Polymer, polymer solution, photosensitive resin composition and cured product

Abstract

To provide a polymer having alkali solubility appropriate for a pattern formation by photo-lithography and also capable of obtaining a cured resin film having high water repellency and fluid repellency.SOLUTION: A polymer includes a structural unit expressed by a formula (NB), a structural unit including a carboxy group, and a structural unit expressed by a formula (1-5).SELECTED DRAWING: Figure 1

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 for imparting water repellency and liquid repellency to a part of a member has been demanded, and a method for forming a fine pattern having water repellency and liquid repellency by photolithography technology has been proposed.

[0003] As 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 represented by perfluorooctanesulfonic acid (PFOS) or perfluorooctanoic acid (PFOA) is generally used to coat a 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 effects on the environment and the human body, and there is a global movement to regulate its use. From the above circumstances, 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 from a perfluoropolyether group-containing silane-based water repellent hydrolyzed in the presence of a catalyst and water.

[0004] Regarding the technology of microfabricating a photosensitive material film by photolithography technology, various technologies have been developed for the purpose of improving the accuracy of resist patterns with the miniaturization of patterns. Examples of this type of technology include the technology described in Patent Document 2. Patent Document 2 discloses a polymer containing a norbornene-type repeating unit having a maleimide group and a maleic anhydride-type repeating unit, and at least a part of the maleic anhydride-type repeating unit is ring-opened. In Patent Document 2, in addition to the above repeating units, a repeating unit derived from a norbornene monomer having a pentafluorophenyl group is introduced to improve the thermal stability of the polymer for film formation and reduce the dielectric constant.

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 polymer described in Patent Document 1 is used as a water repellent and a film is formed on a substrate and patterned, the water repellency of the obtained pattern is not sufficient, and there is room for improvement in terms of the accuracy of pattern formation. In addition, substances having a perfluorinated methyl group (-CF3) or a perfluorinated methylene group (-CF2-) are classified as PFAS, and in recent years, regulations on PFAS-related substances have advanced due to concerns about bioaccumulation and environmental accumulation, and the polymer described in Patent Document 1 also falls under PFAS. Further, the polymer described in Patent Document 2 may not obtain sufficient liquid repellency because it has a maleimide pendant group.

Means for Solving the Problems

[0007] The present inventors have found that by adjusting the constituent components of the polymer used in the photosensitive resin composition, while not falling under PFAS, the polymer itself has water repellency and liquid repellency and excellent developability, and have 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 structural unit represented by formula (NB), a structural unit represented by formula (1-4), a structural unit represented by formula (1-5), A polymer containing

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The polymer according to any one of [1] to [9], The weight average molecular weight of the polymer is 2,000 or more and 30,000 or less, a polymer.

[11] The polymer according to any one of [1] to

[10] , The fluorine content of the polymer is 10% by mass or more and 40% by mass or less, a polymer.

[12] A polymer solution containing the polymer according to any one of [1] to

[11] .

[13] The polymer solution according to

[12] , which is used to form a partition wall of an organic electroluminescence element, a polymer solution.

[14] The polymer solution according to

[12] or

[13] , A polymer solution further containing a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

[15] The polymer according to any one of [1] to

[11] , and A photo radical polymerization initiator, and a Photosensitive resin composition.

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

[15] .

[17] A structural unit represented by formula (NB), and A structural unit represented by formula (MA), and A polymer containing

Chemical formula

Chemical formula

[0009] According to the present invention, there are provided a polymer having good developability, excellent pattern formability after curing, and the cured product having water repellency and chemical liquid repellency, and a photosensitive resin composition containing the polymer. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

[0011] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the description will be omitted as appropriate. Also, all the drawings are for illustrative purposes only. The shapes and dimensional ratios of the members in the drawings do not necessarily correspond to actual articles. 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 groups (atomic groups) in this specification, notations that do not indicate whether they are substituted or unsubstituted include both those without substituents and those with substituents. For example, the term "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0013] The notation "(meth)acryl" in this specification represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate". In particular, the "(meth)acryloyl group" in this specification represents a concept that includes an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0014] <First Embodiment> (Polymer P(I)) The polymer of the present invention according to the first embodiment (referred to as "polymer P(I)" in this specification) is a structural unit represented by formula (NB) and a structural unit containing a structure represented by formula (1-4) and a structure represented by formula (1-5).

[0015] [Chemical Formula]

[0016] 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, and a1 is 0, 1 or 2.

[0017] [Chemical Formula]

[0018] [Chemical]

[0019] In formula (1-5), R 5 is an organic group having 1 to 30 carbon atoms. In the polymer, R 1 , R 2 , R 3 , R 4 and R 5 at least one of which is a group having a pentafluorophenyl group, R 1 , R 2 , R 3 , R 4 and R 5 none of which contains a substituted or unsubstituted maleimide moiety.

[0020] The polymer P(I) of this embodiment has a structural unit represented by formula (NB) or a structural unit represented by formula (1-5), or both having a group having a pentafluorophenyl group. The polymer P(I) has high water repellency and liquid repellency by having a group having a pentafluorophenyl group.

[0021] The polymer P(I) of this embodiment contains a structural unit derived from a cyclic olefin represented by formula (NB). The structural unit represented by 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. Further, the polymer P(I) of this embodiment contains a structural unit containing a carboxy group represented by formula (1-4). As a result, the acid value of the polymer P(I) can be designed to a relatively large value, and as a result, the polymer P(I) has appropriate sensitivity and developability for patterning formation by photolithography.

[0022] In the structural unit represented by formula (NB) constituting the polymer P(I), R 1 ~R 4 , and R 5At least one of them 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 a combination of a linear or branched alkylene group and a cyclic alkylene group. The group "-X 11 -" in the 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 the formula (pf) include a pentafluorophenyl group (in the formula (pf), "-X 11 -" is a single bond), and a pentafluorobenzyl group (in the formula (pf), "-X 11 -" is a methylene group), which are preferred.

[0023] In the polymer P(I) of the present embodiment, in the structural unit represented by the above formula (NB) that constitutes the polymer P(I), R 1 ~R 4 and R 5 in the structural unit represented by the above formula (1-5) 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 include a structural unit derived from a monomer having a substituted or unsubstituted maleimide pendant group.

[0024] In the structural unit represented by the above formula (NB) that constitutes the polymer P(I), R 1 ~R 4Examples of the organic group having 1 to 30 carbon atoms that can constitute 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] In addition, R 1~R 4 The organic group having 1 to 30 carbon atoms that can constitute 4 may contain at least one atom selected from O, N, S, P, and Si in its structure. R 1 ~R 4 When 1 to 4 are a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 1 ~R 4 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0029] In the structural unit represented by the formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0030] The proportion of the structural unit represented by the formula (NB) in all the structural units constituting the polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, still more preferably 35 to 60 mol%.

[0031] In one embodiment, in the polymer P(I), at least one of R 1 , R 2 , R 3 and R 4 is a group having a pentafluorophenyl group represented by the formula (pf), R 1 , R 2 , R 3 and R 4 the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, and the structural unit represented by the formula (1-5) has a configuration that is the structural unit represented by the formula (1-3).

[0032]

Chemical formula

[0033] In the formula (1-3), R s is a group having one (meth)acryloyl group represented by the formula (2a).

[0034]

Chemical formula

[0035] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 preferably has a total carbon number of 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 is preferably an alkylene group as the divalent organic group. Some of the -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0036] X 10 is more preferably a linear alkylene group having a total carbon number of 3 to 6 as the divalent organic group. By appropriately selecting the carbon number (the chain length of X 10 X 10 ), the structural unit represented by formula (2) is more likely to participate in the cross-linking reaction, and the sensitivity can be increased.

[0037] X 10 The divalent organic group (for example, an alkylene group) of X may be substituted with any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like. 10 In addition, the divalent organic group of X

[0038] When the polymer P(I) contains the structural unit represented by formula (1-3), the proportion of the structural unit represented by formula (2) in all the structural units of the polymer P(I) is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.

[0039] In one embodiment, in the polymer P(I), R in the formula (NB) 1 , R 2 , R 3 and R 4 at least one of them is a group having a pentafluorophenyl group represented by the formula (pf), R 1 , R 2 , R 3 and R 4 the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, It has a configuration in which the structural unit represented by the formula (1-5) is the structural unit represented by the formula (1-2).

[0040]

Chemical formula

[0041] In the structural unit represented by the formula (1-2), R p is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 9 (meth)acryloyl groups, more preferably a group containing 3 to 6 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in R p , the sensitivity in the exposure treatment of the polymer P(I) containing this can be further enhanced. Also, it becomes easier to achieve a high degree of compatibility between the sensitivity and the alkali solubility of the polymer P(I).

[0042] R in the formula (1-2) p is preferably a group represented by the formula (1b), a group represented by the formula (1c), or a group represented by the formula (1d), and contains at least one selected from these. By being such a group, there is a tendency to easily obtain the above various effects.

[0043]

Chemical formula

[0044] In the formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms). A plurality of Xs 1 may be the same or different. X 1 ’ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X’-Z’- (X’ is an alkylene group having 1 to 6 carbon atoms, and Z’ is -O- or -COO-). X 2 is a (k + 1)-valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom in view of further improving sensitivity (ease of polymerization), etc. k may be 2 or 3, but is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0045] X 1 When X is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, X 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2- (methylene group).

[0046] X 1 When X is a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0047] X 1When ’ is an alkylene group having 1 to 6 carbon atoms, the specific embodiments thereof are the same as X 1 as described above. X 1 When ’ is a group represented by -X’-Z’, the specific embodiments of X’ are the same as those of X above.

[0048] X 2 Examples of the (k + 1)-valent organic group having 1 to 12 carbon atoms of X include any group obtained by removing (k + 1) hydrogen atoms from any organic compound. Here, the “any organic compound” is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, more preferably 100 or less. X 2 is, for example, a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing (k + 1) hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0049]

Chemical formula

[0050] In formula (1c), k, R, X 1 and X 2 are respectively synonymous with R, k, X 1 and X 2 in formula (1b), and a plurality of Rs may be the same as or different from each other, and a plurality of X 1 may be the same as or different from each other. X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4and X 5 is, independently of each other, a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0051] R, k, X 1 and X 2 For the specific embodiments, preferred embodiments, etc. of, they are the same as those described in formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms of and include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of the divalent organic group having 1 to 6 carbon atoms of and include a linear or branched alkylene group. The number of carbon atoms of the linear or branched alkylene group is preferably 1 to 3.

[0052]

Chemical formula

[0053] In formula (1d), n is an integer of 2 to 5, preferably 2 or 3. For the specific embodiments, preferred embodiments, etc. of R, they are the same as those described in formula (1b).

[0054] When the polymer P(I) contains a structural unit represented by formula (1-2), the proportion of the structural unit represented by formula (1-2) in all the structural units of the polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0055] When the polymer P(I) contains structural units containing two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by the formula (1-2), or structural units containing one (meth)acryloyl group represented by the formula (1-3), or a combination thereof, the photosensitive resin composition containing the polymer P(I) has excellent sensitivity when subjected to photolithography processing. This is considered to be because the (meth)acryloyl group contained in the structural unit represented by the formula (1-2) or the formula (1-3) promotes the curing reaction (polymerization reaction). In the design of a normal photosensitive resin composition, when the curability is increased in an attempt to increase the sensitivity, the curing tends to proceed too far and the developability tends to deteriorate. On the other hand, when an attempt is made to improve the developability, the curing tends to be insufficient. The polymer P(I) of the present invention can achieve both good sensitivity and developability in a good balance by containing either or both of the structural unit represented by the formula (1-2) and the structural unit represented by the formula (1-3).

[0056] In one embodiment, at least one of R 1 , R 2 , R 3 and R 4 in the formula (NB) is a group having a pentafluorophenyl group represented by the formula (pf), R 1 , R 2 , R 3 and R 4 the remainder of which is a hydrogen atom or an organic group having 1 to 30 carbon atoms, The structural unit represented by the formula (1-5) has a configuration that is the structural unit represented by the formula (1-51).

[0057]

Chemical formula

[0058] In the formula (1-51), R 51 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. R 51Examples of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms that can constitute 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, etc.

[0059] 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, a decyl group, etc.

[0060] Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group, etc. Examples of the alkynyl group include an ethynyl group, etc. Examples of the alkylidene group include a methylidene group, an ethylidene group, etc. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthracenyl group.

[0061] Examples of the aralkyl group include a benzyl group, a phenethyl group, etc. Examples of the alkaryl group include a tolyl group, a xylyl group, etc. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc.

[0062] Polymer P(I) has high alkali solubility by containing a structural unit represented by formula (1-51). As a result, the photosensitive resin composition containing Polymer P(I) has excellent developability when subjected to a photolithography method using an aqueous alkali solution as a developer. When Polymer P(I) contains a structural unit represented by formula (1-51), the ratio of the structural unit represented by formula (1-51) in all the structural units of Polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0063] In one embodiment, R in the polymer P(I) in the formula (NB) 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 5 in the formula (4) is a group having a pentafluorophenyl group represented by the above formula (pf).

[0064] In one embodiment, at least one of R 1 , R 2 , R 3 and R 4 in the polymer P(I) in the formula (NB) is a group having a pentafluorophenyl group represented by the above formula (pf), R 1 , R 2 , R 3 and R 4 the remainder are a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 5 in the formula (4) is a group having a pentafluorophenyl group represented by the above formula (pf).

[0065] In one embodiment, the polymer P(I) may contain a structural unit represented by the formula (4) composed of the structure represented by the formula (1-4) and the structure represented by the formula (1-5). The structural unit represented by the formula (4) is, for example, a structural unit derived from a maleic anhydride monomer. In the formula (4), R 5 is synonymous with R 5 in the formula (1-5).

[0066]

Chemical formula

[0067] By containing the structural unit represented by the formula (4), the polymer P(I) has high alkali solubility. As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an aqueous alkali solution as a developer.

[0068] When the polymer P(I) contains a structural unit represented by the formula (4), the proportion of the structural unit represented by the formula (4) in all the structural units of the polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0069] In one embodiment, the polymer P(I) may contain at least one selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2).

[0070]

Chemical formula

[0071]

Chemical formula

[0072] In the formulas (1) and (2), R p and R s have the same meanings as those in the above formulas (1-2) and (1-3).

[0073] When the polymer P(I) contains a structural unit represented by the formula (1), the proportion of the structural unit represented by the formula (1) in all the structural units of the polymer P(I) is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0074] When the polymer P(I) contains a structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) in all the structural units of the polymer P(I) is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0075] In one embodiment, the polymer P(I) may contain a structural unit derived from maleic anhydride represented by the formula (MA).

[0076]

Chemical formula

[0077] The structural unit derived from maleic anhydride represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups (the structural unit represented by the above formula (3)). Therefore, the polymer P(I) containing the said structural unit has excellent developability. When the polymer P(I) contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) in all the structural units of the polymer P(I) is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0078] In one embodiment, the polymer P(I) may contain a structural unit derived from maleic anhydride represented by formula (3). By containing the structural unit represented by formula (3), the polymer P(I) has high alkali solubility. As a result, when the photosensitive resin composition containing the polymer P(I) is subjected to a photolithography method using an aqueous alkaline solution as a developer, it has excellent developability. The proportion of the structural unit represented by formula (3) in all the structural units of the polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0079]

Chemical formula

[0080] In one embodiment, the polymer P(I) may contain a structural unit represented by formula (1-1).

[0081]

Chemical formula

[0082] In the structural unit represented by formula (1-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of this alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, and the like. X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, and the like. When Q is the alkyl group and X is the alkylene group, any carbon atom of the alkyl group of Q and the alkylene group of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring, and the like. In formula (1-1), an embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0083] An embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following formula (1a), or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0084]

Chemical formula

[0085] In formula (1a), R is a hydrogen atom or a methyl group.

[0086] When the polymer P(I) contains a structural unit represented by the formula (1-1), the proportion of the structural unit represented by the formula (1-1) in all the structural units of the polymer P(I) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%.

[0087] When the polymer P(I) contains the structural unit of the formula (1-1) and the structural unit of the formula (1-4), the polymer P(I) will have both a (meth)acryloyl group (the “-Z” group in the formula (1-1)) and a carboxyl group represented by the formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. Thus, since the polymer P(I) has a polymerizable group and a carboxyl group present in the same polymer molecule, the double bond equivalent and the acid value can be designed to relatively large values. In other resins such as (meth)acrylic resins, it is difficult to increase the content of both the polymerizable group and the carboxyl group. Due to having such a structure, the polymer P(I) can achieve both high sensitivity and developability at a high level.

[0088] In one embodiment, the polymer P(I) may contain a structural unit represented by the formula (13) consisting of the structure represented by the formula (1-4) and the structure represented by the formula (1-51).

[0089]

Chemical formula

[0090] In the formula (13), R 51 has the same meaning as that in the formula (1-51).

[0091] Since the polymer P(I) contains the structural unit represented by the formula (13), it has high alkali solubility. As a result, when the photosensitive resin composition containing the polymer P(I) is subjected to a photolithography method using an aqueous alkali solution as a developer, it has excellent developability.

[0092] When the polymer P(I) contains a structural unit represented by the formula (13), the proportion of the structural unit represented by the formula (13) in all the structural units of the polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0093] In one embodiment, the polymer P(I) may contain a structural unit represented by the formula (11). The structural unit represented by the formula (11) is a structural unit composed of the structure of the formula (1-5) and the structure of the formula (1-1).

[0094]

Chemical formula

[0095] In the formula (11), R 5 is synonymous with that in the above formula (1-5), and Z, Q, and X are synonymous with those in the above formula (1-1).

[0096] In one embodiment, the polymer P(I) may contain at least one of the structural unit represented by the formula (8) and the structural unit represented by the formula (9). Here, the structural unit of the formula (8) is a structural unit composed of the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2), and the structural unit of the formula (9) is a structural unit composed of the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-3).

[0097]

Chemical formula

[0098]

Chemical formula

[0099] In the formula (8), Q, X, and Z are synonymous with the formula (1-1), and R p is synonymous with that in the formula (1-2). In the formula (9), Z, Q, and X are synonymous with the formula (1-1), and R Sis synonymous with that in formula (1-3).

[0100] When the polymer P(I) contains a structural unit represented by formula (8), the proportion of the structural unit represented by formula (8) in all the structural units of the polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. When the polymer P(I) contains a structural unit represented by formula (9), the proportion of the structural unit represented by formula (9) in all the structural units of the polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0101] In one embodiment, the polymer P(I) may contain a structural unit represented by the following formula (5) composed of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-4). By including this structural unit, both sensitivity and developability can be achieved with a better balance.

[0102]

Chemical formula

[0103] In formula (5), Z, X, and Q are synonymous with those in formula (1-1). When the polymer P(I) contains a structural unit represented by formula (5), the proportion of the structural unit represented by formula (5) in all the structural units of the polymer P(I) is preferably 1 to 12 mol%, more preferably 1 to 9 mol%.

[0104] In one embodiment, the polymer P(I) may contain a structural unit represented by formula (12). The structural unit represented by formula (12) is a structural unit composed of the structure of formula (1-51) and the structure of formula (1-1).

[0105]

Chemical formula

[0106] In formula (12), R 51is synonymous with that in the above formula (1-51), Z, Q, and X are synonymous with those in the above formula (1-1).

[0107] From the viewpoint of the effects of the present invention, the polymer P(I) may further contain a structural unit represented by the following formula (6) composed of two structural units represented by the formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0108] [Chemical formula]

[0109] In the formula (6), Z, X, and Q are synonymous with those in the formula (1-1). A plurality of Zs, a plurality of Qs, and a plurality of Xs may be the same or different from each other.

[0110] When the polymer P(I) contains a structural unit represented by the formula (6), the proportion of the structural unit represented by the formula (6) in all the structural units of the polymer P(I) is preferably 1 to 10 mol%, more preferably 1 to 8 mol%.

[0111] 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 when synthesizing the polymer, the amount of the remaining raw materials after synthesis, the presence of peaks in various spectra (for example, IR spectrum, 1 1H-NMR spectrum, 13 13C-NMR spectrum), and the peak area.

[0112] The weight average molecular weight Mw of the polymer P(I) is, for example, 2,000 to 30,000. The weight average molecular weight Mw of the polymer P(I) is preferably 4,000 to 20,000, more preferably 5,000 to 10,000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkaline developer can be adjusted. In addition, the dispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of the polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P(I) can be made homogeneous, which is preferable. These values can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0113] The glass transition temperature of the polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. The polymer P(I) has a relatively high glass transition temperature due to having a group containing a pentafluorophenyl group. This is preferable in terms of the pattern formed on the substrate being able to exist stably 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).

[0114] The acid value of the polymer P(I) is 60 mgKOH / g or more and 150 mgKOH / g or less, preferably 70 mgKOH / g or more and 140 mgKOH / g or less. Also, the double bond equivalent of the polymer P1 is 100 g / mol or more and 900 g / mol or less, preferably 200 g / mol or more and 850 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less. When the acid value of the polymer P(I) is 60 mgKOH / g or more, good developability can be obtained. Also, when the double bond equivalent is 900 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be increased.

[0115] In addition, if the acid value of the polymer P(I) is too large, there is a concern that the exposed portion may be easily dissolved during development with an alkaline developer, resulting in an increase in the exposure amount required for photocuring or an insufficient pattern shape. Therefore, in this embodiment, the upper limit value of the acid value is set to 150 mgKOH / g. On the other hand, if the double bond equivalent of the polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too high), unexposed areas or low-exposure areas tend to be difficult to dissolve during development with an alkaline developer, and residual films are likely to occur during development. Also, if the double bond equivalent is too small, there are concerns about excessive increase in molecular weight due to crosslinking and excessive decrease in solubility. Therefore, in this embodiment, the lower limit value of the double bond equivalent is set to 100 g / mol.

[0116] By having the above configuration, the polymer P(I) of this embodiment can have an alkali dissolution rate of 10 nm / s or more, preferably 20 nm / s or more, more preferably 50 nm / s or more, and particularly more preferably 100 nm / s or more. The upper limit is not particularly limited, but can be, for example, 1000 nm / s or less. In the present specification, the alkali dissolution rate is the value measured under the following conditions. (Method for measuring alkali dissolution rate) Dissolve the polymer P(I) in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, spin-coat the obtained polymer solution onto a wafer, dry the PGMEA, and pre-bake it at a temperature of 100°C for 2 minutes to produce a resin film with a film thickness of 1 μm ± 0.2. Immerse this resin film, together with the wafer, in an aqueous solution of 2.38% by mass tetramethylammonium hydroxide (TMAH) at a temperature of 23°C. Observe the immersed wafer visually and measure the time until the resin film dissolves and the interference pattern disappears, and divide the film thickness before immersion (1 μm ± 0.2) by that time to calculate the alkali dissolution rate (nm / second).

[0117] By adjusting the acid value and / or double bond equivalent of the polymer P(I), it is possible to achieve both higher sensitivity and developability at a higher level.

[0118] The acid value and double bond equivalent of the polymer P(I) can be determined by spectrum measurement or the like. For example, they can be determined by the following procedure (more specifically, refer to the examples). (1) From the 1 H-NMR chart, determine the area (integrated value) of the peaks corresponding to the hydrogen atoms of the carboxy group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond. (2) From the area determined in (1) and the area of the peak derived from the standard substance, determine the amount of the carboxy group and the amount of the carbon-carbon double bond. (3) Convert the amount of the carboxy group determined in (2) to acid value (mgKOH / g). Also, convert the amount of the polymerizable carbon-carbon double bond determined in (2) to double bond equivalent (g / mol).

[0119] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values by appropriately designing the ratio of the structural units introduced into polymer P(I), particularly the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2).

[0120] The content (ratio) of each structural unit contained in polymer P(I) of the present embodiment can be estimated / calculated from the charged amount (molar amount) of the raw materials during polymer synthesis, the amount of the remaining raw materials after synthesis, the peak area of various spectra (for example, 1 the peak area of H-NMR), etc.

[0121] The fluorine content contained in polymer P(I) is preferably 10% by mass or more and 40% by mass or less, more preferably 12% by mass or more and 35% by mass or less, and even more preferably 14% by mass or more and 30% by mass or less. By adjusting the fluorine content within such a range, a polymer P(I) excellent in water repellency and alkali solubility can be obtained.

[0122] (Method for producing polymer P(I)) (First aspect) In polymer P(I), at least one of R 1 , R 2 , R 3 and R 4 is a group having a pentafluorophenyl group represented by formula (pf), and R 1 , R2 , R 3 and R 4 The remainder of and is a hydrogen atom or an organic group having 1 to 30 carbon atoms. When the structural unit represented by formula (1-5) is the structural unit represented by formula (1-2) and / or the structural unit represented by formula (1-3), it can be produced (synthesized) by the following steps aI, aII, and aIII. Step aI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); Step aII-i: Reacting the raw material polymer obtained in step aI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a first polymer precursor (Ia) containing a structural unit represented by formula (NB) and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0123] When polymer P(I) further contains a structural unit represented by formula (3), after step aII-i, the following step aII-ii is carried out. Step aII-ii is an optional step carried out as necessary. Step aII-ii: Treating the polymer precursor (Ia) with water in the presence of a base catalyst to obtain a second polymer precursor (referred to as "polymer precursor (Ib)") containing a structural unit represented by formula (NB), a structural unit represented by formula (3), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0124] When polymer P(I) contains the structural unit of formula (13) as the structural unit represented by formula (4), after step aI or after step aII-i, the following step aII-iii is carried out. Step aII-iii is an optional step carried out as necessary. Step aII-iii: React the raw material polymer obtained in step aI or the polymer precursor (Ia) obtained in step aII-i with the alcohol represented by formula (AL) in the presence of a basic catalyst to obtain a third polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (13), and a structural unit represented by formula (MA) (the precursor when passing through the raw material polymer, referred to as "polymer precursor (Ic-i)"), or a third polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (13), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) (the precursor when passing through the polymer precursor (Ia), referred to as "polymer precursor (Ic-ii)"). Here, the structural unit represented by formula (13) has a structure including the structural unit represented by formula (1-51) and the structural unit represented by formula (1-4), and is a structural unit obtained by the reaction of the structural unit represented by formula (MA) in the polymer precursor (Ia) with the alcohol represented by formula (AL). R 51 -OH (AL) In formula (AL), R 51 is synonymous with R 51 in the above (1-51).

[0125] Step aIII-i: React the first polymer precursor (Ia) obtained in step aII-i, the second polymer precursor (Ib) obtained in step aII-ii, or the third polymer precursor (Ic-i) or (Ic-ii) obtained in step aII-iii with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1-1), and optionally further containing a structural unit represented by formula (MA).

[0126] When the above step aII-ii is not carried out, in order to obtain a polymer P(I) further containing a structural unit represented by formula (3), after step aIII-i, the following step aIII-ii may be carried out. Step aIII-ii: Without performing step aII-ii, the polymer P(I) obtained through step aII-i or step aII-iii and step aIII-i is treated with water in the presence of a base catalyst to obtain a polymer P(I) containing at least the structural unit represented by formula (NB), the structural unit represented by formula (1-1), and the structural unit represented by formula (3), and optionally further containing the structural unit represented by formula (MA).

[0127] Hereinafter, each step will be described. (Step aI) The step of preparing a raw material polymer containing the structural unit represented by formula (NB) and the structural unit represented by formula (MA) in step aI can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm) and maleic anhydride. Here, at least one of R 1 , R 2 , R 3 and R 4 is a group having a pentafluorophenyl group represented by formula (pf), and the rest of R 1 , R 2 , R 3 and R 4 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2. Note that the monomer represented by formula (PFNBm) is a compound not corresponding to PFAS.

[0128] [Chemical formula]

[0129] Examples of the monomer represented by formula (NBm) include 5-pentafluorobenzylbicyclo[2.2.1]hept-2-ene, 5-pentafluorophenylbicyclo[2.2.1]hept-2-ene, and the like.

[0130] The polymerization method is not limited, but radical polymerization using a radical polymerization initiator is preferred. As the radical polymerization initiator, for example, azo compounds, organic peroxides, etc. can be used. Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), and the like. Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding the polymerization initiator, only one kind may be used, or two or more kinds may be used in combination.

[0131] As the solvent used in the polymerization reaction, for example, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used. The polymerization solvent may be a single solvent or a mixed solvent.

[0132] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by the formula (NBm), maleic anhydride, and a polymerization initiator in a solvent, charging them into a reaction vessel, and then heating to allow the addition polymerization to proceed. The heating temperature is, for example, 50 to 80 °C, and the heating time is, for example, 5 to 20 hours. When charging into the reaction vessel, the molar ratio of the monomer represented by the formula (NBm) to maleic anhydride (MAm) is preferably (NBm):(MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 0.5:0.8 to 0.7:0.5. Through such a process, the "raw material polymer" can be obtained. The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. Typically, it is a random copolymer or an alternating copolymer. Generally, maleic anhydride is known as a monomer with strong alternating copolymerizability.

[0133] After the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be performed. Specifically, the organic phase containing the synthesized raw material polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol, 2-propanol, 1-butanol, etc. to precipitate the monomer. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0134] (Step aII-i) In step aII-i, the raw material polymer obtained in step aI and a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound are reacted in the presence of a basic catalyst, so that a part of the structural unit represented by formula (MA) contained in the raw material polymer is ring-opened, and the structural unit represented by formula (1) and / or the structural unit represented by formula (2) are formed, and a polymer precursor containing the structural unit represented by formula (NB), and the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA) is obtained. Here, the polymer precursor obtained is referred to as "polymer precursor (Ia)" for convenience of explanation.

[0135] More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), etc. can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0136] When obtaining a polymer precursor containing a structural unit represented by formula (NB) and both a structural unit represented by formula (1) and a structural unit represented by formula (2), next, a polyfunctional (meth)acrylic compound is added to the above solution. Further, a basic catalyst is added. Then the solution is appropriately mixed to obtain a uniform solution and a polymer precursor containing at least the structural unit of formula (NB) and the structural unit of formula (1) (step aII(1)).

[0137] Examples of the polyfunctional (meth)acrylic compound that can be used here include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). k, R, X in formula (1b-m) 1 , X 1 ’, and X 2 are defined and have specific embodiments similar to those in formula (1b) described above. Also, k, R, X in formula (1c-m) 1 , X 2 , X 3 , X 4 , X 5 , and X 6 are defined and have specific embodiments similar to those in formula (1c) described above. n and R in formula (1d-m) are the same as those in formula (1d) described above.

[0138]

Chemical formula

[0139]

Chemical formula

[0140]

Chemical formula

[0141] Next, a polymer precursor containing a structural unit of formula (NB), a structural unit of formula (1), and a structural unit of formula (2) can be obtained by reacting the polymer obtained in step aII-i with a monofunctional (meth)acrylic compound in the presence of a basic catalyst (step aII(2)).

[0142] As the basic catalyst, amine compounds, nitrogen-containing heterocyclic compounds, etc. known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as the catalyst. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass with respect to 100 parts by mass of the raw material polymer. It should be noted that if the basic catalyst is used in excess, the amount of acid required for neutralization increases, and there is a possibility that purification becomes complicated.

[0143] By heating the above solution preferably at 60 to 80 °C for about 3 to 9 hours, ring-opening of the structural unit of formula (MA) contained in the raw material polymer / formation of the structural unit of formula (1) is carried out.

[0144] For example, during the above heating, by adding a monofunctional (meth)acrylic compound having a hydroxy group to the reaction system, ring-opening of the structural unit of formula (MA) contained in the raw material polymer / formation of the structural unit of formula (2) is carried out, and a polymer P(I) having a structural unit represented by formula (2) is produced.

[0145] From the viewpoint of steric hindrance of the reaction, a monofunctional (meth)acrylic compound having a hydroxy group tends to react more easily with the raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxy group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), it is preferable not to initially charge a monofunctional (meth)acrylic compound having a hydroxy group into the reaction system but to add it to the reaction system later. Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following formula (2a-m). In formula (2a-m), X 10The definition of O and R is the same as that in formula (2a).

[0146] [Chemical formula]

[0147] Specific examples of the compound represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and the like.

[0148] When obtaining the polymer precursor (Ia) containing either the structural unit represented by formula (NB) or either one of the structural units represented by formula (1) and formula (2), after step (I), only one of step aII(1) and step aII(2) may be carried out.

[0149] (Step aII-ii) When carrying out step aII-ii, the polymer precursor (Ia) obtained in step aII-i is treated with water in the presence of a basic catalyst. By step aII-ii, the structural unit represented by formula (MA) contained in the polymer precursor (Ia) obtained in step aII-i undergoes ring-opening, and the structural unit represented by formula (3) is formed, thereby producing a second polymer precursor (referred to as "polymer precursor (Ib)") containing the structural unit represented by formula (NB), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (3). When a part of the structural unit represented by formula (MA) undergoes ring-opening and a part of the structural unit of formula (MA) remains without undergoing ring-opening, the polymer precursor (Ib) may further contain the structural unit represented by formula (MA).

[0150] Examples of the basic catalyst used in Step aII-ii include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0151] In Step aII-ii, water is added to the reaction system containing the polymer precursor (Ia) obtained in Step aII-i, and the resulting reaction solution is heated, preferably at 60 to 80°C, for about 0.25 to 6 hours, whereby the structural unit of formula (MA) contained in the polymer precursor (Ia) undergoes ring-opening to form the structural unit represented by formula (3). The basic catalyst can be used as it is the catalyst remaining in the reaction system obtained in Step aII-i. Therefore, Step aII-ii is preferably carried out by adding water in situ to the reaction mixture obtained in Step aII-i without performing any post-treatment on the reaction mixture obtained in Step aII-i.

[0152] (Step aII-iii) In Step aII-iii, the starting polymer obtained in Step aI, or the polymer precursor (Ia) obtained in Step aII-i, and the alcohol compound represented by formula (AL) are reacted in the presence of a basic catalyst, whereby a part of the structural unit represented by formula (MA) contained in the starting polymer or the polymer precursor (Ia) undergoes ring-opening to form the structural unit represented by formula (13). By carrying out Step aII-iii on the starting polymer, a polymer precursor (Ic-i) containing the structural unit represented by formula (NB), the structural unit represented by formula (13), and the structural unit represented by formula (MA) is produced. Alternatively, by carrying out Step aII-iii on the polymer precursor (Ia), a polymer precursor (Ic-ii) containing the structural unit represented by formula (NB), the structural unit represented by formula (13), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA) is produced.

[0153] In step aII-iii, an alcohol represented by formula (AL) is added to a reaction system containing the raw material polymer or the polymer precursor (Ia) obtained in step aII-i. By stirring and mixing this mixed solution, a polymer precursor (Ic-i) or a polymer precursor (Ic-ii) can be obtained. When step aII-iii is carried out on the polymer precursor (Ia), the basic catalyst can be directly used as the catalyst remaining in the reaction system obtained in step aII-i. Therefore, step aII-iii is preferably carried out by adding water to this reaction mixture in situ without performing any post-treatment on the reaction mixture obtained in step aII-i.

[0154] (Step aIII-i) In step aIII-i, the polymer precursor (Ia) obtained in step aII-i, the polymer precursor (Ib) obtained in step aII-ii, or the polymer precursor (Ic-i) or (Ic-ii) obtained in step aII-iii is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, so that the carboxy group (structural unit (1-4)) in the polymer precursor (Ia) / polymer precursor (Ib) / polymer precursor (Ic-i) or (Ic-ii) reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound, and a structural unit represented by formula (1-1) is formed. When the polymer precursor (Ia) obtained in step aII-i is used, polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is produced by step aIII-i. When a part of the structural unit of formula (MA) remains without ring-opening, polymer P(I) further contains a structural unit represented by formula (MA). When using the polymer precursor (Ib) obtained in step aII-i, by step aIII-i, a polymer P(I) is produced that contains a structural unit represented by formula (NB), a structural unit represented by formula (1), and / or a structural unit represented by formula (2), a structural unit represented by formula (5), and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9). When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When a part of the structural unit represented by formula (3) possessed by the polymer precursor (Ib) remains unreacted, the resulting polymer P(I) contains a structural unit of formula (3) or a structural unit of formula (1-4). When using the polymer precursor (Ic-i) obtained in step aII-iii, by step aIII-i, a polymer P(I) is produced that contains a structural unit represented by formula (NB), a structural unit represented by formula (13), and a structural unit represented by formula (12). When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When using the polymer precursor (Ic-ii) obtained in step aII-iii, by step aIII-i, a polymer P(I) is produced that contains a structural unit represented by formula (NB), a structural unit represented by formula (13), a structural unit represented by formula (12), a structural unit represented by formula (1), and / or a structural unit represented by formula (2), a structural unit represented by formula (5), and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9). When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA).

[0155] The reaction between the polymer precursors (Ia), (Ib), (Ic-i) or (Ic-ii) and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst can be directly used as the catalyst remaining in the reaction system obtained in Step aII-i, Step aII-ii or Step aII-iii. Therefore, in Step aIII-i, without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) obtained in Step aII-i, Step aII-ii or Step aII-iii, or neutralizing the basic catalyst contained in the mixture, the epoxy group-containing (meth)acrylic compound is preferably added in situ to the reaction mixture containing the polymer precursor obtained in Step aII-i, Step aII-ii or Step aII-iii.

[0156] Specifically, the reaction solution obtained by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) is heated preferably at 60 to 80 °C for about 1 to 9 hours, so that the carboxyl group of the polymer precursor (Ia), (Ib), (Ic-i) or (Ic-ii) (structural unit (1-4)) reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound, forming the structural unit represented by formula (1-1) and generating the target polymer P(I).

[0157] Examples of the epoxy group-containing (meth)acrylic compound include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, etc., and one or more selected therefrom can be used.

[0158] The addition amount of the epoxy group-containing (meth)acrylic compound is desirably 0.1 to 3.0 moles per mole of the carboxyl group of the polymer precursor.

[0159] After step aIII-i, for the removal of unnecessary components other than the desired polymer P(I), it is preferable to appropriately perform the following steps.

[0160] First, the reaction solution diluted with an organic solvent and added with an acid (e.g., formic acid, citric acid, etc.) above is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of polymer P(I) is obtained.

[0161] (Step aIII-ii) When carrying out step aIII-ii, the polymer P(I) obtained in step aIII-i is treated with water. By step aIII-ii, the structural unit represented by formula (MA) contained in the polymer P(I) obtained in step aIII-i is ring-opened, and the structural unit represented by formula (3) is formed.

[0162] In step aIII-ii, water is added to the organic solution of the polymer P(I) obtained in step aIII-i, and the resulting reaction solution is heated preferably at 60 to 80 °C for about 0.25 to 6 hours. Thereby, the structural unit of formula (MA) contained in the polymer P(I) is ring-opened, and the structural unit represented by formula (3) is generated.

[0163] After step aIII-i or step aIII-ii, for the purification of the desired polymer P(I), the following steps may be further carried out. First, an excessive amount of toluene is added to the organic solution of the polymer P(I) obtained through step aIII-i or step aIII-ii to reprecipitate the polymer P(I). Further, the polymer powder obtained by reprecipitation is washed several times (e.g., 2 times) with toluene. Furthermore, for the removal of the acid and basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (e.g., 3 times). By drying the polymer powder after washing with ion-exchanged water at, for example, 30 to 60 °C for 16 hours or more, the high-purity polymer P(I) of this embodiment can be obtained.

[0164] (Second aspect) Polymer P(I) is R in formula (NB) 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and when R in formula (4) 5 is a group having a pentafluorophenyl group represented by the above formula (pf), it can be produced (synthesized) by the following steps bI, bII, and bIII. Step bI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); Step bII-i: Reacting the raw material polymer obtained in step bI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a first polymer precursor (Ia) containing a structural unit represented by formula (NB) and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0165] When polymer P(I) further contains a structural unit represented by formula (3), after step bII-i, the following step bII-ii is carried out. Step bII-ii is an optional step carried out as necessary. Step bII-ii: Treating the polymer precursor (Ia) with water in the presence of a base catalyst to obtain a second polymer precursor (referred to as "polymer precursor (Ib)") containing a structural unit represented by formula (NB), a structural unit represented by formula (3), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0166] Then, R 5In order to introduce the structural unit represented by formula (4) which is a group represented by formula (pf), after step bI or after step bII-i, the following step bII-iii is carried out. Step bII-iii is an optional step carried out as necessary. Step bII-iii: Reacting the raw material polymer obtained in step bI or the polymer precursor (Ia) obtained in step bII-i with an alcohol compound having a pentafluorophenyl group in the presence of a basic catalyst to obtain a third polymer precursor containing the structural unit represented by formula (NB), the structural unit represented by formula (4), and the structural unit represented by formula (MA) (precursor when passing through the raw material polymer, referred to as "polymer precursor (Ic-i)"), or a third polymer precursor containing the structural unit represented by formula (NB), the structural unit represented by formula (4), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA) (precursor when passing through the polymer precursor (Ia), referred to as "polymer precursor (Ic-ii)"). Here, the structural unit represented by formula (4) is a structural unit composed of the structural unit represented by formula (1-5) (wherein R in formula (1-5) 5 is a group represented by formula (pf)) and the structural unit represented by formula (1-4), and is a structural unit obtained by the reaction of the structural unit represented by formula (MA) in the polymer precursor (Ia) with the pentafluorophenyl group-containing alcohol compound.

[0167] Step bIII-i: Reacting the first polymer precursor (Ia) obtained in step bII-i, the second polymer precursor (Ib) obtained in step bII-ii, or the third polymer precursor (Ic-i) or (Ic-ii) obtained in step bII-iii with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) containing the structural unit represented by formula (NB) and the structural unit represented by formula (1-1), and optionally further containing the structural unit represented by formula (MA).

[0168] When the above step bII-ii is not carried out, in order to obtain the polymer P(I) further containing the structural unit represented by the formula (3), after step bIII-i, the following step bIII-ii may be carried out. Step bIII-ii: Without carrying out step bII-ii, the polymer P(I) obtained through step bII-i or step bII-iii and step bIII-i is treated with water in the presence of a base catalyst to obtain a polymer P(I) containing at least the structural unit represented by the formula (NB), the structural unit represented by the formula (1-1), and the structural unit represented by the formula (3), and optionally further containing the structural unit represented by the formula (MA).

[0169] Hereinafter, each step will be described. (Step bI) The step of preparing a raw material polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) in step bI can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by the formula (NBm) and maleic anhydride. Here, R in the formula (NBm) 1 , R 2 , R 3 and R 4 are a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.

[0170]

Chemical formula

[0171] Examples of the monomer represented by formula (NBm) include norbornene, bicyclo[2.2.1]hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, 5-norbornene-2,3-dicarboxylic anhydride, and the like. When polymerizing, only one type of the monomer represented by formula (NBm) may be used, or two or more types may be used in combination.

[0172] The polymerization method is the same as in the above step aI.

[0173] (Step bII-i) In step bII-i, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, so that a part of the structural unit represented by formula (MA) contained in the raw material polymer undergoes ring opening, and the structural unit represented by formula (1) and / or the structural unit represented by formula (2) are formed, and a polymer precursor containing the structural unit represented by formula (NB), and the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA) is obtained. Here, the polymer precursor obtained is referred to as "polymer precursor (Ia)" for convenience of explanation. Step bII-i is carried out in the same manner as step aII-i above.

[0174] (Step bII-ii) When carrying out step bII-ii, the polymer precursor (Ia) obtained in step bII-i is treated with water in the presence of a basic catalyst. By step bII-ii, the structural unit represented by formula (MA) contained in the polymer precursor (Ia) obtained in step bII-i undergoes ring-opening, and a structural unit represented by formula (3) is formed, thereby producing a second polymer precursor (referred to as "polymer precursor (Ib)") containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (3). When a part of the structural unit represented by formula (MA) undergoes ring-opening and a part of the structural unit of formula (MA) remains without undergoing ring-opening, the polymer precursor (Ib) may further contain a structural unit represented by formula (MA). Step bII-ii is carried out in the same manner as step aII-ii described above.

[0175] (Step bII-iii) In step bII-iii, by reacting the raw material polymer obtained in step bI or the polymer precursor (Ia) obtained in step bII-i with an alcohol compound having a pentafluorophenyl group in the presence of a basic catalyst, a part of the structural unit represented by formula (MA) contained in the raw material polymer or the polymer precursor (Ia) undergoes ring-opening, and a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)) is formed. By carrying out step bII-iii on the raw material polymer, a polymer precursor (Ic-i) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), and a structural unit represented by formula (MA) is generated. Alternatively, by carrying out step bII-iii on the polymer precursor (Ia), a polymer precursor (Ic-ii) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) is generated.

[0176] In step bII-iii, an alcohol compound having a pentafluorophenyl group is added to a reaction system containing a raw material polymer or the polymer precursor (Ia) obtained in step aII-i. By stirring and mixing this mixed solution, the polymer precursor (Ic-i) or the polymer precursor (Ic-ii) can be obtained. Examples of the alcohol compound having a pentafluorophenyl group that can be used include 2,3,4,5,6-pentafluorobenzyl alcohol and 2,3,4,5,6-pentafluorophenol. Step bII-iii is carried out in the same manner as step aII-iii described above.

[0177] (Step bIII-i) In step bIII-i, the polymer precursor (Ia) obtained in step aII-i, the polymer precursor (Ib) obtained in step bII-ii, or the polymer precursor (Ic-i) or (Ic-ii) obtained in step aII-iii is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. By the reaction of the carboxy group (structural unit (1-4)) in the polymer precursor (Ia) / polymer precursor (Ib) / polymer precursor (Ic-i) or (Ic-ii) with the epoxy group of the epoxy group-containing (meth)acrylic compound, the structural unit represented by formula (1-1) is formed. When the polymer precursor (Ia) obtained in step bII-i is used, step bIII-i produces the polymer P(I) containing the structural unit represented by formula (NB), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (8) and / or the structural unit represented by formula (9). When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains the structural unit represented by formula (MA). When using the polymer precursor (Ib) obtained in step bII-i, according to step bIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1), and / or a structural unit represented by formula (2), a structural unit represented by formula (5), and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When a part of the structural unit represented by formula (3) in the polymer precursor (Ib) remains unreacted, the resulting polymer P(I) contains a structural unit of formula (3) or formula (1-4). When using the polymer precursor (Ic-i) obtained in step bII-iii, according to step bIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), and a structural unit represented by formula (11) (R in formula (11) 5 is a group represented by formula (pf)) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When using the polymer precursor (Ic-ii) obtained in step bII-iii, according to step bIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), a structural unit represented by formula (11) (R in formula (11) 5 is a group represented by formula (pf)), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (5) and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). Step bIII-i is carried out in the same manner as step aIII-i above.

[0178] (Step bIII-ii) When performing Step bIII-ii, the polymer P(I) obtained in Step bIII-i is treated with water. By Step bIII-ii, the structural unit represented by formula (MA) contained in the polymer P(I) obtained in Step bIII-i undergoes ring-opening, and the structural unit represented by formula (3) is formed. Step bIII-ii is performed in the same manner as Step aIII-ii described above.

[0179] (Third Aspect) In the polymer P(I), at least one of R 1 , R 2 , R 3 and R 4 is a group having a pentafluorophenyl group represented by formula (pf), and the remainder of R 1 , R 2 , R 3 and R 4 is a hydrogen atom or an organic group having 1 to 30 carbon atoms. When R 5 in formula (4) is a group having a pentafluorophenyl group represented by the above formula (pf), it can be produced (synthesized) by the following Steps cI, cII, and cIII. Step cI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); Step cII-i: A step of reacting the raw material polymer obtained in Step aI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a first polymer precursor (Ia) containing a structural unit represented by formula (NB), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0180] When the polymer P(I) further contains a structural unit represented by the formula (3), after the step cII-i, the following step cII-ii is carried out. Step cII-ii is an optional step carried out as necessary. Step cII-ii: Treating the polymer precursor (Ia) with water in the presence of a base catalyst to obtain a second polymer precursor (referred to as "polymer precursor (Ib)") containing a structural unit represented by the formula (NB), a structural unit represented by the formula (3), and a structural unit represented by the formula (1) and / or a structural unit represented by the formula (2), and optionally further containing a structural unit represented by the formula (MA).

[0181] Next, R 5 In order to introduce a structural unit represented by the formula (4) in which is a group represented by the formula (pf), after the step cI or after the step cII-i, the following step cII-iii is carried out. Step cII-iii is an optional step carried out as necessary. Step cII-iii: Reacting the raw material polymer obtained in the step cI or the polymer precursor (Ia) obtained in the step cII-i with an alcohol compound having a pentafluorophenyl group in the presence of a basic catalyst to obtain a third polymer precursor (precursor when passing through the raw material polymer, referred to as "polymer precursor (Ic-i)") containing a structural unit represented by the formula (NB), a structural unit represented by the formula (4), and a structural unit represented by the formula (MA), or a third polymer precursor (precursor when passing through the polymer precursor (Ia), referred to as "polymer precursor (Ic-ii)") containing a structural unit represented by the formula (NB), a structural unit represented by the formula (4), a structural unit represented by the formula (1) and / or a structural unit represented by the formula (2), and a structural unit represented by the formula (MA). Here, the structural unit represented by the formula (4) is a structural unit composed of a structural unit represented by the formula (1-5) (wherein in the formula (1-5), R 5 is a group represented by the formula (pf)) and a structural unit represented by the formula (1-4), and is a structural unit obtained by the reaction of the structural unit represented by the formula (MA) in the polymer precursor (Ia) with the pentafluorophenyl group-containing alcohol compound.

[0182] Step cIII-i: Reacting the first polymer precursor (Ia) obtained in step cII-i, the second polymer precursor (Ib) obtained in step cII-ii, or the third polymer precursor (Ic-i) or (Ic-ii) obtained in step cII-iii with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1-1), and optionally further containing a structural unit represented by formula (MA).

[0183] When the above step cII-ii is not carried out, in order to obtain a polymer P(I) further containing a structural unit represented by formula (3), after step cIII-i, the following step cIII-ii may be carried out. Step cIII-ii: Treating the polymer P(I) obtained through step cII-i or step cII-iii and step cIII-i without carrying out step cII-ii with water in the presence of a base catalyst to obtain a polymer P(I) containing at least a structural unit represented by formula (NB), a structural unit represented by formula (1-1), and a structural unit represented by formula (3), and optionally further containing a structural unit represented by formula (MA).

[0184] Hereinafter, each step will be described. (Step cI) The step of preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA) in step cI can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm) and maleic anhydride. Here, at least one of R 1 , R 2 , R 3 and R 4 is a group having a pentafluorophenyl group represented by formula (pf), and the rest of R 1 , R 2 , R 3 and R 4 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2. Step cI is carried out in the same manner as step aI above.

[0185] (Step cII-i) In step cII-i, the raw material polymer obtained in step cI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, so that a part of the structural unit represented by formula (MA) contained in the raw material polymer is ring-opened, and the structural unit represented by formula (1) and / or the structural unit represented by formula (2) are formed, and a polymer precursor containing the structural unit represented by formula (NB), and the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (MA) is obtained. Here, the polymer precursor obtained is referred to as "polymer precursor (Ia)" for convenience of explanation. Step cII-i is carried out in the same manner as step aII-i above.

[0186] (Step cII-ii) When carrying out step bII-ii, the polymer precursor (Ia) obtained in step bII-i is treated with water in the presence of a basic catalyst. By step bII-ii, the structural unit represented by formula (MA) contained in the polymer precursor (Ia) obtained in step bII-i is ring-opened, and the structural unit represented by formula (3) is formed, and a second polymer precursor (referred to as "polymer precursor (Ib)") containing the structural unit represented by formula (NB), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (3) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit of formula (MA) remains without ring-opening, the polymer precursor (Ib) may further contain the structural unit represented by formula (MA). Step cII-ii is carried out in the same manner as step aII-ii above.

[0187] (Step cII-iii) In step cII-iii, the raw material polymer obtained in step cI or the polymer precursor (Ia) obtained in step cII-i is reacted with an alcohol compound having a pentafluorophenyl group in the presence of a basic catalyst, so that a part of the structural unit represented by formula (MA) contained in the raw material polymer or the polymer precursor (Ia) undergoes ring opening, and the structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)) is formed. By performing step bII-iii on the raw material polymer, a polymer precursor (Ic-i) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), and a structural unit represented by formula (MA) is produced. Alternatively, by performing step bII-iii on the polymer precursor (Ia), a polymer precursor (Ic-ii) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) is produced. Step cII-iii is carried out in the same manner as the above step bII-iii.

[0188] (Step cIII-i) In step cIII-i, the polymer precursor (Ia) obtained in step cII-i, the polymer precursor (Ib) obtained in step cII-ii, or the polymer precursor (Ic-i) or (Ic-ii) obtained in step cII-iii is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, so that the carboxy group (structural units (1-4)) in the polymer precursor (Ia) / polymer precursor (Ib) / polymer precursor (Ic-i) or (Ic-ii) reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound, and the structural unit represented by formula (1-1) is formed. When using the polymer precursor (Ia) obtained in step cII-i, according to step cIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When using the polymer precursor (Ib) obtained in step cII-i, according to step cIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (5) and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When a part of the structural unit represented by formula (3) in the polymer precursor (Ib) remains unreacted, the resulting polymer P(I) contains a structural unit of formula (3) or formula (1-4). When using the polymer precursor (Ic-i) obtained in step cII-iii, according to step bIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), and a structural unit represented by formula (11) (R in formula (11) 5 is a group represented by formula (pf)) is generated. When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). When using the polymer precursor (Ic-ii) obtained in step cII-iii, according to step cIII-i, a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (4) (R in formula (4) 5 is a group represented by formula (pf)), a structural unit represented by formula (11) (R in formula (11) 5is a group represented by formula (pf)), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (5) and / or a structural unit represented by formula (6), and a structural unit represented by formula (8) and / or a structural unit represented by formula (9). When a part of the structural unit of formula (MA) remains without ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA). Step cIII-i is carried out in the same manner as step aIII-i described above.

[0189] (Step cIII-ii) When carrying out step cIII-ii, the polymer P(I) obtained in step cIII-i is treated with water. By step cIII-ii, the structural unit represented by formula (MA) contained in the polymer P(I) obtained in step cIII-i undergoes ring-opening to form a structural unit represented by formula (3). Step cIII-ii is carried out in the same manner as step aIII-ii described above.

[0190] <Second Embodiment> (Polymer P(II)) The polymer P in the second embodiment (hereinafter referred to as "polymer P(II)") is a structural unit represented by formula (NB) and a structural unit represented by formula (MA). [Chemical Formula] [Chemical Formula]

[0191] In formula (NB), R 1 , R 2 , R 3 and R 4 at least one of which is a group having a pentafluorophenyl group, the remaining R 1 , R 2 , R 3 and R4 Each is independently hydrogen or an organic group having 1 to 30 carbon atoms, a1 is 0, 1, or 2, R 1 、R 2 、R 3 、and R 4 none of them contains a substituted or unsubstituted maleimide moiety.

[0192] Polymer P(II) is a raw material polymer used in the production of polymer P(I) in the first embodiment and is the polymer obtained in the above steps aI and cI.

[0193] The weight average molecular weight Mw of polymer P(II) is, for example, 2,000 to 20,000. The weight average molecular weight Mw of polymer P(II) is preferably 2,500 to 18,000, and particularly preferably 3,000 to 15,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the weight average molecular weight of polymer P(I) obtained from this polymer P(II), and as a result, the sensitivity of polymer P(I) and its solubility in an alkaline developer can be adjusted to a desired level. Also, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of polymer P(II) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0.

[0194] [Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P(I). The polymer solution of this embodiment may contain at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds together with polymer P(I).

[0195] (Polyfunctional (meth)acrylic compound) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of this embodiment may be an unreacted product of the (meth)acrylic compound used in the above step aII in the production of the polymer P, or may be one added separately.

[0196] Examples of the polyfunctional (meth)acrylic compound that can be blended in the polymer solution include, but are not limited to, the compounds represented by the following formulas (1b-p), the compounds represented by formula (1c-p), and the compounds represented by formula (1d-p).

[0197]

Chemical formula

[0198]

Chemical formula

[0199]

Chemical formula

[0200] The definitions and specific embodiments of k, R, X 1 , X 1 ’ and X 2 in formula (1b-p) are the same as those in the above formula (1b). Also, the definitions and specific embodiments of k, R, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 in formula (1c-p) are the same as those in the above formula (1c).

[0201] Y in formula (1b-p), formula (1c-p) and formula (1d-p) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0202] In the compounds of formula (1b-p), formula (1c-p) and formula (1d-p) where Y is a hydrogen atom, it may be an unreacted monomer (i.e., the compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p)), or it can also be added separately. In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

[0203] When a polyfunctional (meth)acrylic compound is blended in the polymer solution of this embodiment separately from the unreacted substances of the polyfunctional (meth)acrylic compound used in the production of polymer P(I), the blending amount can be such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less with respect to the peak area of polymer P(I).

[0204] (monofunctional (meth)acrylic compound) Examples of the monofunctional (meth)acrylic compound blended in the polymer solution of this embodiment include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 and the definitions of R are the same as those in formula (2a).

[0205] [Chemical formula]

[0206] When a monofunctional (meth)acrylic compound is blended in the polymer solution of this embodiment separately from the unreacted substances of the monofunctional (meth)acrylic compound used in the production of polymer P(I), the blending amount can be such that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less with respect to the peak area of polymer P(I).

[0207] 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.

[0208] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is used in such an amount that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0209] [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 a resin material of the photosensitive resin composition described below.

[0210] [Photosensitive Resin Composition] The photosensitive resin composition of this embodiment contains the above-described polymer P(I) and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment contains the above-described polymer solution of this embodiment and a photopolymerization initiator. Each component will be described below.

[0211] (Photopolymerization Initiator) Examples of the photopolymerization initiator used in the photosensitive resin composition of this embodiment include free radical photopolymerization initiators. As the free radical photopolymerization initiator, known compounds can be used. For example, alkylphenone 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 compounds such as benzophenone, 4,4’ - bis(dimethylamino)benzophenone, 2 - carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2 - ethylthioxanthone, 2 - isopropylthioxanthone, 2 - chlorothioxanthone, 2,4 - dimethylthioxanthone, 2,4 - diethylthioxanthone; halomethylated triazine 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 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 mentioned. The photo radical polymerization initiator may be used alone or in combination of two or more kinds.; 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).

[0212] By including the above components, the photosensitive resin composition of the present 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.

[0213] (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. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0214] 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.

[0215] 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, dark blue, 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.

[0216] 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.

[0217] The colorant (especially the pigment) can be one having an appropriate average particle diameter according to the purpose and application. However, when transparency is required especially for a color filter, a small average particle diameter of 0.1 μm or less is preferable. On the other hand, when hiding power is required for paints, etc., a large average particle diameter of 0.5 μm or more is preferable.

[0218] 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.

[0219] 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.

[0220] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0221] By containing a nonionic surfactant, the coatability is improved when the photosensitive resin composition is applied onto a substrate to obtain a resin film, 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.

[0222] 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 the present 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 compounding amount of the surfactant is preferably 0.01 to 10% by weight based on 100 parts by mass of the resin.

[0223] (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.

[0224] 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 component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0225] (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.

[0226] When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and application. 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.

[0227] (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 photoinitiator (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.

[0228] 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 a crosslinkable group (polymerizable double bond) of the same type as the crosslinkable group 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.

[0229] 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 tris(acryloyloxyethyl) isocyanurate, tris(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tris(acryloyloxyethyl) isocyanurate, alkylene oxide-added tris(methacryloyloxyethyl) isocyanurate, etc.; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate, etc.; 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.; And the like can be mentioned.

[0230] 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 preferred.

[0231] 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. 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.

[0232] (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, development 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.

[0233] [Use] 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.

[0234] 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 development 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 developing step is included. In addition, the above printing step is preferably performed by an inkjet method.

[0235] The partition walls manufactured using the photosensitive resin composition of this embodiment have sufficient water repellency and 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 of the performance as an organic EL and improvement of the yield can be achieved.

[0236] Each step for manufacturing an organic EL element will be described.

[0237] · 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, and a copper-clad laminate. 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. Surface treatment may be performed to improve adhesion.

[0238] 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, or the like. Drying of the photosensitive resin composition applied on the substrate is typically performed by heat treatment using a hot plate, hot air, an oven, or the like. 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.

[0239] 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, and the coating conditions.

[0240] · 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 preferable. 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 preferable. The amount of exposure light 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 .

[0241] Note that after exposure, the photosensitive resin film may be heated again 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.

[0242] · Development process By developing the exposed photosensitive resin film with an appropriate developer, a partition wall can be formed.

[0243] In the development process, development can be performed using an appropriate developer by methods such as the dipping method, the paddle method, or the spray method. 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 wall is obtained.

[0244] 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. The developer may contain, for example, water-soluble organic solvents such as methanol and ethanol, and surfactants.

[0245] 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.

[0246] 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.

[0247] Note that additional processing may be performed after development and before the printing process. For example, after development, washing with a rinsing solution may be performed. Examples of the rinsing 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, etc. As the atmospheric 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.

[0248] · 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.

[0249] 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.

[0250] The ink (material liquid 4) is not particularly limited, but is typically a polymer material and / or a low molecular weight material capable of forming an organic light-emitting layer dissolved or dispersed in an organic solvent. Examples of the organic solvent here include anisole and cyclohexylbenzene, but other organic solvents can also be used.

[0251] 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, etc.

[0252] Examples of the "low molecular weight 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.

[0253] 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.

[0254] 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.

[0255] 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.

Examples

[0256] Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

[0257] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·NB: 2-Norbornene ·PFBNB: 5-Pentafluorobenzylbicyclo[2.2.1]hept-2-ene (Promelas, LLC) ·C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (Promelas, LLC) ·PFSt: 2,3,4,5,6-pentafluorostyrene ·BuOH: 1-butanol ·PFBA: 2,3,4,5,6-pentafluorobenzyl alcohol ·MAN: maleic anhydride ·4-HBA: 4-hydroxybutyl acrylate ·GMA: glycidyl methacrylate ·MEK: methyl ethyl ketone ·V-601: dimethyl 2,2’-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, azo polymerization initiator)

[0258] <Synthesis of Raw Material Polymer> (Synthesis of Raw Material Polymer 1) Into a reaction vessel equipped with a stirrer and a cooling tube, maleic anhydride (588.36 g, 6.0 mol), 2-norbornene (564.90 g, 6.0 mol), and dimethyl 2,2’-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, trade name: V-601, 55.26 g, 0.24 mol) were weighed and added. These were dissolved in a mixed solvent consisting of 1716.8 g of methyl ethyl ketone and 188.3 g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated with stirring at 65 °C for 1.5 hours and further heated at 80 °C for 6 hours to polymerize maleic anhydride and 2-norbornene to prepare a polymerization solution. The polymerization solution obtained above was dropped into 14230.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3557.5 g of methanol and then dried under vacuum at 120 °C to obtain 1027.2 g of a polymer (raw material polymer 1) having a structural unit derived from 2-norbornene 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 7,200, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.83.

[0259] (Synthesis of Raw Polymer 2) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB, 381.01 g, 1.221 mol), maleic anhydride (MAN, 119.73 g, 1.221 mol), dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 30.14 g, 0.131 mol), and methyl ethyl ketone (MEK, 94.86 g) were added and stirred until dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated and reacted at an internal temperature of 60 °C for 18 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into methanol (2000.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (2000.0 g) and then vacuum dried at a temperature of 120 °C to obtain 90.50 g of a polymer (raw polymer 2) having a structural unit derived from C4F9NB and a structural unit derived from maleic anhydride. The resulting polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 6,400, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.51. Also, the resulting polymer was 19 measured using 19F-NMR. As a result, the fluorine content of the polymer was 39.9 wt%.

[0260] The fluorine content of the synthesized polymer was measured by the following method. Approximately 100 mg of the polymer and approximately 60 mg of (trifluoromethyl)benzene as an internal standard substance were weighed and dissolved in approximately 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. 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 spectral chart and the signal of CF3 (-63 ppm, 3F) of the internal standard substance, the amounts of CF3 (mol / g) and CF2 (mol / g) in the polymer were calculated. From the total amounts of CF3 (mol / g) and CF2 (mol / g) in the calculated polymer, the fluorine content (wt / %) in the polymer was calculated.

[0261] (Synthesis of Raw Polymer 3) Into a reaction vessel equipped with a stirrer and a cooling tube, maleic anhydride (117.67 g, 1.200 mol), 2,3,4,5,6-pentafluorostyrene (PFSt, 232.92 g, 1.200 mol), dimethyl 2,2'-azobis(2-methylpropionate) (V-601, 11.05 g, 0.048 mol), and methyl ethyl ketone (MEK, 514.81 g) were added and stirred and dissolved. 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 8 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into methanol (3506.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (3506.0 g) and then vacuum dried at a temperature of 120 °C to obtain 25.04 g of a polymer (raw polymer 3) having a structural unit derived from PFSt and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 25,000, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.27.

[0262] (Synthesis of Raw Polymer 4) 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. Next, 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 obtained 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.

[0263] The fluorine content of the synthesized raw material polymer was measured by the following method. Approximately 100 mg of the polymer and approximately 60 mg of (trifluoromethyl)benzene as an internal standard substance were weighed and dissolved in approximately 1 g of acetone-d6. For this solution, 19 F-NMR measurement was performed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). From the integration ratio of the signal of C6F5 (-135 to -170 ppm, 5F) corresponding to the pentafluorophenyl group of the polymer and the signal of CF3 (-63 ppm, 3F) of the internal standard substance in the obtained spectrum chart, 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.

[0264] 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.

[0265] (Evaluation of water and liquid repellency of raw material polymer) The contact angles of the obtained raw material polymers 1 to 4 with respect to water and PGMEA (propylene glycol monomethyl ether acetate) were measured by the following method. The results are shown in Table 1. Each raw material polymer was dissolved in 2-heptanone to prepare a polymer solution with a solid content concentration of 30% by mass. The prepared polymer solution was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 °C for 120 seconds to obtain a thin film with a thickness of 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 prepared liquid droplet was 2 μL, the observation time was 10 seconds after droplet deposition, and the average value of 5 measurements 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 70° or more, the water repellency is good; if it is 75° or more, the water repellency is better; if it is 80° or more, it can be considered that the water repellency is particularly excellent. If the contact angle with respect to PGMEA is 8° or more, the liquid repellency is good; if it is 12° or more, the liquid repellency is better; if it is 14° or more, it can be considered that the liquid repellency is particularly excellent.

[0266] Table 1 shows the presence or absence of PFAS for raw material polymers 1 to 4. "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.

[0267]

Table 1

[0268] <Synthesis of Polymer P> Using the above raw material polymer, Polymer P was prepared by the following method.

[0269] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw material polymer 1 with a monofunctional (meth)acrylic compound. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (0.052 mol in terms of MA calculated from the charged amount of raw material polymer 1) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added, and the mixture was reacted at 70 °C for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction 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, 8.7 g of Polymer P1 in which the structural unit derived from maleic anhydride in raw material polymer 1 was ring-opened with 4-HBA was obtained. 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. Also, by GPC measurement of Polymer P1, the disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, 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 was ring-opened with 4-HBA.

[0270] (Preparation Example 2) The MA units of the raw material polymer 2 were 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 P2. The details are described below. First, 10.00 g of MEK was added to 10 g of the raw material polymer 2 (0.024 mol in terms of MA conversion calculated from the charged amount of the raw material polymer 2) to prepare a solution. Then, 2.19 g (0.015 mol) of 4-HBA was added to this solution, and then 1.50 g (0.015 mol) of triethylamine was added, and the mixture was reacted at 70 °C for 6 hours. Further, 1.03 g (0.007 mol) of GMA was added, and the mixture was reacted at 70 °C for 4 hours. The prepared reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with 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, 8.3 g of polymer P2 was obtained, in which the structural unit derived from maleic anhydride in the raw material polymer 2 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA) and reacted with GMA. For the obtained polymer P2, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P2. The results are shown in Table 2.

[0271] Also, by GPC measurement of polymer P2, the disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P2 does not contain unreacted monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that polymer P2 has a structure in which the structural unit derived from maleic anhydride of the raw material polymer 2 was ring-opened with 4-HBA and a structure in which GMA was introduced.

[0272] Furthermore, the fluorine content of the obtained polymer P2 was measured in the same manner as the measurement of the fluorine content of the raw material polymer 2. The results are shown in Table 2.

[0273] (Preparation Example 3) Using 10.00 g of raw material polymer 4 (0.027 mol in terms of MA conversion calculated from the charged amount of raw material polymer 4) instead of raw material polymer 2, and 4-HBA (2.42 g, 0.017 mol) and GMA (1.15 g, 0.008 mol), in the same manner as Preparation Example 2, the MA units of raw material polymer 4 were ring-opened with a monofunctional (meth)acrylic compound and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to obtain 9.8 g of polymer P3. For the obtained polymer P3, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P3. The results are shown in Table 2.

[0274] Furthermore, the fluorine content of the obtained polymer P3 was measured in the same manner as the measurement of the fluorine content of the raw material polymer 4. The results are shown in Table 2.

[0275] Also, by GPC measurement of polymer P3, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P3 does not contain unreacted monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that polymer P3 has a structure in which the maleic anhydride-derived structural unit of raw material polymer 4 was ring-opened with 4-HBA and a structure in which GMA was introduced.

[0276] (Preparation Example 4) Using 10.00 g of raw material polymer 4 (0.027 mol in terms of MA conversion calculated from the charged amount of raw material polymer 4) instead of raw material polymer 1, and 4-HBA (4.84 g, 0.034 mol), in the same manner as Preparation Example 1, a polymer P4 in which the MA units of raw material polymer 4 were ring-opened with a monofunctional (meth)acrylic compound (4-HBA) was prepared.

[0277] Also, by GPC measurement of Polymer P4, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed. From this, it was confirmed that the obtained Polymer P4 does not contain unreacted monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that Polymer P4 has a structure in which the maleic anhydride-derived structural unit of starting material polymer 4 was ring-opened with 4-HBA. The weight average molecular weight, polydispersity, and fluorine content of the obtained Polymer P4 were measured in the same manner as in Preparation Example 3. The results are shown in Table 2.

[0278] (Preparation Example 5) Polymer P5 in which the MA unit of starting material polymer 5 was ring-opened with 1-butanol was prepared. Details are described below. First, 19.34 g of MEK was added to 10.00 g of starting material polymer 4 (0.027 mol in terms of MA calculated from the charged amount of starting material polymer 4) to prepare a solution. Next, 2.49 g (0.034 mol) of 1-butanol (BuOH) was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added, followed by reacting at 70 °C for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following procedure. · 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, 9.7 g of Polymer P5 in which the structural unit derived from maleic anhydride in starting material polymer 4 was ring-opened with 1-butanol was obtained. By GPC measurement of Polymer P5, disappearance of the peak of the 1-butanol used was confirmed. From this, it was confirmed that the obtained Polymer P5 does not contain unreacted 1-butanol. Also 13By \(^{13}\)C-NMR measurement, it was confirmed that the polymer P5 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 4 is ring-opened with 1-butanol. The weight average molecular weight, polydispersity, and fluorine content of the obtained polymer P5 were measured in the same manner as in Preparation Example 3. The results are shown in Table 2.

[0279] (Preparation Example 6) A polymer P6 in which the MA unit of the raw material polymer 1 was ring-opened with 2,3,4,5,6-pentafluorobenzyl alcohol was prepared. Details are described below. First, 40.78 g of MEK was added to 10.00 g of the raw material polymer 1 (0.052 mol in terms of MA calculated from the charged amount of the raw material polymer 1) to prepare a solution. Next, 12.88 g (0.065 mol) of 2,3,4,5,6-pentafluorobenzyl alcohol (PFBA) was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added, followed by reacting at 70 °C for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Thereafter, 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. Thus, 10.2 g of the polymer P6 in which the structural unit derived from maleic anhydride in the raw material polymer 1 was ring-opened with PFBA was obtained.

[0280] Also, by GPC measurement of the polymer P6, the disappearance of the used 2,3,4,5,6-pentafluorobenzyl alcohol was confirmed. Thereby, it was confirmed that the obtained polymer P6 does not contain unreacted alcohol compounds. Also 13 By \(^{13}\)C-NMR measurement, it was confirmed that the polymer P6 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 1 was ring-opened with 2,3,4,5,6-pentafluorobenzyl alcohol.

[0281] Furthermore, the fluorine content of the obtained polymer P6 was measured in the same manner as in Preparation Example 3. The results are shown in Table 2.

[0282] (Preparation Example 7) A polymer P7 in which the MA unit of the raw material polymer 4 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA) was prepared in the same manner as in Preparation Example 6, except that 10.00 g of the raw material polymer 4 (0.027 mol in terms of MA conversion calculated from the charged amount of the raw material polymer 4) was used instead of the raw material polymer 1, and 2,3,4,5,6-pentafluorobenzyl alcohol (PFBA, 6.65 g, 0.034 mol) was used.

[0283] Also, by GPC measurement of the polymer P7, the disappearance of the used 2,3,4,5,6-pentafluorobenzyl alcohol was confirmed. Thereby, it was confirmed that the obtained polymer P7 does not contain unreacted alcohol compounds. Also 13 By 13C-NMR measurement, it was confirmed that the polymer P7 has a structure in which the maleic anhydride-derived structural unit of the raw material polymer 4 was ring-opened with 2,3,4,5,6-pentafluorobenzyl alcohol.

[0284] Furthermore, the fluorine content of the obtained polymer P7 was measured in the same manner as in Preparation Example 3. The results are shown in Table 2.

[0285] (Preparation Example 8) The MA unit of the raw material polymer 4 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA), and further 2,3,4,5,6-pentafluorobenzyl alcohol was added and ring-opened to prepare a polymer P8. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw material polymer 4 (0.027 mol in terms of MA conversion calculated from the charged amount of raw material polymer 4) to prepare a solution. Next, 3.46 g (0.017 mol) of 2,3,4,5,6-pentafluorobenzyl alcohol (PFBA) was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added, followed by reacting at 70 °C for 4 hours to prepare a reaction solution. Next, without post-treating the obtained reaction solution, 2.52 g (0.017 mol) of 4-HBA was added to this reaction solution, and the reaction was carried out at 70 °C for 4 hours. The prepared reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with an aqueous formic acid solution and an aqueous citric acid solution. The obtained reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with 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 dried at 40 °C for 12 hours. As a result, 10.5 g of polymer P8 was obtained, in which the structural unit derived from maleic anhydride in raw material polymer 4 was ring-opened with PFBA and then ring-opened with 4-HBA.

[0286] Regarding the obtained polymer P8, GPC measurement was carried out to measure the weight-average molecular weight and polydispersity of polymer P8. The results are shown in Table 2. Also, by GPC measurement of polymer P8, the disappearance of the peaks of the monofunctional (meth)acrylic compound used and the peak of pentafluorobenzyl alcohol was confirmed. Thereby, it was confirmed that the obtained polymer P8 does not contain unreacted monofunctional (meth)acrylic compound nor pentafluorobenzyl alcohol. Also 13 By C-NMR measurement, it was confirmed that polymer P8 has a structure in which the structural unit derived from maleic anhydride of raw material polymer 4 was ring-opened with PFBA and 4-HBA.

[0287] Furthermore, the fluorine content of the obtained polymer P8 was measured in the same manner as in Preparation Example 3. The results are shown in Table 2.

[0288] (Physical Property Evaluation) The double bond equivalent of each polymer P prepared in Preparation Examples 1 to 8 was measured by the method shown below.

[0289] (Double Bond Equivalent) The double bond equivalent of the polymer was measured by the following method. About 50 mg of the polymer and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. For this solution, using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.) 1 1H-NMR measurement was performed. From the integration ratio of the signal (5.8 - 6.7 ppm, 3H) derived from the acryloyl group and the signal (8.1 ppm, 4H) of the phenyl group of the internal standard substance in the obtained spectrum chart, the amount of acryloyl groups (mol / g) in the polymer was calculated, and from the integration ratio of the signal (5.6 - 5.8 ppm, 2H) derived from the methacryloyl group and the signal (8.1 ppm, 4H) of the phenyl group of the internal standard substance, the amount of methacryloyl groups (mol / g) in the polymer was calculated. Here, the signal derived from the methacryloyl group at 6.0 - 6.1 ppm is minute and overlaps with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The double bond amount (mol / g) was calculated from the total of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and from the double bond amount, the double bond equivalent (g / mol) was calculated. The results are shown in Table 2. The smaller the value of the double bond equivalent, the larger the amount of C=C double bonds per unit mass of the polymer.

[0290] Table 2 shows the presence or absence of PFAS correspondence for each polymer P prepared in Preparation Examples 1 to 8.

[0291] [Table 2]

[0292] (Examples 1 to 6, Comparative Examples 1 and 2) In each of the examples and comparative examples, a resin composition was prepared and evaluated for the following items. <Evaluation> [Alkali dissolution rate of resin composition] The polymers P1 to P8 obtained in Preparation Examples 1 to 8 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 8 having a solid content concentration of 30% by mass. Next, the resin compositions 1 to 8 were spin-coated on a wafer, PGMEA was dried, and then pre-baked at a temperature of 100 °C for 2 minutes to prepare a resin film having a thickness of about 1 μm. This resin film was immersed, together with the wafer, in 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 visually observing the immersed wafer 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 10 nm / s or more, it can be used without problems as a photosensitive material. If it is 20 nm / s or more, it can be considered that the developability is good. If it is 50 nm / s or more, it can be considered to be better. Furthermore, if it is 100 nm / s or more, it can be considered to be particularly good.

[0293] [Evaluation of water repellency and chemical resistance of resin composition] The resin compositions 1 to 8 prepared above 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 having 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 prepared liquid droplet 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 75° or more, it can be said that the water repellency is not a problem. If it is 77° or more, the water repellency is good. If it is 79° or more, the water repellency is better. If it is 80° or more, it can be regarded as particularly excellent in water repellency. If the contact angle with respect to PGMEA is 5° or more, it can be said that the liquid repellency is not a problem. If it is 8° or more, the liquid repellency is good. If it is 9° or more, the liquid repellency is better. If it is 10° or more, it can be regarded as particularly excellent in liquid repellency.

[0294]

Table 3

[0295] The polymer of Comparative Example 1, where Polymer P is a fluorine-free and PFAS-non-corresponding polymer, had a high alkali dissolution rate and was excellent in developability. However, the contact angle value was low, and it was inferior in water repellency and liquid repellency. The polymer of Comparative Example 2, which contains a copolymer of norbornene and maleic anhydride with a fluoroalkyl group directly linked to the norbornene skeleton, had a high alkali dissolution rate and was excellent in developability. It had a high contact angle with respect to water and was excellent in water repellency. However, it corresponded to PFAS, the contact angle value with respect to PGMEA was low, and it was inferior in liquid repellency. The resin compositions of Examples 1 to 6, where Polymer P is a copolymer of norbornene and maleic anhydride and is PFAS-non-corresponding with a pentafluorophenyl group, had an alkali solubility suitable for pattern formation by photolithography. The polymer alone had a high contact angle value with respect to water and PGMEA, and had high water repellency and liquid repellency. In addition, the fluorine-free and PFAS-non-applicable raw material polymer 1 had low contact angle values with respect to water and PGMEA, and was inferior in water and liquid repellency. The PFAS-applicable raw material polymer 2 containing a copolymer of norbornene and maleic anhydride in which a fluoroalkyl group was directly linked to the norbornene skeleton had a high contact angle with respect to water and was excellent in water repellency, but had a low contact angle value with respect to PGMEA and was inferior in liquid repellency. The PFAS-non-applicable raw material polymer 3, which was a copolymer of styrene and maleic anhydride and had a pentafluorophenyl group, had a high contact angle with respect to water and was excellent in water repellency, but had a low contact angle value with respect to PGMEA and was inferior in liquid repellency. The PFAS-non-applicable raw material polymer 4, which was a copolymer of norbornene and maleic anhydride and had a pentafluorophenyl group, had high contact angle values with respect to water and PGMEA and had high water and liquid repellency.

Explanation of symbols

[0296] 1 Substrate 2 Partition wall 2a Upper surface (upper surface of the 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 (NB), a structural unit represented by formula (1-4), and a structural unit represented by formula (1-5), wherein in formula (NB), 【Chemical 1】 in formula (1-5), 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, 【Chemical Formula 2】 [Chemical Formula 3] the polymer. R ５ is an organic group, However, R １ , R ２ , R ３ , R ４ and R ５ at least one of which is a group having a pentafluorophenyl group, R １ 、 R ２ 、 R ３ 、 R ４ and R ５ none of which contains a substituted or unsubstituted maleimide moiety

2. The polymer according to claim 1, wherein the structural unit represented by formula (1-5) is a structural unit represented by formula (1-3). R in the formula (NB) １ , R ２ , R ３ and R ４ at least one of which is a group having a pentafluorophenyl group, R １ 、 R ２ 、 R ３ and R ４ The remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms,

3. 【Chemical Formula 4】 In formula (1-3), R ｓ is a group having one (meth)acryloyl group represented by formula (2a), 【Chemical Formula 5】 In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group, a polymer. The polymer according to claim 1, wherein the structural unit represented by formula (1-5) is a structural unit represented by formula (1-2), R in the formula (NB) １ , R ２ , R ３ and R ４ at least one of which is a group having a pentafluorophenyl group R １ 、 R ２ 、 R ３ and R ４ The remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, in formula (1b), 【Chemical Formula 6】 In formula (1-2), R ｐ is at least one group having two or more (meth)acryloyl groups, which is selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d). 【Chemical Formula 7】 k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, in formula (1c), X １ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs １ may be the same or different X １ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ is a (k + 1)-valent organic group having 1 to 12 carbon atoms, [Chemical Formula 8] in formula (1d), k, R, X １ and X ２ are, respectively, R, k, X in formula (1b) １ and X ２ and are synonymous with, and a plurality of Rs may be the same as or different from each other, and a plurality of Xs １ may be the same as or different from each other X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is a divalent organic group having 1 to 6 carbon atoms, 【Chemical Formula 9】 n is an integer from 2 to 5, and R is independently a hydrogen atom or a methyl group.

4. The polymer according to claim 1, wherein the structural unit represented by formula (1-5) is a structural unit represented by formula (1-51). R in the formula (NB) １ , R ２ , R ３ and R ４ at least one of which is a group having a pentafluorophenyl group, R １ 、 R ２ 、 R ３ and R ４ The remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms,

5. 【Chemical Formula 10】 In formula (1-51), R ５１ is a polymer which is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. The polymer according to claim 1.

6. R in the formula (NB) １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, R in the formula (4) ５ is a polymer which is a group having a pentafluorophenyl group. The polymer according to claim 1.

7. R in the formula (NB) １ , R ２ , R ３ and R ４ at least one of which is a group having a pentafluorophenyl group, R １ 、 R ２ 、 R ３ and R ４ The remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R in the formula (4) ５ is a polymer which is a group having a pentafluorophenyl group. The polymer according to claim 1, wherein the polymer contains a structural unit represented by formula (4).

8. 【Chemical 11】 In formula (4), R ５ is synonymous with R in formula (1-5), a polymer. ５ ​ The polymer according to claim 1, wherein the polymer further contains a structural unit represented by formula (MA).

9. 【Chemical 12】 The polymer according to claim 1, wherein the polymer further contains a structural unit represented by formula (1-1), in formula (1-1), 【Chemical 13】 Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and when Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group.

10. The polymer according to claim 1, wherein the weight average molecular weight of the polymer is 2,000 or more and 30,000 or less.

11. 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.

12. A polymer solution containing the polymer according to any one of claims 1 to 11.

13. The polymer solution according to claim 12, which is used for forming a partition wall of an organic electroluminescence element.

14. ​ The polymer solution according to claim 12, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

15. A polymer according to any one of claims 1 to 11, And a photo radical polymerization initiator, A photosensitive resin composition.

16. A cured product formed from the photosensitive resin composition according to claim 15.

17. A structural unit represented by formula (NB), A structural unit represented by formula (MA), A polymer comprising 【Chemical Formula 14】 【Chemical Formula 15】 In formula (NB), R １ , R ２ , R ３ and R ４ at least one of which is a group having a pentafluorophenyl group, The remaining 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 R １ 、R ２ 、R ３ 、and R ４ none of which contains a substituted or unsubstituted maleimide moiety Polymer.

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