOAcNBNB / MAN = 50 / 50 resulting in 0.038 moles of MA equivalent) instead of raw material polymer 6, the preparation was carried out in the same manner as in Preparation Example 4. The MA units of raw material polymer 14 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 10.2 g of polymer P14. GPC analysis of polymer P14 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P14 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P14 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 14 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0369] (Preparation Example 15) Except for using raw material polymer 10 (10.00 g, with an MA equivalent mole of 0.052 moles calculated with a composition ratio of NB / MAN = 50 / 50 for raw material polymer 10) instead of raw material polymer 6, the MA units of raw material polymer 10 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 7.3 g of polymer P15. GPC analysis of polymer P15 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P15 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P15 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 10 is ring-opened with 4-HBA, and a structure in which GMA is introduced.

[0370] (Preparation Example 16) Polymer P16 was prepared by ring-opening the maleic anhydride-derived structural units (MA units) of raw material polymer 16 with a monofunctional (meth)acrylic compound (HEMA). Details are described below. First, MEK (20.00g) was added to raw material polymer 16 (10.00g, equivalent to 0.052 moles of MA calculated using a composition ratio of NB / MAN = 50 / 50 for raw material polymer 16) to prepare a solution. Next, HEMA (6.77g, 0.052 moles) was added to this solution, followed by triethylamine (1.50g, 0.015 moles), and the mixture was reacted at 70°C for 6 hours. The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified using the following procedure. • The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of water. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, 8.2 g of polymer P16 was obtained by ring-opening the maleic anhydride-derived structural units in the raw material polymer with HEMA. GPC analysis of polymer P16 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P16 did not contain any unreacted (meth)acrylic compound. 1 ¹H-NMR measurements confirmed that polymer P16 has a structure in which the MA units of the raw material polymer 16 are ring-opened with HEMA.

[0371] (Preparation Example 17) Except for using raw material polymer 18 (10.00 g, with an MA equivalent mole of 0.052 moles calculated using a composition ratio of NB / MAN = 50 / 50 for raw material polymer 18) instead of raw material polymer 7, the MA units of raw material polymer 18 were ring-opened with a monofunctional (meth)acrylic compound to obtain 7.7 g of polymer P17. GPC analysis of polymer P17 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P17 did not contain any unreacted monofunctional (meth)acrylic compound. Also 131C-NMR measurements confirmed that polymer P17 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 18 is ring-opened at 4-HBA.

[0372] (Preparation Example 18) Except for using raw material polymer 19 (10.00 g, with an MA equivalent mole of 0.044 moles calculated using a composition ratio of NB / MAN / PhMI = 50 / 25 / 25) instead of raw material polymer 7, and using 6.28 g (0.044 moles) of 4-HBA, the preparation was carried out in the same manner as in Preparation Example 12, and the MA units of raw material polymer 19 were ring-opened with a monofunctional (meth)acrylic compound to obtain 7.3 g of polymer P18. GPC analysis of polymer P18 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P18 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P18 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 19 is ring-opened at 4-HBA.

[0373] [Table 5] [Table 6] [Table 7]

[0374] [Examples B1-B15, Comparative Examples B1-B3] In each example, the physical properties of polymer P produced in the above preparation example were evaluated for the following items.

[0375] (PFAS-eligible polymer P) Table 4 shows the PFAS classification of polymers P1 to P18. "PFAS classified" indicates that polymer P is derived from a monomer classified as PFAS, while "PFAS not classified" indicates that polymer P is derived from a monomer not classified as PFAS.

[0376] (Water-repellent and liquid-repellent properties of polymer P alone) In Examples B1-B15 and Comparative Examples B1-B3, polymers P1-P18 obtained in Preparation Examples 1-18 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1-18 with a solid content concentration of 30% by mass. Resin compositions 1-18 obtained in each example were rotate-coated onto 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 approximately 1.0 μm (±0.2 μm). The contact angles of this thin film with respect to water and with respect to PGMEA were measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). In this experiment, the volume of the prepared droplet was 2 μL, the observation time was 30 seconds after droplet placement, and the average of five measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°). Next, the thin film after contact angle measurement was heated at 230°C for 60 minutes to cure it and 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 4.

[0377] A contact angle of 92° or higher indicates good water repellency, 94° or higher indicates better water repellency, 96° or higher indicates excellent water repellency, and 98° or higher indicates particularly excellent water repellency. A contact angle of 4° or higher indicates good liquid repellency, 6° or higher indicates better liquid repellency, 10° or higher indicates excellent liquid repellency, and 12° or higher indicates particularly excellent liquid repellency.

[0378] (Alkali dissolution rate of polymer P) Resin compositions 1, 2, 3, 4, 6, 7, 9, 10, 12, 13, and 14-17, used to demonstrate the water-repellent and liquid-repellent properties of polymer P alone, were spin-coated onto a wafer. Subsequently, a resin film with a thickness of approximately 1 μm was fabricated by pre-baking at 100°C for 2 minutes. The resin film, along with the wafer, was immersed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer and measuring the earlier of the time it took for the resin film to dissolve and the interference pattern to disappear, or the time it took for the resin film to peel off, and then dividing the film thickness by that time. The results are shown in Table 4. If polymer P is alkaline soluble, an alkaline dissolution rate of 5 nm / s or higher indicates that it can be used without problems as a photosensitive material; a rate of 100 nm / s or higher indicates good developability; a rate of 300 nm / s or higher indicates better developability; and a rate of 500 nm / s or higher indicates particularly good developability.

[0379] (Refractive index of polymer P) The refractive index of the polymers was measured using the following method. First, the polymers obtained in Examples B1-B3, B5, B7-B15, and Comparative Examples B1 and B3 were dissolved in MEK to prepare solutions with solid content concentrations of 20.0%, 10.0%, 5.0%, and 2.5%. For polymers P2, P7, and P9 from Comparative Example B2, Example B4, and Example B6, vacuum drying was performed at room temperature, the PGMEA solvent was removed by distillation, and then the polymers 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 without polymers using a Kyoto Electronics Manufacturing Co., Ltd. refractometer (RA-600). For each polymer, the refractive index against solid content concentration was plotted, and the refractive index at 589 nm was calculated from the approximation curve obtained by linear approximation of the obtained plots, where the solid content concentration was 100%. The results are shown in Table 4. 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.

[0380] (Tackiness of polymer P) The tackiness of polymer P was evaluated using the following method. The polymer P obtained in each preparation example was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. This solution was then rotary coated onto a 3-inch silicon wafer to form a coating film of 2 ± 0.2 μm after drying, and then dried at 100°C for 2 minutes to obtain the coated film. The tackiness of the obtained coating film was checked by touch. The results were evaluated in a sensory test using the following criteria. The sensory test method involved pressing an index finger onto the coating film for 3 seconds, and then lifting the finger straight up to evaluate the degree to which the coating film stuck to the finger. The results are shown in Table 4. A coating without tackiness is easier to handle. A: When you lift your finger, the coating does not stick to your finger. B: When you lift your finger, the coating film sticks to your finger, but it comes off immediately. C: When you release your finger, the coated film lifts slightly before separating.

[0381] (Water-repellent and liquid-repellent properties of photosensitive resin compositions) For polymers P1, P3, P4, P6, P10, P12-P16, and P18, which have (meth)acryloyl groups, the water-repellent and liquid-repellent properties of the cured films of photosensitive resin compositions were evaluated. First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids content concentration was 30% by mass. Polymers P1, P3, P4, P6, P10, P12-P16, P18 (polymers P from Preparation Examples 1, 3, 4, 6, 10, 12-16, and 18, respectively): 5 parts by mass • Polymer P1: 95 parts by mass • Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass • Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass • Adhesion enhancer (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass • Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass The obtained photosensitive resin composition was rotary coated onto 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 A with a thickness of approximately 2.0 μm (±0.2 μm). This thin film A was subjected to a 100 mJ / cm² treatment using a Canon g+h+i-line mask aligner (PLA-501F). 2 Thin film B was obtained by exposing the photosensitive resin composition to the g+h+i line with the specified exposure dose. Using this thin film B, the water-repellent and liquid-repellent properties of the cured film were evaluated under both undeveloped and developed conditions. In cases where development was not performed, thin film B was heated at 230°C for 60 minutes to cure it and obtain thin film C. Using a tactile meter (automatic contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of thin film C with respect to water and the contact angle with respect to PGMEA were measured, and the water-repellent and liquid-repellent properties of the cured photosensitive resin composition were evaluated. For development, thin film B was developed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain exposed and developed thin film D. Thin film D was heated at 230°C for 60 minutes to cure it and obtain thin film E. Using a contact angle meter (Kyowa Interface Science Co., Ltd. automatic contact angle meter DM-501), the contact angle of thin film E with respect to water and PGMEA was measured, and the water-repellent and liquid-repellent properties of the cured photosensitive resin composition were evaluated. In this experiment, the volume of the prepared droplet was 2 μL, the observation time was 30 seconds after droplet placement, and the average of five measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°). The results are shown in Table 4.

[0382] When development is not performed, a contact angle of the cured film with respect to water of 95° or higher indicates good water repellency, 97° or higher indicates better water repellency, 98° or higher indicates particularly excellent water repellency, and 100° or higher indicates particularly excellent water repellency. When development is performed, a contact angle of the cured film with respect to water of 70° or higher indicates good water repellency, 80° or higher indicates better water repellency, 90° or higher indicates particularly excellent water repellency, and 95° or higher indicates particularly excellent water repellency. When development is not performed, a contact angle of the cured film with respect to PGMEA of 25° or higher indicates good liquid repellency, 30° or higher indicates better liquid repellency, 33° or higher indicates particularly excellent liquid repellency, and 35° or higher indicates particularly excellent liquid repellency. When developing is performed, a contact angle of the cured film with respect to PGMEA of 10° or more indicates good water repellency, 15° or more indicates better water repellency, 20° or more indicates particularly excellent water repellency, and 25° or more indicates particularly superior water repellency.

[0383] [Table 8]

[0384] Although polymers P1 and P2 of comparative examples B1 and B2, which do not contain a silicone structure, are not subject to PFAS regulations, they exhibited low water repellency and liquid repellency. Polymer P3 of Comparative Example B3, which contains a fluorine-containing structure, is classified as PFAS and exhibited high liquid repellency but low water repellency. Polymers P4 to P18 in Examples B1 to B15, which include a silicone structure, are PFAS-free and exhibited high water and liquid repellency before and after curing. Polymers P5, P8, P9, and P11 (Examples B2, B5, B6, and B8, respectively), in which aminosilicone was introduced into a raw material polymer containing a silicone structure, and polymer P17 (Example B14), which had a high Si content, exhibited superior water repellency. The cured photosensitive resin compositions prepared from polymers P4, P6, P10, P12-P16, and P18, which have (meth)acryloyl groups and contain a silicone structure, exhibited excellent water repellency and liquid repellency in both the undeveloped and developed cases. [Explanation of symbols]

[0385] 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), A structural unit derived from maleic anhydride, which includes the structure represented by formula (1-4), A polymer comprising a silicone-containing structural unit having at least one structure selected from structures represented by formulas (SI-1) to (SI-3), 【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】 【Transformation 3】 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, 【Chemistry 4】 In formula (SI-2), R ｂ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｂ ' are each 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 represents an integer greater than or equal to 1. polymer.

2. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (1-2) and at least one structural unit selected from the structural units represented by formula (1-3), 【Transformation 6】 In formula (1-2), R ｐ This is a group having two or more (meth)acryloyl groups, 【Transformation 7】 In formula (1-3), R ｓ A polymer that has one (meth)acryloyl group.

3. The polymer according to claim 1, The polymer further comprises structural units represented by formula (1-5), 【Transformation 8】 In formula (1-5), R ５１ A polymer is a linear, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms.

4. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (1-1), 【Chemistry 9】 In formula (1-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom, or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. A polymer in which Q is the alkyl group and X is the alkylene group, and Q and X may condense to form a cyclic group.

5. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (MA). 【Chemistry 10】

6. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (B1) or formula (B2), 【Chemistry 11】 【Chemistry 12】 In formulas (B1) and (B2), Rd is a group represented by formula (SI-4), formula (SI-5), or formula (SI-6), 【Chemistry 13】 In formula (SI-4), R ｆ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｆ 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 14】 In formula (SI-5), R ｇ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｇ ' is a divalent organic group having 1 to 30 carbon atoms, n represents an integer greater than or equal to 1, 【Chemistry 15】 In formula (SI-6), R ｈ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｈ Each of these is independently a divalent organic group having 1 to 30 carbon atoms. n is a polymer representing an integer greater than or equal to 1.

7. The polymer according to claim 2, The polymer includes the structure represented by formula (1-2), R in equation (1-2) ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), 【Chemistry 16】 In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X １ X is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented as -Z-X- (where Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X groups. １ They may be the same or different. X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ This is an organic group with 1 to 12 carbon atoms and a (k+1) valency. 【Chemistry 17】 In formula (1c), k, R, X １ and X ２ These are R, k, and X in equation (1b), respectively. １ and X ２ This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X １ They may be the same or different from each other. X ３ This is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ４ and X ５ Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X ６ It is a divalent organic group having 1 to 6 carbon atoms. [Chemistry 18] In formula (1d), n is an integer between 2 and 5. R is independently either a hydrogen atom or a methyl group. polymer.

8. The polymer according to claim 2, The polymer includes a structure represented by the above formula (1-3), R in the above formula (1-3) ｓ This is a base represented by formula (2a), 【Chemistry 19】 In formula (2a), X １０ A polymer in which R is a divalent organic group and R is either a hydrogen atom or a methyl group.

9. The polymer according to claim 1, The structural unit represented by formula (NB) includes the structural unit represented by formula (ES), 【Chemistry 20】 In the formula (ES), R ３１ , R ３２ , R ３３ and R ３４ At least one of them is an alkyl ester-containing group represented by formula (es), R ３１ , R ３２ , R ３３ and R ３４ The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a ３ is 0, 1, or 2, -X ３ -C(=O)-O-R ３５ (es) In formula (es), X ３ This is an alkylene group having 1 to 20 carbon atoms. R ３５ This is a polymer consisting of alkyl groups with 1 to 3 carbon atoms.

10. The polymer according to claim 1, The structural unit represented by formula (NB) includes the structural unit represented by formula (CA), 【Chemistry 21】 In formula (CA), R ４１ , R ４２ , R ４３ and R ４４ At least one of them is a carboxyl group-containing group represented by formula (ca), R ４１ , R ４２ , R ４３ and R ４４ The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a ４ is 0, 1, or 2, -X ４ -C (=O) -OH (ca) In formula (ca), X ４ This is a polymer consisting of alkylene groups with 1 to 20 carbon atoms.

11. The polymer according to claim 1, The structural unit represented by formula (NB) further comprises at least one structural unit represented by formula (NB-a), 【Chemistry 22】 In equation (NB-a), R ５１ , R ５２ , R ５３ and R ５４ At least one of them is a linear, branched, or cyclic hydrocarbon group having 2 to 30 carbon atoms, a polyoxyalkyl group having 2 to 30 carbon atoms, and the following formula (5a): 【Chemistry 23】 At least one group selected from, where * represents a bond in formula (5a), R ５１ , R ５２ , R ５３ and R ５４ The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a ５ A polymer in which is 0, 1, or 2.

12. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (MI), 【Chemistry 24】 In the formula (MI), R ６１ This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ６２ and R ６３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

13. The polymer according to claim 1, A polymer having a weight-average molecular weight of 2,000 or more and 50,000 or less.

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

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

16. A polymer solution comprising the polymer described in any one of claims 1 to 15.

17. The polymer solution according to claim 16, A polymer solution further containing a silicone compound.

18. The polymer solution according to claim 16, A polymer solution used to form partitions or coatings for organic electroluminescent elements.

19. A polymer according to any one of claims 1 to 15, Including a photosensitive agent, Photosensitive resin composition.

20. A cured product formed from the photosensitive resin composition described in claim 19.

21. A structural unit represented by formula (NB), Structural units represented by formula (MA), A polymer comprising a silicone-containing structural unit having at least one structure selected from structures represented by formulas (SI-1) to (SI-3), 【Chemistry 25】 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 26】 【Chemistry 27】 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, 【Chemistry 28】 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, 【Chemistry 29】 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. polymer.

22. The polymer according to claim 21, The structural unit represented by formula (NB) includes the structural unit represented by formula (ES), 【Transformation 30】 In the formula (ES), R ３１ , R ３２ , R ３３ and R ３４ at least one of which is an alkyl ester-containing group represented by the formula (es), and R ３１ , R ３２ , R ３３ and R ３４ the rest are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a ３ is 0, 1, or 2, -X ３ -C(=O)-O-R ３５ (es) In formula (es), X ３ This is an alkylene group having 1 to 20 carbon atoms. R ３５ This is a polymer consisting of alkyl groups with 1 to 3 carbon atoms.

23. The polymer according to claim 21, The structural unit represented by formula (NB) includes the structural unit represented by formula (CA), 【Chemistry 31】 In formula (CA), R ４１ , R ４２ , R ４３ and R ４４ At least one of them is a carboxyl group-containing group represented by formula (ca), R ４１ , R ４２ , R ４３ and R ４４ The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a ４ is 0, 1, or 2, -X ４ -C (=O) -OH (ca) In formula (ca), X ４ This is a polymer consisting of alkylene groups with 1 to 20 carbon atoms.

24. The polymer according to claim 21, The structural unit represented by formula (NB) further comprises at least one structural unit represented by formula (NB-a), 【Chemistry 32】 In equation (NB-a), R ５１ , R ５２ , R ５３ and R ５４ At least one of them is a linear, branched, or cyclic hydrocarbon group having 2 to 30 carbon atoms, a polyoxyalkyl group having 2 to 30 carbon atoms, and the following formula (5a): 【Transformation 33】 At least one group selected from, where * represents a bond in formula (5a), R ５１ , R ５２ , R ５３ and R ５４ The remaining atoms are, independently, hydrogen atoms or alkyl groups having 1 to 30 carbon atoms. a ５ A polymer in which is 0, 1, or 2.

25. The polymer according to claim 21, The polymer further comprises a structural unit represented by formula (MI), 【Transformation 34】 In the formula (MI), R ６１ This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ６２ and R ６３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

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