Polymer, polymer solution, photosensitive resin composition, resin film, and electronic device

Abstract

To provide a polymer that has alkali solubility suitable for pattern formation by photolithography, and in which a resin film after curing has high water repellency and liquid repellency.SOLUTION: A polymer contains a structural unit represented by formula (NB) and a structural unit derived from a maleic anhydride having a specific carboxyl group, and has a specific structure containing a fluorine-containing alkyl group at a main chain terminal.SELECTED DRAWING: None

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 by photolithography technology, and then a functional film is uniformly coated on the fine pattern. In particular, from the viewpoint of waterproofing and wettability control, a method is required to impart water repellency or liquid repellency to a part of a component, and a method has been proposed to form a fine pattern with water repellency or liquid repellency by photolithography technology.

[0003] As a means for imparting water repellency or liquid repellency to a pattern, a method of coating a fine pattern with a fluorine-based water repellent or liquid repellent, such as a perfluoroalkyl group-containing compound, is commonly used. However, compounds containing long-chain perfluoroalkyl groups (carbon number of C8 or more) used as water repellents or liquid repellents are difficult to decompose. Therefore, there are concerns about the effects of long-chain perfluoroalkyl group-containing compounds, such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), on the environment and human body, and the development of alternatives is being widely carried out. Perfluoropolyether group-containing compounds have attracted attention as alternatives to long-chain perfluoroalkyl group-containing compounds. These compounds have low biopersistence and environmental accumulation, and exhibit high water repellency. In addition, from the viewpoint of ease of use, compounds in which the terminal having a reactive group is a hydrolyzable silane are mainly used. However, fluorine-containing silane-based water repellents do not react sufficiently with the substrate when applied to the substrate and heated, and sufficient durability cannot be obtained. In response to these problems, 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 agent that has been hydrolyzed in the presence of a catalyst and water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-174508 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the water repellent agent described in Patent Document 1 is formed into a film on a substrate and a pattern is formed, the water repellency of the obtained pattern is not sufficient, and there is room for improvement in terms of the accuracy of the pattern formation. [Means for solving the problem]

[0006] The present inventors have found that by adjusting the components of the polymer used in the photosensitive resin composition, the polymer itself has water repellency and liquid repellency as well as excellent developability, and have arrived at the present invention.

[0007] According to the present invention, there are provided a polymer, a polymer solution, a photosensitive resin composition, and a cured product as shown below. [1] A structural unit represented by the formula (NB), A structural unit derived from maleic anhydride containing a structure represented by formula (1-4), A polymer comprising: The polymer has an organic group including a structure represented by formula (t) at a main chain terminal, [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2; [ka] -X 21 -R 21 (t) In formula (t), X 21 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 21 is a fluorine-containing alkyl group having 1 to 30 carbon atoms; polymer. [2] The polymer according to item [1], The polymer according to claim 1, The organic group containing a group represented by formula (t) is a group represented by formula (ti), [ka] In formula (ti), R 22 represents an alkylene group which may have a substituent, X 21 and R 21 has the same meaning as in the above formula (t), [3] The polymer according to item [1] or [2], R in the above formula (t) 21 is a perfluoroalkyl group having 1 to 30 carbon atoms. [4] The polymer according to any one of items [1] to [3], The structural unit derived from maleic anhydride includes a structure represented by formula (1-2): [ka] In formula (1-2), R p is a group having two or more (meth)acryloyl groups. [5] The polymer according to any one of items [1] to [4], The structural unit derived from maleic anhydride includes a structure represented by formula (1-3): [ka] In formula (1-3), R sis a group having one (meth)acryloyl group, [6] The polymer according to any one of items [1] to [5], The structural unit derived from maleic anhydride includes a structure represented by formula (1-5): [ka] In the formula (1-5), r3 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. [7] The polymer according to item [4], R in the above formula (1-2) p is at least one selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d), [ka] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a (k+1)-valent organic group having 1 to 12 carbon atoms, [ka] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a single bond or a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents 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, [ka] In formula (1d), n is an integer from 2 to 5; R is independently a hydrogen atom or a methyl group. [8] The polymer according to item [5], R in the above formula (1-3) s is a group represented by formula (2a), [ka] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. [9] The polymer according to item [4], The structural unit derived from maleic anhydride includes a structural unit represented by formula (1), [ka] In formula (1), R p is a group having two or more (meth)acryloyl groups.

[10] The polymer according to item [5], The structural unit derived from maleic anhydride includes a structural unit represented by formula (2): [ka] In formula (2), R sis a group having one (meth)acryloyl group,

[11] The polymer according to item [6], The structural unit derived from maleic anhydride includes a structural unit represented by formula (4), [ka] In formula (4), R 5 is a straight-chain, branched-chain or cyclic hydrocarbon group having 1 to 10 carbon atoms,

[12] The polymer according to any one of items [1] to

[11] , The polymer, wherein the structural unit derived from maleic anhydride includes a structural unit represented by formula (3): [ka]

[13] The polymer according to any one of items [1] to

[12] , The polymer, wherein the structural units derived from maleic anhydride further include a structural unit represented by the formula (MA): [ka]

[14] The polymer according to any one of items [1] to

[13] , The structural unit derived from maleic anhydride includes a structure represented by formula (1-1), [ka] In formula (1-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

[15] The polymer according to item

[14] , The structural unit derived from maleic anhydride includes a structural unit represented by formula (5): [ka] In formula (5), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

[16] The polymer according to item

[14] , The structural unit derived from maleic anhydride further includes a structural unit represented by formula (8): [ka] In formula (8), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R p is a group having two or more (meth)acryloyl groups.

[17] The polymer according to item

[14] , The structural unit derived from maleic anhydride further includes a structural unit represented by formula (9): [ka] In formula (9), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R s is a group having one (meth)acryloyl group,

[18] The polymer according to item

[14] , The structural unit derived from maleic anhydride further includes a structural unit represented by formula (9): [ka] In formula (6), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

[19] The polymer according to any one of items [1] to

[18] , The weight average molecular weight of the polymer is 2,000 or more and 20,000 or less.

[20] The polymer according to any one of items [1] to

[19] , The fluorine content of the polymer is 1% by mass or more and 10% by mass or less.

[21] A polymer solution comprising the polymer according to any one of items [1] to

[20] .

[22] The polymer solution according to item

[21] , which is used for forming a partition wall of an organic electroluminescence element.

[23] The polymer solution according to item

[21] or

[22] , The polymer solution further comprises a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

[24] A polymer according to any one of items [1] to

[20] , A photoradical polymerization initiator, Photosensitive resin composition.

[25] A cured product formed from the photosensitive resin composition according to item

[24] .

[26] A structural unit represented by the formula (NB), A structural unit represented by the formula (MA), A polymer comprising: The polymer has an organic group including a structure represented by formula (t) at a main chain terminal, [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2; [ka] -X 21 -R 21 (t) In formula (t), X 21 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 21 is a fluorine-containing alkyl group having 1 to 30 carbon atoms; polymer.

[27] The polymer according to item

[26] , The organic group containing a group represented by formula (t) is a group represented by formula (ti), [ka] In formula (ti), R 22 represents an alkylene group which may have a substituent, X 21 and R 21 has the same meaning as in the above formula (t), Effect of the Invention

[0008] According to the present invention, there are provided a polymer having alkali solubility suitable for pattern formation by photolithography and having high water repellency and liquid repellency to give a resin film after curing, and a photosensitive resin composition containing the polymer that can be suitably used for producing a partition wall of an organic electroluminescence element. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram for explaining a schematic method for producing an organic EL element by a printing method. [Diagram 2] FIG. 2 is a diagram for explaining a method for producing an organic EL element by a printing method, and is a diagram showing a part of the cross section of FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the embodiments of the present invention will be described. In this specification, the expression "a to b" in the explanation of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less."

[0011] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, the term "alkyl group" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0012] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0013] [Polymer P] The polymer of the present invention (referred to as "polymer P" in this specification) will be described. Unless otherwise specified, structural units or compounds represented by the same structural formula have the same definitions throughout all embodiments, and preferred embodiments are also the same.

[0014] First Embodiment (Polymer P(I)) The polymer of the invention according to the first embodiment, referred to herein as "polymer P(I)", is A structural unit represented by the formula (NB) A structural unit derived from maleic anhydride containing a structure represented by formula (1-4), Including, The polymer has an organic group containing a structure represented by formula (t) at the end of the main chain.

[0015] [ka]

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

[0017] [ka]

[0018] -X 21 -R 21 (t) In formula (t), X 21 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 21 is a fluorine-containing alkyl group having 1 to 30 carbon atoms.

[0019] The polymer P(I) of this embodiment has an organic group having a fluorine-containing alkyl group represented by formula (t) at its terminal. This allows the polymer P(I) to have high water repellency and liquid repellency. The polymer P(I) of this embodiment also includes a structural unit derived from maleic anhydride, which contains a carboxyl group represented by formula (1-4). This allows the acid value of the polymer P(I) to be designed to be relatively large, and as a result, the polymer P(I) has sensitivity and developability suitable for patterning by photolithography. Furthermore, the polymer P(I) of this embodiment includes a structural unit derived from a cyclic olefin represented by formula (NB). The structural unit represented by formula (NB) is chemically robust. Therefore, the structural unit polymer P(I) is stable and has a small weight loss when subjected to heat treatment.

[0020] In the structural unit represented by the above formula (NB) constituting the polymer P(I), R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above include saturated or unsaturated, linear, branched or cyclic hydrocarbon groups, alkoxy groups, and heterocyclic groups having 1 to 30 carbon atoms, as well as carboxy groups. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups.

[0021] Examples of the 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, and a decyl group.

[0022] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

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

[0024] In the structural unit represented by the formula (NB), R 1 , R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, and more preferably hydrogen. In addition, R 1 , R 2 , R 3 and R 4 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 a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, and more preferably 0.

[0025] The proportion of the structural unit represented by formula (NB) in all structural units constituting the polymer P(I) is preferably from 25 to 75 mol %, more preferably from 30 to 65 mol %, and further preferably from 35 to 60 mol %.

[0026] The polymer P(I) contains a structural unit derived from maleic anhydride, which contains a structure represented by formula (1-4). The proportion of the structural unit represented by formula (1-4) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 2 to 7 mol %.

[0027] In the organic group having a structure represented by formula (t) present at the terminal of the polymer P(I), X 21 represents a single bond or alkylene having 1 to 3 carbon atoms, preferably alkylene having 1 to 3 carbon atoms, and more preferably alkylene having 1 to 2 carbon atoms. R in formula (t) 21 is a linear or branched fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched fluoroalkyl group having 1 to 15 carbon atoms. Here, the fluoroalkyl group includes a fluorinated alkyl group in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom, and a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. R in formula (t) 21 is preferably a perfluoroalkyl group, which can increase the fluorine content of the resulting polymer P(I), thereby improving the water repellency and liquid repellency of the polymer P(I).

[0028] The proportion of the organic group containing the structure represented by formula (t) in all structural units of the polymer P(I) is preferably 0.5 to 10 mol %, more preferably 1 to 5 mol %.

[0029] In one embodiment, the organic group having a structure represented by formula (t) is a group represented by formula (ti). [ka]

[0030] In formula (ti), X 21 and R 21 has the same meaning as in the above formula (t). R 22 represents an alkylene group which may have a substituent, and this alkylene group may be any of linear, branched, and cyclic, and may also be a combination of a linear or branched alkylene group and a cyclic alkylene group.

[0031] R 22 The linear or branched alkylene group constituting the formula (I) preferably has 1 to 5 carbon atoms in the main chain, more preferably 1 to 4 carbon atoms, further preferably 1 to 3 carbon atoms, and most preferably 3 carbon atoms. Specific examples of linear alkylene groups include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. R 22Examples of the branched alkylene group that can constitute the above include a group in which a linear or branched alkyl group is bonded to the linear alkylene group. The alkyl group is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Specific examples of branched alkylene groups include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The cyclic alkylene group preferably has a carbon number of 3 to 20, and more preferably 3 to 12. In addition, the cyclic alkylene group may be either monocyclic or polycyclic. R 22 The monocyclic alkylene group that can constitute the above is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alkylene group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The cyclic alkylene group may have a straight-chain or branched-chain alkyl group bonded to the carbon atom that constitutes the ring. Examples of the alkyl group include the same as those described above.

[0032] R 22The alkylene group constituting the formula (I) may have a substituent. The alkylene group "has a substituent" means that some or all of the hydrogen atoms in the alkylene group are replaced with groups or atoms other than hydrogen atoms. R 22 Preferred examples of the substituent that the alkylene group constituting the formula (I) may have include a cyano group.

[0033] R 22 When is an alkylene group having a cyano group, a preferred example is -C(CH3)(CN)-(CH2) n -, -C(CH3)2-(CH2) n In the formula, n is an integer of 0 to 4, preferably 0 to 3, particularly preferably 0 to 2, and most preferably 2.

[0034] The structural unit derived from maleic anhydride in the polymer P(I) may include a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3).

[0035] [ka]

[0036] In formula (1-2), R p is a group having two or more (meth)acryloyl groups.

[0037] [ka]

[0038] In formula (1-3), R s is a group having one (meth)acryloyl group.

[0039] When the polymer P(I) contains a structural unit containing two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2), or a structural unit containing one (meth)acryloyl group represented by formula (1-3), or a combination of these, the photosensitive resin composition containing the polymer P(I) has excellent sensitivity when subjected to photolithography processing. This is believed to be because the (meth)acryloyl group contained in the structural unit represented by formula (1-2) or formula (1-3) promotes the curing reaction (polymerization reaction).

[0040] 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 sensitivity of the polymer P(I) containing the same can be further increased in exposure treatment. In addition, it becomes easier to achieve a high degree of compatibility between the sensitivity and alkali solubility of the polymer P(I).

[0041] R in formula (1-2) p is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and includes at least one selected from these. By being such a group, it tends to be easy to obtain the various effects described above.

[0042] [ka]

[0043] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is (k+1) with carbon number 1 to 12 is a 0.1-valent organic group. R is preferably a hydrogen atom in view of further improving sensitivity (ease of polymerization) and the like. Although k may be 2 or 3, it is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0044] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

[0045] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0046] X 1 When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X described above.

[0047] X 2 The (k+1)-valent organic group having 1 to 12 carbon atoms may be any group obtained by removing (k+1) hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which (k+1) hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which (k+1) hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0048] [ka]

[0049] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents 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.

[0050] R, k, X 1and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0051] [ka]

[0052] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. Specific embodiments and preferred embodiments of R are the same as those explained in formula (1b).

[0053] When the polymer P(I) contains a structural unit represented by formula (1-2), the proportion of the structural unit represented by formula (1-2) in all structural units of the polymer P(I) is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

[0054] In the structural unit represented by formula (1-3) which can constitute the polymer P(I), R Sis a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P(I) contains either or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), thereby achieving a good balance between the sensitivity and the developability.

[0055] R S is, for example, a group represented by the following formula (2a).

[0056] [ka]

[0057] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. X 10 As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0058] X 10 The divalent organic group X is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 The number of carbon atoms (X 10 By appropriately selecting the chain length of the structural unit represented by formula (2), the structural unit represented by formula (2) can be more easily involved in the crosslinking reaction, thereby increasing the sensitivity.

[0059] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

[0060] When the polymer P(I) contains a structural unit represented by formula (1-3), the proportion of the structural unit represented by formula (2) in all structural units of the polymer P(I) is preferably 5 to 30 mol %, more preferably 10 to 20 mol %.

[0061] When the polymer P(I) contains both the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), the total proportion of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3) in the 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 all the structural units constituting the polymer P(I).

[0062] The polymer P(I) may contain, as a structural unit derived from maleic anhydride, at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0063] [ka]

[0064] [ka]

[0065] In formula (1) and formula (2), R p and R s has the same meaning as in the above formula (1-2) and formula (1-3).

[0066] 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 structural units of the polymer P(I) is preferably 0.5 to 25 mol %, more preferably 1 to 18 mol %.

[0067] 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 structural units of the polymer P(I) is preferably 0.5 to 35 mol %, more preferably 2 to 25 mol %.

[0068] The polymer P(I) of the present embodiment may contain a structural unit derived from maleic anhydride represented by formula (3) in addition to the above structural units. The polymer P(I) has high alkali solubility due to the structural unit represented by formula (3). As a result, a photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. The proportion of the structural unit represented by formula (3) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 2 to 7 mol %. [ka]

[0069] The structural unit derived from maleic anhydride in the polymer P(I) of the present embodiment may include a structural unit represented by formula (1-1).

[0070] [ka]

[0071] 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 alkyl group having 1 to 6 carbon atoms. Examples of the 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, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q may be bonded to any carbon atom of the alkylene group of X to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, and a naphthalene ring. In the formula (1-1), an embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0072] An embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following formula (1a), or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0073] [ka]

[0074] In formula (1a), R is a hydrogen atom or a methyl group.

[0075] When the polymer P(I) contains a structural unit represented by formula (1-1), the proportion of the structural unit represented by formula (1-1) in all structural units of the polymer P(I) is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %.

[0076] When the polymer P(I) contains a structural unit of the formula (1-1) and a structural unit of the formula (1-4), the polymer P(I) has both a (meth)acryloyl group (the "-Z" group in the formula (1-1)) and a carboxyl group represented by the formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, the polymer P(I) can be designed to have a relatively large double bond equivalent and acid value due to the presence of a polymerizable group and a carboxyl group in the same polymer molecule. It is difficult to increase the content of both the polymerizable group and the carboxyl group in other resins such as (meth)acrylic resins. The polymer P(I) can achieve both high sensitivity and developability due to the presence of such a structure.

[0077] The polymer P(I) can contain at least one of a structural unit represented by formula (8) and a structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2), and the structural unit of formula (9) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-3).

[0078] [ka]

[0079] [ka]

[0080] In formula (8), Q, X, and Z are the same as those in formula (1-1), and R p has the same meaning as in formula (1-2). In formula (9), Z, Q, and X are the same as those in formula (1-1), and R S has the same meaning as in formula (1-3).

[0081] When the polymer P(I) contains a structural unit represented by formula (8), the proportion of the structural unit represented by formula (8) in all structural units of the polymer P(I) is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %. When the polymer P(I) contains a structural unit represented by formula (9), the proportion of the structural unit represented by formula (9) in all structural units of the polymer P(I) is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0082] The polymer P(I) may contain a structural unit represented by the following formula (5) which is composed of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-4). By containing this structural unit, both the sensitivity and the developability can be achieved in a better balance.

[0083] [ka]

[0084] In formula (5), Z, X, and Q have the same meanings as in formula (1-1). When the polymer P(I) contains a structural unit represented by formula (5), the proportion of the structural unit represented by formula (5) in all structural units of the polymer P(I) is preferably 1 to 12 mol %, more preferably 1 to 9 mol %.

[0085] From the viewpoint of the effects of the present invention, the polymer P(I) may further contain a structural unit represented by the following formula (6) consisting of two structural units represented by the formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0086] [ka]

[0087] In formula (6), Z, X, and Q have the same meanings as in formula (1-1). A plurality of Z's, a plurality of Q's, and a plurality of X's may be the same or different.

[0088] When the polymer P(I) contains a structural unit represented by formula (6), the proportion of the structural unit represented by formula (6) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 1 to 8 mol %.

[0089] The polymer P(I) may contain structural units derived from maleic anhydride, including a structure represented by formula (1-5).

[0090] [ka]

[0091] In formula (1-5), R 5 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. R 5 Examples of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms that can constitute the above group include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group.

[0092] Examples of the 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, and a decyl group.

[0093] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

[0094] Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0095] The polymer P(I) has high alkali solubility due to the inclusion of the structural unit represented by formula (1-5). As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. When the polymer P(I) contains the structural unit represented by formula (1-5), the proportion of the structural unit represented by formula (1-5) in the total structural units of the polymer P(I) is preferably 5 to 40 mol %, more preferably 10 to 30 mol %.

[0096] In one embodiment, the 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).

[0097] [ka]

[0098] In formula (4), R 5 has the same meaning as in formula (1-5).

[0099] The polymer P(I) has high alkali solubility due to the structural unit represented by formula (5). As a result, a photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer.

[0100] When the polymer P(I) contains a structural unit represented by formula (5), the proportion of the structural unit represented by formula (5) in all structural units of the polymer P(I) is preferably 5 to 40 mol %, more preferably 10 to 30 mol %.

[0101] In one embodiment, the polymer P(I) may contain a structural unit represented by formula (11). The structural unit represented by formula (11) is a structural unit composed of a structure represented by formula (1-5) and a structure represented by formula (1-1).

[0102] [ka]

[0103] In formula (11), R 5 is defined as the same as in the above formula (1-5), Z, Q and X have the same meanings as in the above formula (1-1).

[0104] The polymer P(I) may contain structural units derived from maleic anhydride represented by the formula (MA).

[0105] [ka]

[0106] The structural unit derived from maleic anhydride represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P(I) containing the structural unit has excellent developability. When the polymer P(I) contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, of all the structural units of the polymer P(I).

[0107] The content (ratio) of each structural unit contained in the polymer P(I) can be determined by the amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1H-NMR spectrum, 13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0108] The weight average molecular weight Mw of the polymer P(I) is, for example, 2,000 to 20,000. The weight average molecular weight Mw of the polymer P(I) is preferably 3,000 to 15,000, and more preferably 4,000 to 10,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer. The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P(I) of this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P(I) can be made uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0109] The glass transition temperature of the polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. The polymer P(I) has a relatively high glass transition temperature due to the inclusion of a structural unit represented by the formula (NB) and a structural unit represented by the formula (HF). This is preferable in that a pattern formed on a substrate can be stably present in the manufacture of a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0110] The acid value of the polymer P(I) is 60 mgKOH / g or more and 150 mgKOH / g or less, preferably 70 mgKOH / g or more and 140 mgKOH / g or less, and the double bond equivalent of the polymer P1 is 100 g / mol or more and 900 g / mol or less, preferably 200 g / mol or more and 850 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less. When the polymer P(I) has an acid value of 60 mgKOH / g or more, good developability can be obtained, and when the double bond equivalent is 900 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be increased.

[0111] If the acid value of the polymer P(I) is too large, the exposed portion may be easily dissolved during development with an alkaline developer, which may increase the amount of exposure required for photocuring or result in an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH / g. In addition, if the double bond equivalent of the polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too large), the unexposed or low-exposed areas tend to be difficult to dissolve during development with an alkaline developer, and a residual film tends to be generated during development. In addition, if the double bond equivalent is too small, crosslinking causes an excessive increase in molecular weight, which may lead to an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0112] The polymer P(I) of the present embodiment has the above-mentioned constitution, and therefore its alkali dissolution rate can be 500 nm / s or more, preferably 1,000 nm / s or more, more preferably 1,250 nm / s or more, and particularly preferably 1,500 nm / s or more. The upper limit is not particularly limited, but may be, for example, 3,000 nm / s or less. In the present specification, the alkali dissolution rate is a value measured under the following conditions. (Method of measuring alkaline dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid concentration of 30 mass%. The obtained polymer solution is then spin-coated on a wafer, the PGMEA is dried, and the wafer is pre-baked at a temperature of 100°C for 2 minutes to prepare a resin film with a thickness of 1 μm ± 0.2. This resin film is immersed together with the wafer in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23°C. The immersed wafer is visually observed to measure the time until the resin film dissolves and the interference pattern disappears, and the alkaline dissolution rate (nm / sec) is calculated by dividing the film thickness before immersion (1 μm ± 0.2) by this time.

[0113] By adjusting the acid value and / or double bond equivalent of the polymer P(I), it is possible to achieve both sensitivity and developability at a higher level.

[0114] The acid value and double bond equivalent of the polymer P(I) can be determined by spectrum measurement, etc. For example, they can be determined by the following procedure (for more details, see the Examples). (1) Polymer 1 From the H-NMR chart, the areas (integral values) of the peaks corresponding to the hydrogen atoms of the carboxyl group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond are determined. (2) From the area determined in (1) and the area of ​​the peak derived from the standard substance, the amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated. (3) Convert the amount of carboxyl groups obtained in (2) into an acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) into a double bond equivalent (g / mol).

[0115] 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), in particular the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2).

[0116] The content (ratio) of each structural unit contained in the polymer P(I) of the present embodiment can be determined by the amount (molar amount) 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 H-NMR peak area, etc.

[0117] The fluorine content in the polymer P(I) is preferably 1.0% by mass to 10% by mass, more preferably 1.5% by mass to 8.0% by mass, and even more preferably 2.0% by mass to 5.0% by mass. By adjusting the fluorine content within such a range, a polymer P(I) having excellent water repellency, liquid repellency, and alkali solubility can be obtained.

[0118] (Production method of polymer P(I)) The polymer P(I) can be produced (synthesized) by any method. Typically, the polymer P(I) can be produced by the following steps aI, aII, and aIII. Step aI: preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA) and having an organic group containing a structure represented by formula (t) at its terminal; Step aII-i: A step of reacting the raw material polymer obtained in step aI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound), and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a first polymer precursor (Ia) containing a structural unit represented by formula (NB), as well as a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA), and having an organic group containing a structure represented by formula (t) at its terminal.

[0119] When the polymer P(I) further contains a structural unit represented by formula (3), the following step aII-ii is carried out after step aII-i. Step aII-ii is an optional step that is carried out as necessary. Step aII-ii: A step of treating the polymer precursor (Ia) with water in the presence of a base catalyst to obtain a second polymer precursor (referred to as "polymer precursor (Ib)") comprising a structural unit represented by formula (NB), a structural unit represented by formula (3), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further comprising a structural unit represented by formula (MA), and having an organic group containing a structure represented by formula (t) at its terminal.

[0120] When the polymer P(I) contains a structural unit represented by formula (4), the following step aII-iii is carried out after step aI or after step aII-i. Step aII-iii is an optional step that is carried out as necessary. Step aII-iii: A step of reacting the raw polymer obtained in step aI or the polymer precursor (Ia) obtained in step aII-i with an alcohol represented by formula (AL) in the presence of a basic catalyst to obtain a third polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (4), and a structural unit represented by formula (MA) (a precursor obtained via a raw polymer, referred to as "polymer precursor (Ic-i)"), or a third polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (4), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) (a precursor obtained via a polymer precursor (Ia), referred to as "polymer precursor (Ic-ii)"). Here, the structural unit represented by formula (4) has a structure containing a structural unit represented by formula (1-5) and a structural unit represented by formula (1-4), and is a structural unit obtained by reacting a structural unit represented by formula (MA) in the polymer precursor (Ia) with an alcohol represented by formula (AL). R 5 -OH (AL) In formula (AL), R 5 is R in (1-5) above. 5 is synonymous with.

[0121] Step aIII-i: A step of reacting the first polymer precursor (Ia) obtained in step aII-i, the second polymer precursor (Ib) obtained in step aII-ii, or the third polymer precursor (Ic-i) or (Ic-ii) obtained in step aII-iii with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1-1), and optionally further containing a structural unit represented by formula (MA).

[0122] If the above step aII-ii is not carried out, the following step aIII-ii may be carried out after step aIII-i in order to obtain a polymer P(I) further comprising a structural unit represented by formula (3). Step aIII-ii: A step of treating the polymer P(I) obtained through step aII-i or step aII-iii, and step aIII-i, without carrying out step aII-ii, with water in the presence of a base catalyst to obtain a polymer P(I) containing at least a structural unit represented by formula (NB), a structural unit represented by formula (1-1), and a structural unit represented by formula (3), and optionally further containing a structural unit represented by formula (MA).

[0123] Each step will be described below. (Process aI) In step aI, the step of preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA) and having an organic group containing a structure represented by formula (t) at its terminal can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm) and maleic anhydride in the presence of a fluorine-containing radical polymerization initiator. 1 , R 2 , R 3 and R 4 and the definition of a1 is the same as that in formula (NB).

[0124] [ka]

[0125] Examples of the monomer represented by the formula (NBm) include norbornene, bicyclo[2.2.1]-hept-2-ene (trivial name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride. In the polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more kinds.

[0126] As the fluorine-containing polymerization initiator, a fluorine-containing azo compound having an organic group containing a structure represented by formula (t) at both ends, a fluorine-containing organic peroxide, etc. The polymerization initiator may be used alone or in combination of two or more kinds. The fluorine-containing azo compound may be a compound represented by formula (AZ). By using the compound represented by formula (AZ) as a radical polymerization initiator, a polymer P(I) having an organic group represented by formula (ti) at the main chain terminal can be obtained.

[0127] [ka]

[0128] In formula (AZ), R 21 , R 22 , and X 21 has the same meaning as in formula (ti).

[0129] Specific examples of the fluorine-containing azo compound represented by the formula (AZ) include the compounds shown below. [ka] [ka]

[0130] The solvent used in the polymerization reaction may be, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0131] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by formula (NBm), maleic anhydride, and the above-mentioned fluorine-containing polymerization initiator in a solvent, charging the resulting solution into a reaction vessel, and then heating the mixture to cause addition polymerization. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours. The molar ratio of the monomer represented by formula (NBm) to maleic anhydride (MAm) when charged into a reaction vessel is preferably (NBm):(MAm)=0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 0.5:0.8 to 0.7:0.5. Through such a process, a "raw polymer" can be obtained. The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0132] After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol, 2-propanol, or 1-butanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

[0133] (Step aII-i) In step aII-i, the raw polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, whereby some of the structural units represented by formula (MA) contained in the raw polymer are ring-opened to form structural units represented by formula (1) and / or structural units represented by formula (2), thereby obtaining a polymer precursor having a structural unit represented by formula (NB), as well as a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA), and an organic group having a structure represented by formula (t) at the end. For convenience of explanation, the polymer precursor obtained here is referred to as "polymer precursor (Ia)".

[0134] More specifically, first, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), etc. can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0135] When obtaining a polymer precursor containing both the structural unit represented by formula (NB) and the structural unit represented by formula (1) and the structural unit represented by formula (2), next, add a polyfunctional (meth)acrylic compound to the above solution.Further, add a basic catalyst.Then, mix the solution appropriately to obtain a homogeneous solution, and obtain a polymer precursor containing at least the structural unit represented by formula (NB) and the structural unit represented by formula (1) (step aII(1)).

[0136] Examples of the polyfunctional (meth)acrylic compound that can be used herein include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). 1 , X1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiment of are the same as those in the above formula (1c). n and R in formula (1d-m) are the same as those in the above formula (1d).

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] Next, the polymer obtained in step aII-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor containing the structural unit of formula (NB), the structural unit of formula (1), and the structural unit of formula (2) (step aII(2)).

[0141] As the basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as catalysts. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of the raw material polymer. Note that if an excessive amount of the basic catalyst is used, the amount of acid required for neutralization increases, and purification may become complicated.

[0142] The solution is heated preferably at 60 to 80° C. for about 3 to 9 hours to open the structural unit of formula (MA) contained in the raw material polymer and form the structural unit of formula (1).

[0143] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating, the structural unit of formula (MA) contained in the raw polymer is ring-opened / the structural unit of formula (2) is formed, and a polymer P(I) having a structural unit represented by formula (2) is produced.

[0144] From the viewpoint of steric hindrance of the reaction, etc., a monofunctional (meth)acrylic compound having a hydroxyl group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxyl group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), it is preferable not to charge a monofunctional (meth)acrylic compound having a hydroxyl group into the reaction system from the beginning, but to add it to the reaction system. Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0145] [ka]

[0146] Specific examples of the compound 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.

[0147] In order to obtain a polymer precursor (Ia) containing a structural unit represented by formula (NB) and either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of step aII(1) and step aII(2) may be carried out after step (I).

[0148] (Step aII-ii) When carrying out step aII-ii, the polymer precursor (Ia) obtained in step aII-i is treated with water in the presence of a basic catalyst. By step aII-ii, the structural unit represented by formula (MA) contained in the polymer precursor (Ia) obtained in step aII-i is ring-opened to form a structural unit represented by formula (3), and a second polymer precursor (referred to as "polymer precursor (Ib)") containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (3) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit of formula (MA) remains without being ring-opened, the polymer precursor (Ib) may further contain a structural unit represented by formula (MA).

[0149] The basic catalyst used in step aII-ii includes an amine compound such as triethylamine, pyridine, or dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.

[0150] In step aII-ii, water is added to the reaction system containing the polymer precursor (Ia) obtained in step aII-i, and the resulting reaction solution is heated, preferably at 60 to 80° C. for about 0.25 to 6 hours, to open the structural unit of formula (MA) contained in the polymer precursor (Ia) and generate a structural unit represented by formula (3). The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII-i as it is. Therefore, it is preferable to carry out step aII-ii in situ by adding water to the reaction mixture obtained in step aII-i without carrying out any post-treatment of the reaction mixture.

[0151] (Step aII-iii) In step aII-iii, the raw polymer obtained in step aI or the polymer precursor (Ia) obtained in step aII-i is reacted with an alcohol compound represented by formula (AL) in the presence of a basic catalyst, whereby a part of the structural units represented by formula (MA) contained in the raw polymer or the polymer precursor (Ia) is ring-opened to form structural units represented by formula (4). By subjecting the raw polymer to step aII-iii, a polymer precursor (Ic-i) containing a structural unit represented by formula (NB), a structural unit represented by formula (4), and a structural unit represented by formula (MA) is produced. Alternatively, by subjecting polymer precursor (Ia) to step aII-iii, a polymer precursor (Ic-ii) containing a structural unit represented by formula (NB), a structural unit represented by formula (4), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) is produced.

[0152] In step aII-iii, the alcohol represented by formula (AL) is added to the reaction system containing the raw polymer or the polymer precursor (Ia) obtained in step aII-i. By stirring and mixing this mixed solution, the polymer precursor (Ic-i) or the polymer precursor (Ic-ii) can be obtained. When carrying out step aII-iii on the polymer precursor (Ia), the basic catalyst remaining in the reaction system obtained in step aII-i can be used as it is. Therefore, it is preferable to carry out step aII-iii in situ by adding water to the reaction mixture obtained in step aII-i without carrying out any post-treatment of the reaction mixture.

[0153] (Step aIII-i) In step aIII-i, the polymer precursor (Ia) obtained in step aII-i, the polymer precursor (Ib) obtained in step aII-ii, or the polymer precursor (Ic-i) or (Ic-ii) obtained in step aII-iii is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, whereby a structural unit represented by formula (1-1) is formed by a reaction between the carboxy group (structural unit (1-4)) in the polymer precursor (Ia) / polymer precursor (Ib) / polymer precursor (Ic-i) or (Ic-ii) and the epoxy group in the epoxy group-containing (meth)acrylic compound. When the polymer precursor (Ia) obtained in step aII-i is used, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is produced in step aIII-i. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When the polymer precursor (Ib) obtained in step aII-i is used, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (5) and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is produced by step aIII-i. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When a part of the structural unit represented by formula (3) of the polymer precursor (Ib) remains unreacted, the resulting polymer P(I) contains a structural unit of formula (3) or formula (1-4). When the polymer precursor (Ic-i) obtained in step aII-iii is used, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4), and a structural unit represented by formula (11) is produced in step aIII-i. When a part of the structural unit of formula (MA) remains without being ring-opened, the polymer P(I) further contains a structural unit represented by formula (MA). When the polymer precursor (Ic-ii) obtained in step aII-iii is used, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4), a structural unit represented by formula (11), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (5) and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is produced by step aIII-i. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA).

[0154] The reaction of the polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) with the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII-i, step aII-ii or step aII-iii. Therefore, step aIII-i is preferably carried out in situ by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in step aII-i, step aII-ii or step aII-iii without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) obtained in step aII-i, step aII-ii or step aII-iii or neutralizing the basic catalyst contained in the mixture.

[0155] Specifically, an epoxy group-containing (meth)acrylic compound is further added to a reaction mixture containing polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) to obtain a reaction solution, which is then heated, preferably at 60 to 80°C, for about 1 to 9 hours. In this way, a structural unit represented by formula (1-1) is formed by a reaction between the carboxyl group (structural unit (1-4)) of polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) and the epoxy group of the epoxy group-containing (meth)acrylic compound, thereby producing the target polymer P(I).

[0156] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, and the like, and one or more selected from these can be used.

[0157] The amount of the epoxy group-containing (meth)acrylic compound added is desirably 0.1 to 3.0 mol per 1 mol of the carboxyl group of the polymer precursor.

[0158] After the step aIII-i, it is preferable to appropriately further carry out the following steps in order to remove unnecessary components other than the desired polymer P(I).

[0159] First, the reaction solution diluted with an organic solvent and to which an acid (e.g., formic acid, citric acid, etc.) has been added is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate 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.

[0160] (Step aIII-ii) When the step aIII-ii is carried out, the polymer P(I) obtained in the step aIII-i is treated with water. In the step aIII-ii, the structural unit represented by the formula (MA) contained in the polymer P(I) obtained in the step aIII-i is ring-opened to form the structural unit represented by the formula (3).

[0161] In step aIII-ii, water is added to the organic solution of the polymer P(I) obtained in step aIII-i, and the resulting reaction solution is heated for about 0.25 to 6 hours, preferably at 60 to 80° C. This causes the ring-opening of the structural unit of formula (MA) contained in the polymer P(I), producing a structural unit represented by formula (3).

[0162] After step aIII-i or step aIII-ii, the following further steps may be carried out for the purification of the desired polymer P(I). First, an excess amount of toluene is added to the organic solution of the polymer P(I) obtained through step aIII-i or step aIII-ii to reprecipitate the polymer P(I), and the polymer powder obtained by the reprecipitation is further washed several times (e.g., twice) with toluene. Furthermore, in order to remove the acid or basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (for example, three times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more, to obtain a high-purity polymer P(I) of this embodiment.

[0163] Second Embodiment (Polymer P(II)) The polymer P in the second embodiment (hereinafter referred to as “polymer P(II)”) is A structural unit represented by the formula (NB) A structural unit represented by the formula (MA), The polymer has an organic group containing a structure represented by formula (t) at the end of the main chain.

[0164] [ka]

[0165] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2.

[0166] [ka]

[0167] -X 21 -R 21 (t) In formula (t), X21 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 21 is a fluorine-containing alkyl group having 1 to 30 carbon atoms.

[0168] The polymer P(II) is a raw material polymer used in the production of the polymer P(I) in the first embodiment, and is a polymer obtained in the above-mentioned step aI.

[0169] The weight average molecular weight Mw of the polymer P(II) is, for example, 1,000 to 15,000. The weight average molecular weight Mw of the polymer P(II) is preferably 1,500 to 10,000, and particularly preferably 2,000 to 7,500. By appropriately adjusting the weight average molecular weight, it becomes possible to adjust the weight average molecular weight of the polymer P(I) obtained from this polymer P(II), and as a result, it is possible to adjust the sensitivity of the polymer P(I) and the solubility in an alkaline developer to a desired level. The dispersity of the polymer P(II) (weight average molecular weight Mw / number average molecular weight Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 4.0, and further preferably from 1.0 to 3.0.

[0170] [Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P(I). The polymer solution of this embodiment may contain at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound together with the polymer P(I).

[0171] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that can be contained in the polymer solution of this embodiment may be an unreacted (meth)acrylic compound used in the above-mentioned step aII in the production of polymer P, or may be one that has been added separately.

[0172] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into the polymer solution include, but are not limited to, compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] k, R, and X in formula (1b-p) 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiments of are the same as those in the above formula (1c).

[0177] In formulae (1b-p), (1c-p) and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0178] The compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p) in which Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p)) or may be added separately. In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0179] When a polyfunctional (meth)acrylic compound is blended into the polymer solution of the present embodiment in addition to the unreacted polyfunctional (meth)acrylic compound used in the production of the polymer P(I), the blending amount can be such that the peak area attributable to the polyfunctional (meth)acrylic compound in a 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 of the peak area of ​​the polymer P(I).

[0180] (Monofunctional (meth)acrylic compound) The monofunctional (meth)acrylic compound to be blended in the polymer solution of the present embodiment includes a compound represented by the following formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0181] [ka]

[0182] When a monofunctional (meth)acrylic compound is blended into the polymer solution of the present embodiment in addition to the unreacted monofunctional (meth)acrylic compound used in the production of the polymer P(I), the blending amount can be such that the peak area attributable to the monofunctional (meth)acrylic compound in a 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 of the peak area of ​​the polymer P(I).

[0183] The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. The organic solvent may be one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc.

[0184] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0185] [Preparation of polymer solution] The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

[0186] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment contains the above-mentioned polymer P(I) and a photopolymerization initiator. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution of the present embodiment and a photopolymerization initiator. Each component will be described below.

[0187] (Photopolymerization initiator) The photopolymerization initiator used in the photosensitive resin composition of the present embodiment may be a photoradical polymerization initiator. As the photoradical polymerization initiator, a known compound may be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl ... -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, etc.; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc.; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-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)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-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 kinds. 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, relative to 100 parts by mass of the polymer P(I).

[0188] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, and therefore has excellent developability and processability in photolithography.

[0189] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0190] Examples of 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, pyrromethene pigments, and dye lake pigments.

[0191] Examples of inorganic pigments that can be used include white pigments and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0192] As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

[0193] Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. When transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0194] Depending on the purpose and use, the colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc.

[0195] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and use. In order to achieve a balance between the coloring concentration and the dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0196] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0197] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied onto a substrate to obtain a resin film, making it possible to obtain a coating film of uniform thickness, and also makes it possible to prevent residues and pattern lifting during development of the coating film.

[0198] The nonionic surfactant is, for example, a compound containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorine-based surfactants include, but are not limited to, Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited. When a surfactant is used, the amount of the surfactant added is preferably 0.01 to 10% by weight based on 100 parts by weight of the resin.

[0199] (solvent) The photosensitive resin composition may typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. may be used.

[0200] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (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 the solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0201] (Light blocking agent) The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

[0202] When the photosensitive resin composition contains a light-shielding agent, the amount of the light-shielding agent may be appropriately set depending on the purpose and use. In order to achieve a balance between the light-shielding performance and the dispersion stability of the light-shielding agent, the amount of the light-shielding agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0203] (Crosslinking agent) The photosensitive resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer P (capable of chemically bonding with the polymer P) through the action of active chemical species generated from the photopolymerization initiator. The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

[0204] The crosslinking agent is preferably, for example, 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 above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

[0205] Specific examples of 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 ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(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 hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether; vinyl ether group-containing (meth)acrylic acid esters, such as 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, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; 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 allyl (meth)acrylate; 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 reacting polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0206] Of 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.

[0207] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount of the crosslinking agent may be appropriately set according to the purpose and use. As an example, the amount of the crosslinking agent may be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, relative to 100 parts by mass of the photosensitive resin.

[0208] (Other additives) The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0209] [Application] A film can be formed using the above-mentioned photosensitive resin composition, and the film can be exposed and developed to form a pattern, to obtain a patterned film. This film can be used as a partition wall for an organic electroluminescence (EL) element.

[0210] A method for producing an organic electroluminescence element using the photosensitive resin composition of the present embodiment includes the steps of: a film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition; an exposure step of pattern-exposing the photosensitive resin film; a developing step of developing the exposed photosensitive resin film to obtain partition walls; a printing process in which an ink (material liquid) in which an organic material is dissolved or dispersed in an organic solvent is printed on the area surrounded by the partition wall on the substrate obtained in the developing process; Includes. The printing step is preferably carried out by an inkjet method.

[0211] The partition wall produced using the photosensitive resin composition of the present embodiment has sufficient water repellency and liquid repellency even after development. Therefore, during the production of an organic EL device, it is possible to prevent the material liquid (ink) from mixing between adjacent pixels. This can provide effects such as improved performance as an organic EL device and improved yield.

[0212] Each step for manufacturing an organic EL element will be described.

[0213] ·Film formation process The substrate here is not particularly limited, and examples thereof include a glass substrate, a plastic substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper-clad laminate, etc. When an organic EL element is produced, a glass substrate is typically used. The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on its surface, and may be surface-treated to improve adhesion.

[0214] The method for forming a photosensitive resin film using the photosensitive resin composition is not particularly limited, and may be, for example, spin coating using a spinner, spray coating using a spray coater, bar coating, immersion, printing, roll coating, an inkjet method, or the like. The photosensitive resin composition applied onto the substrate is typically dried by heating with a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., and preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, and preferably about 30 to 300 seconds.

[0215] The thickness of the photosensitive resin film is not particularly limited and may be adjusted appropriately depending on the pattern to be finally 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 content of the solvent in the photosensitive resin composition, the coating method, and the coating conditions.

[0216] Exposure process The exposure is carried out by applying actinic rays to the photosensitive resin film through a suitable photomask or the like. Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably g-ray, h-ray, or i-ray from a mercury lamp, and particularly preferably i-ray. Two or more light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection, or a stepper is preferred. The amount of light for exposure may be appropriately adjusted depending on the amount of photosensitizer in the photosensitive resin film, but is, for example, 100 to 500 mJ / cm 2 That's about it.

[0217] After exposure, the photosensitive resin film may be heated again (post-exposure bake) if necessary. The temperature is, for example, 70 to 150° C., and preferably 90 to 120° C. The time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds.

[0218] ·Development process The exposed photosensitive resin film is developed with an appropriate developer to form the partition walls.

[0219] In the development step, development can be performed using an appropriate developer, for example, by a dipping method, a paddle method, a spray method, etc. By the development, the exposed part (in the case of a positive type) or the unexposed part (in the case of a negative type) of the photosensitive resin film is dissolved and removed, and the partition wall structure is obtained.

[0220] There is no particular limitation on the type of developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used. Specific examples of the alkaline aqueous solution include: (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous organic amine solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Specific examples of the organic solvent include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether. The developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

[0221] 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.

[0222] Through the above steps, a partition wall can be formed on the substrate, more specifically, a region surrounded by the partition wall (opening) can be provided on the substrate.

[0223] After development and before the printing process, additional processing may be carried out. For example, after development, washing with a rinse solution may be performed. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more. The partition walls may be cured by heating. 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, within a range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a temperature-programmable heating oven, or the like. The atmospheric gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Heating may also be performed under reduced pressure.

[0224] Printing process (explained with reference to Figs. 1 and 2) An ink (material liquid 4) in which an organic material is dissolved or dispersed in an organic solvent is injected into the region (opening 3) on the substrate surrounded by the partition obtained in the development process. Then, typically, the organic solvent in the ink (material liquid 4) is dried to form pixels 5.

[0225] The method of injecting the ink (material liquid 4) is preferably an inkjet method. For example, while an inkjet head 10 as shown in Fig. 1 is moved relatively to the substrate 1, etc., three types of ink (material liquid 4) corresponding to the three colors of RGB are injected in predetermined amounts into predetermined openings 3. In other words, the ink (material liquid 4) is inkjet printed onto the openings 3.

[0226] The ink (material liquid 4) is not particularly limited, but typically comprises a polymeric material and / or a low molecular weight material capable of forming an organic light emitting layer dissolved or dispersed in an organic solvent. Examples of the organic solvent include anisole and cyclohexylbenzene, but other organic solvents can also be used.

[0227] Examples of "polymer materials capable of forming an organic light-emitting layer" include polyphenylenevinylene and its derivatives, polyacetylene and its derivatives, polyphenylene and its derivatives, polyparaphenyleneethylene and its derivatives, poly3-hexylthiophene and its derivatives, and polyfluorene and its derivatives.

[0228] The "low molecular weight material capable of forming an organic light emitting layer" may be a combination of a dopant material and a host material. 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]quinolizin-9-yl)vinyl]-4H-pyran-4-ylidene]malononitrile). Examples of the host material include DPVBi (4,4'-bis(2,2-diphenylethenyl)biphenyl) and Alq3 (tris(8-quinolinolato)aluminum).

[0229] The material of the ink (material liquid 4) is appropriately selected from the above materials or other known materials so as to produce the desired RGB color.

[0230] The ink (material liquid 4) printed (injected) into the opening 3 can be dried, for example, in an oven or by hot air drying.

[0231] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0232] The embodiments of the present invention will be described in detail based on examples and comparative examples. However, the present invention is not limited to the examples.

[0233] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride ·NB: 2-Norbornene ·C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene MEK: Methyl ethyl ketone 4-HBA: 4-Hydroxybutyl acrylate ·BuOH: 1-butanol V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (azo polymerization initiator) VEF-066: A fluorine-containing azo polymerization initiator having the following structure [ka]

[0234] <Synthesis of raw polymer> (Synthesis of raw polymer 1) Maleic anhydride (588.36g, 6.0mol), 2-norbornene (564.90g, 6.0mol), and dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-601, 55.26g, 0.24mol) were weighed and placed in a reaction vessel equipped with a stirrer and a cooling tube. These were dissolved in a mixed solvent consisting of 1716.8g of methyl ethyl ketone and 188.3g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to polymerize the maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was dropped into 14230.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3557.5 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 1027.2 g of a polymer (raw polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.83.

[0235] (Synthesis of raw polymer 2) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB, 381.01g, 1.221mol), maleic anhydride (MAN, 119.73g, 1.221mol), dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 30.14g, 0.131mol) and methyl ethyl ketone (MEK, 94.86g) were added and stirred to dissolve. Then, the 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 dropped into methanol (2000.0g) to precipitate a white solid. The obtained white solid was further washed with methanol (2000.0 g) and then vacuum dried at a temperature of 120° C. to obtain 90.50 g of a polymer (raw polymer 2) having a structural unit derived from C4F9NB and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 6,400 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.51. The obtained polymer is 19 The fluorine content of the polymer was measured by F-NMR and found to be 39.9 wt%.

[0236] The fluorine content of the synthesized polymer was measured by the following method. Approximately 100 mg of the polymer and approximately 60 mg of (trifluoromethyl)benzene as an internal standard were weighed and dissolved in approximately 1 g of acetone-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 19F-NMR measurements were performed. The amount of CF3 (mol / g) and the amount of CF2 (mol / g) in the polymer were calculated from the integral ratio of the CF3 signal (-75 to -81 ppm, 3F) and the CF2 signal (-100 to -130 ppm, 2F) of the polymer in the obtained spectrum chart to the internal standard CF3 signal (-63 ppm, 3F). The fluorine content (wt / %) in the polymer was calculated from the total amount of the calculated CF3 amount (mol / g) and CF2 amount (mol / g) in the polymer.

[0237] (Synthesis of raw polymer 3) In a reaction vessel equipped with a stirrer and a cooling tube, maleic anhydride (117.67 g, 1.200 mol), 2-norbornene (112.98 g, 1.200 mol), VEF-066 (46.68 g, 0.048 mol) and methyl ethyl ketone (MEK, 164.44 g) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at an internal temperature of 80°C for 18 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into methanol (1281.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1281.0 g) and then vacuum dried at a temperature of 120°C to obtain 92.0 g of a polymer (raw polymer 3) having a structural unit derived from C4F9NB, a structural unit derived from maleic anhydride and a structural unit derived from VEF-066. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 8,700 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.56. The obtained polymer is 19 The fluorine content of the polymer was determined to be 4.3 wt% by F-NMR.

[0238] Table 1 below shows the monomer charging ratio and polymerization initiator type used in the synthesis of the raw polymer, as well as the weight average molecular weight (Mw), polydispersity (Mw / Mn) and fluorine content of the obtained raw polymer.

[0239] (Evaluation of water and liquid repellency of raw polymers) The contact angles of the obtained raw polymers 1 to 3 with water and PGMEA (propylene glycol monomethyl ether acetate) were measured by the following method. The results are shown in Table 1. Each raw polymer was dissolved in 2-heptanone to prepare a polymer solution with a solid content of 30% by mass. The prepared polymer solution was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film with a thickness of approximately 1.0 μm (±0.2 μm). The contact angle of this thin film with respect to water and PGMEA was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). The amount of droplets prepared was 2 μL, the observation time was 10 seconds after the droplets landed, and the average value of five measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°). A contact angle with water of 75° or more is considered to be good water repellency, a contact angle with water of 85° or more is considered to be better water repellency, and a contact angle with water of 95° or more is considered to be particularly excellent water repellency. A contact angle with PGMEA of 6° or more is considered to be good liquid repellency, a contact angle with PGMEA of 8° or more is considered to be better liquid repellency, and a contact angle with PGMEA of 10° or more is considered to be particularly excellent liquid repellency.

[0240] [Table 1]

[0241] <Synthesis of polymer P> Using the above raw polymer, polymer P was produced by the following method.

[0242] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA unit of raw material polymer 1 with a monofunctional (meth)acrylic compound. The details are described below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol of MA calculated from the amount of raw polymer 1) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the following reprecipitation method. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 8.7 g of polymer P1 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with 4-HBA. The obtained polymer P1 was subjected to GPC measurement to measure the weight average molecular weight and polydispersity of the polymer P1. The fluorine content of the polymer P1 was also measured. 19 The results were measured using F-NMR, and are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P1, which confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that the polymer P1 had a structure in which a structural unit derived from maleic anhydride was ring-opened with 4-HBA.

[0243] (Preparation Example 2) Polymer P2 was prepared by ring-opening the MA units of raw polymer 2 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 2 (0.024 mol in terms of MA calculated from the amount of raw polymer 2 charged) was used instead of raw polymer 1.

[0244] Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P2, which confirmed that the obtained polymer P2 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that the polymer P2 had a structure in which the structural unit derived from maleic anhydride in the raw material polymer 2 was ring-opened with 4-HBA. The weight average molecular weight, polydispersity, and fluorine content of the obtained polymer P2 were measured in the same manner as in Preparation Example 1. The results are shown in Table 2.

[0245] (Preparation Example 3) Polymer P3 was prepared by ring-opening the MA units of raw polymer 3 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 3 (0.052 mol in terms of MA calculated from the amount of raw polymer 3 charged) was used instead of raw polymer 1.

[0246] Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P3, which confirmed that the obtained polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P3 had a structure in which the structural unit derived from maleic anhydride in raw material polymer 3 was ring-opened with 4-HBA. The weight average molecular weight, polydispersity, and fluorine content of the obtained polymer P3 were measured in the same manner as in Preparation Example 1. The results are shown in Table 2.

[0247] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA unit of raw polymer 3 with 1-butanol. The details are described below. First, 48.85 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol in terms of MA calculated from the amount of raw polymer 3) to prepare a solution. Next, 4.82 g (0.065 mol) of 1-butanol (BuOH) was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the following procedure. The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 7.8 g of polymer P4 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 3 with 1-butanol. The weight average molecular weight and polydispersity of the obtained polymer P4 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of 1-butanol used was confirmed by GPC measurement of the polymer P4, which confirmed that the obtained polymer P4 did not contain unreacted 1-butanol.

[0248] (Physical property evaluation) The acid value and double bond equivalent of each of the polymers P prepared in Preparation Examples 1 to 4 were measured by the methods described below.

[0249] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were performed. 1The amount of carboxyl groups is calculated from the integral value of the H peak (around 12.4 ppm) of the polymer's carboxyl group (-COOH) using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as the standard. The acid value (mgKOH / g) can then be calculated from this amount. The higher the acid value, the greater the amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. When the acid value is 50 gKOH / g or more, it can be considered that the polymer has a carboxy group necessary for the polymer to have sufficient developability.

[0250] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR was measured. The amount of acryloyl groups in the polymer (mol / g) was calculated from the integral ratio of the signal derived from the acryloyl group (5.6-5.8 ppm, 3H) in the obtained spectrum chart to the signal of the phenyl group of the internal standard (8.1 ppm, 4H). The double bond equivalent (g / mol) was calculated from the calculated amount of acryloyl groups in the polymer (mol / g). The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of the polymer.

[0251] [Table 2]

[0252] (Examples 1-2, Comparative Examples 1-2) In each of the Examples and Comparative Examples, a resin composition was prepared and evaluated for the following items. <Evaluation> [Alkaline dissolution rate of resin composition] Polymers P1, P2, P3 and P4 obtained in Preparation Examples 1 to 4 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1, 2, 3 and 4 having a solid content concentration of 30 mass %. Next, the above-mentioned resin compositions 1 to 4 were spin-coated onto the wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of about 1 μm. This resin film was immersed together with the wafer in a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 3. If the alkali dissolution rate is 500 nm / s or more, it can be used as a photosensitive material without any problems, if it is 1,000 nm / s or more, the developability can be considered good, if it is 1,250 nm / s or more, it can be considered better, and if it is 1,500 nm / s or more, it can be considered particularly good.

[0253] [Evaluation of water and liquid repellency of resin compositions] The resin compositions 1 to 4 prepared above were spin-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 having a thickness of about 1.0 μm (±0.2 μm). The contact angle of this thin film with respect to water and PGMEA was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). The amount of droplets prepared was 2 μL, the observation time was 30 seconds after the droplets landed, and the average value of five measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°). If the contact angle with water is 75° or more, it can be said that the water repellency is satisfactory, if it is 77° or more, it can be said that the water repellency is good, if it is 79° or more, it can be said that the water repellency is better, and if it is 81° or more, it can be said that the water repellency is particularly excellent. If the contact angle with PGMEA is 7° or more, it can be said that the liquid repellency is satisfactory, if it is 9° or more, it can be said that the liquid repellency is good, if it is 11° or more, it can be said that the liquid repellency is better, and if it is 13° or more, it can be said that the liquid repellency is particularly excellent.

[0254] [Evaluation of water and liquid repellency of photosensitive resin compositions] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration was 30% by mass. Polymers P1 to P4 (Polymers P in Preparation Examples 1 to 4, respectively): 100 parts by mass Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by weight Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight Surfactant (DIC Corporation, F-556): 0.5 parts by weight The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A having a thickness of about 2.0 μm (±0.2 μm). This thin film A was irradiated with 100 mJ / cm using a Canon g+h+i line mask aligner (PLA-501F). 2 The film was exposed to g+h+i rays at an exposure dose of 1000×g+h+i to obtain thin film B. The contact angle of this thin film B with water and with PGMEA was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). The amount of droplets prepared was 2 μL, the observation time was 30 seconds after the droplets landed, and the average value of five measurements was taken as the contact angle with water (°) or the contact angle with PGMEA (°). If the contact angle with water is 75° or more, it can be said that the water repellency is satisfactory, if it is 77° or more, it can be said that the water repellency is good, if it is 79° or more, it can be said that the water repellency is better, and if it is 81° or more, it can be said that the water repellency is particularly excellent. If the contact angle with PGMEA is 1° or more, it can be said that the liquid repellency is satisfactory, if it is 3° or more, it can be said that the liquid repellency is good, if it is 5° or more, it can be said that the liquid repellency is better, and if it is 7° or more, it can be said that the liquid repellency is particularly excellent.

[0255] The results of the alkaline dissolution rate and contact angle are shown in Table 3.

[0256] [Table 3]

[0257] The photosensitive resin composition of Comparative Example 1, in which polymer P is a non-fluorine-containing polymer, had a large contact angle with water and high water repellency, but a low contact angle with PGMEA and poor liquid repellency. The polymer of Comparative Example 1 had a low contact angle with water and PGMEA, and poor water and liquid repellency. The photosensitive resin composition of Comparative Example 2, which is a copolymer of norbornene and maleic anhydride having a fluoroalkyl group at , had a large contact angle with both water and PGMEA and high water and liquid repellency, but had a low alkali dissolution rate and poor developability. The photosensitive resin compositions of Examples 1 and 2, in which Polymer P was a copolymer of norbornene and maleic anhydride and had a fluorine-containing group at the end, had alkali solubility suitable for pattern formation by photolithography, and the cured resin film and the polymer alone had high water repellency and liquid repellency. Furthermore, raw material polymer 3, which is a copolymer of norbornene and maleic anhydride and has a fluorine-containing group at the end, had a large contact angle with both water and PGMEA and was excellent in water repellency and liquid repellency. [Explanation of symbols]

[0258] 1 Board 2 Bulkhead 2a Top surface (top surface of bulkhead) 3 Opening 4 Material liquid 5 pixels 5R, 5G, 5B pixels 10 Inkjet head

Claims

1. A structural unit represented by formula (NB), A structural unit derived from maleic anhydride containing a structure represented by formula (1-4), A polymer comprising: The polymer has an organic group including a structure represented by formula (t) at a main chain terminal, 【Chemistry 1】 In formula (NB), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a １ is 0, 1 or 2, 【Chemistry 2】 -X ２１ -R ２１ (t) In formula (t), X ２１ is a single bond or an alkylene group having 1 to 3 carbon atoms, R ２１ is a fluorine-containing alkyl group having 1 to 30 carbon atoms; polymer.

2. 2. The polymer of claim 1 , The organic group containing a group represented by formula (t) is a group represented by formula (t-i), 【Chemistry 3】 In formula (t-i), R ２２ represents an alkylene group which may have a substituent, X ２１ and R ２１ has the same meaning as in formula (t) above.

3. 2. The polymer of claim 1 , R in the formula (t) ２１ is a perfluoroalkyl group having 1 to 30 carbon atoms.

4. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes a structure represented by formula (1-2): 【Chemistry 4】 In formula (1-2), R ｐ is a group having two or more (meth)acryloyl groups.

5. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes a structure represented by formula (1-3): 【Chemistry 5】 In formula (1-3), R ｓ is a group having one (meth)acryloyl group.

6. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes a structure represented by formula (1-5): 【Chemistry 6】 In formula (1-5), R ５ is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms.

7. 5. The polymer of claim 4, R in the formula (1-2) ｐ is at least one selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d), 【Chemistry 7】 In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are a plurality of X １ 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'- (X' represents an alkylene group having 1 to 6 carbon atoms, and Z' represents -O- or -COO-), X ２ is a (k+1)-valent organic group having 1 to 12 carbon atoms, 【Chemistry 8】 In formula (1c), k, R, X １ and X ２ respectively represent R, k, and X in formula (1b). １ and X ２ Each R may be the same or different; each X may be the same or different. １ may be the same or different, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ each independently represents 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, 【Chemistry 9】 In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group.

8. 6. The polymer of claim 5, R in the formula (1-3) ｓ is a group represented by formula (2a), 【Chemistry 10】 In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group.

9. 5. The polymer of claim 4, The structural unit derived from maleic anhydride includes a structural unit represented by formula (1), 【Chemistry 11】 In formula (1), R ｐ is a group having two or more (meth)acryloyl groups.

10. 6. The polymer of claim 5, The structural unit derived from maleic anhydride includes a structural unit represented by formula (2): 【Chemistry 12】 In formula (2), R ｓ is a group having one (meth)acryloyl group.

11. 7. The polymer of claim 6, The structural unit derived from maleic anhydride includes a structural unit represented by formula (4): 【Chemistry 13】 In formula (4), R ５ is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms.

12. 2. The polymer of claim 1 , The polymer, wherein the structural unit derived from maleic anhydride includes a structural unit represented by formula (3): 【Chemistry 14】

13. 2. The polymer of claim 1 , The polymer, wherein the structural units derived from maleic anhydride further include a structural unit represented by the formula (MA): 【Chemistry 15】

14. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes a structure represented by formula (1-1): 【Chemistry 16】 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

15. 15. The polymer of claim 14, The structural unit derived from maleic anhydride includes a structural unit represented by formula (5): 【Chemistry 17】 In formula (5), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

16. 15. The polymer of claim 14, The structural unit derived from maleic anhydride further includes a structural unit represented by formula (8): 【Chemistry 18】 In formula (8), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R ｐ is a group having two or more (meth)acryloyl groups.

17. 15. The polymer of claim 14, The structural unit derived from maleic anhydride further includes a structural unit represented by formula (9): 【Chemistry 19】 In formula (9), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R ｓ is a group having one (meth)acryloyl group.

18. 15. The polymer of claim 14, The structural unit derived from maleic anhydride further includes a structural unit represented by formula (9): 【Chemistry 20】 In formula (6), 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; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

19. 2. The polymer of claim 1 , The weight average molecular weight of the polymer is 2,000 or more and 20,000 or less.

20. 2. The polymer of claim 1 , The fluorine content of the polymer is 1% by mass or more and 10% by mass or less.

21. A polymer solution comprising the polymer according to any one of claims 1 to 20.

22. 22. The polymer solution according to claim 21, which is used for forming a partition wall of an organic electroluminescence element.

23. 22. The polymer solution of claim 21, The polymer solution further comprises a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

24. A polymer according to any one of claims 1 to 20, A photoradical polymerization initiator, Photosensitive resin composition.

25. A cured product formed from the photosensitive resin composition according to claim 24.

26. A structural unit represented by formula (NB), A structural unit represented by formula (MA), A polymer comprising: The polymer has an organic group including a structure represented by formula (t) at a main chain terminal, 【Chemistry 21】 In formula (NB), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a １ is 0, 1 or 2, 【Chemical 22】 -X ２１ -R ２１ (t) In formula (t), X ２１ is a single bond or an alkylene group having 1 to 3 carbon atoms, R ２１ is a fluorine-containing alkyl group having 1 to 30 carbon atoms; polymer.

27. 27. The polymer of claim 26, The organic group containing a group represented by formula (t) is a group represented by formula (t-i), 【Chemistry 23】 In formula (t-i), R ２２ represents an alkylene group which may have a substituent, X ２１ and R ２１ is ti to that in formula (t).

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