Polymer, polymer solution, photosensitive resin composition, and cured product

Abstract

To provide a polymer that has superior water repellency along with excellent developability.SOLUTION: A polymer comprises: a norbornene structural unit having a fluoroalkyl group represented by formula (NB); a norbornene structural unit having a hydroxyfluoroalkyl group; and structural units derived from maleic anhydride, including at least one structural unit selected from among a structural unit having two or more (meth)acryloyl groups and a structural unit having one (meth)acryloyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer, a polymer solution containing the polymer, a photosensitive resin composition containing the polymer solution, and a cured product of the photosensitive resin composition. [Background technology]

[0002] In the field of advanced devices such as semiconductor elements and display panels, a method has been proposed in which a photosensitive material film is processed into a fine pattern by photolithography technology, and then a functional film is uniformly coated on the fine pattern. In particular, from the viewpoint of waterproofing and wettability control, a method for imparting water repellency to a part of a component is required, and a method for forming a water-repellent fine pattern by photolithography technology has been proposed.

[0003] As a means for imparting water repellency to a pattern, a method of coating a fine pattern with a fluorine-based water repellent agent, such as a perfluoroalkyl group-containing compound, is commonly used. However, the long-chain perfluoroalkyl group-containing compound (carbon number of C8 or more) used as a water repellent agent is difficult to decompose. Therefore, there are concerns about the effects of long-chain perfluoroalkyl group-containing compounds, such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), on the environment and human body, and the development of alternatives is being widely carried out. Perfluoropolyether group-containing compounds have attracted attention as alternatives to long-chain perfluoroalkyl group-containing compounds. These compounds have low biopersistence and environmental accumulation, and exhibit high water repellency. In addition, from the viewpoint of ease of use, compounds in which the terminal having a reactive group is a hydrolyzable silane are mainly used. However, fluorine-containing silane-based water repellents do not react sufficiently with the substrate when applied to the substrate and heated, and sufficient durability cannot be obtained. In response to these problems, Patent Document 1 proposes a method for increasing the reactivity between the substrate and the film by forming a film of a perfluoropolyether group-containing silane-based water repellent agent that has been hydrolyzed in the presence of a catalyst and water. [Prior art documents] [Patent documents]

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

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

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

[0007] According to the present invention, there are provided a polymer, a polymer solution, a photosensitive resin composition, and a cured product as shown below. [1] A structural unit represented by the formula (NB), A structural unit represented by the formula (HF), A structural unit derived from maleic anhydride, which includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3), A polymer comprising: [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms, 1 , R 2 , R 3 and R 4the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a1 is 0, 1 or 2; [ka] In the formula (HF), R 21 , R 22 , R 23 and R 24 at least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group; 21 , R 22 , R 23 and R 24 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a2 is 0, 1 or 2; [ka] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, [ka] In formula (1-3), R s is a group having one (meth)acryloyl group, polymer. [2] The polymer according to item [1], The structural unit derived from maleic anhydride includes a structure represented by formula (1-2), R in the above formula (1-2) p is at least one selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d), [ka] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a (k+1)-valent organic group having 1 to 12 carbon atoms, [ka] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a single bond or a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms, [ka] In formula (1d), n is an integer from 2 to 5; R is independently a hydrogen atom or a methyl group. polymer. [3] The polymer according to item [1] or [2], The structural unit derived from maleic anhydride includes a structure represented by formula (1-3), R in the above formula (1-3) s is a group represented by formula (2a), [ka] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. [4] The polymer according to any one of items [1] to [3], The polymer, wherein the structural unit derived from maleic anhydride includes a structure represented by formula (1-4): [ka] [5] The polymer according to any one of items [1] to [4], The structural unit derived from maleic anhydride includes at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), [ka] In formula (1), R p is a group having two or more (meth)acryloyl groups, [ka] In formula (2), R s is a group having one (meth)acryloyl group, [6] The polymer according to any one of items [1] to [5], The polymer, wherein the structural unit derived from maleic anhydride further includes a structural unit represented by formula (3): [ka] [7] The polymer according to any one of items [1] to [6], The structural unit derived from maleic anhydride includes a structure represented by formula (1-1), [ka] In formula (1-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. [8] The polymer according to item [7], The structural unit derived from maleic anhydride includes at least one selected from a structural unit represented by formula (8) and a structural unit represented by formula (9), [ka] In formula (8), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R p is a group having two or more (meth)acryloyl groups, [ka] In formula (9), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R s is a group having one (meth)acryloyl group, [9] The polymer according to item [7], The structural unit derived from maleic anhydride further includes a structural unit represented by formula (5): [ka] In formula (5), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

[10] The polymer according to item [7], The structural unit derived from maleic anhydride further includes a structural unit represented by formula (6): [ka] In formula (6), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

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

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

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

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

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

[12] , The fluorine content of the polymer is 20% by mass or more and 50% by mass or less.

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

[13] .

[15] The polymer solution according to item

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

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

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

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

[16] .

[18] A structural unit represented by the formula (NB), A structural unit represented by the formula (HF), A structural unit represented by the formula (MA), A polymer comprising: [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms, 1 , R 2 , R 3 and R 4 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a1 is 0, 1 or 2; [ka] In the formula (HF), R 21 , R 22 , R 23 and R 24 at least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group; 21 , R 22 , R23 and R 24 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a2 is 0, 1 or 2; [ka] polymer. Effect of the Invention

[0008] According to the present invention, there are provided a polymer which has good developability, excellent pattern formability after curing, and a cured product thereof which has water repellency, and a photosensitive resin composition containing said polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the embodiments of the present invention will be described. In this specification, the expression "a to b" in the explanation of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less."

[0010] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, the term "alkyl group" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0011] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0012] [Polymer P] The polymer of the present invention (referred to as "polymer P" in this specification) will be described. Unless otherwise specified, structural units or compounds represented by the same structural formula have the same definitions throughout all embodiments, and preferred embodiments are also the same.

[0013] First Embodiment (Polymer P(I)) The polymer of the invention according to the first embodiment, referred to herein as "polymer P(I)", is A structural unit represented by the formula (NB) A structural unit represented by the formula (HF), and a structural unit derived from maleic anhydride, which includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3).

[0014] [ka]

[0015] In formula (NB), R 1 , R 2 , R 3 and R 4 At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms, 1 , R 2 , R 3 and R 4 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a1 is 0, 1 or 2.

[0016] [ka] In the formula (HF), R 21 , R 22 , R 23 and R 24 at least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group; 21 , R 22, R 23 and R 24 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a2 is 0, 1 or 2.

[0017] [ka]

[0018] In formula (1-2), R p is a group having two or more (meth)acryloyl groups.

[0019] [ka] In formula (1-3), R s is a group having one (meth)acryloyl group.

[0020] The polymer P(I) of this embodiment contains a combination of a structural unit derived from a cyclic olefin having a fluorine-containing alkyl group represented by formula (NB) and a structural unit derived from a cyclic olefin having a fluorine-containing hydroxyalkyl group represented by formula (HF). This allows the polymer P(I) to have both high water repellency and excellent developability. Furthermore, the structural unit represented by formula (NB) and the structural unit represented by formula (HF) are chemically robust. Therefore, the polymer P(I) containing these as structural units has a small weight loss when subjected to heat treatment and is stable.

[0021] The polymer P(I) of this embodiment contains a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3). In other words, the polymer P(I) contains either one or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). This allows the photosensitive resin composition containing the polymer P(I) to have excellent sensitivity when subjected to photolithography processing. This is believed to be because the (meth)acryloyl group contained in the structural unit represented by formula (1-2) or formula (1-3) promotes the curing reaction (polymerization reaction).

[0022] In the structural unit represented by the above formula (NB) constituting the polymer P(I), a1 is 0, 1 or 2, preferably a1 is 0 or 1, and more preferably a1 is 0.

[0023] In the structural unit represented by the above formula (NB) constituting the polymer P(I), R 1 , R 2 , R 3 and R 4 At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms, 1 , R 2 , R 3 and R 4 The remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. R 1 , R 2 , R 3 and R 4 The fluorine-containing alkyl group having 1 to 30 carbon atoms, which may constitute at least one of the above, is preferably a fluoroalkyl group having 1 to 20 carbon atoms, and more preferably a fluoroalkyl group having 1 to 15 carbon atoms. The fluoroalkyl group includes a fluorinated alkyl group in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom, and a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. R 1 , R 2 , R 3 and R 4Examples of the alkyl group having 1 to 30 carbon atoms that may constitute at least one of the above include linear or branched alkyl groups having 1 to 30 carbon atoms.

[0024] In one embodiment, R 1 , R 2 , R 3 and R 4 is a fluorine-containing alkyl group having 1 to 30 carbon atoms, and the rest are hydrogen atoms. 1 , R 2 , R 3 and R 4 Any one of R is a perfluoroalkyl group having 1 to 30 carbon atoms, and the rest are hydrogen atoms. 1 , R 2 , R 3 and R 4 When any one of them is a fluorine-containing organic group having 1 to 30 carbon atoms and the remainder is a hydrogen atom, the film-forming property of the photosensitive resin composition containing this polymer P(I) can be improved, and the water repellency of the obtained cured film can be improved.

[0025] The proportion of the structural unit represented by formula (NB) in all structural units constituting the polymer P(I) is preferably from 10 to 55 mol %, more preferably from 20 to 45 mol %, and further preferably from 25 to 40 mol %.

[0026] In the structural unit represented by the above formula (HF) constituting the polymer P(I), a2 is 0, 1 or 2, preferably a2 is 0 or 1, and more preferably a2 is 0.

[0027] In the structural unit represented by the above formula (NB) constituting the polymer P(I), R 21 , R 22 , R 23 and R 24 at least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group; 21 , R 22 , R 23 and R 24The remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. R 21 , R 22 , R 23 and R 24 The fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group, which can constitute at least one of the above, is a hydroxyfluorinated alkyl group in which at least one hydrogen of the alkyl group is substituted with a hydroxyl group and at least one hydrogen of the alkyl group is substituted with a fluorine atom, preferably a hydroxyfluoroalkyl group having 1 to 20 carbon atoms, more preferably a hydroxyfluoroalkyl group having 1 to 15 carbon atoms. R 21 , R 22 , R 23 and R 24 Examples of the alkyl group having 1 to 30 carbon atoms that may constitute at least one of the above include linear or branched alkyl groups having 1 to 30 carbon atoms.

[0028] In one embodiment, R 21 , R 22 , R 23 and R 24 is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having a hydroxy group, and the rest is a hydrogen atom. 21 , R 22 , R 23 and R 24 Any one of R is a fluoroalkyl group having 1 to 30 carbon atoms and having one hydroxyl group, and the rest are hydrogen atoms. 21 , R 22 , R 23 and R 24 When any one of them is a fluoroalkyl group having a hydroxy group having 1 to 30 carbon atoms, and the remainder is a hydrogen atom, the developability of the photosensitive resin composition containing this polymer P(I) can be improved, and the water repellency of the obtained cured film can be improved.

[0029] The proportion of the structural unit represented by formula (HF) in all structural units constituting polymer P(I) is preferably 5 to 30 mol%, more preferably 6 to 28 mol%, and further preferably 7 to 25 mol%. By setting the proportion of the structural unit represented by formula (HF) in polymer P(I) within the above range, it is possible to obtain polymer P(I) with a highly improved balance of sensitivity, alkali solubility, and water repellency.

[0030] The polymer P(I) contains a structural unit having two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2), or a structural unit having one (meth)acryloyl group represented by formula (1-3), or a combination thereof. By containing such a structural unit, the polymer P(I) has better sensitivity in exposure processing.

[0031] In the structural unit represented by formula (1-2), R p R is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 9 (meth)acryloyl groups, and more preferably a group containing 3 to 6 (meth)acryloyl groups. p By optimizing the number of (meth)acryloyl groups contained in, the sensitivity of the polymer P(I) containing the same can be further increased in exposure treatment. In addition, it becomes easier to achieve a high degree of compatibility between the sensitivity and alkali solubility of the polymer P(I).

[0032] R in formula (1-2) p is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and includes at least one selected from these. By being such a group, it tends to be easy to obtain the various effects described above.

[0033] [ka]

[0034] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a (k+1)-valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom in view of further improving sensitivity (ease of polymerization) and the like. Although k may be 2 or 3, it is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0035] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

[0036] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0037] X 1When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X above.

[0038] X 2 The (k+1)-valent organic group having 1 to 12 carbon atoms may be any group obtained by removing (k+1) hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which (k+1) hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which (k+1) hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0039] [ka]

[0040] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0041] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0042] [ka]

[0043] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. Specific embodiments and preferred embodiments of R are the same as those explained in formula (1b).

[0044] When the polymer P(I) contains a structural unit represented by formula (1-2), the proportion of the structural unit represented by formula (1-2) in all structural units of the polymer P(I) is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

[0045] In the structural unit represented by formula (1-3) which can constitute the polymer P(I), R Sis a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P(I) contains either or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), thereby achieving a good balance between the sensitivity and the developability.

[0046] R S is, for example, a group represented by the following formula (2a).

[0047] [ka]

[0048] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. X 10 As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0049] X 10 The divalent organic group X is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 The number of carbon atoms (X 10 By appropriately selecting the chain length of the structural unit represented by formula (2), the structural unit represented by formula (2) can be more easily involved in the crosslinking reaction, thereby increasing the sensitivity.

[0050] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

[0051] When the polymer P(I) contains a structural unit represented by formula (1-3), the proportion of the structural unit represented by formula (2) in all structural units of the polymer P(I) is preferably 5 to 30 mol %, more preferably 10 to 20 mol %.

[0052] When the polymer P(I) contains both the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), the total proportion of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3) in the polymer P(I) is preferably 5 to 40 mol %, more preferably 10 to 35 mol %, and even more preferably 15 to 30 mol %, based on all the structural units constituting the polymer P(I).

[0053] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (1-1) in addition to the above structural units.

[0054] [ka]

[0055] In the structural unit represented by formula (1-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q may be bonded to any carbon atom of the alkylene group of X to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, and a naphthalene ring. In the formula (1-1), an embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0056] 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.

[0057] [ka]

[0058] In formula (1a), R is a hydrogen atom or a methyl group.

[0059] When the polymer P(I) contains a structural unit represented by formula (1-1), the proportion of the structural unit represented by formula (1-1) in all structural units of the polymer P(I) is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %.

[0060] The polymer P(I) may contain a structural unit represented by formula (1-4).

[0061] [ka]

[0062] When the polymer P(I) contains a structural unit of the formula (1-1) and a structural unit of the formula (1-4), the polymer P(I) has both a (meth)acryloyl group (the "-Z" group in the formula (1-1)) and a carboxyl group represented by the formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, the polymer P(I) can be designed to have a relatively large double bond equivalent and acid value due to the presence of a polymerizable group and a carboxyl group in the same polymer molecule. It is difficult to increase the content of both the polymerizable group and the carboxyl group in other resins such as (meth)acrylic resins. The polymer P(I) can achieve both high sensitivity and developability due to the presence of such a structure.

[0063] The polymer P(I) may contain at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0064] [ka]

[0065] [ka]

[0066] In formula (1) and formula (2), R p and R s has the same meaning as in the above formula (1-1) and formula (1-2).

[0067] When the polymer P(I) contains a structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all structural units of the polymer P(I) is preferably 0.5 to 25 mol %, more preferably 1 to 18 mol %.

[0068] When the polymer P(I) contains a structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in all structural units of the polymer P(I) is preferably 0.5 to 35 mol %, more preferably 2 to 25 mol %.

[0069] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (3) in addition to the above structural units. The polymer P(I) has high alkali solubility due to the structural unit represented by formula (3). As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. The proportion of the structural unit represented by formula (3) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 2 to 7 mol %. [ka]

[0070] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (MA) in addition to the above structural units. The structural unit represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P(I) has excellent developability. When the polymer P(I) contains a structural unit represented by formula (MA), the structural unit represented by formula (MA) accounts for preferably 3 to 40 mol %, more preferably 10 to 30 mol %, of all structural units of the polymer P(I).

[0071] The polymer P(I) can contain at least one of a structural unit represented by formula (8) and a structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2), and the structural unit of formula (9) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-3).

[0072] [ka]

[0073] [ka]

[0074] In formula (8), Q, X, and Z are the same as those in formula (1-1), and R p is synonymous with formula (1-2). In formula (9), Z, Q, and X are the same as those in formula (1-1), and R S is synonymous with formula (1-3).

[0075] When the polymer P(I) contains a structural unit represented by formula (8), the proportion of the structural unit represented by formula (8) in all structural units of the polymer P(I) is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %. When the polymer P(I) contains a structural unit represented by formula (9), the proportion of the structural unit represented by formula (9) in all structural units of the polymer P(I) is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0076] The polymer P(I) may contain a structural unit represented by the following formula (5) which is composed of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-4). By containing this structural unit, both the sensitivity and the developability can be achieved in a better balance.

[0077] [ka]

[0078] In formula (5), Z, X, and Q have the same meanings as in formula (1-1). When the polymer P(I) contains a structural unit represented by formula (5), the proportion of the structural unit represented by formula (5) in all structural units of the polymer P(I) is preferably 1 to 12 mol %, more preferably 1 to 9 mol %.

[0079] From the viewpoint of the effects of the present invention, the polymer P(I) may further contain a structural unit represented by the following formula (6) consisting of two structural units represented by the formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0080] [ka]

[0081] In formula (6), Z, X, and Q have the same meanings as in formula (1-1). A plurality of Z's, a plurality of Q's, and a plurality of X's may be the same or different.

[0082] When the polymer P(I) contains a structural unit represented by formula (6), the proportion of the structural unit represented by formula (6) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 1 to 8 mol %.

[0083] The polymer P(I) may contain structural units derived from maleic anhydride represented by the formula (MA).

[0084] [ka]

[0085] The structural unit derived from maleic anhydride represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P(i) containing the structural unit has excellent developability. When the polymer P(I) contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, of all the structural units of the polymer P(I).

[0086] The content (ratio) of each structural unit contained in the polymer P(I) can be determined by the amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum,13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0087] The weight average molecular weight Mw of the polymer P(I) is, for example, 2,000 to 20,000. The weight average molecular weight Mw of the polymer P(I) is preferably 3,000 to 15,000, and more preferably 4,000 to 10,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer. The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P(I) of this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P(I) can be made uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0088] The glass transition temperature of the polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. The polymer P(I) has a relatively high glass transition temperature due to the inclusion of a structural unit represented by the formula (NB) and a structural unit represented by the formula (HF). This is preferable in that a pattern formed on a substrate can be stably present in the manufacture of a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0089] The acid value of the polymer P(I) is 30 mgKOH / g or more and 150 mgKOH / g or less, preferably 50 mgKOH / g or more and 140 mgKOH / g or less, and the double bond equivalent of the polymer P1 is 100 g / mol or more and 1,500 g / mol or less, preferably 200 g / mol or more and 1,400 g / mol or less, more preferably 200 g / mol or more and 1,300 g / mol or less. When the acid value of the polymer P(I) is 60 mgKOH / g or more, good developability can be obtained, and when the double bond equivalent is 1,500 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be increased.

[0090] If the acid value of the polymer P(I) is too large, the exposed portion may be easily dissolved during development with an alkaline developer, which may increase the amount of exposure required for photocuring or result in an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH / g. In addition, if the double bond equivalent of the polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too large), the unexposed or low-exposed areas tend to be difficult to dissolve during development with an alkaline developer, and a residual film tends to be generated during development. In addition, if the double bond equivalent is too small, crosslinking causes an excessive increase in molecular weight, which may lead to an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0091] The polymer P(I) of the present embodiment has the above-mentioned constitution, and thus its alkali dissolution rate can be 16 nm / s or more, preferably 25 nm / s or more, more preferably 27 nm / s or more, and particularly preferably 30 nm / s or more. The upper limit is not particularly limited, but may be, for example, 100 nm / s or less. In the present specification, the alkali dissolution rate is a value measured under the following conditions. (Method of measuring alkaline dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid concentration of 30 mass%. The obtained polymer solution is then spin-coated on a wafer, the PGMEA is dried, and the wafer is pre-baked at a temperature of 100°C for 2 minutes to prepare a resin film with a thickness of 1 μm ± 0.2. This resin film is immersed together with the wafer in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23°C. The immersed wafer is visually observed to measure the time until the resin film dissolves and the interference pattern disappears, and the alkaline dissolution rate (nm / sec) is calculated by dividing the film thickness before immersion (1 μm ± 0.2) by this time.

[0092] By adjusting the acid value and / or double bond equivalent of the polymer P(I), it is possible to achieve both sensitivity and developability at a higher level.

[0093] The acid value and double bond equivalent of the polymer P(I) can be determined by spectrum measurement, etc. For example, they can be determined by the following procedure (for more details, see the Examples). (1) Polymer 1 From the H-NMR chart, the areas (integral values) of the peaks corresponding to the hydrogen atoms of the carboxyl group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond are determined. (2) From the area determined in (1) and the area of ​​the peak derived from the standard substance, the amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated. (3) Convert the amount of carboxyl groups obtained in (2) into an acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) into a double bond equivalent (g / mol).

[0094] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P(I), in particular the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2).

[0095] The content (ratio) of each structural unit contained in the polymer P(I) of the present embodiment can be determined by the amount (molar amount) of the raw material charged during polymer synthesis, the amount of the raw material remaining after synthesis, the peak area of ​​each spectrum (for example, 1 It can be estimated / calculated from the H-NMR peak area, etc.

[0096] The fluorine content in the polymer P(I) is preferably 20% by mass or more and 50% by mass or less, more preferably 23% by mass or more and 45% by mass or less, and even more preferably 26% by mass or more and 42% by mass or less. By adjusting the fluorine content within such a range, a polymer P(I) having excellent water repellency and alkali solubility can be obtained.

[0097] (Production method of polymer P(I)) The polymer P(I) can be produced (synthesized) by any method. Typically, the polymer P(I) can be produced by the following steps aI, aII, and aIII. Step aI: preparing a raw polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), and a structural unit represented by formula (MA); Step aII: A step of reacting the raw polymer obtained in step aI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a polymer P(I) (sometimes referred to as "polymer precursor (a)") that contains a structural unit represented by formula (NB), a structural unit represented by formula (HF), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further contains a structural unit represented by formula (MA). Here, the structural unit represented by formula (1) contains a structure represented by formula (1-2), and the structural unit of formula (2) is a structural unit that contains a structure represented by formula (1-3).

[0098] When the polymer P(I) (polymer precursor (a)) further comprises a structural unit represented by formula (3), the following step aIII-i is carried out. Step aIII-i: In step aII, a polymer precursor (a) (corresponding to the polymer P(I) in the above step aII) containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), 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 prepared, and then the polymer precursor (a) is treated with water in the presence of a base catalyst to obtain a polymer P(I) (sometimes referred to as "polymer precursor (b)") containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), 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).

[0099] When the polymer P(I) further contains a structural unit represented by formula (1-1), the following step aIII-ii is carried out. Step aIII-ii: A step of preparing a polymer precursor (a) (corresponding to the polymer P(I) in the above step aII) containing the structural unit represented by formula (NB), the structural unit represented by formula (HF), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and optionally further the structural unit represented by formula (MA) obtained in step aII, and reacting the polymer precursor (a) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I). Here, the polymer P(I) obtained via step aII and the subsequent step aIII-ii may contain structural units represented by formula (8) and / or formula (9).

[0100] Either step aIII-i or step aIII-ii may be carried out. When both steps are carried out, it is preferable to carry out step aIII-ii after step aIII-i. When carrying out step aIII-ii after step aIII-i, step aIII-ii is a step of reacting the polymer precursor (b) obtained in step aIII-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) that may contain structural units represented by formula (8) and / or formula (9), structural units represented by formula (5), and structural units represented by formula (6).

[0101] In the case where both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used in step aII, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step aI, and then react the monofunctional (meth)acrylic compound with the resulting reaction mixture.

[0102] Each step will be described below. (Process aI) In step aI, the step of preparing a raw polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), and a structural unit represented by formula (MA) can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (HFm), and a monomer represented by formula (MAm) (maleic anhydride). 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that of formula (NB). 21 , R 22 , R 23 and R 24 The definition of is the same as that in formula (HF).

[0103] [ka]

[0104] Examples of the monomer represented by formula (NBm) include the following norbornene compounds having a fluoroalkyl group. In the polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more.

[0105] [ka]

[0106] [ka]

[0107] Examples of the monomer represented by formula (HFm) include the following norbornene compounds having a hydroxyfluoroalkyl group. In the polymerization, the monomer represented by formula (FHm) may be used alone or in combination of two or more.

[0108] [ka]

[0109] [ka]

[0110] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used. Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more kinds.

[0111] The solvent used in the polymerization reaction may be, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0112] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by formula (NBm), the monomer represented by formula (HFm), the monomer represented by formula (MAm) and a polymerization initiator in a solvent, charging the resulting solution into a reaction vessel, and then heating the resulting solution to cause addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. When charged into a reaction vessel, the molar ratio of the total amount (NBm+HFm) of the monomer represented by formula (NBm) and the monomer represented by formula (HFm) to the monomer represented by formula (MAm) is preferably (NBm+HFm):(MAm)=0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. The molar ratio of the monomer represented by formula (NBm) to the monomer represented by formula (HFm) is preferably (NBm):(HFm)=9.5:0.5 to 2:8, more preferably 9:1 to 7:3. Through such a process, a "raw polymer" can be obtained. The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0113] After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

[0114] (Step aII) In step aII, the raw polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, whereby a part of the structural unit represented by formula (MA) contained in the raw polymer is ring-opened to form a structural unit represented by formula (1) and / or a structural unit represented by formula (2), thereby obtaining a polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally containing a structural unit represented by formula (MA). The polymer precursor obtained here can be used as the polymer P(I) of this embodiment, but for convenience of explanation, it is referred to as a polymer precursor.

[0115] More specifically, first, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), etc. can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0116] When obtaining a polymer precursor that contains the structural unit represented by formula (NB), the structural unit represented by formula (HF), and both the structural unit represented by formula (1) and the structural unit represented by formula (2), next, add a polyfunctional (meth)acrylic compound to the above solution.Further, add a basic catalyst.Then, mix the solution appropriately to obtain a homogeneous solution, and obtain a polymer precursor that contains at least the structural unit represented by formula (NB), the structural unit represented by formula (HF), and the structural unit represented by formula (1) (step aII-i).

[0117] Examples of the polyfunctional (meth)acrylic compound that can be used herein include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiment of are the same as those in the above formula (1c). n and R in formula (1d-m) are the same as those in the above formula (1d).

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] Next, the polymer obtained in step aII-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor containing the structural unit of formula (NB), the structural unit of formula (HF), the structural unit of formula (1), and the structural unit of formula (2) (step aII-ii).

[0122] As the basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as catalysts. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of the raw material polymer. Note that if an excessive amount of the basic catalyst is used, the amount of acid required for neutralization increases, and purification may become complicated.

[0123] The solution is heated preferably at 60 to 80° C. for about 3 to 9 hours to open the structural unit of formula (MA) contained in the raw material polymer and form the structural unit of formula (1).

[0124] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating, the structural unit of formula (MA) contained in the raw polymer is ring-opened / the structural unit of formula (2) is formed, and a polymer P(I) having a structural unit represented by formula (2) is produced.

[0125] From the viewpoint of steric hindrance of the reaction, etc., a monofunctional (meth)acrylic compound having a hydroxyl group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxyl group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), it is preferable not to charge a monofunctional (meth)acrylic compound having a hydroxyl group into the reaction system from the beginning, but to add it to the reaction system. Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following formula (2a-m). In formula (2a-m), X10 and R is defined as in formula (2a).

[0126] [ka]

[0127] Specific examples of the compound represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

[0128] In the case of obtaining a polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), and either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of step aII-i and step aII-ii may be carried out after step (I).

[0129] (Step aIII-i) When carrying out step aIII-i, a step of treating the polymer precursor obtained in step aII with water in the presence of a basic catalyst is used. Step aIII-i causes the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII to open rings, forming a structural unit represented by formula (3), and a polymer P(I) containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (3) can be produced. When a part of the structural unit represented by formula (MA) is opened and a part of the structural unit of formula (MA) remains without being opened, the polymer P(I) further contains a structural unit represented by formula (MA).

[0130] The basic catalyst used in step aIII-i includes an amine compound such as triethylamine, pyridine, or dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.

[0131] In step aIII-i, water is added to the reaction system containing the polymer precursor obtained in step aII, and the resulting reaction solution is heated, preferably at 60 to 80° C. for about 0.25 to 6 hours, to open the structural unit of formula (MA) contained in this polymer and generate a structural unit represented by formula (3). The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII as it is. Therefore, step aIII-i is preferably carried out in situ by adding water to the reaction mixture obtained in step aII without performing any post-treatment on the reaction mixture obtained in step aII.

[0132] The polymer P(I) of this embodiment can be obtained by the above steps. From the viewpoint of the effects of the present invention, the following steps may be further appropriately carried out in order to remove unnecessary components other than the desired polymer.

[0133] First, the reaction solution diluted with an organic solvent and to which an acid (such as formic acid) has been added is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained.

[0134] The organic solution of the polymer P(I) obtained is purified using the reprecipitation method or the liquid-liquid extraction method. In the reprecipitation method, the organic solution of the polymer P(I) obtained is added to an excess amount of toluene or water to reprecipitate the polymer. The polymer powder obtained by reprecipitation is further washed several times with toluene or water. Furthermore, in order to remove formic acid and the basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (about 1 to 3 times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more to obtain a high-purity polymer. In the liquid-liquid extraction method, water or a mixed solvent of water / methanol is added to the organic solution of the polymer P(I) obtained, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and aqueous phase are separated, and the aqueous phase is removed. Furthermore, water or water / methanol is added to the organic solution of the polymer after the aqueous phase is removed, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and aqueous phase are separated, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, a step of adding water or water / methanol and removing the aqueous phase may be further performed. When water is used as the extraction solvent for liquid-liquid extraction, the remaining amount of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds tends to be large, and when water / methanol is used, the remaining amount of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds tends to be small. The obtained organic solution of polymer P(I) is concentrated by heating under reduced pressure using a rotary evaporator, and then the final solvent (PGMEA, etc.) is added to dilute the solution, and the polymer solution dissolved in the final solvent can be obtained by repeating this operation. In addition, the polymer may be further purified by reprecipitation after the solvent replacement.

[0135] The polymer solution may contain a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound used in synthesizing the polymer P(I). When the polymer solution contains these (meth)acrylic compounds, the peak area derived from the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart is preferably 3 to 50%, particularly 5 to 48%, of the peak area of ​​the polymer P(I), and the peak area derived from the monofunctional (meth)acrylic compound is preferably 1 to 50%, particularly 2 to 35%, of the peak area of ​​the polymer P(I). As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0136] (Step aIII-ii) In step aIII-ii, the polymer obtained in step aII (polymer precursor (a)) or the polymer obtained in step aIII-i (polymer precursor (b)) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, whereby a structural unit represented by formula (1-1) is formed by the reaction between the carboxyl group of the polymer precursor (a) or (b) and the epoxy group of the epoxy group-containing (meth)acrylic compound, and a polymer P (I) containing a structural unit represented by formula (NB), a structural unit represented by formula (HF), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (1-1) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit of formula (MA) remains without being ring-opened, the polymer P (I) further contains a structural unit represented by formula (MA).

[0137] Step aIII-ii is preferably carried out by additionally adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor (b) obtained in step aIII-i.

[0138] The reaction between the polymer precursor (a) or (b) and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII. Therefore, step aIII-ii is preferably carried out in situ by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in step aII without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor obtained in step aII or neutralizing the basic catalyst contained in the mixture.

[0139] Specifically, the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor is heated preferably at 60 to 80°C for about 1 to 9 hours, whereby the carboxyl group of the polymer precursor reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound to form a structural unit represented by formula (1-1), thereby producing polymer P(I).

[0140] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, and the like, and one or more selected from these can be used.

[0141] The amount of the epoxy group-containing (meth)acrylic compound added is desirably 0.1 to 3.0 mol per 1 mol of the carboxyl group of the polymer precursor.

[0142] When the polymer P(I) is a polymer obtained via the polymer precursor (a), the polymer P(I) contains a structural unit represented by formula (NB), a structural unit represented by formula (HF), a structural unit represented by formula (8), a structural unit represented by formula (9), a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (MA).

[0143] When the polymer P(I) is a polymer obtained via the polymer precursor (b), the polymer P(I) contains a structural unit represented by formula (NB), a structural unit represented by formula (HF), a structural unit represented by formula (8), a structural unit represented by formula (9), a structural unit represented by formula (5), a structural unit represented by formula (6), a structural unit represented by formula (1), a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (MA).

[0144] After the step aIII-ii, it is preferable to appropriately further carry out the following steps in order to remove unnecessary components other than the desired polymer P(I).

[0145] First, the reaction solution diluted with an organic solvent and to which an acid (e.g., formic acid, citric acid, etc.) has been added is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of polymer P(I) is obtained.

[0146] An excess amount of toluene is added to the obtained organic solution of the polymer P(I) to reprecipitate the polymer P(I), and the polymer powder obtained by the reprecipitation is further washed several times (e.g., twice) with toluene. Furthermore, in order to remove the acid or basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (for example, three times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more, to obtain a high-purity polymer P(I) of this embodiment.

[0147] Second Embodiment (Polymer P(II)) The polymer P in the second embodiment (hereinafter referred to as “polymer P(II)”) is A structural unit represented by the formula (NB) A structural unit represented by the formula (HF), and a structural unit represented by the formula (MA).

[0148] [ka]

[0149] In formula (NB), R 1 , R 2 , R 3 and R 4 At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms, 1 , R 2 , R3 and R 4 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a1 is 0, 1 or 2.

[0150] [ka]

[0151] In the formula (HF), R 21 , R 22 , R 23 and R 24 at least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxy group; 21 , R 22 , R 23 and R 24 the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a2 is 0, 1 or 2. [ka]

[0152] The polymer P(II) is a raw material polymer used in the production of the polymer P(I) in the first embodiment, and is a polymer obtained in the above-mentioned step aI.

[0153] The weight average molecular weight Mw of the polymer P(II) is, for example, 1,000 to 15,000. The weight average molecular weight Mw of the polymer P(II) is preferably 1,500 to 10,000, and particularly preferably 2,000 to 7,500. By appropriately adjusting the weight average molecular weight, it becomes possible to adjust the weight average molecular weight of the polymer P(I) obtained from this polymer P(II), and as a result, it is possible to adjust the sensitivity of the polymer P(I) and the solubility in an alkaline developer to a desired level. The dispersity of the polymer P(II) (weight average molecular weight Mw / number average molecular weight Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 4.0, and further preferably from 1.0 to 3.0.

[0154] [Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P(I). The polymer solution of this embodiment may contain at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound together with the polymer P(I).

[0155] (Polyfunctional (meth)acrylic compound) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that can be contained in the polymer solution of this embodiment may be an unreacted (meth)acrylic compound used in the above-mentioned step aII in the production of polymer P, or may be one that has been added separately.

[0156] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into the polymer solution include, but are not limited to, compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] k, R, and X in formula (1b-p) 1 , X 1 ' and X 2The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiments of are the same as those in the above formula (1c).

[0161] In formulae (1b-p), (1c-p) and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0162] The compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p) in which Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p)) or may be added separately. In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0163] When a polyfunctional (meth)acrylic compound is blended into the polymer solution of the present embodiment in addition to the unreacted polyfunctional (meth)acrylic compound used in the production of the polymer P(I), the blending amount can be such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​the polymer P(I).

[0164] (Monofunctional (meth)acrylic compound) The monofunctional (meth)acrylic compound to be blended in the polymer solution of the present embodiment includes a compound represented by the following formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0165] [ka]

[0166] When a monofunctional (meth)acrylic compound is blended into the polymer solution of the present embodiment in addition to the unreacted monofunctional (meth)acrylic compound used in the production of the polymer P(I), the blending amount can be such that the peak area attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​the polymer P(I).

[0167] The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. The organic solvent may be one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc.

[0168] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0169] [Preparation of polymer solution] The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

[0170] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment contains the above-mentioned polymer P(I) and a photopolymerization initiator. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution of the present embodiment and a photopolymerization initiator. Each component will be described below.

[0171] (Photopolymerization initiator) The photopolymerization initiator used in the photosensitive resin composition of the present embodiment may be a photoradical polymerization initiator. As the photoradical polymerization initiator, a known compound may be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl ... -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, etc.; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc.; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer P(I).

[0172] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, and therefore has excellent developability and processability in photolithography.

[0173] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0174] Examples of organic pigments that can be used include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, and dye lake pigments.

[0175] Examples of inorganic pigments that can be used include white pigments and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0176] As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

[0177] Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. When transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0178] Depending on the purpose and use, the colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc.

[0179] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and use. In order to achieve a balance between the coloring concentration and the dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0180] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0181] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied onto a substrate to obtain a resin film, making it possible to obtain a coating film of uniform thickness, and also makes it possible to prevent residues and pattern lifting during development of the coating film.

[0182] The nonionic surfactant is, for example, a compound containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorine-based surfactants include, but are not limited to, Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited. When a surfactant is used, the amount of the surfactant added is preferably 0.01 to 10% by weight based on 100 parts by weight of the resin.

[0183] (solvent) The photosensitive resin composition may typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. may be used.

[0184] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof. The amount of the solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0185] (Light blocking agent) The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

[0186] When the photosensitive resin composition contains a light-shielding agent, the amount of the light-shielding agent may be appropriately set depending on the purpose and use. In order to achieve a balance between the light-shielding performance and the dispersion stability of the light-shielding agent, the amount of the light-shielding agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0187] (Crosslinking agent) The photosensitive resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer P (capable of chemically bonding with the polymer P) through the action of active chemical species generated from the photopolymerization initiator. The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

[0188] The crosslinking agent is preferably, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

[0189] Specific examples of crosslinking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene polyfunctional (meth)acrylates such as ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether; vinyl ether group-containing (meth)acrylic acid esters, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0190] Of these, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0191] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount of the crosslinking agent may be appropriately set according to the purpose and use. As an example, the amount of the crosslinking agent may be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, relative to 100 parts by mass of the photosensitive resin.

[0192] (Other additives) The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0193] [Application] A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, and then exposing and developing the film to form a pattern.

[0194] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. EXAMPLES

[0195] EXAMPLES Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these.

[0196] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·C4F9NB: 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene C6F 13 NB: 5-perfluorohexylbicyclo[2.2.1]hept-2-ene HFANB: Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol MAN: Maleic anhydride ·GMA: Glycidyl methacrylate MEK: Methyl ethyl ketone PEMP: pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) 4-HBA: 4-Hydroxybutyl acrylate A-TMM-3LM-N: A mixture of the following two compounds. The amount of the compound on the left in the mixture based on gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0197] [ka]

[0198] <Synthesis of raw polymer> (Synthesis of raw polymer 1) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB, 381.01g, 1.221mol), maleic anhydride (MAN, 119.73g, 1.221mol), V-601, 30.14g, 0.131mol) and methyl ethyl ketone (MEK, 94.86g) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the reaction was carried out at an internal temperature of 60°C for 18 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into methanol (2000.0g) to precipitate a white solid. The obtained white solid was further washed with methanol (2000.0 g) and then vacuum dried at a temperature of 120° C. to obtain 90.50 g of a polymer (raw polymer 1) having a structural unit derived from C4F9NB and a structural unit derived from maleic anhydride.

[0199] (Synthesis of raw polymer 2) In a reaction vessel equipped with a stirrer, a condenser, and a dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB, 231.50 g, 0.742 mol), 5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C6F 13 NB, 305.84 g, 0.74 mol), maleic anhydride (MAN, 144.59 g, 1.475 mol), V-601, 36.62 g, 0.16 mol) and methyl ethyl ketone (MEK, 133.38 g) were added and stirred to dissolve. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at an internal temperature of 60°C for 18 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into methanol (1700.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1700.0 g) and then vacuum dried at a temperature of 120°C to obtain a structural unit derived from C4F9NB and a structural unit derived from C6F 13 180.42 g of a polymer (raw polymer 2) having structural units derived from NB and structural units derived from maleic anhydride was obtained.

[0200] (Synthesis of raw polymer 3) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB, 112.98 g, 0.412 mol), maleic anhydride (MAN, 40.40 g, 0.412 mol), and methyl ethyl ketone (MEK, 169.35 g) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, 2,2'-azobisisobutyrate dimethyl (Wako Pure Chemical Industries, Ltd., trade name: V-601, 3.80 g, 0.017 mol) was dissolved in MEK (14.33 g), and the solution from which the dissolved oxygen in the system had been removed by nitrogen bubbling was added over 1 hour. Then, the mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into water (3312.0 g) to precipitate a white solid. The obtained white solid was washed twice with a mixed solution of 1380.0 g of water and 460 g of methanol. The obtained white solid was washed three times with toluene (1472 g), and then vacuum dried at a temperature of 120° C. to obtain 57.94 g of a polymer (raw polymer 3) having a structural unit derived from HFANB and a structural unit derived from maleic anhydride.

[0201] (Synthesis of polymer 4) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (CFNB, 75.32 g, 0.241 mol), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., product name: V-601, 7.41 g, 0.032 mol), and methyl ethyl ketone (MEK, 10.73 g) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB, 22.05g, 0.080mol) and maleic anhydride (MAN, 31.55g, 0.322mol) were dissolved in MEK (48.87g), and the solution from which the dissolved oxygen in the system had been removed by nitrogen bubbling was added over 1 hour. Then, the mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into water (2902.0g) to precipitate a white solid. The obtained white solid was washed twice with a mixed solution of 1209.0g of water and 403g of methanol. The obtained white solid was further washed with toluene (1290 g) three times, and then vacuum dried at a temperature of 120° C. to obtain 60.83 g of a polymer (raw polymer 4) having a structural unit derived from C4F9NB, a structural unit derived from HFANB, and a structural unit derived from maleic anhydride.

[0202] (Synthesis of polymer 5) In a reaction vessel equipped with a stirrer, a condenser, and a dropping funnel, 5-perfluorohexylbicyclo[2.2.1]hept-2-ene (CF 13NB, 84.74g, 0.206mol), 2,2'-azobisisobutyrate dimethyl (Wako Pure Chemical Industries, trade name: V-601, 6.31g, 0.027mol) and methyl ethyl ketone (MEK, 11.06g) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB, 18.79g, 0.069mol) and maleic anhydride (MAN, 26.88g, 0.274mol) were dissolved in MEK (50.40g), and the solution from which the dissolved oxygen in the system was removed by nitrogen bubbling was added over 1 hour. Then, the mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into water (2940.0 g) to precipitate a white solid. The obtained white solid was washed twice with a mixed solution of 1225.0 g of water and 408 g of methanol. The obtained white solid was washed three times with toluene (1307 g), and then vacuum dried at a temperature of 120° C. to obtain CF 13 56.28 g of a polymer (raw polymer 5) having structural units derived from NB, structural units derived from HFANB, and structural units derived from maleic anhydride was obtained.

[0203] (Synthesis of raw polymer for evaluation) 588.36g (6.0 mol) of maleic anhydride, 564.90g (6.0 mol) of 2-norbornene, and 55.26g (0.24 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in a reaction vessel equipped with a stirrer and a cooling tube. These were dissolved in a mixed solvent consisting of 1716.8g of methyl ethyl ketone and 188.3g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to polymerize the maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was dropped into 14230.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3557.5 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 1027.2 g of a polymer (raw polymer for evaluation) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.83.

[0204] Table 1 below shows the charging ratio of the monomers used in the synthesis of the raw polymers, as well as the weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the raw polymers.

[0205] [Table 1]

[0206] <Synthesis of polymer P> Using the above raw polymer, polymer P was produced by the following method.

[0207] (Preparation Example 1) A resin mixture (polymer solution P1) containing polymer P1 obtained by ring-opening the MA unit of raw polymer 1 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA) was prepared. Details are described below. First, 125.45g of MEK was added to 60.00g of raw polymer 1 (0.146 mol of MA calculated from the amount of raw polymer 1) to prepare a solution. Next, 36.31g of A-TMM-3LM-N was added to this solution, and then triethylamine (18.00g, 0.178 mol) was added and reacted at a temperature of 70°C for 2 hours. Further, 4-HBA (26.36g, 0.183 mol) was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous solution of formic acid and an aqueous solution of citric acid to remove the aqueous phase from the reaction solution. Liquid-liquid extraction and subsequent solvent exchange were then performed as follows. Liquid-liquid extraction: The reaction solution was diluted with MEK, then a water / methanol mixed solvent was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was then repeated twice. Solvent replacement: The resulting reaction mixture was subjected to solvent removal at 50°C under reduced pressure using a rotary evaporator. When it was confirmed that the solid content of the polymer solution was 27±2% by mass as measured by a heat-drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content was 18% by mass, and mixed until uniform. The same operation was performed to remove the solvent at 50°C under reduced pressure, and the solid content was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content was 18% by mass, and the operation of mixing until uniform was repeated two more times. After that, the solvent was removed or PGMEA was added so that the solid content was 30±3% by mass, and the mixture was stirred until uniform. The above operation removed the solvent used in the reaction, and the solvent was replaced with PGMEA.

[0208] As a result of the above, polymer P1 was obtained in which the structural units derived from maleic anhydride (MA units) in raw polymer 1 were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P1) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution P1 was analyzed by gel permeation chromatography to measure the amounts of polymer P1, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P1. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P1 in a gel permeation chromatography (GPC) chart of the resin mixture. The measurement conditions for gel permeation chromatography are as follows. The GPC measurement device used was a Tosoh HLC-8320GPC EcoSEC. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL / min. Peak position (retention time) Polymer P1: Peak detected before 20 minutes (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Sum of two peaks, 20.0-20.6 minutes and 20.6-21.5 minutes 4-HBA: 21.7 to 22.4 minutes Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0209] Furthermore, the fluorine content of the obtained polymer P1 was measured by the following method. Approximately 100 mg of the polymer and approximately 60 mg of (trifluoromethyl)benzene as an internal standard were weighed and dissolved in approximately 1 g of acetone-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 19 F-NMR measurements were performed. The amount of CF3 (mol / g) and the amount of CF2 (mol / g) in the polymer were calculated from the integral ratio of the CF3 signal (-75 to -81 ppm, 3F) and the CF2 signal (-100 to -130 ppm, 2F) of the polymer in the obtained spectrum chart to the internal standard CF3 signal (-63 ppm, 3F). The fluorine content (wt / %) in the polymer was calculated from the total amount of the calculated CF3 amount (mol / g) and CF2 amount (mol / g) in the polymer.

[0210] (Preparation Example 2) A resin mixture (polymer solution P2) containing polymer P2 obtained by ring-opening the MA units of raw polymer 2 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA) was prepared in the same manner as in Preparation Example 1, except that raw polymer 2 60.00 g (0.130 mol in terms of MA calculated from the amount of raw polymer 2 charged) was used instead of raw polymer 1, and 32.36 g of A-TMM-3LM-N and 4-HBA (23.50 g, 0.163 mol) were used. A resin mixture (polymer solution P2) containing polymer P2 obtained by ring-opening the MA units of raw material polymer 2 with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound was prepared.

[0211] The obtained polymer solution P2 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 1 to measure the amounts of polymer P2, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P2, and the fluorine content. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P2 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0212] (Preparation Example 3) The MA unit of the raw material polymer 3 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to prepare a polymer P3. The details are described below. First, 13.11 g of MEK was added to 10 g of raw polymer 3 (0.027 moles of MA calculated from the amount of raw polymer 3 charged) to prepare a solution. Next, 4-HBA (2.42 g, 0.017 moles) was added to this solution, and then triethylamine (1.50 g, 0.015 moles) was added, and the mixture was reacted at a temperature of 70°C for 6 hours. After that, GMA (1.15 g, 0.008 moles) was added, and the mixture was reacted at a temperature of 70°C for 4 hours. The reaction solution was diluted with MEK and treated with an aqueous solution of formic acid and an aqueous solution of citric acid to remove the aqueous phase from the reaction solution. The polymer was then purified by the reprecipitation method described below. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, the structural unit derived from maleic anhydride in the raw material polymer 3 was ring-opened with the monofunctional (meth)acrylic compound (4-HBA) and reacted with GMA to obtain polymer P3. The weight average molecular weight and polydispersity of the obtained polymer P3 were measured by GPC. The fluorine content of the polymer P3 was measured in the same manner as in Preparation Example 1. The results are shown in Table 2.

[0213] Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P3, which confirmed that the obtained polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P3 had a structure in which the structural unit derived from maleic anhydride in raw material polymer 3 was ring-opened with 4-HBA, and a structure in which GMA was introduced.

[0214] (Preparation Example 4) A resin mixture (polymer solution P4) containing polymer P4 obtained by ring-opening the MA units of raw polymer 4 with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound was prepared in the same manner as in Preparation Example 1, except that raw polymer 4 60.00 g (0.150 mol in terms of MA calculated from the amount of raw polymer 4 charged) was used instead of raw polymer 1, and 37.17 g of A-TMM-3LM-N and 4-HBA (23.50 g, 0.187 mol) were used.

[0215] The obtained polymer solution P4 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 1 to measure the amounts of polymer P4, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P4, and the fluorine content. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P4 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0216] (Preparation Example 5) A resin mixture (polymer solution P5) containing polymer P5 obtained by ring-opening the MA units of raw polymer 5 with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound was prepared in the same manner as in Preparation Example 1, except that 60.00 g of raw polymer 5 (0.126 mol in terms of MA calculated from the amount of raw polymer 5 charged) was used instead of raw polymer 1, and 31.31 g of A-TMM-3LM-N and 4-HBA (22.73 g, 0.158 mol) were used.

[0217] The obtained polymer solution P5 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 1 to measure the amounts of polymer P5, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P5, and the fluorine content. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P5 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0218] (Preparation Example 6) Polymer P6 was produced in the same manner as in Preparation Example 3, except that 10.00 g of Raw Polymer 4 (0.025 mol in terms of MA calculated from the amount of Raw Polymer 4 charged) was used instead of Raw Polymer 3, and 4-HBA (2.25 g, 0.016 mol) and GMA (1.06 g, 0.007 mol) were used. The MA units of Raw Polymer 4 were ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA). The weight average molecular weight and polydispersity of the obtained polymer P6 were measured by GPC. The fluorine content of the polymer P6 was measured in the same manner as in Preparation Example 1. The results are shown in Table 2.

[0219] Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P3, which confirmed that the obtained polymer P6 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P6 had a structure in which the structural unit derived from maleic anhydride in raw material polymer 4 was ring-opened with 4-HBA, and a structure in which GMA was introduced.

[0220] (Preparation Example 7) A resin mixture (polymer solution P7) containing polymer P7 obtained by ring-opening the MA unit of raw material polymer 4 with a trifunctional (meth)acrylic compound and water was prepared. Details are described below. First, 141.07 g of MEK was added to 60.00 g of raw polymer 4 (0.150 mol of MA calculated from the amount of raw polymer 4) to prepare a solution. Next, 37.17 g of A-TMM-3LM-N was added to this solution, and then triethylamine (18.00 g, 0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Next, water (3.00 g, 0.167 mol) was added to the resulting reaction solution without post-treatment, and the reaction was carried out at 70° C. for 2 hours. The reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Liquid-liquid extraction and solvent replacement were then carried out in the same manner as in Preparation Example 1. In this way, a resin mixture (polymer solution P7) containing polymer P7 obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water was prepared.

[0221] The obtained polymer solution P7 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 1 to measure the amounts of polymer P7 and free polyfunctional (meth)acrylic compound contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P7, and the fluorine content. The results are shown in Table 2. The amount of free (meth)acrylic compound is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compound to the peak area of ​​polymer P7 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0222] (Preparation Example 8) Polymer P8 was prepared by ring-opening the MA unit of raw material polymer 5 with a monofunctional (meth)acrylic compound, as described in detail below. First, 27.66 g of MEK was added to 10.00 g of raw polymer 5 (0.021 mol in terms of MA calculated from the amount of raw polymer 5 charged) to prepare a solution. Next, 4-HBA (3.79 g, 0.026 mol) was added to this solution, and then triethylamine (3.00 g, 0.030 mol) was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the following reprecipitation method. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 5.3 g of polymer P8 was obtained in which the structural units derived from maleic anhydride in raw polymer 5 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P8 were measured by GPC measurement. The fluorine content of the polymer P8 was measured in the same manner as in Preparation Example 1. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P8, which confirmed that the obtained polymer P8 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P8 had a structure in which structural units derived from maleic anhydride were ring-opened with 4-HBA.

[0223] (Preparation of polymer for evaluation) Instead of raw polymer 3, 10.00 g of raw polymer for evaluation (0.052 moles of MA calculated from the amount of raw polymer for evaluation) was used, and 4-HBA (4.69 g, 0.033 moles) and GMA (2.22 g, 0.016 moles) were used. In the same manner as in Preparation Example 3, the MA unit of the raw polymer for evaluation was ring-opened with a monofunctional (meth)acrylic compound, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P6. GPC measurement was performed on the obtained polymer for evaluation to measure the weight average molecular weight and polydispersity of polymer P8, and the weight average molecular weight of the polymer for evaluation was 6,100 and the polydispersity was 2.20.

[0224] (Physical property evaluation) The double bond equivalent of each of the polymers P prepared in Preparation Examples 1 to 8 was measured by the method described below.

[0225] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR was measured. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 3H) derived from the acryloyl group in the obtained spectrum chart to the signal (8.1 ppm, 4H) derived from the phenyl group of the internal standard substance, and the amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 2H) derived from the phenyl group of the internal standard substance to the signal (8.1 ppm, 4H). Here, the signal derived from the methacryloyl group at 6.0-6.1 ppm was small and overlapped with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The amount of double bonds (mol / g) was calculated from the sum of the amount of acryloyl groups (mol / g) and the amount of methacryloyl groups (mol / g) in the calculated polymer, and the double bond equivalent (g / mol) was calculated from the amount of double bonds. The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of the polymer.

[0226] [Table 2]

[0227] (Examples 1 to 5, Comparative Examples 1 to 3) In each of the Examples and Comparative Examples, a resin composition was prepared and evaluated for the following items. <Evaluation> [Alkaline dissolution rate of resin composition] Polymers P3, P6 and P8 obtained in Preparation Examples 3, 6 and 8 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 6 and 8 having a solid content concentration of 30 mass %. Next, the above-mentioned resin compositions 6 and 8, or resin compositions 1, 2, 4, 5 and 7 consisting of polymer solutions P1, P2, P4, 5 and P7 obtained in Preparation Examples 1, 2, 4, 5 and 7 were spin-coated onto the wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100°C for 2 minutes to prepare a resin film with a thickness of approximately 1 μm. This resin film was immersed together with the wafer in a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 3. If the alkali dissolution rate is 16 nm / s or higher, it can be used as a photosensitive material without any problems, if it is 25 nm / s or higher, the developability can be considered to be good, if it is 270 nm / s or higher, it can be considered to be even better, and if it is 30 nm / s or higher, it can be considered to be particularly good.

[0228] [Evaluation of Water Repellency of Photosensitive Resin Composition] Water repellency evaluation was performed on mixtures of the fluorine-free evaluation polymer and the fluorine-containing polymer P of Preparation Examples 1 to 8. First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid concentration was 30 mass%. Polymers P3, P6, and P8 (polymers P in Preparation Examples 3, 6, and 8, respectively) or resin compositions 1, 2, 4, 5, and 7 (polymer solutions P1, P2, P4, P5, and P7 in Preparation Examples 1, 2, 4, 5, and 7, respectively): 5 parts by mass (Here, for Resin Compositions 1, 2, 4, 5, and 7, the solid contents (polymers P1, P2, P4, P5, and P7) and the polyfunctional (meth)acrylic compound were weighed out to be 100 parts by mass.) Polymer for evaluation: 95 parts by weight Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by weight Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight Surfactant (DIC Corporation, F-556): 0.5 parts by weight The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A having a thickness of about 2.0 μm (±0.2 μm). This thin film A was irradiated with 100 mJ / cm using a Canon g+h+i line mask aligner (PLA-501F). 2 The sample was exposed to g+h+i rays at an exposure dose of 100 nm. After exposure, the thin film was developed (with the wafer immersed) in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 60 seconds, resulting in a 100 mJ / cm 2 A thin film B was obtained by exposure and development at an exposure dose of 100 nm. The contact angle of this thin film B with water was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. Automatic Contact Angle Meter DM-501). The amount of droplets prepared was 2 μL, the observation time was 30 seconds after the droplets landed, and the average value of five measurements was taken as the contact angle with water. If the contact angle with water is 60° or more, it can be said that there is no problem with the water repellency, if it is 63° or more, the water repellency is good, if it is 67° or more, the water repellency is even better, and if it is 70° or more, the water repellency can be considered to be particularly excellent.

[0229] The results of the alkaline dissolution rate and contact angle are shown in Table 3.

[0230] [Table 3]

[0231] The photosensitive resin compositions of Comparative Examples 1 and 2, in which polymer P was a copolymer of norbornene having a fluoroalkyl group and maleic anhydride, had a large contact angle and high water repellency, but had a low alkali dissolution rate and poor developability. In the photosensitive resin composition of Comparative Example 3, in which polymer P was a copolymer of norbornene having a hydroxyfluoroalkyl group and maleic anhydride, the alkaline solubility of polymer P was very high and the developability was excellent, but the contact angle value was small and the water repellency was poor. The photosensitive resin compositions of Examples 1 to 5, in which polymer P was a copolymer of norbornene having a fluoroalkyl group, norbornene having a hydroxyfluoroalkyl group, and maleic anhydride, had alkali solubility suitable for pattern formation by photolithography, and the cured resin film had high water repellency.

Claims

1. A structural unit represented by formula (NB), A structural unit represented by formula (HF), A structural unit derived from maleic anhydride, which includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3), A polymer comprising: 【Chemistry 1】 In formula (NB), R １ , R ２ , R ３ and R ４ At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms; １ , R ２ , R ３ and R ４ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a １ is 0, 1 or 2, 【Chemistry 2】 In the formula (HF), R ２１ , R ２２ , R ２３ and R ２４ At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxyl group, ２１ , R ２２ , R ２３ and R ２４ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a ２ is 0, 1 or 2, 【Chemistry 3】 In formula (1-2), R ｐ is a group having two or more (meth)acryloyl groups, 【Chemistry 4】 In formula (1-3), R ｓ is a group having one (meth)acryloyl group; polymer.

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

3. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes a structure represented by formula (1-3), R in the formula (1-3) ｓ is a group represented by formula (2a), 【Chemistry 8】 In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group.

4. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride comprises a structure represented by formula (1-4). 【Chemistry 9】

5. 2. The polymer of claim 1 , The structural unit derived from maleic anhydride includes at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), 【Chemistry 10】 In formula (1), R ｐ is a group having two or more (meth)acryloyl groups, 【Chemistry 11】 In formula (2), R ｓ is a group having one (meth)acryloyl group.

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

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

8. 8. The polymer of claim 7, The structural unit derived from maleic anhydride includes at least one selected from a structural unit represented by formula (8) and a structural unit represented by formula (9), 【Chemistry 14】 In formula (8), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R ｐ is a group having two or more (meth)acryloyl groups, 【Chemistry 15】 In formula (9), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R ｓ is a group having one (meth)acryloyl group.

9. 8. The polymer of claim 7, The structural unit derived from maleic anhydride further includes a structural unit represented by formula (5): 【Chemistry 16】 In formula (5), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

10. 8. The polymer of claim 7, The structural unit derived from maleic anhydride further includes a structural unit represented by formula (6): 【Chemistry 17】 In formula (6), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

11. 2. The polymer of claim 1 , The polymer, wherein the structural units derived from maleic anhydride further include a structural unit represented by the formula (MA): 【Chemistry 18】

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

13. 2. The polymer of claim 1 , The fluorine content of the polymer is 20% by mass or more and 50% by mass or less.

14. A polymer solution comprising the polymer according to any one of claims 1 to 13.

15. 15. The polymer solution of claim 14, The polymer solution further comprises a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

16. A polymer according to any one of claims 1 to 13, A photoradical polymerization initiator, Photosensitive resin composition.

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

18. A structural unit represented by formula (NB), A structural unit represented by formula (HF), A structural unit represented by formula (MA), A polymer comprising: 【Chemistry 19】 In formula (NB), R １ , R ２ , R ３ and R ４ At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms; １ , R ２ , R ３ and R ４ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a １ is 0, 1 or 2, 【Chemistry 20】 In the formula (HF), R ２１ , R ２２ , R ２３ and R ２４ At least one of R is a fluorine-containing alkyl group having 1 to 30 carbon atoms and having at least one hydroxyl group, ２１ , R ２２ , R ２３ and R ２４ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a ２ is 0, 1 or 2; 【Chemistry 21】 polymer.

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