Polymer, polymer solution, photosensitive resin composition and cured product

Abstract

To provide a polymer having water repellency and fluid repellency in itself while having excellent thermostability even being non-pertinent to PFAS.SOLUTION: A polymer includes a structural unit expressed by a formula (PFNB) and a structural unit derived from a cyclic olefin. (In the formula, at least one of R21 to R24 is a group having a pentafluorophenyl group, and the residue is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a2 is 0, 1 or 2).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 Art

[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 microfabricated by photolithography technology, and a functional film is uniformly coated on the fine pattern. Among them, from the viewpoints of waterproofness and wettability control, a method of imparting water repellency and liquid repellency to a part of a member is required, and a method of forming a fine pattern having water repellency and liquid repellency by photolithography technology has been proposed.

[0003] As a means for imparting water repellency and liquid repellency to a pattern, a fluorine-based water repellent and liquid repellent containing a long-chain perfluoroalkyl group-containing compound typified by perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are generally used by coating the fine pattern. However, since the long-chain perfluoroalkyl group-containing compound used as a water repellent and liquid repellent is hardly decomposable and has high bioaccumulation, there are concerns about its impact on the environment and the human body, and there is a movement worldwide to regulate its use. From the above circumstances, the development of substitutes for long-chain perfluoroalkyl group-containing compounds has been widely carried out. As a substitute for long-chain perfluoroalkyl group-containing compounds, perfluoropolyether group-containing compounds have attracted attention. This compound has relatively low bioresiduality and environmental accumulation and exhibits high water repellency. Also, from the viewpoint of ease of use, a compound having a hydrolyzable silane at the terminal having a reactive group is mainly used. However, a fluorine-containing silane-based water repellent does not sufficiently react with a substrate only by coating and heating on the substrate, and sufficient durability cannot be obtained. In response to such problems, Patent Document 1 proposes a method of enhancing the reactivity between a substrate and a film-forming material by forming a film of a perfluoropolyether group-containing silane-based water repellent hydrolyzed in the presence of a catalyst and water.

[0004] As a technology related to the use of fluoropolymers in electronic devices, the technology described in Patent Document 2 can be cited. Patent Document 2 describes a technology in which a polymer containing a norbornene-type repeating unit having a hydrocarbyl group or a maleimide group and a norbornene-type repeating unit having a perhalocarbyl group is used as a material for an intermediate layer of an electronic device. In Patent Document 2, by introducing a repeating unit derived from a norbornene monomer having a pentafluorophenyl group, the thermal stability of the film-forming polymer is improved and the dielectric constant is reduced.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, when the water repellent described in Patent Document 1 is formed into a film on a substrate and patterned, the water repellency of the resulting pattern is not sufficient, and there is room for improvement in terms of the heat resistance of the pattern. In addition, substances having a perfluorinated methyl group (-CF3) or a perfluorinated methylene group (-CF2-) are classified as PFAS, and in recent years, due to concerns about bioaccumulation and environmental persistence, regulations on PFAS-related substances have been progressing, and the polymer described in Patent Document 1 also falls under PFAS. Further, the polymer described in Patent Document 2 may not provide sufficient liquid repellency because it has a maleimide pendant group.

Means for Solving the Problems

[0007] The inventor has found that by adjusting the constituent components of the polymer used in the photosensitive resin composition, the polymer itself has water repellency and liquid repellency and excellent heat resistance while not corresponding to PFAS, and thus has reached the present invention.

[0008] According to the present invention, there are provided the following polymer, polymer solution, photosensitive resin composition, and cured product: [1] A polymer containing a structural unit represented by formula (PFNB), a structural unit represented by formula (NB), wherein,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Effects of the Invention

[0009] According to the present invention, there are provided a polymer that is free of PFAS and whose cured product has water repellency and liquid repellency as well as high heat resistance, and a photosensitive resin composition containing the polymer.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be described. In this specification, the notation "a to b" in the description 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".

[0012] In the notation of a group (atomic group) in this specification, a notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

[0014] <First Embodiment> (Polymer P(I)) The polymer of the present invention according to the first embodiment (hereinafter referred to as "polymer P(I)") contains a structural unit represented by formula (PFNB) and a structural unit represented by formula (NB).

[0015]

Chemical formula

[0016] In formula (PFNB), R 21 、R 22 、R 23 and R 24 At least one of them is a group having a pentafluorophenyl group, and the rest of R 21 、R 22 、R 23 and R 24 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a2 is 0, 1 or 2.

[0017]

Chemical formula

[0018] In formula (NB), R 1 、R 2 、R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2, none of the aforementioned R 21 、R 22 、R 23 、R 24 、R 1 、R 2 、R 3 、R 4 contains a substituted or unsubstituted maleimide moiety.

[0019] The polymer P(I) of the present embodiment contains a structural unit represented by the formula (PFNB) in which a group having a pentafluorophenyl group is introduced into the side chain. By having a group having a pentafluorophenyl group, the polymer P(I) has high water repellency and liquid repellency. Further, the structural unit represented by the formula (PFNB) is chemically robust due to the cyclic olefin skeleton. Therefore, the polymer P(I) containing this as a structural unit has a small weight loss when subjected to heat treatment and is stable. As a result, a cured product of a photosensitive resin composition containing such a polymer P(I) has high heat resistance.

[0020] The polymer P(I) of the present embodiment contains a structural unit derived from a cyclic olefin represented by the formula (NB). The structural unit represented by the formula (NB) is chemically robust. Therefore, the polymer P(I) containing the structural unit has a small weight loss when subjected to heat treatment and is stable.

[0021] In the polymer P(I) of the present embodiment, R in the formula (PFNB) constituting the polymer P(I) 21 , R 22 , R 23 and R 24 , and R in the structural unit represented by the above formula (NB) 1 , R 2 , R 3 , R 4 do not include either a substituted maleimide moiety or an unsubstituted maleimide moiety. In other words, the polymer P(I) of the present embodiment does not contain a structural unit derived from a monomer having a substituted or unsubstituted maleimide pendant group.

[0022] R in the formula (PFNB) 21 , R 22 , R 23 and R 24 at least one of which is a group having a pentafluorophenyl group represented by the formula (pf). -X 11 -C6F5(pf) In the formula (pf), -C6F5 is a pentafluorophenyl group, and -X 11- is a single bond, or an alkylene group having 1 to 20 carbon atoms, or an oxyalkylene group having 1 to 20 carbon atoms. This alkylene group may be linear, branched or cyclic, or may be a combination of a linear or branched alkylene group and a cyclic alkylene group. The group "-X 11 -" in formula (pf) is preferably a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 6 carbon atoms. Examples of the group represented by formula (pf) include a pentafluorophenyl group (in formula (pf), "-X 11 -" is a single bond), and a pentafluorobenzyl group (in formula (pf), "-X 11 -" is a methylene group).

[0023] In the structural unit represented by the above formula (PFNB) that constitutes polymer P(I), R 21 ~R 24 Examples of the organic group having 1 to 30 carbon atoms that can constitute them include saturated or unsaturated, linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, heterocyclic groups, and carboxy groups. Examples of the hydrocarbon 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.

[0024] 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.

[0025] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include 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.

[0026] Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like. Examples of the alkaryl group include a tolyl group, a xylyl group, and the like. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. 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 neopentyl oxy group, an n-hexyloxy group, and the like. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, and the like.

[0027] In addition, R 21 ~R 24 The organic group having 1 to 30 carbon atoms that can form R

[0028] In one embodiment, one of R 21 ~R 24 is a group having a pentafluorophenyl group, and the remaining three are hydrogen atoms or alkyl groups, more preferably hydrogen atoms.

[0029] In the structural unit represented by the formula (PFNB), a2 is preferably 0 or 1, more preferably 0.

[0030] The proportion of the structural unit represented by the formula (PFNB) in all the structural units constituting the polymer P(I) is preferably 15 to 80 mol%, more preferably 20 to 75 mol%, and still more preferably 25 to 70 mol%.

[0031] In the structural unit represented by the above formula (NB) constituting the polymer P(I), R1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can form ~R include saturated or unsaturated, linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, heterocyclic groups, and 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.

[0032] Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

[0033] Examples of the alkenyl group include allyl group, pentenyl group, vinyl group and the like. Examples of the alkynyl group include ethynyl group and the like. Examples of the alkylidene group include methylidene group, ethylidene group and the like. Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, anthracenyl group.

[0034] Examples of the aralkyl group include benzyl group, phenethyl group and the like. Examples of the alkaryl group include tolyl group, xylyl group and the like. Examples of the cycloalkyl group include adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group and the like. Examples of the heterocyclic group include epoxy group, oxetanyl group and the like.

[0035] In addition, R 1 ~R 4 The organic group having 1 to 30 carbon atoms that can constitute ~ may contain at least one atom selected from O, N, S, P, and Si in its structure.

[0036] R 1 ~R 4 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0037] In the structural unit represented by the formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0038] The proportion of the structural unit represented by the formula (NB) in all the structural units constituting the polymer P(I) is preferably 20 to 85 mol%, more preferably 25 to 80 mol%, and still more preferably 30 to 75 mol%.

[0039] In one embodiment, the polymer P(I) contains a structural unit represented by the formula (ES) as the structural unit represented by the formula (NB).

[0040]

Chemical formula

[0041] In the formula (ES), R 31 、R 32 、R 33 and R 34 at least one of is an alkyl ester-containing group represented by the formula (es), and R 31 、R 32 、R 33 and R 34 the rest of are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a3 is 0, 1 or 2, -X 3 -C(=O)-O-R 35 (es) In the formula (es), X3 is an alkylene group having 1 to 20 carbon atoms, R 35 is an alkyl group having 1 to 3 carbon atoms.

[0042] The structural unit represented by formula (ES) has a cyclic olefin skeleton having an alkyl ester group (-C(=O)-O-R 35 ) in formula (es). Due to the cyclic olefin skeleton, the structural unit represented by formula (ES) is chemically robust. Therefore, polymer P(I) containing this as a structural unit has little weight loss when subjected to heat treatment and is stable.

[0043] In the structural unit represented by the above formula (ES) that can constitute polymer P(I), a3 is 0, 1, or 2, preferably a3 is 0 or 1, and more preferably a3 is 0.

[0044] In the structural unit represented by the above formula (ES) that can constitute polymer P(I), R 31 , R 32 , R 33 and R 34 at least one of is a group represented by formula (es), and the rest of R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. -X 3 -C(=O)-O-R 35 (es) In the group represented by formula (es), X 3 is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 14 carbon atoms, and more preferably an alkylene group having 3 to 10 carbon atoms. The alkylene group as X 3 is linear or branched, preferably linear.

[0045] R 35 in formula (es) is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group.

[0046] R in the structural unit represented by formula (ES) 31 , R 32 , R 33 or R 34 Examples of the alkyl group having 1 to 30 carbon atoms that can constitute R include linear or branched alkyl groups having 1 to 30 carbon atoms. Specific examples of the alkyl group having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

[0047] R other than the group represented by formula (es) in the structural unit represented by formula (ES) 31 , R 32 , R 33 or R 34 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

[0048] In one embodiment, at least one of R 31 , R 32 , R 33 and R 34 is a group represented by formula (es), R 35 in formula (es) is an alkyl group having 1 to 3 carbon atoms, and the rest of R 31 , R 32 , R 33 and R 34 are hydrogen atoms. Preferably, any one of R 31 , R 32 , R 33 and R 34 is a group represented by formula (es), R 35 in formula (es) is an alkyl group having 1 to 3 carbon atoms, and R 31 , R 32 , R 33 and R 34The remaining three of them are hydrogen atoms. Since the formula (ES) has such a structure, the film-forming property of the photosensitive resin composition containing the resulting polymer P(I) can be improved, and the water repellency and liquid repellency of the cured film obtained by curing the photosensitive resin composition can be improved.

[0049] When the polymer P(I) contains a structural unit represented by the formula (ES), the proportion of the structural unit represented by the formula (ES) in all the structural units constituting the polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and still more preferably 35 to 75 mol%.

[0050] When the polymer P(I) contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (ES), the balance of sensitivity, water repellency, and liquid repellency is improved at a high level.

[0051] In one embodiment, the polymer P(I) contains a structural unit represented by the formula (CA) as a structural unit represented by the formula (NB).

[0052]

Chemical formula

[0053] In the formula (CA), R 41 、R 42 、R 43 and R 44 At least one of is a carboxy group-containing group represented by the formula (ca), and the rest of R 41 、R 42 、R 43 and R 44 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a4 is 0, 1 or 2, -X 4 -C(=O)-OH (ca) In the formula (ca), X 4 is an alkylene group having 1 to 20 carbon atoms.

[0054] The structural unit represented by formula (CA) has a cyclic olefin skeleton having a carboxy group (-C(=O)-OH in formula (ca)). The structural unit represented by formula (ES) is chemically robust due to the cyclic olefin skeleton. Therefore, the polymer P(I) containing this as a structural unit has little weight loss when subjected to heat treatment and is stable.

[0055] In the structural unit represented by the above formula (CA) that can constitute the polymer P(I), a4 is 0, 1, or 2, preferably a4 is 0 or 1, and more preferably a4 is 0.

[0056] In the structural unit represented by the above formula (CA) that constitutes the polymer P(I), R 41 , R 42 , R 43 and R 44 at least one of which is a group represented by formula (ca), and the rest of R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. -X 4 -C(=O)-OH (ca) In the group represented by formula (ca), X 4 is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 14 carbon atoms, and more preferably an alkylene group having 3 to 10 carbon atoms. The alkylene group as X 4 is linear or branched, preferably linear.

[0057] R 41 , R 42 , R 43 or R 44Examples of the alkyl group having 1 to 30 carbon atoms that can constitute the group include linear or branched alkyl groups having 1 to 30 carbon atoms. Specific examples of the alkyl group having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

[0058] R other than the group represented by the formula (ca) in the structural unit represented by the formula (CA) 41 、R 42 、R 43 or R 44 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

[0059] In one embodiment, at least one of R 41 、R 42 、R 43 and R 44 is a group represented by the formula (ca), and the rest of R 41 、R 42 、R 43 and R 44 is a hydrogen atom. Preferably, any one of R 41 、R 42 、R 43 and R 44 is a group represented by the formula (ca), and the remaining three of R 41 、R 42 、R 43 and R 44 are hydrogen atoms. By having such a structure in the formula (CA), the film-forming property of the photosensitive resin composition containing the obtained polymer P(I) can be improved, and the water repellency and chemical resistance of the cured film obtained by curing the photosensitive resin composition can be improved.

[0060] When the polymer P(I) contains a structural unit represented by the formula (CA), the proportion of the structural unit represented by the formula (CA) in all the structural units constituting the polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and even more preferably 35 to 75 mol%.

[0061] When the polymer P(I) contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (CA), the balance of sensitivity, alkali solubility, water repellency, and liquid repellency is improved at a high level.

[0062] In one embodiment, the polymer P(I) contains at least one structural unit represented by the formula (NB-a) as the structural unit represented by the formula (NB).

[0063]

Chemical formula

[0064] In the formula (NB-a), R 51 、R 52 、R 53 and R 54 at least one of them is at least one group selected from the following formula (5a):

Chemical formula

[0065] The structural unit represented by the formula (NB-a) is chemically robust due to the cyclic olefin skeleton. Therefore, the polymer P(I) containing this as a structural unit has a small weight loss when subjected to heat treatment and is stable.

[0066] In the structural unit represented by the above formula (NB-a) that can constitute polymer P(I), a5 is 0, 1, or 2; preferably, a5 is 0 or 1; more preferably, a5 is 0.

[0067] In the structural unit represented by the above formula (NB-a) that can constitute polymer P(I), R 51 , R 52 , R 53 and R 54 at least one of them is at least one group selected from the following formula (5a):

Chemical formula

[0068] Examples of the alkyl group having 1 to 30 carbon atoms that can constitute R 51 , R 52 , R 53 or R 54 in the structural unit represented by formula (NB-a) include linear or branched alkyl groups having 1 to 30 carbon atoms. Specific examples of the alkyl group having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and the like.

[0069] As R 51 , R 52 , R 53 or R 54 other than the group represented by the above formula (5a) in the structural unit represented by formula (NB-a), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, and a hydrogen atom is more preferred.

[0070] In one embodiment, R 51 , R 52 , R 53 and R 54 at least one of which is any of the above formula (5a), and the remainder of R 51 , R 52 , R 53 and R 54 is a hydrogen atom. Preferably, any one of R 51 , R 52 , R 53 and R 54 is any of the above formula (5a), and the remaining three of R 51 , R 52 , R 53 and R 54 are hydrogen atoms. When the formula (NB-a) has such a structure, the film-forming property of the photosensitive resin composition containing the resulting polymer P(I) can be improved, and the water repellency and chemical repellency of the cured film obtained by curing the photosensitive resin composition can be improved.

[0071] When the polymer P(I) contains a structural unit represented by the formula (NB-a), the proportion of the structural unit represented by the formula (CA) in all the structural units constituting the polymer P(I) is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, and still more preferably 35 to 75 mol%.

[0072] When the polymer P(I) contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (NB-a), the balance of sensitivity, alkali solubility, water repellency, and chemical repellency is improved at a high level.

[0073] The content (ratio) of each structural unit contained in the polymer P(I) can be estimated / calculated from the charged amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, the presence of peaks in various spectra (e.g., IR spectrum, 1 1H-NMR spectrum, 13 13C-NMR spectrum), and peak areas.

[0074] The weight average molecular weight Mw of the polymer P(I) is, for example, from 10,000 to 200,000. The weight average molecular weight Mw of the polymer P(I) is preferably from 15,000 to 100,000, more preferably from 20,000 to 60,000. By appropriately adjusting the weight average molecular weight, the film-forming property and the solubility in an alkaline developer can be adjusted. Also, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P(I) of the present embodiment is preferably from 1.0 to 5.0, more preferably from 1.0 to 4.0, and even more preferably from 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.

[0075] The glass transition temperature of the polymer P(I) is preferably from 100 to 250 °C, more preferably from 120 to 230 °C. The polymer P(I) has a relatively high glass transition temperature by having a group containing a pentafluorophenyl group. This is preferable in that the pattern formed on the substrate can stably exist in the manufacture of liquid crystal display devices and solid-state imaging devices. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0076] The fluorine content contained in the polymer P(I) is preferably from 10% by mass to 40% by mass, more preferably from 10% by mass to 35% by mass, and even more preferably from 10% by mass to 30% by mass. By adjusting the fluorine content within such a range, a polymer P(I) excellent in water repellency and chemical resistance can be obtained.

[0077] (Method for producing polymer P(I)) Polymer P(I) can be produced (synthesized) by any method, but from the viewpoint of improving heat resistance, an addition polymerization method is preferred. Polymer P(I) (addition polymer) can be obtained, for example, by coordination polymerization using a metal catalyst. In coordination polymerization, a polymer (P) is obtained by polymerizing a monomer in a solution in the presence of a transition metal catalyst (NiCOLE R. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 37, 3003-3010 (1999)).

[0078] Typical nickel and platinum catalysts as metal catalysts used in coordination polymerization are described in International Publication No. WO1997 / 033198 and the like. Examples of metal catalysts for coordination polymerization include known metal catalysts such as (toluene)bis(perfluorophenyl)nickel, (mesitylene)bis(perfluorophenyl)nickel, (benzene)bis(perfluorophenyl)nickel, bis(tetrahydro)bis(perfluorophenyl)nickel, bis(ethyl acetate)bis(perfluorophenyl)nickel, bis(dioxane)bis(perfluorophenyl)nickel, and the like.

[0079] As the reaction solvent, for example, single solvents or mixed solvents such as toluene, ethyl acetate, cyclohexanone, 2-heptane, xylene, mesitylene, decalin, cyclohexane, benzene, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), anisole, terpenoid can be used, but are not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0080] The polymer P(I) of the present embodiment is obtained by directly polymerizing monomers by the above method. However, depending on the polymerization system, if the monomer contains an acidic group, the catalyst and the like may be deactivated and the polymerization may not proceed properly. In this case, a protecting group is introduced into the acidic group for polymerization, and after the polymer is formed, deprotection is carried out to obtain the polymer P(I) having an acidic group. Alternatively, a functional group capable of chemically reacting with the acidic group may be introduced into the monomer, and after the polymer synthesis, the functional group may be converted into an acidic group by a polymer reaction.

[0081] As described above, the polymer P(I) of the present embodiment can be obtained by using a monomer in which a hydrogen atom capable of ionizing an acidic group in a cyclic olefin monomer is substituted with another structure, polymerizing this, and then deprotecting to introduce the original hydrogen atom. Specific examples of the functional group capable of substitution with a hydrogen atom include a tertiary butyl group, a tertiary butoxycarbonyl group, a tetrahydropyran-2-yl group, a trialkylsilyl group such as a trimethylsilyl group, and a methoxymethyl group. Deprotection, that is, restoration of the acidic group by elimination of these protecting groups from the monomer, can be carried out by the method in the case of using the functional group as a protecting group for the acidic functional group. In addition, confirmation of the deprotection of the polymer can be carried out, for example, by 1 confirming that the peak derived from the protecting group has disappeared in the 1H-NMR spectrum of the polymer.

[0082] Typically, the polymer P(I) can be produced using the steps described below. Hereinafter, a production method (production method a) when the polymer P(I) contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (ES), a production method (production method b) when it contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (CA), and a production method (production method c) when it contains a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (NB-a) will be described. The polymer P(I) of the present embodiment can be produced in a high yield by using the following steps.

[0083] (Production method a) The polymer P (referred to as "polymer P(Ia)") containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (ES) can be prepared by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (PFNBm) and a monomer represented by formula (ESm) in the presence of a metal catalyst. Here, R in formula (PFNBm) 21 , R 22 , R 23 and R 24 as well as the definition of a2 are the same as those in formula (PFNB). Also, R in formula (ESm) 31 , R 32 , R 33 and R 34 as well as the definition of a3 are the same as those in formula (ES). Note that the monomer represented by formula (PFNBm) is a compound that does not fall under PFAS.

[0084]

Chemical formula

[0085] Examples of the monomer represented by formula (PFNBm) include 5-pentafluorobenzylbicyclo[2.2.1]hept-2-ene, 5-pentafluorophenylbicyclo[2.2.1]hept-2-ene, and the like. Only one type of the monomer represented by formula (PFNBm) may be used, or two or more types may be used in combination.

[0086]

Chemical formula

[0087] The monomer represented by formula (ESm) is available, for example, from Promelas, LLC. Also, during polymerization, only one type of the monomer represented by formula (ESm) may be used, or two or more types may be used in combination.

[0088] The synthesis of polymer P(Ia) is carried out by dissolving the monomer represented by formula (PFNBm), the monomer represented by formula (ESm), and a catalyst in a reaction solvent, charging them into a reaction vessel, and then heating to allow the polymerization to proceed. The heating temperature is, for example, 40 to 80 °C, and the heating time is, for example, 1 to 20 hours.

[0089] By the above process, a polymer P(Ia) containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (ES) can be obtained. Polymer P(Ia) may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc.

[0090] Note that after the synthesis of polymer P(Ia), a step of removing unreacted monomers, remaining catalysts, etc. may be carried out. Specifically, the reaction mixture containing the reaction product, unreacted monomers, and catalyst is treated with acetic acid and hydrogen peroxide solution to deactivate the catalyst. Then this solution is mixed with a poor solvent such as water, methanol, 2-propanol, 1-butanol, heptane, etc. to precipitate polymer P(Ia) and dissolve unreacted monomers. By filtering and drying this precipitate, the target reaction product, polymer P(Ia), can be isolated and purified.

[0091] (Production method b) A polymer P (referred to as "polymer P(Ib)") containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (CA) can be produced by (step b1) polymerizing (addition polymerization) a monomer composition containing the monomer represented by formula (PFNBm) and the monomer represented by formula (ESm) described in the above "production method a" in the presence of a metal catalyst to obtain a polymer P(Ia) containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (ES), and (step b2) hydrolyzing the polymer P(Ia) obtained in step b1 to obtain a polymer P(Ib) containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (CA).

[0092] Step b1 is the same as the above-mentioned "Manufacturing Method a", and a monomer composition containing a monomer represented by the formula (PFNBm) and a monomer represented by the formula (ESm) is polymerized (ring-opening metathesis polymerization) in the presence of a catalyst to obtain a polymer P(Ia) containing a structural unit represented by the formula (PFNB) and a structural unit represented by the formula (ES).

[0093] In the subsequent step b2, the polymer P(Ib) containing the structural unit represented by the formula (PFNB) and the structural unit represented by the formula (ES) obtained in step b1 is hydrolyzed to obtain a polymer P(Ib) containing the structural unit represented by the formula (PFNB) and the structural unit represented by the formula (CA). Step b2 involves treating the reaction mixture containing the polymer P(Ia) obtained in step b1 with a base, whereby the alkyl ester group represented by the formula (es) in the structural unit (ES) in the polymer P(Ia) is hydrolyzed to generate a group represented by the formula (ca). Examples of the base to be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqueous sodium hydroxide solution, etc.

[0094] After the synthesis of the polymer P(Ib), a step of removing unreacted monomers, remaining catalysts, etc. may be performed. Specifically, the reaction mixture containing the reaction product, unreacted monomers, and catalyst is treated with an aqueous citric acid solution to deactivate the catalyst. Then, this solution is mixed with a poor solvent such as water, methanol, 2-propanol, 1-butanol, heptane, etc. to precipitate the polymer P(Ic) and dissolve the unreacted monomers. By filtering and drying this precipitate, the target reaction product, the polymer P(Ib), can be isolated and purified.

[0095] (Manufacturing Method c) The polymer P (referred to as "polymer P(Ic)") containing a structural unit represented by formula (PFNB) and a structural unit represented by formula (NB-a) can be produced by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (PFNBm) and a monomer represented by formula (NB-am) described in the above "Production Method a" in the presence of a metal catalyst. Here, R 51 , R 52 , R 53 and R 54 as well as the definition of a5 are the same as those in formula (NB-a).

[0096]

Chemical formula

[0097] Examples of the monomer represented by formula (NB-am) include a series of compounds represented by the following (5). When polymerizing, only one kind of the monomer represented by formula (NB-am) may be used, or two or more kinds may be used in combination.

[0098]

Chemical formula

[0099] The synthesis of polymer P(Ic) can be carried out using an addition reaction similar to that described in the above "Production Method a".

[0100] [Polymer solution] The polymer solution of the present embodiment contains the above-mentioned polymer P(I). The polymer P(I) may be a single kind, or may be a mixture of two or more kinds, such as a mixture of polymer P(Ia) and polymer P(Ib).

[0101] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

[0102] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, and the like. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is used in an amount such that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0103] [Manufacture of Polymer Solution] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as the resin material of the photosensitive resin composition described below.

[0104] [Photosensitive Resin Composition] The photosensitive resin composition of this embodiment contains the above-mentioned polymer P(I) and a photoinitiator. That is, the photosensitive resin composition of this embodiment contains the above-mentioned polymer solution of this embodiment and a photoinitiator. Each component will be described below.

[0105] (Photoinitiator) Examples of the photopolymerization initiator used in the photosensitive resin composition of this embodiment include photo radical polymerization initiators. As the photo radical polymerization initiator, known compounds can be used. For example, alkylphenone-based compounds such as 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-methylpropan-1-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; benzophenone-based compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone-based compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; halomethylated triazine-based compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole-based 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, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Imidazole 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, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; etc. are included. The photo radical polymerization initiator may be used alone or in combination of two or more.; The photo radical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the polymer P(I).

[0106] By including the above components, the photosensitive resin composition of this embodiment has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method.

[0107] (Colorant) As one aspect, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state imaging device. Various pigments or dyes can be used as the colorant. As the pigment, an organic pigment or an inorganic pigment can be used.

[0108] As the organic pigment, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments, etc. can be used.

[0109] As the inorganic pigment, white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (lead yellow, cadmium-based, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

[0110] 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 kind of colorant or may contain two or more kinds of colorants.

[0111] The colorant (especially pigment) can be one having an appropriate average particle diameter according to the purpose and application. In particular, when transparency such as that of a color filter is required, a small average particle diameter of 0.1 μm or less is preferable. In addition, when hiding power such as that of a paint is required, a large average particle diameter of 0.5 μm or more is preferable.

[0112] 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. according to the purpose and application.

[0113] When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose and application. However, from the viewpoint of achieving both coloring density and dispersion stability of the colorant, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0114] (Surfactant) The photosensitive resin composition of this embodiment can contain a surfactant, and a nonionic surfactant is preferable as the surfactant.

[0115] By containing a nonionic surfactant, the coatability when applying the photosensitive resin composition onto a substrate to obtain a resin film becomes good, and a coating film with a uniform thickness can be obtained. In addition, residues and pattern lifting during development of the coating film can be prevented.

[0116] The nonionic surfactant is, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a 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 the fluorine-based surfactant include MegaFac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, but are not limited thereto. When using a surfactant, the blending amount of the surfactant is preferably 0.01 to 10% by weight based on 100 parts by mass of the resin.

[0117] (Solvent) The photosensitive resin composition can typically contain a solvent. An organic solvent is preferably used as the solvent. Specifically, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

[0118] Examples of the solvent 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 a mixture thereof. The amount of the solvent used is not particularly limited, but it is used in an amount such that the concentration of the non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0119] (Light-shielding agent) The resin composition of this embodiment can contain a light-shielding agent. The photosensitive resin composition may contain only one kind of light-shielding agent or two or more kinds.

[0120] When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and use. However, from the viewpoint of achieving both light-shielding performance and dispersion stability of the light-shielding agent, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0121] (Crosslinking agent) The photosensitive resin composition of this embodiment can contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it can crosslink the polymer P by the action of the active chemical species generated from the photopolymerization initiator (i.e., it can chemically bond to the polymer P). The crosslinking agent may not only chemically bond with the polymer, but may also react with other crosslinking agents to form bonds.

[0122] The crosslinking agent is preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not correspond to the aforementioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinkable group as the crosslinkable group (polymerizable double bond) of the polymer in terms of further improving uniform curability, sensitivity, etc. There is no particular upper limit to the number of functional groups (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0123] Specific examples of the crosslinking agent include polyfunctional (meth)acrylates such as 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 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, 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, ethylene oxide-added dipentaerythritol hexavinyl ether; (Meth)acrylic acid 2-vinyloxyethyl, (meth)acrylic acid 3-vinyloxypropyl, (meth)acrylic acid 1-methyl-2-vinyloxyethyl, (meth)acrylic acid 2-vinyloxypropyl, (meth)acrylic acid 4-vinyloxybutyl, (meth)acrylic acid 4-vinyloxycyclohexyl, (meth)acrylic acid 5-vinyloxypentyl, (meth)acrylic acid 6-vinyloxyhexyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth)acrylic acid p-vinyloxymethylphenylmethyl, (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(vinyloxyethoxyethoxyethoxy)ethyl and other vinyl ether group-containing (meth)acrylic acid esters; 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, ethylene oxide-added dipentaerythritol hexaallyl ether, etc.; 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, alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate, etc.; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0124] Among them, 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 preferable.

[0125] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one kind of crosslinking agent or two or more kinds of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount thereof may be appropriately set according to the purpose and application. As an example, the amount of the crosslinking agent can be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, based on 100 parts by mass of the photosensitive resin.

[0126] (Other Additives) The photosensitive resin composition may contain components such as fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropy aids, silane coupling agents, and polyhydric phenol compounds according to various purposes and required characteristics.

[0127] [Applications] By forming a film using the above-mentioned photosensitive resin composition and exposing and developing the film to form a pattern, a patterned film can be obtained. This film can be used as a partition wall of an organic electroluminescence (EL) element.

[0128] A method for manufacturing an organic electroluminescence element using the photosensitive resin composition of the present embodiment is a film forming step of forming a photosensitive resin film on a substrate using the above-mentioned 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 a partition wall, A printing step of printing an ink (material liquid) in which an organic material is dissolved or dispersed in an organic solvent in a region surrounded by partition walls on a substrate obtained in a development step is included. Note that the above printing step is preferably performed by an inkjet method.

[0129] The partition walls produced using the photosensitive resin composition of this embodiment have sufficient water repellency and chemical liquid repellency even after development. Therefore, when manufacturing an organic EL element, mixing of the material liquid (ink) between adjacent pixels can be suppressed. As a result, effects such as improvement in the performance and yield of the organic EL can be achieved.

[0130] Each step for manufacturing an organic EL element will be described.

[0131] · Film formation step The substrate here is not particularly limited, and examples 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 manufacturing an organic EL element, a glass substrate is typically used. The substrate may be an unprocessed substrate or a substrate with electrodes or elements formed on its surface. It may be surface-treated to improve adhesion.

[0132] The method for forming a photosensitive resin film using the photosensitive resin composition is not particularly limited. For example, it can be performed by spin coating using a spinner, spray coating using a spray coater, bar coating, dipping, printing, roll coating, the inkjet method, etc. Drying of the photosensitive resin composition applied on the substrate is typically performed by heat treatment using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. Also, the heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

[0133] The film thickness of the photosensitive resin film is not particularly limited and may be appropriately adjusted according to the pattern to be finally obtained. The film thickness of the photosensitive resin film is usually 0.5 to 10 μm, preferably 1 to 5 μm. Note that the film thickness can be adjusted by changing the content of the solvent in the photosensitive resin composition, the coating method, the coating conditions, etc.

[0134] · Exposure process Exposure is performed by applying actinic rays to the photosensitive resin film through an appropriate photomask or the like. Examples of the actinic rays include X-rays, electron beams, ultraviolet rays, visible light, etc. Light with a wavelength of 200 to 500 nm is preferred. In terms of pattern resolution and handleability, the light source is preferably the g-line, h-line or i-line of a mercury lamp, and particularly preferably the i-line. Also, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferred. The exposure light amount may be appropriately adjusted according to the amount of the photosensitizer in the photosensitive resin film, etc. For example, it is about 100 to 500 mJ / cm 2 degree.

[0135] Note that after exposure, the photosensitive resin film may be reheated as necessary (Post Exposure Bake). The temperature is, for example, 70 to 150 °C, preferably 90 to 120 °C. Also, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.

[0136] · Development process By developing the exposed photosensitive resin film with an appropriate developer, a partition can be formed.

[0137] In the development process, development can be performed using an appropriate developer by methods such as the dipping method, the paddle method, the spray method, etc. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) of the photosensitive resin film is eluted and removed, and the structure of the partition is obtained.

[0138] The developable developer is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used. Specific examples of the alkaline aqueous solution include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine, and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, and the like. Water-soluble organic solvents such as methanol and ethanol, and surfactants may be added to the developer.

[0139] 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.

[0140] Through the above steps, a partition wall can be formed on the substrate. More specifically, a region (opening) surrounded by the partition wall can be provided on the substrate.

[0141] Note that additional processing may be performed after development and before the printing process. For example, after development, washing with a rinse solution may be performed. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more. Alternatively, the partition walls may be heated and cured. The heating temperature is typically 150 to 400 °C, preferably 160 to 300 °C, more preferably 200 to 250 °C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be carried out using a hot plate, an oven, a temperature-programmable heating oven, or the like. As the atmosphere gas during the heat treatment, air or an inert gas such as nitrogen or argon may be used. Further, heating may be performed under reduced pressure.

[0142] · Printing process (described 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 a region (opening 3) surrounded by partition walls on a substrate obtained in the developing process. Then, typically by drying the organic solvent of the ink (material liquid 4), the pixel 5 can be formed.

[0143] The injection method of the ink (material liquid 4) is preferably the inkjet method. For example, while relatively moving an inkjet head 10 as shown in FIG. 1 with respect to a substrate 1 or the like, three types of inks (material liquids 4) corresponding to the three RGB colors are injected in a predetermined amount into a predetermined opening 3. In other words, the ink (material liquid 4) is inkjet printed onto the opening 3.

[0144] The ink (material liquid 4) is not particularly limited, but is typically a material in which a polymer material and / or a low molecular weight material capable of forming an organic light-emitting layer is dissolved or dispersed in an organic solvent. Examples of the organic solvent here include anisole and cyclohexylbenzene, but other organic solvents can also be used.

[0145] Examples of the "polymer material capable of forming an organic light-emitting layer" include polyphenylene vinylene and its derivatives, polyacetylene and its derivatives, polyphenylene and its derivatives, polyparaphenylene ethylene and its derivatives, poly-3-hexylthiophene and its derivatives, polyfluorene and its derivatives, and the like.

[0146] Examples of the "low-molecular material capable of forming an organic light-emitting layer" include combinations of a dopant material and a host material. Examples of the dopant material include BCzVBi (4,7-diphenyl-1,10-phenanthroline), coumarin, rubrene, 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), and the like. Examples of the host material include DPVBi (4,4'-bis(2,2-diphenylethenyl)biphenyl), Alq3 (tris(8-quinolinolato)aluminum), and the like.

[0147] The material of the ink (material liquid 4) is appropriately selected from the above materials and other known materials so that the desired color development of RGB occurs.

[0148] The drying of the ink (material liquid 4) printed (injected) into the opening 3 can be performed, for example, by an oven, hot air drying, or the like.

[0149] The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope capable of achieving the object of the present invention are included in the present invention.

Example

[0150] Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

[0151] The compounds used in the examples may be indicated by the following abbreviations or trade names. · PFBNB: 5-pentafluorobenzylbicyclo[2.2.1]hept-2-ene (manufactured by Promelas, LLC) · C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (Promelas, LLC) · EPEsNB: The following compound (Promelas, LLC)

Chem.

Chem.

Chem.

[0152] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0153] (Preparation Example 1) - Synthesis of Raw Material Polymer 1 Into a reaction vessel equipped with a stirrer and a cooling pipe, maleic anhydride (117.67 g, 1.200 mol), 5-pentafluorobenzylbicyclo[2.2.1]hept-2-ene (PFBNB, 328.89 g, 1.200 mol), dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 27.63 g, 0.120 mol), and methyl ethyl ketone (MEK, 121.22 g) were added and stirred to dissolve. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated and reacted at an internal temperature of 80 °C for 18 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into methanol (5496.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (2748.0 g) and then vacuum dried at a temperature of 120 °C to obtain 114.15 g of a polymer (raw material polymer 4) having a structural unit derived from PFBNB and a structural unit derived from maleic anhydride. The resulting polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,300, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.47. - Synthesis of Polymer P1 The MA unit of raw material polymer 1 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA) and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to prepare polymer P1. Details are described below. First, MEK (10.00 g) was added to raw material polymer 1 (10 g, 0.027 mol in terms of MA calculated from the charged amount of raw material polymer 1) to prepare a solution. Then, 4-HBA (2.42 g, 0.017 mol) was added to this solution, and then triethylamine (1.50 g, 0.015 mol) was added, and the mixture was reacted at a temperature of 70 °C for 6 hours. Further, GMA (1.15 g, 0.008 mol) was added, and the mixture was reacted at a temperature of 70 °C for 4 hours. The prepared reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with an aqueous formic acid solution and an aqueous citric acid solution. Then, the polymer was purified by the following reprecipitation method. ·Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excess amount of water was repeated twice. The obtained reaction product was vacuum dried at 40 °C for 12 hours. As described above, 9.8 g of polymer P1 was obtained by ring-opening the structural unit derived from maleic anhydride in raw material polymer 1 with a monofunctional (meth)acrylic compound (4-HBA) and reacting it with GMA. For the obtained polymer P1, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P1. The results are shown in Table 2.

[0154] Also, by GPC measurement of polymer P1, the disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thus, it was confirmed that the obtained polymer P1 does not contain unreacted monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that polymer P1 has a structure in which the structural unit derived from maleic anhydride of raw material polymer 1 is ring-opened with 4-HBA and a structure in which GMA is introduced.

[0155] (Preparation Example 2) Toluene (88.46 g), ethyl acetate (10.35 g), EPEsNB (12.56 g, 0.065 mol), and C4F9NB (13.45 g, 0.043 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, this mixture was purged with nitrogen for 30 minutes while heating at 53 °C. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.52 g, 0.0011 mol) in 4.7 g of toluene was introduced into the aforementioned glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (0.97 g, 0.054 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0156] After raising the temperature of the reaction solution to 50 °C, acetic acid (7.60 g, 0.127 mol), 30% hydrogen peroxide solution (14.81 g, 0.131 mol), ion-exchanged water (29.50 g), and 2-propanol (3.29 g) were added. After stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1169.6 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1169.6 g), and then washed twice with water (643.3 g). By vacuum drying the obtained white powder at a temperature of 40 °C, 16.7 g of a polymer (polymer P2) having structural units derived from EPEsNB and C4F9NB was obtained.

[0157] (Preparation Example 3) Toluene (86.29 g), ethyl acetate (10.12 g), EPEsNB (15.07 g, 0.078 mol), and C4F9NB (10.38 g, 0.033 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.54 g, 0.0011 mol) in 4.8 g of toluene was added to the above-mentioned glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.00 g, 0.055 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0158] After raising the temperature of the reaction solution to 50 °C, acetic acid (7.44 g, 0.124 mol), 30% hydrogen peroxide solution (14.49 g, 0.128 mol), ion-exchanged water (28.87 g), and 2-propanol (3.22 g) were added. After stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1165.4 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1165.4 g), and then washed twice with water (641.0 g). The obtained white powder was vacuum dried at a temperature of 40 °C to obtain 17.1 g of a polymer (polymer P3) having structural units derived from EPEsNB and C4F9NB.

[0159] (Preparation Example 4) Toluene (97.08 g), ethyl acetate (11.29 g), and PFBNB (28.35 g, 0.103 mol) were placed in a glass apparatus to obtain a reaction solution. Then, nitrogen purging was performed for 30 minutes while heating this solution at 53 °C. Next, a solution in which (toluene)bis(perfluorophenyl)nickel (0.50 g, 0.0010 mol) was dissolved in 4.51 g of toluene was introduced into the above-mentioned glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (0.93 g, 0.052 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0160] After raising the temperature of the reaction solution to 50 °C, acetic acid (8.27 g, 0.138 mol), 30% hydrogen peroxide solution (16.12 g, 0.142 mol), ion-exchanged water (28.53 g), and 2-propanol (3.59 g) were added. After stirring for 30 minutes, it was allowed to stand for 30 minutes, and the lower-phase extraction solution separated into two phases was removed to recover the polymer solution. The polymer solution obtained above was dropped into methanol (887.5 g) to precipitate a white solid. The obtained white solid was further washed with methanol (887.5 g), and then washed twice with water (488.1 g). The obtained white powder was vacuum dried at a temperature of 40 °C to obtain 17.9 g of a polymer (polymer P4) consisting of structural units derived from PFBNB.

[0161] (Preparation Example 5) Toluene (130.87 g), ethyl acetate (15.73 g), and EPEsNB (39.47 g, 0.175 mol) were placed in a glass device to obtain a reaction solution. Subsequently, while heating this solution at 50°C, nitrogen purging was performed for 30 minutes. Next, a solution in which (toluene)bis(perfluorophenyl)nickel (0.56 g, 0.0012 mol) was dissolved in 10.72 g of toluene was introduced into the aforementioned glass device, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding 30% hydrogen peroxide solution (0.52 g, 0.029 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0162] After the reaction solution was heated to 50°C, acetic acid (11.48 g, 0.191 mol), 30% hydrogen peroxide solution (22.36 g, 0.197 mol), ion-exchanged water (51.05 g), and 2-propanol (11.48 g) were added. After stirring for 30 minutes, it was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. Subsequently, ion-exchanged water (83.11 g) and 2-propanol (21.77 g) were added. After stirring for 30 minutes, it was allowed to stand for 30 minutes and separated into two phases. The operation of removing the lower-phase extraction solution and recovering the polymer solution was repeated 3 times. The polymer solution obtained above was dropped into a mixed solution of methanol (376.0 g) and 2-propanol (752.0 g) to precipitate a white solid. The obtained white solid was further washed with a mixed solution of methanol (1176.7 g) and 2-propanol (752.0 g). By vacuum drying the obtained white powder at 40°C, 29.1 g of a polymer (polymer P5) composed of structural units derived from EPEsNB was obtained.

[0163] (Preparation Example 6) Toluene (81.73 g), ethyl acetate (9.62 g), EPEsNB (15.07 g, 0.078 mol), and PFBNB (9.11 g, 0.033 mol) were placed in a glass device to obtain a mixture containing each monomer. Subsequently, while heating this mixture at 53°C, nitrogen purging was performed for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.54 g, 0.0011 mol) in 4.8 g of toluene was added to the glass device described above, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.00 g, 0.055 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0164] After the reaction solution was heated to 50°C, acetic acid (7.07 g, 0.118 mol), 30% hydrogen peroxide solution (13.77 g, 0.121 mol), ion-exchanged water (27.44 g), and 2-propanol (3.06 g) were added. After stirring for 30 minutes, it was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1095.7 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1095.7 g), and then washed with water (602.6 g) twice. By vacuum-drying the obtained white powder at a temperature of 40°C, 18.5 g of a polymer (polymer P6) having structural units derived from EPEsNB and PFBNB was obtained.

[0165] (Preparation Example 7) Toluene (97.64 g), ethyl acetate (11.44 g), EPEsNB (11.93 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were placed in a glass device to obtain a mixture containing each monomer. Then, while heating this mixture at 53°C, nitrogen purging was performed for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) in 5.4 g of toluene was added to the glass device described above, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0166] After raising the temperature of the reaction solution to 50 °C, acetic acid (8.40 g, 0.140 mol), 30% hydrogen peroxide solution (16.37 g, 0.136 mol), ion-exchanged water (32.62 g), and 2-propanol (3.64 g) were added. After stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1049.8 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1049.8 g) and then washed with water (721.8 g) twice. The obtained white powder was vacuum-dried at 40 °C to obtain 22.4 g of a polymer (polymer P7) having structural units derived from EPEsNB and PFBNB.

[0167] (Preparation Example 8) Toluene (100.86 g), ethyl acetate (11.77 g), EPEsNB (5.65 g, 0.029 mol), and PFBNB (23.92 g, 0.087 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.56 g, 0.0012 mol) in 5.08 g of toluene was introduced into the above-described glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.05 g, 0.058 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0168] After raising the temperature of the reaction solution to 50 °C, acetic acid (8.64 g, 0.144 mol), 30% hydrogen peroxide solution (16.82 g, 0.148 mol), ion-exchanged water (33.52 g), and 2-propanol (3.74 g) were added. After stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1072.9 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1072.9 g), and then the operation of washing with water (737.6 g) was performed twice. The obtained white powder was vacuum-dried at a temperature of 40 °C to obtain 20.8 g of a polymer (polymer P8) having structural units derived from EPEsNB and PFBNB.

[0169] (Preparation Example 9) Toluene (97.64 g), ethyl acetate (11.44 g), EPEsNB (11.93 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution in which (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) was dissolved in 5.36 g of toluene was introduced into the above-described glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0170] For the removal of ethyl acetate, the reaction solution was subjected to removal of 17.0 g of the solvent at 50 °C under reduced pressure using a rotary evaporator, and further toluene (17.0 g) was added. After the obtained reaction solution was heated to 62 °C, methanol (43.47 g), tetrahydrofuran (66.54 g), and toluene (36.42 g) were added. Further, a mixed solution of sodium hydroxide (12.03 g, 0.301 mol) and water (108.30 g) was added, and a hydrolysis reaction was performed for 3 hours. After the hydrolyzed reaction solution was cooled to 40 °C, 2-propanol (45.23 g) and toluene (16.66 g) were added. Further, a mixed solution of citric acid (115.62 g, 0.602 mol) and water (115.62 g) was added, and after stirring at 40 °C for 30 minutes, it was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (2152.7 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1076.4 g) and then washed with water (1076.4 g) twice. By vacuum drying the obtained white powder at 40 °C, 20.5 g of a polymer (polymer P9) having a hydrolyzate of EPEsNB and a structural unit derived from PFBNB was obtained.

[0171] (Preparation Example 10) Toluene (100.86 g), ethyl acetate (11.77 g), EPEsNB (5.65 g, 0.029 mol), and PFBNB (23.92 g, 0.087 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution obtained by dissolving (toluene)bis(perfluorophenyl)nickel (0.56 g, 0.0012 mol) in 5.08 g of toluene was introduced into the above-described glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.05 g, 0.058 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0172] For the removal of ethyl acetate, 18.0 g of the solvent was removed from the reaction solution at 50 °C under reduced pressure using a rotary evaporator, and further toluene (18.0 g) was added. After the obtained reaction solution was heated to 62 °C, methanol (44.67 g) and tetrahydrofuran (68.37 g) were added. Further, a mixed solution of sodium hydroxide (5.70 g, 0.143 mol) and water (51.30 g) was added, and a hydrolysis reaction was carried out for 3 hours. After cooling the hydrolyzed reaction solution to 40 °C, 2-propanol (46.47 g) and toluene (17.12 g) were added. Further, a mixed solution of citric acid (54.77 g, 0.285 mol) and water (110.05 g) was added. After stirring at 40 °C for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1865.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (932.5 g), and then washed with water (932.5 g) twice. The obtained white powder was vacuum dried at 40 °C to obtain 19.1 g of a polymer (polymer P10) having a hydrolyzate of EPEsNB and a structural unit derived from PFBNB.

[0173] (Preparation Example 11) Toluene (91.44 g), ethyl acetate (10.76 g), MeOAcNB (10.21 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) in 5.4 g of toluene was introduced into the above-described glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, and then the solution was cooled to room temperature.

[0174] After raising the temperature of the reaction solution to 50 °C, acetic acid (7.90 g, 0.132 mol), 30% hydrogen peroxide solution (15.40 g, 0.136 mol), ion-exchanged water (30.68 g), and 2-propanol (3.43 g) were added. After stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and separated into two phases. The lower-phase extraction solution was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (2889.2 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1444.6 g), and then washed with water (1589.1 g) twice. The obtained white powder was vacuum-dried at 40 °C to obtain 20.2 g of a polymer (polymer P11) having structural units derived from MeOAcNB and PFBNB.

[0175] (Preparation Example 12) Toluene (105.12 g), ethyl acetate (12.28 g), PhOAcNB (14.01 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, this mixture was purged with nitrogen for 30 minutes while heating at 53 °C. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) in 5.4 g of toluene was added to the above-described glass apparatus, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0176] After the reaction solution was heated to 50 °C, acetic acid (9.01 g, 0.150 mol), 30% hydrogen peroxide solution (17.55 g, 0.155 mol), ion-exchanged water (34.96 g), and 2-propanol (3.90 g) were added. After stirring for 30 minutes, it was allowed to stand for 30 minutes, and the lower-phase extraction solution separated into two phases was removed to recover the polymer solution. The polymer solution obtained above was dropped into methanol (2986.6 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1493.3 g), and then washed with water (1642.6 g) twice. The obtained white powder was vacuum-dried at 40 °C to obtain 20.1 g of a polymer (polymer P12) having structural units derived from PhOAcNB and PFBNB.

[0177] (Preparation Example 13) Toluene (91.44 g), ethyl acetate (10.76 g), MeOAcNB (10.21 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were placed in a glass apparatus to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was performed for 30 minutes. Next, a solution in which (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) was dissolved in 5.4 g of toluene was introduced into the above-described glass apparatus, and a reaction solution was obtained after 3 hours. By adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, the reaction was stopped, and then it was cooled to room temperature.

[0178] For the removal of ethyl acetate, the reaction solution was subjected to removal of 32.0 g of the solvent at 50 °C under reduced pressure using a rotary evaporator, and further toluene (32.0 g) was added. After raising the temperature of the obtained reaction solution to 62 °C, methanol (41.00 g), tetrahydrofuran (62.75 g), and toluene (36.42 108.15 g) were added. Further, a mixed solution of sodium hydroxide (12.03 g, 0.301 mol) and water (108.30 g) was added, and a hydrolysis reaction was carried out for 3 hours. After cooling the reaction solution after hydrolysis to 40 °C, 2-propanol (42.65 g) and toluene (15.72 g) were added. Further, a mixed solution of citric acid (115.62 g, 0.602 mol) and water (115.62 g) was added, and after stirring at 40 °C for 30 minutes, it was allowed to stand for 30 minutes. The lower-phase extraction solution separated into two phases was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1182.8 g) to precipitate a white solid. The obtained white solid was further washed with methanol (591.40 g), and then the operation of washing with water (591.40 g) was performed twice. By vacuum-drying the obtained white powder at a temperature of 40 °C, 21.4 g of a polymer (polymer P13) having a hydrolyzate of MeOAcNB and a structural unit derived from PFBNB was obtained.

[0179] (Preparation Example 14) Toluene (105.12 g), ethyl acetate (12.28 g), PhOAcNB (14.01 g, 0.061 mol), and PFBNB (16.83 g, 0.061 mol) were added to a glass device to obtain a mixture containing each monomer. Then, while heating this mixture at 53 °C, nitrogen purging was carried out for 30 minutes. Next, a solution prepared by dissolving (toluene)bis(perfluorophenyl)nickel (0.60 g, 0.0012 mol) in 5.4 g of toluene was added to the above-mentioned glass device, and a reaction solution was obtained after 3 hours. The reaction was stopped by adding water (1.11 g, 0.061 mol) to the reaction solution after polymerization, and then it was cooled to room temperature.

[0180] For the removal of ethyl acetate, the reaction solution was evaporated under reduced pressure at 50 °C using a rotary evaporator to remove 37.0 g of the solvent, and then toluene (37.0 g) was added. After heating the obtained reaction solution to 62 °C, methanol (46.70 g), tetrahydrofuran (71.48 g), and toluene (46.70 g) were added. Further, a mixed solution of sodium hydroxide (12.03 g, 0.301 mol) and water (108.30 g) was added, and a hydrolysis reaction was carried out for 3 hours. After cooling the reaction solution after hydrolysis to 40 °C, 2-propanol (48.58 g) and toluene (17.90 g) were added. Further, a mixed solution of citric acid (115.62 g, 0.602 mol) and water (115.62 g) was added, and after stirring at 40 °C for 30 minutes, it was allowed to stand for 30 minutes. The lower-phase extraction solution separated into two phases was removed, and the polymer solution was recovered. The polymer solution obtained above was dropped into methanol (1169.1 g) to precipitate a white solid. The obtained white solid was further washed with methanol (584.6 g), and then the operation of washing with water (584.6 g) was carried out twice. The obtained white powder was vacuum dried at a temperature of 40 °C to obtain 15.2 g of a polymer (polymer P14) comprising a hydrolyzate of PhOAcN and a structural unit derived from PFBNB.

[0181] <Measurement of physical properties of polymer P> (Monomer introduction ratio, molecular weight) For the polymers P2 to P14 obtained in each preparation example, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC) measurement, and the consumption amount of each monomer was calculated to calculate the ratio of each monomer introduced into the polymer P. Table 1 below shows the charging ratio of the raw material monomers used for the synthesis of the polymer P, the ratio of the raw material monomers introduced into the polymer P, the weight average molecular weight (Mw) of the polymer P, and the polydispersity (Mw / Mn). The measurement conditions for the gas chromatography measurement are as follows. · GC apparatus: GC-2030 (Shimadzu Corporation) · Carrier gas: N2 · Detector: Flame ionization detector (FID), FID temperature: 300 °C · Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GL Sciences Inc.) · Vaporization chamber temperature: 210 °C · Column flow rate: 0.64 mL / min · Column temperature rising conditions: Hold at 50 °C for 5 min, raise the temperature to 300 °C at 20 °C / min, and hold at 300 °C for 10 min

[0182] (Fluorine content) The fluorine content of the polymers P obtained in Preparation Examples 1 to 3 and 6 to 14 was measured by the following method. About 100 mg of the polymer and about 60 mg of (trifluoromethyl)benzene as an internal standard substance were weighed and dissolved in about 1 g of acetone-d6. For this solution, using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.) 19F-NMR measurement was performed. For Adjustment Examples 1 to 3, from the integration ratios of the signals of CF3 (-75 to -81 ppm, 3F) and CF2 (-100 to -130 ppm, 2F) of the polymer in the obtained spectrum chart and the signal of CF3 (-63 ppm, 3F) of the internal standard substance, and for Adjustment Examples 6 to 10, from the integration ratio of the signal of C6F5 (-135 to -170 ppm, 5F) corresponding to the pentafluorophenyl group of the polymer in the obtained spectrum chart and the signal of CF3 (-63 ppm, 3F) of the internal standard substance, the amount of C6F5 (mol / g) in the polymer was calculated. From the calculated amount of C6F5 (mol / g) in the polymer, the fluorine content (wt%) in the polymer was calculated. The results are shown in Table 1.

[0183] Table 1 below shows the charging ratios of the monomers used in the synthesis of the raw material polymer, the types of polymerization initiators, and the weight average molecular weight (Mw), polydispersity (Mw / Mn), and fluorine content of the obtained raw material polymer.

[0184] Furthermore, Table 1 shows the presence or absence of PFAS in Polymer P. "PFAS applicable" indicates that Polymer P is a polymer derived from a monomer applicable to PFAS, and "PFAS not applicable" indicates that Polymer P is a polymer derived from a fluorine-containing compound monomer not classified as PFAS.

[0185] [Table 1]

[0186] (Examples 1 to 9, Comparative Examples 1 to 5) In each of the examples and comparative examples, a resin composition was prepared and evaluated for the following items.

[0187] [Alkali dissolution rate of Polymer P] Polymers P1, P9, P10, and P14 obtained in Preparation Examples 1, 9, 10, and 14 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1, 9, 10, and 14 with a solid content concentration of 30% by mass. Next, the resin compositions 1, 9, 10, and 14 were spin-coated onto the wafer, PGMEA was dried, and then pre-baked at a temperature of 100°C for 2 minutes to produce a resin film with a thickness of approximately 1 μm. This resin film was immersed, together with the wafer, in an aqueous solution of 2.38% by mass of TMAH (tetramethylammonium hydroxide) at a temperature of 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by observing the immersed wafer visually and measuring the time until the resin film dissolved and the interference pattern disappeared, and then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 5 nm / s or more, it can be used without problems as a photosensitive material. If it is 10 nm / s or more, it can be regarded as having good developability. If it is 20 nm / s or more, it can be regarded as being better. If it is further 50 nm / s or more, it can be regarded as being particularly good.

[0188] [PGMEA Solubility of Polymer P] The PGMEA solubility was evaluated by the appearance evaluation of the polymer solution when the polymer P obtained in each adjustment example was dissolved in propylene glycol monomethyl ether acetate (PGMEA) with a solid content concentration of 30% by mass. If the evaluation result is A, it can be said that the PGMEA solubility is good. If it is A, it can be said that the PGMEA solubility is poor. A: The polymer solution is transparent and has no precipitate or insoluble matter. B: There are precipitate and insoluble components in the polymer solution.

[0189] [Water and Liquid Repellency of Polymer P] Polymers P1 to P3, P5 to P14 obtained in Preparation Examples 1 to 3, 5 to 14 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 3, 5 to 14 with a solid content concentration of 30% by mass. For the polymer P4 obtained in Preparation Example 4, it was dissolved in toluene to prepare a resin composition 4 with a solid content concentration of 30% by mass. The obtained resin compositions 1 to 14 were spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100 °C for 120 seconds to obtain a thin film with a thickness of about 1.0 μm (±0.2 μm). Using a contact angle meter (automatic contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of this thin film with respect to water and the contact angle with respect to PGMEA were measured. At this time, the amount of the liquid droplet prepared was 2 μL, the observation time was 30 seconds after droplet deposition, and the average value measured 5 times was taken as the contact angle (°) with respect to water or the contact angle (°) with respect to PGMEA. If the contact angle with respect to water is 80° or more, the water repellency is good; if it is 85° or more, the water repellency is better; if it is 90° or more, it can be considered that the water repellency is particularly excellent. If the contact angle with respect to PGMEA is 10° or more, the liquid repellency is good; if it is 15° or more, the liquid repellency is better; if it is 18° or more, it can be considered that the liquid repellency is particularly excellent. The results are shown in Table 2.

[0190] [Heat resistance of Polymer P] The heat resistance of Polymer P was evaluated using the 1% weight loss temperature (Td1) and the 5% weight loss temperature (Td5) as indices. The measurement method is as follows. 1 mg of the obtained Polymer P was set in a thermogravimetric-differential thermal analyzer (STA7200RV manufactured by Hitachi High-Tech Science Corporation). This was heated from 35 °C to 500 °C at a heating rate of 10 °C / min in a nitrogen atmosphere. At this time, the temperature (Td1) at which 1% of thermal weight loss occurred and the temperature (Td5) at which 5% of thermal weight loss occurred were read with respect to the weight of the set Polymer P. If Td1 is 150 °C or more, the heat resistance is good; if it is 200 °C or more, the heat resistance is better; if it is 250 °C or more, it can be considered that the heat resistance is particularly excellent. If Td5 is 200 °C or more, the heat resistance is good; if it is 250 °C or more, the heat resistance is better; if it is 300 °C or more, it can be considered that the heat resistance is particularly excellent. The results are shown in Table 2.

[0191]

Table 2

[0192] The polymer P, which is a copolymer of norbornene and maleic anhydride and does not contain PFAS having a pentafluorophenyl group, and the polymer P1 of Comparative Example 1 has appropriate alkali solubility for pattern formation by photolithography and solubility in PGMEA, but has low heat resistance, water repellency, and chemical resistance. The polymers P2 and P3 of Comparative Examples 2 and 3 are excellent in PGMEA solubility, heat resistance, water repellency, and chemical resistance, but fall under the category of PFAS and are subject to use restrictions. The polymer of Comparative Example 4, which does not contain PFAS, was excellent in heat resistance and water repellency, but was inferior in PGMEA solubility and chemical resistance. The polymer of Comparative Example 5, which does not contain fluorine and does not contain PFAS, was excellent in heat resistance and chemical resistance, but was inferior in PGMEA solubility and water repellency. The polymers P6 to P14 of Examples 1 to 9, which are fluorine-containing polymers that do not contain PFAS, have excellent solubility in PGMEA, excellent heat resistance, and high contact angle values of the polymer alone with respect to water and PGMEA, and have high water repellency and chemical resistance. Further, the polymers P9 and P10 of Examples 4 and 5 containing the structural unit represented by the formula (CA) and the polymer P14 of Example 9 containing the structural unit of the hydrolyzate of PhOAcNB had appropriate alkali solubility for pattern formation by photolithography.

Explanation of symbols

[0193] 1 Substrate 2 Partition wall 2a Upper surface (upper surface of partition wall) 3 Opening 4 Material liquid 5 Pixel 5R, 5G, 5B Pixel 10 Inkjet head

Claims

1. A polymer comprising a structural unit represented by formula (PFNB) and a structural unit represented by formula (NB). In formula (PFNB), In formula (NB), 【Chemical 1】 A polymer. R ２１ , R ２２ , R ２３ and R ２４ at least one of which is a group having a pentafluorophenyl group, and R ２１ , R ２２ , R ２３ and R ２４ the remainder of which are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ２ is 0, 1 or 2, [Chemical 2]

2. R １ 、 R ２ 、 R ３ and R ４ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, a １ is 0, 1 or 2, and Said R ２１ 、R ２２ 、R ２３ 、R ２４ 、R １ 、R ２ 、R ３ 、R ４ none of them contains a substituted or unsubstituted maleimide moiety The polymer according to claim 1, wherein the structural unit represented by formula (NB) includes a structural unit represented by formula (ES). In formula (ES), In formula (es),

3. 【Chemical 3】 The polymer according to claim 1, wherein the structural unit represented by formula (NB) includes a structural unit represented by formula (CA). R ３１ 、 R ３２ 、 R ３３ and R ３４ at least one of which is an alkyl ester-containing group represented by the formula(s), and R ３１ 、 R ３２ 、 R ３３ and R ３４ the remainder of each is independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a ３ is 0, 1 or 2, and -X ３ -C(=O)-O-R ３５ (es) In formula (CA), X ３ is an alkylene group having 1 to 20 carbon atoms, R ３５ is a polymer that is an alkyl group having 1 to 3 carbon atoms. In formula (ca),

4. The polymer according to claim 1, wherein the structural unit represented by formula (NB) further includes at least one structural unit represented by formula (NB-a). [Chemical Formula 4] In formula (NB-a), R ４１ , R ４２ , R ４３ and R ４４ at least one of which is a carboxy group-containing group represented by formula (ca), and R ４１ , R ４２ , R ４３ and R ４４ the rest are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a ４ is 0, 1 or 2, and -X ４ -C(=O)-OH (ca) At least one group selected from, where in formula (5a), * represents a bond. X ４ is a polymer which is an alkylene group having 1 to 20 carbon atoms.

5. The polymer according to claim 1, wherein the weight average molecular weight of the polymer is 10,000 or more and 200,000 or less.

6. 【Chemical Formula 5】 The polymer according to claim 1, wherein the fluorine content of the polymer is 10% by mass or more and 40% by mass or less. R ５１ 、 R ５２ 、 R ５３ and R ５４ At least one of them is the following formula (5a): [Chemical Formula 6]

7. R ５１ , R ５２ , R ５３ and R ５４ The remainder of each is, independently, a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. a ５ is a polymer which is 0, 1 or 2. A polymer solution containing the polymer according to any one of claims 1 to 6.

8. The polymer solution according to claim 7, which is used to form a partition wall of an organic electroluminescence element.

9. A photosensitive resin composition comprising the polymer according to any one of claims 1 to 6 and a photo radical polymerization initiator.

10. A cured product formed from the photosensitive resin composition according to claim 9. ​ ​ ​ ​ ​ ​ ​ ​ ​

Images