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

Abstract

This polymer is not subject to PFAS regulations and possesses water-repellent and liquid-repellent properties. [Solution] A polymer comprising a structural unit represented by formula (IN), a structural unit derived from maleic anhydride containing a structure represented by formula (1-4), and a structural unit having a siloxane bond. TIFF2026125351000113.tif45139 TIFF2026125351000114.tif29153

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 (IN), Structural units derived from maleic anhydride, including the structure represented by formula (1-4), A polymer comprising a structural unit having a siloxane bond, [ka] In formula (IN), R 61 ~R 68 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] polymer. [2] [1] The polymer described above, The structural unit having a siloxane bond includes at least one structural unit selected from the structural units represented by formula (SI-1), formula (SI-2), formula (SI-3), formula (B1), and formula (B2). [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 independently represents an alkyl group having 1 to 30 carbon atoms, R b ’ each independently represents a divalent organic group having 1 to 30 carbon atoms, n represents an integer of 1 or more,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

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

[10] , A polymer having a silicon content of 2% by mass or more and 30% by mass or less.

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

[11] .

[13]

[12] The polymer solution described above, A polymer solution further containing a silicone compound. A polymer as described in

[14]

[12] or

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

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

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

[16] or

[15] .

[17] A structural unit represented by formula (IN), The structural unit represented by formula (MA), A polymer comprising a structural unit having a siloxane bond, [ka] In formula (IN), R 61 ~R 68 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] polymer.

[18]

[17] The polymer described above, The structural unit having a siloxane bond includes at least one structural unit selected from the structural units represented by formula (SI-1), formula (SI-2), formula (SI-3), formula (B1), and formula (B2). [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, [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. A polymer as described in

[19]

[17] or

[18] , The polymer further comprises a structural unit represented by formula (MI), [ka] In the formula (MI), R 31 This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 32 and R 33Each 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 (IN), Structural units derived from maleic anhydride, including the structure represented by formula (1-4), It includes structural units having siloxane bonds.

[0016] [ka]

[0017] In formula (IN), R 61 ~R 68 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0018] [ka]

[0019] The polymer P(I) of this embodiment has a structural unit represented by formula (IN). The structural unit represented by formula (IN) is a structural unit derived from indene monomer. The structural unit represented by formula (IN) is chemically robust. Therefore, polymer P(I) containing this as a structural unit exhibits little weight loss and is stable when subjected to heat treatment. Thus, a photosensitive resin composition containing polymer P(I) can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors that require heat resistance.

[0020] In the structural unit represented by formula (IN) that constitutes polymer P(I), R 61 ~R 68 Organic groups having 1 to 30 carbon atoms that can constitute these groups include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

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

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

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

[0024] The proportion of structural units represented by formula (IN) in the total structural units constituting polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, and even more preferably 35 to 60 mol%. By setting the proportion of structural units represented by formula (IN) in polymer P(I) within the above range, the heat resistance of polymer P(I) can be improved, and the balance between sensitivity, alkali solubility, and heat discoloration resistance can be improved to a high level.

[0025] The polymer P(I) of this embodiment includes structural units derived from maleic anhydride monomers, which include structures represented by formula (1-4). By including structural units containing carboxyl groups represented by formulas (1-4) in polymer P(I), the acid value of polymer P(I) can be designed to be relatively large, and as a result, polymer P(I) has appropriate sensitivity and developability for pattern formation by photolithography. Structural units represented by formulas (1-4) can be obtained, for example, by reacting structural units derived from maleic anhydride with a carboxyl group-containing compound.

[0026] The proportion of structural units represented by formula (1-4) in the total structural units constituting polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0027] The polymer P(I) of this embodiment contains structural units having siloxane bonds. The polymer P(I) possesses high water and liquid repellency due to the presence of structural units having siloxane bonds. The polymer P(I) of this embodiment has structural units having siloxane bonds incorporated into its polymer backbone. In other words, the polymer P(I) has substituents having siloxane bonds covalently linked. A polymer P(I) having such a structure exhibits improved water and liquid repellency, as well as excellent heat resistance, compared to a mixture of a polymer without siloxane bond-containing groups and a silicone compound.

[0028] In one embodiment, polymer P(I) includes at least one structural unit selected from structural units represented by formulas (SI-1), (SI-2), (SI-3), (B1), and (B2) as structural units having siloxane bonds.

[0029] [ka]

[0030] 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.

[0031] [ka]

[0032] 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.

[0033] [ka]

[0034] 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.

[0035] R in the group represented by formula (SI-1) 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.

[0036] 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.

[0037] 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 between 1 and 30, more preferably between 2 and 20, and more preferably between 3 and 10.

[0038] 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").

[0039] 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%.

[0040] R in the group represented by formula (SI-2) 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.

[0041] 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.

[0042] 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").

[0043] 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%.

[0044] R in the structural unit represented by formula (SI-3) cEach 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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").

[0049] When the polymer P(I) contains a structural unit represented by the formula (SI-3), the proportion of the group represented by the formula (SI-3) in all the structural units of the polymer P(I) is preferably 0.25 to 15 mol%, more preferably 0.5 to 7 mol%.

[0050]

Chemical formula

[0051]

Chemical formula

[0052] In the formulas (B1) and (B2), R d is a group represented by the formula (SI-4), the formula (SI-5) or the formula (SI-6).

[0053]

Chemical formula

[0054] In the group represented by the formula (SI-4), R f is each independently an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms of R f is preferably 1 to 20, more preferably 1 to 10. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like.

[0055] In the group represented by the formula (SI-4), R f’ is each independently a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. The number of carbon atoms of R f’ is preferably 1 to 20, more preferably 1 to 10. <00007​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 3010, more preferably 1 to 5, and more preferably 1 to 3.

[0057] 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").

[0058] [ka]

[0059] 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.

[0060] 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.

[0061] The group represented by the 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) and a polysiloxane compound in which one amino group (-NH2) is introduced at one end of the polysiloxane (sometimes referred to as "monoamino silicone with one end type" in this specification).

[0062]

Chemical formula

[0063] R in the group represented by the formula (SI-6) h is, independently of each other, an alkyl group having 1 to 30 carbon atoms. The carbon number of R h is preferably 1 to 20, more preferably 1 to 10. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like.

[0064] R in the group represented by the formula (SI-6) h’ is, independently of each other, a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched alkylene group. The carbon number of R g’ is preferably 1 to 20, more preferably 1 to 10. n in the group represented by the formula (SI-6) represents an integer of 1 or more, preferably 1 or more and 500 or less, more preferably 10 or more and 250 or less, still more preferably 20 or more and 200 or less.

[0065] The group represented by the 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) and a polysiloxane compound in which two amino groups (-NH2) are introduced at both ends of the polysiloxane (sometimes referred to as "diamino silicone with both ends type" in this specification).

[0066] 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%.

[0067] 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%.

[0068] 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).

[0069] 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).

[0070] In one embodiment, polymer P(I) comprises structural units represented by formula (1-2) and / or structural units represented by formula (1-3). Preferably, structural units derived from maleic anhydride, which include the structure represented by formula (1-4) described above, comprise structural units represented by formula (1-2) and / or structural units represented by formula (1-3).

[0071] [ka]

[0072] In formula (1-2), R pThis is a group having two or more (meth)acryloyl groups.

[0073] [ka]

[0074] In formula (1-3), R s This is a group having one (meth)acryloyl group.

[0075] 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).

[0076] 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).

[0077] 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.

[0078] [ka]

[0079] 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.

[0080] 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).

[0081] 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)-.

[0082] 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.

[0083] 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 2 The 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).

[0084] [ka]

[0085] In formula (1c), k, R, X 1 and X 2 These are R, k, and X in equation (1b), respectively. 1and X 2 is synonymous with, and the plurality of Rs may be the same as or different from each other, and the plurality of Xs 1 may be the same as or different from each other, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0086] R, k, X 1 and X 2 For the specific embodiments, preferred embodiments, etc. of, it is the same as those described in formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms for and X include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (such as an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of the divalent organic group having​​​​​​​​​​​​​​​​​When polymer P(I) contains structural units represented by formula (1-2), the proportion of structural units represented by formula (1-2) to the total structural units of polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0090] 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.

[0091] R S This is a group represented, for example, by the following formula (2a).

[0092] [ka]

[0093] 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 10 A 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.

[0094] 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 10By appropriately selecting the chain length, the structural unit represented by formula (2a) becomes more readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0095] 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.

[0096] 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%.

[0097] 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).

[0098] 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).

[0099] [ka]

[0100]

Chem.

[0101] In formulas (1) and (2), R p and R s are synonymous with those in the above formulas (1-2) and (1-3).

[0102] When the polymer P(I) contains a structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all the structural units of the polymer P(I) is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0103] When the polymer P(I) contains a structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in all the structural units of the polymer P(I) is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0104] In one embodiment, the polymer P(I) contains a structural unit represented by formula (l-5). Preferably, the structural unit derived from maleic anhydride containing the structure represented by the above formula (1-4) contains the structural unit represented by formula (1-5).

[0105]

Chem.

[0106] In formula (1-5), R 51 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. R 51 Examples of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms that can constitute R

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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%.

[0111] 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).

[0112] [ka]

[0113] In formula (4), R 51 This is equivalent to the one in equation (1-5).

[0114] Polymer P(I) has high alkali solubility due to the presence of structural units represented by formula (4). 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.

[0115] When polymer P(I) contains structural units represented by formula (4), the proportion of structural units represented by formula (4) to the total structural units of polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0116] In one embodiment, polymer P(I) contains a structural unit represented by formula (1-1). Preferably, the structural unit derived from maleic anhydride containing the structure represented by formula (1-4) described above contains the structural unit represented by formula (1-1).

[0117] [ka]

[0118] 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.

[0119] 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.

[0120] [ka]

[0121] In formula (1a), R is either a hydrogen atom or a methyl group.

[0122] 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%.

[0123] 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.

[0124] 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). Both the structural unit represented by formula (8) and the structural unit represented by formula (9) are structural units obtained by reacting a predetermined compound with a structural unit derived from maleic anhydride.

[0125] [ka]

[0126] [ka]

[0127] 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).

[0128] 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%.

[0129] Polymer P(I) may contain a structural unit represented by formula (11). The structural unit represented by formula (11) is a structural unit consisting of the structure of formula (1-5) and the structure of formula (1-1). The structural unit represented by formula (11) is a structural unit obtained by reacting a predetermined compound with a structural unit derived from maleic anhydride.

[0130] [ka]

[0131] In formula (11), R 51 This is equivalent to the one in equation (1-5) above, and Z, Q, and X are equivalent to the ones in equation (1-1) above.

[0132] Polymer P(I) may contain structural units derived from maleic anhydride represented by formula (MA).

[0133] [ka]

[0134] 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%.

[0135] [ka]

[0136] In one embodiment, polymer P(I) contains a structural unit represented by formula (MI). The structural unit represented by formula (MI) is a structural unit derived from a maleimide monomer. [ka]

[0137] In the formula (MI), R 31 This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 32 and R 33 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0138] In the structural unit represented by the above formula (MI) that can constitute polymer P(I), R 31 R is a hydrogen atom or an organic group having 1 to 30 carbon atoms. 32 and R 33 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. In the structural unit represented by formula (MI), R 32 and R 33 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 32 and R 33 It is preferable that it be a hydrogen atom. R in equation (MI) 31 Organic groups having 1 to 30 carbon atoms that can constitute this include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups. 31 Preferably, it is a hydrocarbon group having 1 to 25 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably a hydrocarbon group having 1 to 15 carbon atoms.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] R in the structural unit represented by formula (MI) 31 Preferred elements include hydrogen atoms, alkyl groups, aryl groups, or aralkyl groups. R in the structural unit represented by formula (MI) 31 , R 32 and R 33 By selecting appropriately, in particular, R 31 By selecting R, the alkali solubility of the resulting polymer P(I) can be adjusted. For example, R 31 By using a hydrogen atom, the alkali solubility of the resulting polymer P(I) can be improved. 31 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 31 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, R 31 As an organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected.

[0143] 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.

[0144] The polymer P(I) of this embodiment preferably consists only of the structural units described above and substantially contains no other structural units. Other structural units refer, for example, to structural units derived from norbornene monomer. Substantially containing no other structural units means that the proportion of other structural units among all structural units constituting polymer P(I) is 0.1 mol% or less, and preferably contains none at all, i.e., the proportion of other structural units is 0 mol%.

[0145] 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.

[0146] The weight-average molecular weight Mw of polymer P(I) is, for example, 2,000 to 300,000. Preferably, the weight-average molecular weight Mw of polymer P(I) is 10,000 to 200,000, more preferably 50,000 to 100,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted. Furthermore, the polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P(I) in this embodiment is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 8.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P(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.

[0147] The glass transition temperature of polymer P(I) is preferably 50 to 250°C, and more preferably 70 to 230°C. Polymer P(I) has a relatively high glass transition temperature due to the inclusion of structural units represented by formula (ST). 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).

[0148] The acid value of polymer P(I) is preferably 30 mg KOH / g or more and 150 mg KOH / g or less, more preferably 40 mg KOH / g or more and 140 mg KOH / g or less. The double bond equivalent of polymer P1 is preferably 100 g / mol or more and 2,000 g / mol or less, more preferably 200 g / mol or more and 1,900 g / mol or less, and even more preferably 200 g / mol or more and 1,800 g / mol or less. By having an acid value of 30 mgKOH / g or higher for polymer P(I), good developability can be obtained. Furthermore, by having a double bond equivalent of 2,000 g / mol or less, the sensitivity of the photosensitive resin composition containing polymer P(I) can be increased.

[0149] 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.

[0150] 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.

[0151] 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).

[0152] 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).

[0153] The content (ratio) of each structural unit contained in polymer P(I) of this embodiment depends on the amount (moles) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak areas of various spectra (for example, 1 It can be estimated / calculated from the peak area of ​​the 1H-NMR spectrum, etc.

[0154] The silicon content in polymer P(I) is preferably 2% to 30% by mass, more preferably 3% to 25% by mass, and even more preferably 4% to 10% by mass. By adjusting the silicon content within this range, polymer P(I) with excellent water repellency and liquid repellency can be obtained.

[0155] (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 (IN), a structural unit represented by formula (MA), and a structural unit having a siloxane bond. Step aII: A step in which the raw material polymer obtained in step aI is reacted with a compound having a hydroxyl group to open the ring of the structural unit (MA) in the raw material polymer 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.

[0156] 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 formulas (SI-1) to (SI-3) as structural units having siloxane bonds, then steps aI-i are performed to produce a raw material polymer having structural units having siloxane bonds. Step aI-i: A step of preparing a raw material polymer (referred to as "raw material polymer (i)") containing a structural unit represented by formula (IN), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA).

[0157] If polymer P(I) contains structural units represented by formula (B1) and / or formula (B2) as structural units having siloxane bonds, then steps aI-ii are used as the process for producing the raw material polymer. Steps aI-ii: A step to obtain a polymer (IN-MA) containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA), and then react it with an aminosilicone represented by formula (SI-4-m), formula (SI-5-m), or formula (SI-6-m) as detailed below to open the ring of the structural unit of formula (MA) and obtain a raw material polymer (referred to as "raw material polymer (ii)") containing a structural unit represented by formula (IN), a structural unit represented by formula (B1) and / or formula (B2), and a 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 a structural unit represented by formula (MA) in a polymer consisting of structural units (IN) and structural units (MA) with aminosilicone.

[0158] If polymer P(I) contains structural units represented by formula (1-2) or formula (1-3), then step aII-i (ring opening of maleic anhydride-derived structural units by (meth)acrylate) is performed after step aI-i or after step aI-ii. Step aII-i: A step to prepare a polymer precursor (the polymer precursor obtained via raw material polymer (i) in step aI-i, or the raw material polymer (ii) obtained in step aI-ii), by reacting with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, wherein the polymer precursor includes a structural unit represented by formula (IN), a structural unit derived from a silicone compound, and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further includes a structural unit represented by formula (MA). (The polymer precursor obtained via raw material polymer (i) is referred to as "polymer precursor (Ib-i)", and the polymer precursor obtained via raw material polymer (ii) is referred to as "polymer precursor (Ib-ii)". 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).

[0159] If polymer P(I) contains structural units represented by formula (1-5), the following step aII-ii (ring opening of maleic anhydride-derived structural units with alcohol) is performed after step aI-i or after step aI-ii. Step aII-ii: A step in which the raw material polymer (i) obtained in step aI-i, or the raw material polymer (ii) obtained in step aI-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 (IN), the structural unit represented by formula (4), the silicone-derived structural unit, and the structural unit represented by formula (MA) (polymer P obtained via raw material polymer (i) is referred to as "polymer precursor (Ic-i)", and polymer P obtained via raw material polymer (ii) is 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 a structural unit represented by formula (MA) in the raw material polymer (i) or (ii) with an 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].

[0160] If polymer P(I) contains a structural unit represented by formula (1-1), the following step aIII-i is performed after step aII-i or step aII-ii. Step aIII-i: A step to prepare polymer P(I) containing structural units represented by formula (IN), structural units represented by formula (1-1), and optionally structural units represented by formula (MA), by reacting the polymer precursor (Ib-i) or polymer precursor (Ib-ii) obtained in step aII-i, or the polymer precursor (Ic-i) or polymer precursor (Ic-ii) obtained in step aII-ii, with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst.

[0161] The following describes each step. (Process aI-i) The step of preparing a raw material polymer (i) containing a structural unit represented by formula (IN), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA) in step aI-i can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (INm), 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 (INm), R 61 ~R 68 The definition is the same as that of expression (IN). In equation (SI-1-m), R a , Ra 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).

[0162] 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).

[0163] (Monomer represented by formula (INm)) [ka]

[0164] (Compound represented by formula (SI-1-m)) [ka]

[0165] 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.

[0166] (Compound represented by formula (SI-2-m)) [ka]

[0167] 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.

[0168] (Compound represented by formula (SI-3-m)) [ka]

[0169] 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".

[0170] (Monomer represented by formula (MIm)) [ka]

[0171] 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.

[0172] 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.

[0173] The synthesis of the raw material polymer (i) is carried out by dissolving a monomer represented by formula (INm), one of the silicone compounds represented by formula (SI-1-m), formula (SI-2-m), or formula (SI-3-m), maleic anhydride, and a polymerization initiator in a solvent, charging them into a reaction vessel, and then heating to allow addition polymerization to proceed. The heating temperature is, for example, 50 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 (INm) to maleic anhydride (MAm) is preferably (INm):(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 (INm) is preferably (SI-m):(INm) = 1:100 to 40:100. Through this process, "raw material polymer (i)" can be obtained. The raw material polymer (i) 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.

[0174] Furthermore, after the synthesis of the raw material polymer (i), a step may be performed to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized raw material polymer (i) 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.

[0175] (Step aI-ii) The step in steps aI-ii to prepare a polymer (IN-MA) containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA) can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (INm) and maleic anhydride. Next, the polymer (IN-MA) 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) in the polymer (IN-MA), thereby producing a raw material polymer (ii) containing the structural unit represented by formula (IN), the structural unit represented by formula (B1) and / or formula (B2), and the structural unit represented by formula (MA).

[0176] 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.

[0177] (Aminosilicone represented by formula (SI-4-m)) [ka]

[0178] The aminosilicone represented by formula (SI-4m) 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."

[0179] (Aminosilicone represented by formula (SI-5-m)) [ka]

[0180] The aminosilicone represented by formula (SI-5m) 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".

[0181] (Aminosilicone represented by formula (SI-6-m)) [ka]

[0182] The aminosilicone represented by formula (SI-6m) 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, 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.

[0183] (Step aII-i) In step aII-ii, the raw material polymer (i) obtained in step aI-i, or the raw material polymer (ii) obtained in step aI-ii, is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) contained in the raw material polymer to open rings, forming structural units represented by formula (1) and / or formula (2), thereby obtaining a polymer precursor (Ib-i) or polymer precursor (Ib-ii) containing structural units represented by formula (IN), as well as structural units represented by formula (1) and / or formula (2), and structural units represented by formula (MA). When the raw material polymer (i) is used, the polymer precursor (Ib-i) includes a structural unit represented by formula (IN), a structural unit represented by formula (1) and / or formula (2), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA). The polymer precursor (Ib-ii) obtained via raw material polymer (ii) includes structural units represented by formula (IN), structural units represented by formula (1) and / or formula (2), structural units represented by formula (B1) and / or formula (B2), and structural units represented by formula (MA).

[0184] More specifically, first, a solution is prepared by dissolving the raw material polymer (i) or raw material polymer (ii) 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.

[0185] To obtain a polymer precursor containing the structural unit represented by formula (IN), 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 (IN) and the structural unit of formula (1) (step aII(1)).

[0186] 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 2 The 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.

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] 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 (IN), the structural unit of formula (1), and the structural unit of formula (2) (step aII(2)).

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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 10The definition of R is the same as that in equation (2a).

[0195] [ka]

[0196] 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.

[0197] To obtain a polymer precursor (Ib) containing a structural unit represented by formula (IN), 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.

[0198] (Step aII-ii) In step aII-ii, the raw material polymer (i) obtained in step aI-i, or the raw material polymer (ii) obtained in step aI-ii, is reacted with an alcohol compound (AL) in the presence of a basic catalyst to produce a polymer precursor (Ic) containing structural units represented by formula (IN), formula (4), and formula (MA). When the raw material polymer (i) is used, the polymer precursor (Ic-i) includes a structural unit represented by formula (IN), a structural unit represented by formula (4), any of the structural units represented by formulas (SI-1) to (SI-3), and a structural unit represented by formula (MA). The polymer precursor (Ic-ii) obtained via raw material polymer (ii) includes structural units represented by formula (IN), structural units represented by formula (4), structural units represented by formula (B1) and / or formula (B2), and structural units represented by formula (MA).

[0199] In step aII-ii, an alcohol compound (AL) having a secondary or tertiary hydroxyl group is added to the reaction system containing the raw material polymer (i) or raw material polymer (ii). By stirring this mixed solution, a polymer precursor (Ic) is produced. Examples of usable alcohol compounds (AL) include those represented by (AL) below. R 51 -OH (AL) In equation (AL), R 51 This is R in the above equation (1-5). 61 It is synonymous with [the above].

[0200] (Step aIII-i) In step aIII-i, the polymer precursor (Ib-i) or polymer precursor (Ib-ii) obtained in step aII-i, or the polymer precursor (Ic-i) or polymer precursor (Ic-ii) obtained in step aII-ii, 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)) in these polymer precursors to react with the epoxy groups of the epoxy group-containing (meth)acrylic compound to form a structural unit represented by formula (1-1). Using polymer precursor (Ib-i) or polymer precursor (Ib-ii), the polymer P(I) obtained via step aIII-i comprises structural units represented by formula (8) and / or formula (9). If some of the structural units of formula (MA) remain unopened, the polymer P(I) further comprises structural units represented by formula (MA). Using polymer precursor (Ic-i) or polymer precursor (Ic-ii), the polymer P(I) obtained via step aIII-i contains structural units represented by formula (11).

[0201] The reaction between polymer precursor (Ib-i) or polymer precursor (Ib-ii), or polymer precursor (ci) or polymer precursor (Ic-ii), and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst can be the catalyst remaining in the reaction system obtained in step aII-i or step aII-ii. Therefore, it is preferable to carry out step aIII-i by adding the epoxy group-containing (meth)acrylic compound in situ to the reaction mixture containing the polymer precursor obtained in step aII, without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor obtained in step aII-i or step aII-ii, or neutralizing the basic catalyst contained in the mixture.

[0202] Specifically, the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor 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-i) or polymer precursor (Ib-ii), or polymer precursor (Ic-i) or polymer precursor (Ic-ii), 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).

[0203] 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.

[0204] 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.

[0205] After step aIII, it is preferable to perform the following steps as appropriate to remove unwanted components other than the desired polymer P(I).

[0206] 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.

[0207] After step aIII-i, 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-i 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.

[0208] <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 (IN), The structural unit represented by formula (MA), It includes structural units having siloxane bonds.

[0209] [ka] In formula (IN), R 61 ~R 68 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka]

[0210] Polymer P(II) is a raw material polymer used in the production of polymer P(I) in the first embodiment, and is either raw material polymer (i) obtained in step aI-i or raw material polymer (ii) obtained in step aI-ii.

[0211] In one embodiment, polymer P(II) includes at least one structural unit selected from the structural units represented by the above-mentioned formulas (SI-1), (SI-2), (SI-3), (B1), and (B2) as structural units having siloxane bonds.

[0212] In one embodiment, polymer P(II) includes a structural unit represented by the above formula (MI).

[0213] The weight-average molecular weight Mw of polymer P(II) is, for example, 2,000 to 300,000. The weight-average molecular weight Mw of polymer P(I) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000. 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 20.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 8.0.

[0214] [Polymer solution] The polymer solution of this embodiment contains the polymer P(I) described above. The polymer solution of this embodiment may also contain a silicone compound, or a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, together with the polymer P(I).

[0215] (Silicone compounds) The silicone compound that may be included in the polymer solution of this embodiment may be an unreacted silicone compound used in step aI of the production of polymer P(I), or it may be one that has been added separately.

[0216] 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).

[0217] 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).

[0218] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of this embodiment may be unreacted (meth)acrylic compounds used in step aII-i of the production of polymer P(I), or may be added separately.

[0219] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into polymer solutions include, but are not limited to, the compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0220] [ka]

[0221] [ka]

[0222] [ka]

[0223] k, R, X in equation (1b-p) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in formula (1c) above.

[0224] In formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0225] Compounds in formulas (1b-p), (1c-p), and (1d-p) where Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formulas (1b-p), (1c-p), and (1d-p)) and may be added separately. In equation (1d-p), n is an integer greater than or equal to 2, preferably an integer between 2 and 5, and more preferably an integer between 2 and 3.

[0226] When a polyfunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P(I) or polymer P(II), the amount added may be such that the peak area derived from the polyfunctional (meth)acrylic 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) or polymer P(II).

[0227] (Monofunctional (meth)acrylic compounds) Examples of monofunctional (meth)acrylic compounds incorporated into the polymer solution of this embodiment include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0228] [ka]

[0229] When a monofunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted monofunctional (meth)acrylic compound used in the production of polymer P(I), the amount added may be such that the peak area derived from the monofunctional (meth)acrylic 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) or polymer P(II).

[0230] 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.

[0231] 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.

[0232] [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.

[0233] [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.

[0234] (Photosensitive agent) Examples of photosensitive agents used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators. Known compounds can be used as photoradical polymerization initiators, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1 Alkylphenone compounds such as -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl Benzoin compounds such as benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], etanone, Examples include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of polymer P(I).

[0235] 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.

[0236] (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.

[0237] 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.

[0238] 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.).

[0239] 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0244] 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.

[0245] 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.

[0246] (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.

[0247] 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.

[0248] (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.

[0249] 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.

[0250] (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.

[0251] 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.

[0252] 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:

[0253] 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.

[0254] 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.

[0255] (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.

[0256] The photosensitive resin composition of this embodiment can be designed as either a negative or positive type by appropriately adjusting the type of photosensitive agent and the reactivity of the crosslinking agent, but since the polymer has (meth)acryloyl groups, use in the negative type is preferred.

[0257] [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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] This section describes each step in the manufacturing process of organic EL elements.

[0262] ·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.

[0263] 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.

[0264] 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.

[0265] • 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.

[0266] 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.

[0267] ·Development process A partition can be formed by developing an exposed photosensitive resin film with a suitable developer.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] • 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).

[0274] 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).

[0275] 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.

[0276] 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.

[0277] 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).

[0278] 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.

[0279] The ink (material liquid 4) printed (injected) into the opening 3 can be dried, for example, by an oven or hot air drying.

[0280] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope of achieving the objectives of the present invention are included. [Examples]

[0281] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0282] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride NB:2-Norbornen • IN: Inden • C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (manufactured by Promelas, LLC) • PhMI:N-phenylmaleimide • KF-2001: Side-chain monovalent mercaptosilicone (manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-2012: Single-ended monovalent methacrylate silicone (manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-868: Side-chain aminosilicone (manufactured by Shin-Etsu Chemical Co., Ltd.) 4-HBA: 4-hydroxybutyl acrylate • BuOH: 1-butanol 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)

[0283] <Synthesis of raw material polymers> The raw material polymer was synthesized using the following method.

[0284] (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.

[0285] (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 ratio (weight-average molecular weight (Mw) / (number-average molecular weight (Mn)) of 1.79.

[0286] (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 19Measurements using 1F-NMR revealed that the fluorine content of the polymer was 39.9 wt%.

[0287] In addition, 19 The 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.

[0288] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), indene (58.08 g, 0.500 mol), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol), and methyl ethyl ketone (MEK, 423.83 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 (267.78 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 (1428.13 g). The obtained white solid was further washed twice with methanol (1428.13 g) and vacuum-dried at 120°C to obtain 81.5 g of a polymer (raw material polymer 4) comprising structural units derived from indene 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 25,200, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.23. Raw material polymer 4 1 The H-NMR chart is shown in Figure 7. 13 The 1C-NMR chart is shown in Figure 10.

[0289] (Synthesis of raw material polymer 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), indene (58.08 g, 0.500 mol), KF-2001 (53.58 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, 191.74 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 (178.52 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 (1071.1 g). The obtained white solid was further washed twice with methanol (1071.1 g) and vacuum-dried at 80°C to obtain 141.3 g of a polymer (raw material polymer 5) comprising structural units derived from indene, 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 55,100, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 4.73. Raw material polymer 5 13¹³C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of indene at 123 ppm–132 ppm and 138 ppm–144 ppm, a peak originating from the carbon atoms of the maleic anhydride ester at 170–174 ppm, a peak originating from the carbon atoms bonded to Si at -2 ppm–4 ppm, and a peak in the R atoms of formula (SI-1) at 16–17 ppm. a We confirmed the appearance of a peak originating from one of the C's. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur elements in the polymer was confirmed. 13 Based on 13C-NMR analysis and elemental analysis results, it was confirmed that mercaptosilicone was introduced into raw material polymer 5.

[0290] 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

[0291] 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.

[0292] 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)

[0293] (Synthesis of raw material polymer 6) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, maleic anhydride (49.03 g, 0.500 mol), indene (56.74 g, 0.489 mol), KF-2012 (52.90 g, 0.0109 mol calculated by considering the methacrylic 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, 471.42 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 (158.67 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 (1586.7 g). The obtained white solid was further washed twice with methanol (1586.7 g) and vacuum-dried at 80°C to obtain 154.2 g of a polymer (raw material polymer 6) comprising structural units derived from indene, 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 34,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.59. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 13.5 wt%. Raw material polymer 6 13 ¹¹C-NMR analysis revealed peaks originating from the carbon atoms of the aromatic ring of indene at 123 ppm–132 ppm and 138 ppm–144 ppm, a peak originating from the carbon atoms of the maleic anhydride ester at 170–174 ppm, a peak originating from the carbon atoms bonded to Si at -2 ppm–4 ppm, and CH3 of the methacryloyl group in formula (SI-3) and R in formula (SI-1) around 13 ppm and 18 ppm. c ', R cA peak originating from one of the C groups appeared, and the peak originating from the -CH2=C of the methacryloyl group of the raw material methacrylic silicone (KF-2012) around 123 ppm disappeared, confirming that methacrylic silicone had been introduced into the raw material polymer 6.

[0294] (Synthesis of raw material polymer 7) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 24.52 g (0.250 mol) maleic anhydride, 58.08 g (0.500 mol) indene, 43.29 g (PhMI, 0.250 mol) N-phenylmaleimide, 62.89 g (0.0331 mol when calculated considering the mercapto group equivalent as molecular weight) KF-2001, 4.61 g (0.020 mol) 2,2'-Azobisisobutyrate dimethyl (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.61 g, 0.020 mol) and methyl ethyl ketone (MEK, 614.77 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 (159.84 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 (1918.1 g). The obtained white solid was washed twice with methanol (1918.1 g) and then vacuum-dried at 80°C to obtain 182.8 g of polymer (raw material polymer 7) containing structural units derived from indene, N-phenylmaleimide, KF-2001, and maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 39,200, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.51. Furthermore, the obtained polymer 1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 12.2 wt%. Raw material polymer 7 13¹¹C-NMR analysis revealed peaks originating from the aromatic ring C of indene and N-phenylmaleimide at 123 ppm–132 ppm and 138 ppm–144 ppm, peaks originating from the C of the maleic anhydride ester at 170–174 ppm, peaks originating from the C of the N-phenylmaleimide ester at 174–178 ppm, as well as peaks originating from C bonded to Si at -2 ppm–4 ppm, and R in formula (SI-1) at 16–17 ppm. a We confirmed the appearance of a peak originating from one of the C's. Furthermore, the amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur elements in the polymer was confirmed. 13 Based on 1C-NMR analysis and elemental analysis results, it was confirmed that mercaptosilicone was introduced into the raw material polymer 7.

[0295] (Synthesis of raw material polymer 8) A solution was prepared by adding tetrahydrofuran (300.00g) to raw material polymer 4 (0.148 moles in MA equivalent, calculated with a composition ratio of IN / MAN = 50:50). Next, a solution of KF-868 (15.00g, 0.0017 moles, calculated by considering the amino group equivalent as molecular weight) dissolved in tetrahydrofuran (75.00g) was added to this solution, and the mixture was reacted at 60°C for 4 hours. The polymer was reprecipitated from the prepared reaction solution with methanol (900 g). The polymer powder obtained by reprecipitation was washed with methanol (900 g) twice. The resulting reaction product was vacuum-dried at 40°C for 16 hours. Based on the above, 37.1 g of polymer (raw material polymer 8) was obtained by ring-opening the maleic anhydride-derived structural units in raw material polymer 4 with side-chain type aminosilicone (KF-868). The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 66,700, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 5.33. Furthermore, the obtained polymer1 Measurements using 1H-NMR revealed that the silicon (Si) content of the polymer was 10.5 wt%. Raw material polymer 8 13 ¹¹C-NMR analysis revealed peaks originating from the aromatic ring C of indene at 123 ppm–132 ppm and 138 ppm–144 ppm, peaks originating from the C of maleic anhydride and esters of maleic anhydride ring-opened products at 170–174 ppm, and peaks originating from C bonded to Si at -2 ppm–4 ppm. This confirmed that the raw material polymer 8 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 4 is ring-opened with KF-868.

[0296] 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.

[0297] [Table 1]

[0298] [Examples A1-A4, Comparative Examples A1-A4] The water-repellent, liquid-repellent, and heat-resistant properties of the raw polymers in each example were measured as follows. The results are shown in Table 2.

[0299] (Water-repellent and liquid-repellent properties of the raw polymer alone) In Comparative Examples A1-A4 and Examples A1-A4, 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). 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 (°).

[0300] 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.

[0301] A contact angle of 97° or higher with respect to water indicates good water repellency, 100° or higher indicates better water repellency, and 105° or higher indicates particularly excellent water repellency. A contact angle of 7° 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.

[0302] (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-A4 and Examples A1-A4, the raw polymer (1 mg) was placed in a thermogravimetric / differential thermal analyzer (Hitachi High-Tech Science Corporation, STA7200RV). 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 set polymer were recorded. The results are shown in Table 24. If Td5 is 300°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 320°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 330°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 350°C or higher, the heat resistance is considered particularly excellent.

[0303] (PFAS compliance of raw material polymers) Furthermore, Table 2 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.

[0304] [Table 2]

[0305] The raw material polymers 5-8 in the examples were PFAS-free and exhibited high water and liquid repellency. The raw material polymers 5-8 in the examples all had high Td5, Td10, and Td20 values ​​and possessed excellent heat resistance.

[0306] <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, 1The 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). 1 ¹H-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.

[0307] (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.

[0308] (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.

[0309] (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 13 1C-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%.

[0310] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA units of raw material polymer 4 with a monofunctional (meth)acrylic compound. Details are described below. First, MEK (20.00g) was added to the raw material polymer 4 (10.00g, equivalent to 0.047 moles of MA calculated with a composition ratio of IN / MAN = 50:50) to prepare a solution. Next, 4-HBA (6.73g, 0.047 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, 11.8 g of polymer P4 was obtained by ring-opening the maleic anhydride-derived structural units in raw material polymer 7 with 4-HBA. 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 13 1C-NMR measurements confirmed that polymer P4 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0311] (Preparation Example 5) Except for using raw material polymer 5 (10.00 g, with an MA equivalent mole of 0.047 calculated with a composition ratio of IN / MAN = 50:50) instead of raw material polymer 4, the same procedure as in Preparation Example 4 was followed to obtain 10.7 g of polymer P5, in which the structural units derived from maleic anhydride in raw material polymer 5 were ring-opened with 4-HBA. GPC analysis of polymer P5 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P5 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P5 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0312] (Preparation Example 6) Resin composition 6 containing polymer P6 was obtained by ring-opening the structural units (MA units) derived from maleic anhydride in raw material polymer 5 with 1-butanol, in the same manner as in preparation example 2, except that raw material polymer 5 (10.00 g, with a composition ratio of IN / MAN = 50:50 and an MA equivalent mole of 0.047) was used instead of raw material polymer 2. GPC analysis of polymer P6 confirmed the disappearance of the 1-butanol peak. This confirmed that the obtained polymer P6 did not contain unreacted 1-butanol. Also 131C-NMR measurements confirmed that polymer P6 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 5 is ring-opened with BuOH.

[0313] (Preparation Example 7) Except for using raw material polymer 6 (10.00 g, with an MA equivalent mole of 0.047 calculated with a composition ratio of IN / MAN = 50:50) instead of raw material polymer 4, the same procedure as in Preparation Example 4 was followed to obtain 11.5 g of polymer P7 by ring-opening the maleic anhydride-derived structural units in raw material polymer 6 with 4-HBA. GPC analysis of polymer P7 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P7 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P7 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0314] (Preparation Example 8) Polymer P8 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 (30.00g) was added to the raw material polymer 7 (10.00g, with a composition ratio of IN / MAN / PhMI = 50:25:25, resulting in MA equivalent moles of 0.020) to prepare a solution. Next, 4-HBA (5.73g, 0.040 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 to prepare the 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, 8.8 g of polymer P8 was obtained by ring-opening the maleic anhydride-derived structural units in raw material polymer 7 with 4-HBA. GPC analysis of polymer P8 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P8 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P8 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0315] (Preparation Example 9) Except for using raw material polymer 8 (10.00 g, with an MA equivalent mole of 0.047 calculated with a composition ratio of IN / MAN = 50:50) instead of raw material polymer 4, the same procedure as in Preparation Example 4 was followed to obtain 12.4 g of polymer P9 by ring-opening the maleic anhydride-derived structural units in raw material polymer 8 with 4-HBA. GPC analysis of polymer P9 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P8 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P9 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0316] [Table 3]

[0317] [Examples B1-B5, Comparative Examples B1-B4] In each example, the physical properties of polymer P produced in the above preparation example were evaluated for the following items.

[0318] (PFAS-eligible polymer P) Table 4 shows the PFAS classification of polymers P1 to P9. "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.

[0319] (Water-repellent and liquid-repellent properties of polymer P alone) In Examples B1-B5 and Comparative Examples B1-B4, polymers P1-P9 obtained in Preparation Examples 1-9 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1-9 with a solid content concentration of 30% by mass. Resin compositions 1-9 obtained in each example were rotationally 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.

[0320] If the contact angle with water (before curing) is 95° or higher, the water repellency is good; if it is 100° or higher, the water repellency is better; if it is 102° or higher, the water repellency is excellent; and if it is 105° or higher, the water repellency is particularly excellent. The contact angle with water (after curing) can be considered as follows: 95° or higher indicates good water repellency, 100° or higher indicates better water repellency, 102° or higher indicates excellent water repellency, and 105° or higher indicates particularly excellent water repellency. A contact angle (before curing) of 7° or more indicates good liquid repellency, 10° or more indicates slightly better liquid repellency, 15° or more indicates excellent liquid repellency, and 20° or more indicates particularly excellent liquid repellency. A contact angle (before curing) of 7° or more indicates good liquid repellency, 10° or more indicates slightly better liquid repellency, 15° or more indicates excellent liquid repellency, and 20° or more indicates particularly excellent liquid repellency.

[0321] (Water-repellent and liquid-repellent properties of photosensitive resin compositions) For polymers P1, P3-P5, and P7-P9, which have (meth)acryloyl groups, the water-repellent and liquid-repellent properties of the cured films of the 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-P5, P7-P9: 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.

[0322] 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, 100° or higher indicates particularly excellent water repellency, and 102° or higher indicates particularly superior water repellency. When development is 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, 100° or higher indicates particularly excellent water repellency, and 102° or higher indicates particularly superior water repellency. When development is not performed, a contact angle of the cured film with respect to PGMEA of 27° or higher indicates good liquid-repellent properties, 30° or higher indicates better liquid-repellent properties, 33° or higher indicates particularly excellent liquid-repellent properties, and 35° or higher indicates particularly excellent liquid-repellent properties. When development is performed, a contact angle of the cured film with respect to PGMEA of 25° or higher indicates good liquid-repellent properties, 27° or higher indicates better liquid-repellent properties, 30° or higher indicates particularly excellent liquid-repellent properties, and 32° or higher indicates particularly excellent liquid-repellent properties.

[0323] [Table 4]

[0324] Polymers P1, P2, and P4 of comparative examples B1, B2, and B4, which do not contain a silicone structure, were not subject to PFAS regulations, but both water repellency and liquid repellency were low. 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. The polymer P in Examples B1 to B5, which included a silicone structure, was PFAS-free and exhibited high water and liquid repellency before and after curing. A photosensitive resin composition containing a silicone structure and polymers P5, P7-P9 having (meth)acryloyl groups exhibited high water and liquid repellency before and after development. [Explanation of symbols]

[0325] 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 (IN), A structural unit derived from maleic anhydride, which includes the structure represented by formula (1-4), A polymer comprising a structural unit having a siloxane bond, 【Chemistry 1】 In the formula (IN), R ６１ ~R ６８ Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Chemistry 2】 polymer.

2. The polymer according to claim 1, The structural unit having a siloxane bond includes at least one structural unit selected from the structural units represented by formula (SI-1), formula (SI-2), formula (SI-3), formula (B1), and formula (B2), 【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 an alkyl group having 1 to 30 carbon atoms, R ｂ Each of these is independently a divalent organic group having 1 to 30 carbon atoms. n represents an integer greater than or equal to 1, 【Transformation 5】 In formula (SI-3), R ｃ Each of these is independently an alkyl group having 1 to 30 carbon atoms. R ｃ ' is a divalent organic group having 1 to 30 carbon atoms, R ｃ ’’ is an organic group having 1 to 30 carbon atoms, R ｃ１ is a hydrogen atom or a methyl group, n represents an integer greater than or equal to 1, 【Transformation 6】 【Transformation 7】 In equations (B1) and (B2), R ｄ This is a group represented by formula (SI-4), formula (SI-5), or formula (SI-6), 【Transformation 8】 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 9】 In formula (SI-5), R ｇ Each of these is 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 10】 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.

3. 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), 【Chemistry 11】 In formula (1-2), R ｐ This is a group having two or more (meth)acryloyl groups, 【Chemistry 12】 In formula (1-3), R ｓ A polymer that has one (meth)acryloyl group.

4. The polymer according to claim 1, The polymer further comprises structural units represented by formula (1-5), 【Chemistry 13】 In formula (1-5), R ５１ A polymer is a linear, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms.

5. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (1-1), 【Chemistry 14】 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.

6. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (MA). 【Chemistry 15】

7. The polymer according to claim 1, The polymer further comprises a structural unit represented by formula (MI), 【Chemistry 16】 In the formula (MI), R ３１ This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ３２ and R ３３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

8. The polymer according to claim 3, 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 17】 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 18] 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 19】 In formula (1d), n is an integer between 2 and 5. R is independently either a hydrogen atom or a methyl group. polymer.

9. The polymer according to claim 3, The polymer includes the structure represented by formula (1-2), 【Chemistry 20】 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.

10. The polymer according to claim 1, A polymer having a weight-average molecular weight of 5,000 or more and 300,000 or less.

11. The polymer according to claim 1, A polymer having a silicon content of 2% by mass or more and 30% by mass or less.

12. A polymer solution comprising the polymer described in any one of claims 1 to 11.

13. A polymer solution according to claim 12, A polymer solution further containing a silicone compound.

14. A polymer solution according to claim 12, A polymer solution used to form partitions or coatings for organic electroluminescent elements.

15. A polymer according to any one of claims 1 to 11, Including a photosensitive agent, Photosensitive resin composition.

16. A cured product formed from the photosensitive resin composition described in claim 15.

17. A structural unit represented by formula (IN), Structural units represented by formula (MA), A polymer comprising a structural unit having a siloxane bond, 【Chemistry 21】 In the formula (IN), R ６１ ~R ６８ Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Chemistry 22】 polymer.

18. The polymer according to claim 17, The structural unit having a siloxane bond includes at least one structural unit selected from the structural units represented by formula (SI-1), formula (SI-2), formula (SI-3), formula (B1), and formula (B2), 【Chemistry 23】 In formula (SI-1), R ａ Each of these is 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 24】 In formula (SI-2), R ｂ Each of these is 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 25】 In formula (SI-3), R ｃ Each of these is 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, 【Chemistry 26】 【Chemistry 27】 In equations (B1) and (B2), R ｄ This is a group represented by formula (SI-4), formula (SI-5), or formula (SI-6), 【Chemistry 28】 In formula (SI-4), R ｆ Each of these is 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 29】 In formula (SI-5), R ｇ Each of these is 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, 【Transformation 30】 In formula (SI-6), R ｈ Each of these is 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.

19. The polymer according to claim 17, The polymer further comprises a structural unit represented by formula (MI), 【Chemistry 31】 In the formula (MI), R ３１ This is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ３２ and R ３３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

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