Polymer, polymer solution, photosensitive resin composition and cured product

Abstract

To provide a polymer excellent in sensitiveness, having high alkali solubility and reduced in yellowing.SOLUTION: A polymer has a structure represented by formula (P2). In the formula (P2), n is an integral number of 1-6; p and q represent molar contents of structural unit A and B included in every polymer chain in n []; p and q may be the same or different in every polymer chain in n []; p+q=1; p is 0 or more, and q is 0 or more; X is an organic group with H or C number of 1-30; Y is a 1-30C monovalent-hexavalent organic group derived from a thiol group-containing compound of mono function or 2 or more functions; A represents a structural unit including a styrene structure; B includes a structure having a (meth)acrylic group; and A and B present in a plurality of numbers may be the same or different.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] Liquid crystal display devices and solid-state imaging devices typically include optical components such as color filters, black matrices, spacers (e.g., photospacers, colored spacers, and black spacers), partition materials (e.g., transparent banks and black banks), lenses, and optical filters. Color filters, black matrices, spacers, partition materials, and optical components are configured by forming structures such as patterns and protective films on substrates. Among these structures, photolithography using photosensitive resin compositions is the mainstream method for forming patterns and protective films. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin having, at least in its side chain, a group containing an acidic group and two or more different polymerizable unsaturated groups, a polymerizable compound, and a photopolymerization initiator. Furthermore, an example in Patent Document 1 describes the synthesis of a methacrylic acid / allyl methacrylate / glycidyl adduct as the alkali-soluble resin, and the preparation of a photosensitive resin composition using this. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 147706 Summary of the Invention [Problem to be solved by the invention]

[0004] Photosensitive resin compositions for forming color filters, black matrices, spacers, partition walls, or optical components use resins that undergo polymerization and hardening under light. Color filters, black matrices, spacers, partition walls, or optical components are produced by patterning a photosensitive resin composition through exposure and development, followed by curing. While achieving high sensitivity is generally considered a common goal for photosensitive resin compositions, the increasing complexity and widespread use of display devices and imaging devices has led to a demand for even higher levels of sensitivity. The higher the sensitivity of a photosensitive resin composition, the shorter the exposure time required, improving productivity. Furthermore, photosensitive resin compositions are required to have excellent processability in development processes using alkaline developers. Furthermore, the cured product of a photosensitive resin composition is required to have high transparency. [Means for solving the problem]

[0005] The present inventors have discovered that by improving the polymer used in a photosensitive resin composition and the formulation of the composition, it is possible to obtain a cured resin product that has good sensitivity, high alkali solubility, and reduced yellowing, and have arrived at the present invention.

[0006] According to the present invention, there are provided the following polymer, polymer solution, photosensitive resin composition, and cured product. [1] A polymer having a structure represented by formula (P2): [ka] In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each of the n polymer chains in the brackets [ ], p and q may be the same or different for each of the n polymer chains in the brackets [ ]; p+q=1, p is greater than or equal to 0, and q is greater than or equal to 0; The molar contents of the structural units A and B contained in the polymer are respectively represented by pt , and q t Then, p t +q t = 1, and p t is between 0.55 and 0.85, and q t is between 0.15 and 0.45, X is hydrogen or an organic group having 1 to 30 carbon atoms; Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or di- or higher functional thiol group-containing compound, A represents a structural unit represented by formula (ST), B includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3), Multiple A's and multiple B's may be the same or different, [ka] In the formula (ST), R 40 , R 41 and R 42 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 43 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [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 B 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 fused to form a cyclic group. [3] The polymer according to item [1] or [2], The structural unit B includes a structure represented by formula (1-4): [ka] polymer. [4] The polymer according to any one of items [1] to [3], The structural unit B includes at least one selected from the structural unit represented by formula (1) and the 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, a polymer. [5] The polymer according to any one of items [1] to [4], The structural unit B includes a structural unit represented by formula (3): [ka] polymer. [5] The polymer according to any one of items [1] to [4], The structural unit B includes a structural unit represented by formula (MA): [ka] polymer. [7] The polymer according to any one of items [1] to [6], The structural unit B includes a structure represented by the 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), [ka] 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, [ka] In formula (1c), k, R, X 1 and X 2 are k, R, and X in equation (1b), respectively. 1 and X 2 and plural R may be the same or different, and plural X 1 may be the same or different from each other, X 3 is a single bond or a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms, [ka] In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group. polymer. [8] The polymer according to any one of items [1] to [7], The structural unit B includes a structure represented by the formula (1-3), R in the formula (1-3) s is a group represented by formula (2a), [ka] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. [9] The polymer according to any one of items [1] to [8], The polymer, wherein the thiol group-containing compound is at least one compound selected from the compounds represented by formulae (s-1) to (s-21). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[10] The polymer according to any one of items [1] to [9], The polymer has a weight average molecular weight of 3,000 or more and 30,000 or less.

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

[10] , A polymer, wherein the yellow index of a 25% by mass solution of the polymer in propylene glycol monomethyl ether acetate is 4.0 or less.

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

[11] .

[13] The polymer solution according to item

[12] , A polymer solution used to form color filters, black matrices, spacers, partition materials, or optical components.

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

[11] , a photoradical polymerization initiator; Photosensitive resin composition.

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

[14] . [Effects of the Invention]

[0007] According to the present invention, there is provided a polymer which has good sensitivity and high alkali solubility, and therefore excellent developability, and which also exhibits reduced yellowing, thereby giving a cured product with high transparency. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram (cross-sectional view) schematically illustrating an example of the structure of a liquid crystal display device and / or a solid-state imaging device. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by similar reference numerals, and their description will be omitted where appropriate. Furthermore, all drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual products. In this specification, the expression "a to b" in the description of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less."

[0010] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups having no substituents and groups having a substituent. For example, the term "alkyl group" encompasses 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" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" used herein represents a concept that encompasses both 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 and preferred embodiments in all embodiments.

[0013] Polymer P of this embodiment has a structure represented by formula (P2). Polymer P has a structure in which a polymer chain composed of structural units A and B described in detail below is bonded to a mono- to hexavalent organic group having 1 to 30 carbon atoms, which is represented by "Y" in the formula and is derived from a monofunctional or di- or higher functional thiol group-containing compound. This mono- to hexavalent organic group having 1 to 30 carbon atoms and derived from a mono- or di- or higher functional thiol group-containing compound is typically an organic group having 1 to 30 carbon atoms and containing 1 to 6 thioether groups.

[0014] [ka]

[0015] In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each of the n polymer chains in the brackets [ ], p and q may be the same or different for each of the n polymer chains in the brackets [ ]; p+q=1, p is greater than or equal to 0, and q is greater than or equal to 0; The molar contents of the structural units A and B contained in the polymer are respectively represented by p t , and q t Then, p t +q t =1, p t is 0.55 to 0.85, preferably 0.57 to 0.80, and more preferably 0.60 to 0.75. q t is 0.15 to 0.45, preferably 0.20 to 0.43, and more preferably 0.25 to 0.40. X is hydrogen or an organic group having 1 to 30 carbon atoms. Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or di- or higher functional thiol group-containing compound. A represents a structural unit represented by formula (ST). B includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3). A plurality of As, Bs, and Cs may be the same or different.

[0016] [ka]

[0017] In the formula (ST), R 40 , R 41 and R 42 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 43 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0018] [ka]

[0019] In formula (1-2), R p is a group having two or more (meth)acryloyl groups.

[0020] [ka]

[0021] In formula (1-3), R s is a group having one (meth)acryloyl group.

[0022] The polymer P of this embodiment contains a styrene-derived structural unit represented by formula (ST) as the structural unit A. The structural unit represented by formula (ST) is chemically robust. Therefore, the polymer P containing this structural unit undergoes little weight loss when subjected to heat treatment and is stable. A photosensitive resin composition containing the polymer P containing the structural unit represented by formula (ST) can be suitably used to produce films and filters for use in liquid crystal displays and solid-state imaging devices that require heat resistance. By setting the proportion of the structural unit represented by formula (ST) in the polymer P to fall within the above range, the heat resistance of the polymer P can be improved, and the balance between sensitivity, alkali solubility, and heat discoloration resistance can be improved to a high level.

[0023] Furthermore, polymer P of this embodiment contains, as structural unit B, a structural unit derived from maleic anhydride, including a structure represented by formula (1-2) and / or a structure represented by formula (1-3). In other words, polymer P contains either or both of a structure represented by formula (1-2) and a structure represented by formula (1-3). This allows a photosensitive resin composition containing polymer P to have excellent sensitivity when subjected to photolithography processing. This is thought to be because the (meth)acryloyl group contained in the structure represented by formula (1-2) or formula (1-3) promotes the curing reaction (polymerization reaction).

[0024] The polymer P of this embodiment contains a group represented by "Y" in formula (P2), where "Y" is a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms (referred to as "organic group (i)" in this specification) derived from a monofunctional or di- or higher functional thiol group-containing compound. By containing such an organic group (i), the polymer P has excellent sensitivity in photolithography and higher alkali solubility, and therefore can provide a cured resin product with excellent developability.

[0025] The polymer P represented by formula (P2) of this embodiment contains a structural unit represented by formula (ST) as the structural unit A and an organic group (i) represented by Y. In the polymer P, the structural unit A is present in an amount of 0.55 to 0.85 mol % in the polymer P. Generally, polymers containing structural units derived from thiol group-containing compounds have a yellow color. However, due to the above-described structure, the polymer P of this embodiment has a reduced yellow color and is colorless and transparent, despite containing the organic group (i), which is a structural unit derived from a thiol group-containing compound.

[0026] The structural units contained in the polymer P of this embodiment will be described in detail below. In the structural unit represented by formula (ST) constituting the structural unit A of the polymer P represented by formula (P2), R 40 , R 41 and R 42 Examples of organic groups having 1 to 3 carbon atoms that can constitute R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 40 , R 41 and R 42 is preferably a hydrogen atom.

[0027] R in formula (ST) 43Examples of the organic group having 1 to 30 carbon atoms that can constitute the above include substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic hydrocarbon groups, alkoxy groups, and heterocyclic groups having 1 to 30 carbon atoms, as well as carboxy groups. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups.

[0028] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0029] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

[0030] Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0031] R in the structural unit represented by formula (ST) 43 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. 40 , R 41 and R 42 , and R 43 By appropriately selecting R, the alkali solubility of the resulting polymer P can be adjusted. 43 By making is a lower alkyl group, the alkali solubility of the resulting polymer P can be controlled. In addition, R 43 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxy group, a carboxy group, etc. More specifically, R 43 As an organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected.

[0032] The proportion of the structural units represented by formula (ST) in all structural units constituting polymer P is 55 to 85 mol %, preferably 60 to 80 mol %, and more preferably 65 to 80 mol %. By setting the proportion of the structural units represented by formula (ST) in polymer P within the above range, the heat resistance of polymer P can be improved, and the balance between sensitivity, alkali solubility, and heat discoloration resistance can be improved to a high level.

[0033] In the structure containing two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2) constituting the structural unit B of the polymer P represented by formula (P2), and / or the structure containing one (meth)acryloyl group represented by formula (1-3), R p 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. pBy optimizing the number of (meth)acryloyl groups contained in the polymer P, the sensitivity of the polymer P containing the polymer P in the exposure process can be further increased. Furthermore, it becomes easier to achieve a high degree of compatibility between the sensitivity and alkali solubility of the polymer P. Furthermore, the heat resistance of the polymer P can be improved.

[0034] 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, the above-mentioned various effects tend to be easily obtained.

[0035] [ka]

[0036] 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.

[0037] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 is an alkylene group having 1 to 6 carbon atoms, X 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2- (methylene group).

[0038] X 1 is a group represented by -ZX- (wherein 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 of 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group of 1 to 3 carbon atoms, and even more preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0039] X 1 When X ′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′—, specific embodiments of X′ are the same as those of X above.

[0040] 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 refers to, 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 obtained by removing (k+1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing (k+1) hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxy group). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2may 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).

[0041] [ka]

[0042] In formula (1c), k, R, X 1 and X 2 are k, R, and X in equation (1b), respectively. 1 and X 2 and plural R may be the same or different, and plural X 1 may be the same or different from each other, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0043] k, R, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of formula (1b) 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 Examples of the divalent organic group having 1 to 6 carbon atoms include a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0044] [ka]

[0045] 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).

[0046] When the polymer P contains a structure represented by formula (1-2), the proportion of the structure represented by formula (1-2) in all structural units of the polymer P is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

[0047] In the structure represented by formula (1-3) which can constitute the polymer P, R S is a group containing only one (meth)acryloyl group. In particular, in the design of a typical photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much, resulting in poor developability, while when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P contains either or both of a structural unit represented by formula (1-2) and a structure represented by formula (1-3), thereby achieving a good balance between sensitivity and developability.

[0048] R S is, for example, a group represented by the following formula (2a).

[0049] [ka]

[0050] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10The divalent organic group is preferably, for example, an alkylene group. Some of the -CH2- in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0051] 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.

[0052] 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, such as a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxy groups, and the like.

[0053] When the polymer P contains a structural unit represented by formula (1-3), the proportion of the structural unit represented by formula (1-3) in all structural units constituting the polymer P is preferably 5 to 30 mol %, more preferably 10 to 20 mol %.

[0054] Furthermore, when polymer P contains both the structure represented by formula (1-2) and the structure represented by formula (1-3), the total proportion of the structure represented by formula (1-2) and the structure represented by formula (1-3) in polymer P is preferably 5 to 40 mol %, more preferably 10 to 35 mol %, and even more preferably 15 to 30 mol %, based on all structural units constituting polymer P.

[0055] In polymer P represented by formula (P2), "Y" is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound. Here, the valence of "Y" is the number of functional groups (the number of thiol groups). That is, a monofunctional or difunctional or higher functional thiol group-containing compound contains one or more thiol groups, and organic group (i) bonds to the structural units in [ ]n via 1 to 6 thioether groups derived from the thiol groups. Organic group (i) may have a thiol group that is not involved in the bond with the structural units in [ ]n, and polymer P can be obtained as a mixture of resins where the number of n (the number of bonds) is 1 to 6. The organic group (i) having 1 to 30 carbon atoms is monofunctional or difunctional or higher, preferably difunctional or higher, more preferably trifunctional or higher. There is no particular upper limit, but it is hexafunctional or lower. In view of the effects of the present invention, the valence of the organic group (i) having 1 to 30 carbon atoms is, for example, monovalent to hexavalent, preferably divalent to hexavalent, and more preferably trivalent to hexavalent.

[0056] The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P, and Si. Examples of the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, and heterocyclic groups each having 1 to 6 thioether groups (-S-* (* represents a bond)).

[0057] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include allyl, pentenyl, and vinyl groups.

[0058] Alkynyl groups include ethynyl groups. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group.

[0059] Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0060] Examples of monofunctional or difunctional or higher functional thiol group-containing compounds from which Y in formula (P2) can be derived include compounds represented by the following chemical formulae (s-1) to (s-21). That is, polymer P contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, which is derived from a monofunctional or difunctional or higher functional thiol group-containing compound typified by the following:

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065]

change

[0066]

change

[0067]

change

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074]

change

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] The difunctional or higher functional thiol group-containing compound may be used alone or in combination of two or more. Among them, it is preferable to use a trifunctional to hexafunctional (tri- to hexavalent) thiol group-containing compound having 3 to 6 thiol groups in one molecule, because it has excellent reactivity with other monomers. In this embodiment, the monofunctional or bifunctional or higher functional thiol group-containing compound preferably includes, among the compounds represented by the above formulas (s-1) to (s-21), compounds represented by formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10), and particularly preferably includes compounds represented by formulas (s-1) to (s-3), (s-5), and (s-9).

[0083] When a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) is used as the difunctional or higher thiol group-containing compound, the polymer P of this embodiment can have, for example, a structure represented by the following formula (I).

[0084] [ka]

[0085] In formula (I), A, B, X, p, and q have the same meanings as those in formula (P2). However, for the sake of explanation, in formula (I), p and q for each polymer chain in the four brackets [ ] are respectively represented by p 1 ~p 4 , q 1 ~q 4 It is written as follows. In formula (I), p 1 ~p 4 , q 1 ~q 4 may be the same or different for each polymer chain in the four [ ], and p 1 +q 1 =1, p 2 +q 2 =1, p 3 +q 3 =1, p 4 +q 4 =1. The molar contents of the structural units A and B contained in the polymer represented by formula (I) are respectively represented by p t and q t Then, p t =p 1 +p 2 +p 3 +p 4 , q t =q 1 +q 2 +q 3 +q 4 is.

[0086] In formula (I), the bonding order of A and B is not particularly limited, and either A or B may be bonded to the thioether group. Furthermore, in formula (I), an example is shown in which the compound represented by chemical formula (s-2) is bonded to the four structural units in [ ] via thioether groups derived from the four mercapto groups. However, the compound may have a structure in which 1 to 3 structural units in [ ] are bonded to the thioether groups derived from the four mercapto groups, and an organic group different from the structural units in [ ] is bonded to the remaining thioether group. In this embodiment, polymer P can be obtained as a mixture containing at least one compound to which 1 to 4 structures in [ ] are bonded.

[0087] The polymer P may contain, as a part of the structural unit B, a structure represented by formula (1-1).

[0088] [ka]

[0089] In the structure 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 having 1 to 6 carbon atoms 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 group having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms 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 an alkyl group and X is an 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 formula (1-1), an embodiment in which X is 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.

[0090] More specifically, in formula (1-1), an embodiment in which X is 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 an acryloyl group (-C(=O)-CH=CH2) or a methacryloyl group (-C(=O)-C(CH3)=CH2) is preferably used.

[0091] [ka]

[0092] In formula (1a), R is a hydrogen atom or a methyl group.

[0093] When polymer P contains a structure represented by formula (1-1), the proportion of the structure represented by formula (1-1) in all structural units constituting polymer P is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %.

[0094] The polymer P may contain, as a part of the structural unit B, a structure represented by formula (1-4).

[0095] [ka]

[0096] When polymer P contains the structure of formula (1-1) and the structure of formula (1-4), polymer P has both a (meth)acryloyl group (the "-Z" group in formula (1-1)) and a carboxyl group represented by formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. Because polymer P contains both a polymerizable group and a carboxyl group in the same polymer molecule, the double bond equivalent and acid value can be designed to be relatively large. It is difficult to increase the content of both polymerizable groups and carboxyl groups in other resins, such as (meth)acrylic resins. Because polymer P has this structure, it can achieve high levels of both sensitivity and developability.

[0097] In one embodiment, polymer P may include structural units derived from maleic anhydride represented by formula (MA).

[0098] [ka]

[0099] The structural unit derived from maleic anhydride represented by formula (MA) undergoes ring-opening in an alkaline developer to generate two carboxyl groups (structural unit represented by formula (3) below). Therefore, polymer P containing this structural unit has excellent developability. When polymer P contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) preferably accounts for 1 to 35 mol %, more preferably 2 to 30 mol %, of all structural units of polymer P.

[0100] In one embodiment, polymer P may contain a structural unit derived from maleic anhydride and represented by formula (3). Polymer P has high alkali solubility due to the structural unit represented by formula (3). As a result, a photosensitive resin composition containing polymer P exhibits 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 polymer P is preferably 1 to 10 mol %, more preferably 2 to 7 mol %.

[0101] [ka]

[0102] In one embodiment, the polymer P may include at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0103] [ka]

[0104] [ka]

[0105] In formula (1) and formula (2), R p and R s has the same meaning as in the above formula (1-2) and formula (1-3).

[0106] When polymer P contains a structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all structural units of polymer P is preferably 0.5 to 25 mol %, more preferably 1 to 18 mol %.

[0107] When the polymer P 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 is preferably 0.5 to 35 mol %, more preferably 2 to 25 mol %.

[0108] In one embodiment, the polymer P may include 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).

[0109] [ka]

[0110] [ka]

[0111] In formula (8), Q, X, and Z have the same meanings as in formula (1-1), and R p has the same meaning as in formula (1-2). In formula (9), Z, Q, and X are the same as in formula (1-1), and R S has the same meaning as in formula (1-3).

[0112] When polymer P contains a structural unit represented by formula (8), the proportion of the structural unit represented by formula (8) in all structural units of polymer P is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %. When polymer P contains a structural unit represented by formula (9), the proportion of the structural unit represented by formula (9) in all structural units of polymer P is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0113] In one embodiment, the polymer P may contain a structural unit represented by the following formula (5), which is composed of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-4). By containing this structural unit, both sensitivity and developability can be achieved in a better balance.

[0114] [ka]

[0115] In formula (5), Z, X, and Q have the same meanings as in formula (1-1). When the polymer P 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 is preferably 1 to 12 mol %, more preferably 1 to 9 mol %.

[0116] The polymer P may contain a structural unit represented by the following formula (6), which is composed of two structural units represented by formula (1-1). By containing this structural unit, sensitivity can be further improved.

[0117] [ka]

[0118] In formula (6), Z, X, and Q have the same meanings as in formula (1-1). A plurality of Zs, a plurality of Qs, and a plurality of Xs may be the same or different.

[0119] When polymer P contains a structural unit represented by formula (6), the proportion of the structural unit represented by formula (6) in all structural units of polymer P is preferably 1 to 10 mol %, more preferably 1 to 8 mol %.

[0120] The content (ratio) of each structural unit contained in polymer P can be determined by the amount (molar amount) of raw materials used in synthesizing the polymer, the amount of raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence and area of ​​peaks in the C-NMR spectrum.

[0121] The weight-average molecular weight Mw of the polymer P is, for example, 3,000 to 30,000. The weight-average molecular weight Mw of the polymer P is preferably 3,500 to 20,000, and more preferably 4,000 to 10,000. By appropriately adjusting the weight-average molecular weight, it is possible to adjust the sensitivity and solubility in an alkaline developer. The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P of this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P can be made uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0122] The glass transition temperature of the polymer P is preferably 50 to 250°C, more preferably 70 to 230°C, and the polymer P has a relatively high glass transition temperature. This is preferable in that a pattern formed on a substrate can be stably present when producing 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).

[0123] The acid value of polymer P is 60 mgKOH / g or more and 150 mgKOH / g or less, preferably 70 mgKOH / g or more and 140 mgKOH / g or less, and the double bond equivalent of polymer P1 is 100 g / mol or more and 1,500 g / mol or less, preferably 200 g / mol or more and 1,300 g / mol or less, more preferably 200 g / mol or more and 1,200 g / mol or less. When the acid value of the polymer P is 60 mgKOH / g or more, good developability can be obtained. When the double bond equivalent is 1,500 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P can be increased.

[0124] If the acid value of the polymer P 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. Furthermore, if the double bond equivalent of the polymer P is too small (i.e., if the density of double bonds in the polymer is too large), the unexposed and lightly exposed areas tend to be less soluble during development with an alkaline developer, and a residual film tends to be generated during development. Furthermore, if the double bond equivalent is too small, crosslinking may result in an excessive increase in molecular weight, which may result in an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0125] By virtue of the above-described configuration, the polymer P of this embodiment can have an alkaline dissolution rate of 150 nm / s or more, preferably 200 nm / s or more, more preferably 250 nm / s or more, and particularly preferably 300 nm / s or more. The upper limit is not particularly limited, but may be, for example, 1000 nm / s or less. In the present specification, the alkaline dissolution rate is a value measured under the following conditions: (Method for measuring alkaline dissolution rate) Polymer P is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solids concentration of 30% by mass. The resulting polymer solution is then spin-coated onto a wafer, the PGMEA is dried, and the wafer is pre-baked at 100°C for 2 minutes to prepare a resin film with a thickness of 2 μm ± 0.2 μm. This resin film is then immersed, along with the wafer, in a 0.5% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) at 23°C. The immersed wafer is visually observed to measure the time until the resin film dissolves and the interference pattern disappears. The alkaline dissolution rate (nm / sec) is calculated by dividing the film thickness (2 μm ± 0.2 μm) before immersion by this time.

[0126] By adjusting the acid value and / or double bond equivalent of the polymer P, it is possible to achieve both higher levels of sensitivity and developability.

[0127] The acid value and double bond equivalent of polymer P can be determined by spectroscopic measurement, etc. For example, they can be determined by the following procedures (i) to (iii) (see the Examples for more details). (i) Polymer1 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. (ii) The amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated from the area calculated in (i) above and the area of ​​the peak derived from the standard substance. (iii) The amount of carboxyl groups determined in (ii) above is converted into an acid value (mgKOH / g), and the amount of polymerizable carbon-carbon double bonds determined in (ii) above is converted into a double bond equivalent (g / mol).

[0128] The acid value and double bond equivalent weight of polymer P can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P, particularly the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl groups contained in the structural units represented by formula (1) or formula (2).

[0129] The content (ratio) of each structural unit contained in the polymer P of this embodiment can be determined by the amount (molar amount) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak areas of various spectra (for example, 1 It can be estimated / calculated from the H-NMR peak area, etc.

[0130] The polymer P of this embodiment has the above-described configuration, which reduces coloration, particularly yellowing, and improves colorless transparency. For example, the polymer P of this embodiment has a yellow index of 4.0 or less, preferably 3.0 or less, when dissolved in a 25% by mass propylene glycol monomethyl ether acetate solution. In this specification, the yellow index of a polymer solution is measured under the following conditions. (Yellow index measurement of polymer solution) The weighed polymer P is dissolved in propylene glycol monomethyl ether acetate to prepare a polymer P solution with a concentration of 25% by mass. The obtained polymer P solution is placed in a quartz cell with an optical path length of 1.0 cm, and the yellow index is measured using a spectrophotometer (Konica Minolta's "Colorimeter CR-5"). In this case, the measurement type is transmission measurement, and a quartz cell with an optical path length of 1.0 cm and no solution is used for 100% calibration.

[0131] (Method of manufacturing polymer P) The polymer P can be produced (synthesized) by any method. Typically, the polymer P can be produced by the following steps I, II, and III.

[0132] Step I: preparing a raw material polymer containing a structural unit represented by formula (ST), a structural unit represented by formula (MA), and a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; Step II: A step of reacting the raw material polymer obtained in Step I with a compound having a hydroxy group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxy group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, to prepare a first polymer precursor (a) containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), 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).

[0133] When the polymer P further contains a structural unit represented by formula (3), the following step III-i is carried out after step II: Step III-i is an optional step that is carried out as needed. Step III-i: A step of treating polymer precursor (a) with water in the presence of a base catalyst to obtain a second polymer precursor (referred to as "polymer precursor (b)") containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), 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).

[0134] When the polymer P contains a structural unit represented by formula (1-1), step III-ii is carried out after step II or step III-i. Step III-ii is an optional step that is carried out as needed. Step III-ii: A step of reacting the second polymer precursor (a) obtained in Step II or the second polymer precursor (b) obtained in Step III-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), a structural unit represented by formula (1-1), and optionally further containing a structural unit represented by formula (MA).

[0135] Either step III-i or step III-ii may be carried out. When both steps are carried out, step III-ii is preferably carried out after step III-i. The polymer P obtained by bypassing step III-i and going through steps II and III-ii may contain structural units represented by formula (8) and / or formula (9). When step II, step III-i, and step III-ii are carried out, step III-ii is a step of reacting the polymer precursor (b) obtained in step III-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P 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).

[0136] Each step will be described below. (Process I) In step I, the step of preparing a raw material polymer containing a structural unit represented by formula (ST), a structural unit represented by formula (MA), and a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (STm) and maleic anhydride in the presence of a monofunctional or di- or higher functional thiol group-containing compound. Here, R in formula (STm) 40 , R 41 , R 42 and R 43 The definition of is the same as that of formula (ST).

[0137] (Monomer represented by formula (STm)) [ka]

[0138] Examples of the monofunctional or bifunctional or higher functional thiol group-containing compound include, but are not limited to, the compounds represented by the above formulas (s-1) to (s-21). The monofunctional or bifunctional or higher functional thiol group-containing compound may be used alone or in combination of two or more.

[0139] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferred. Examples of the polymerization initiator that can be used include azo compounds and organic peroxides. 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.

[0140] 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.

[0141] The raw polymer is synthesized by dissolving the monomer represented by formula (STm), maleic anhydride, and a polymerization initiator in a solvent, charging the resulting solution into a reaction vessel, and then heating the mixture to cause addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. When they are charged into a reaction vessel, the molar ratio of the monomer represented by formula (STm) to maleic anhydride (MAm) is preferably (STm):(MAm)=0.55:0.45 to 0.85:0.15.

[0142] The raw polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. Typically, it is a random copolymer or a block copolymer.

[0143] After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw polymer and low-molecular-weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol, 2-propanol, or 1-butanol to precipitate the monomer. The precipitate is filtered and dried, thereby increasing the purity of the raw polymer.

[0144] (Process II) In step II, the starting polymer obtained in step I is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, causing ring-opening of some of the structural units represented by formula (MA) contained in the starting polymer, forming structural units represented by formula (1) and / or structural units represented by formula (2). This produces a polymer precursor containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), and structural units represented by formula (1) and / or structural units 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 of this embodiment, but for convenience of explanation, it will be referred to as "polymer precursor (a)."

[0145] More specifically, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. The organic solvent may be a single solvent or a mixture of solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or tetrahydrofuran (THF). However, the organic solvent is not limited to these, and various organic solvents used in the synthesis of organic compounds or polymers may be used.

[0146] To obtain a polymer precursor (a) containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), and both a structural unit represented by formula (1) and a structural unit represented by formula (2), a polyfunctional (meth)acrylic compound is then added to the above solution. A basic catalyst is then added. The solution is then appropriately mixed to obtain a homogeneous solution, thereby obtaining a polymer precursor (a') containing at least a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), and a structural unit represented by formula (1) (Step II-i).

[0147] 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). 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).

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] Next, the polymer precursor (a') obtained in step II-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor (a) containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit of formula (ST), a structural unit of formula (1), and a structural unit of formula (2) (step II-ii).

[0152] As the basic catalyst, amine compounds, nitrogen-containing heterocyclic compounds, and the like 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 polymer. Note that if an excess amount of the basic catalyst is used, a large amount of acid is required for neutralization, which may make purification more complicated.

[0153] The solution is heated preferably at 60 to 80° C. for about 3 to 9 hours to open the structural units of formula (MA) contained in the raw polymer and form structural units of formula (1).

[0154] For example, by adding a monofunctional (meth)acrylic compound having a hydroxy 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 precursor (a) having the structural unit represented by formula (2) is produced.

[0155] In terms of steric hindrance of the reaction, monofunctional (meth)acrylic compounds having a hydroxy group tend to react more easily with the raw material polymer than polyfunctional (meth)acrylic compounds having a hydroxy group. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable to add the monofunctional (meth)acrylic compound having a hydroxy group to the reaction system rather than to charge it into the reaction system from the beginning. Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 and R are defined as in formula (2a).

[0156] [ka]

[0157] 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.

[0158] When obtaining a polymer precursor (a) containing a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by formula (ST), and either a structural unit represented by formula (1) or a structural unit represented by formula (2), it is sufficient to carry out only one of steps II-i and II-ii after step I.

[0159] (Step III-i) When carrying out step III-i, the polymer precursor (a) obtained in step II is treated with water in the presence of a basic catalyst. Step III-i causes ring-opening of the structural units represented by formula (MA) contained in the polymer precursor (a) obtained in step II, forming structural units represented by formula (3). This allows the production of a polymer P (hereinafter sometimes referred to as "polymer precursor (b)") that contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; structural units represented by formula (ST); structural units represented by formula (1) and / or (2); and structural units represented by formula (3). When some of the structural units represented by formula (MA) are ring-opened and some of the structural units of formula (MA) remain unopened, the polymer precursor (b) further contains structural units represented by formula (MA).

[0160] The basic catalyst used in step III-i includes amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, and nitrogen-containing heterocyclic compounds.

[0161] In step III-i, water is added to a reaction system containing the polymer precursor (a) obtained in step II, and the resulting reaction solution is heated, preferably at 60 to 80°C, for approximately 0.25 to 6 hours, thereby ring-opening the structural unit of formula (MA) contained in this polymer and producing a structural unit represented by formula (3). The basic catalyst remaining in the reaction system obtained in step II can be used as is. Therefore, step III-i is preferably carried out in situ by adding water to the reaction mixture obtained in step II without any post-treatment.

[0162] The polymer P (polymer precursor (a) or polymer precursor (b)) of this embodiment can be obtained by the above steps. However, from the viewpoint of the effects of the present invention, the following steps may be further carried out as appropriate to remove unnecessary components other than the desired polymer.

[0163] First, the reaction solution diluted with an organic solvent and to which an acid (e.g., formic acid) has been added is vigorously stirred in a separatory funnel for at least 3 minutes. The mixture is then left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is then removed. In this way, an organic solution of polymer P (polymer precursor (Ia) or polymer precursor (Ib)) is obtained.

[0164] The resulting organic solution of polymer P (polymer precursor (a) or polymer precursor (b)) is purified using reprecipitation or liquid-liquid extraction. In the reprecipitation method, the resulting organic solution of P (polymer precursor (a) or polymer precursor (b)) is added to an excess amount of toluene or water to reprecipitate the polymer. The polymer powder obtained by reprecipitation is then 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). After washing with ion-exchanged water, the polymer powder is dried, for example, at 30 to 60° C. for 16 hours or more, to obtain a highly pure polymer. In the liquid-liquid extraction method, water or a mixture of water and an alcohol such as methanol, 2-propanol, or 1-butanol is added to the obtained organic solution of polymer P and vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand for at least 30 minutes, after which the organic and aqueous phases are separated and the aqueous phase is removed. Furthermore, water or a mixture of water and alcohol is added to the organic solution of polymer after the aqueous phase has been removed and vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand for at least 30 minutes, after which the organic and aqueous phases are separated and the aqueous phase is removed. In this way, an organic solution of polymer is obtained. If necessary, further steps of adding water or a mixture of water and alcohol and removing the aqueous phase may be carried out. The obtained organic solution of polymer P is concentrated by heating under reduced pressure using a rotary evaporator, and then the final solvent (PGMEA, etc.) is added and the dilution process is repeated to obtain a polymer solution dissolved in the final solvent. In addition, further purification by reprecipitation may be performed after solvent substitution.

[0165] The polymer solution may also contain the polyfunctional (meth)acrylic compound and / or monofunctional (meth)acrylic compound used in synthesizing polymer P. When the polymer solution contains these (meth)acrylic compounds, the amount is preferably such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart is 0.25 to 50%, particularly 0.5 to 30%, of the peak area of ​​polymer P, and the peak area attributable to the monofunctional (meth)acrylic compound is preferably 0.25 to 50%, particularly 0.5 to 30%, of the peak area of ​​polymer P. This allows a photosensitive resin composition containing this polymer solution to have good alkali solubility and good sensitivity in photolithography.

[0166] (Step III-ii) In step III-ii, the polymer obtained in step II (polymer precursor (a)) or the polymer obtained in step III-i (polymer precursor (b)) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, whereby the carboxyl groups of polymer precursor (a) or (b) react with the epoxy groups of the epoxy group-containing (meth)acrylic compound to form structural units represented by formula (1-1). This produces a polymer P containing structural units represented by formula (ST); structural units represented by formula (1) and / or formula (2); and structural units represented by formula (1-1). In cases where some of the structural units represented by formula (MA) are ring-opened and some of the structural units of formula (MA) remain unopened, the polymer P further contains structural units represented by formula (MA).

[0167] Step III-ii is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to a reaction system containing the polymer precursor (b) obtained in Step III-i.

[0168] The reaction of polymer precursor (a) or (b) with an epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst remaining in the reaction system obtained in step II can be used as is. Therefore, step III-ii is preferably carried out in situ by adding an epoxy group-containing (meth)acrylic compound to the reaction mixture containing polymer precursor (a) obtained in step II or the reaction mixture containing polymer precursor (b) obtained in step III-i, without isolating and purifying polymer precursor (a) from the reaction mixture containing polymer precursor (a) obtained in step II or the reaction mixture containing polymer precursor (b) obtained in step III-i, or without neutralizing the basic catalyst contained in the mixture.

[0169] Specifically, an epoxy group-containing (meth)acrylic compound is added to a reaction mixture containing polymer precursor (a) or (b), and the resulting reaction solution is heated preferably at 60 to 80°C for about 1 to 9 hours. This causes a reaction between the carboxyl group of polymer precursor (a) or (b) and 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.

[0170] 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, and glycidyl acrylate, and one or more selected from these can be used.

[0171] The amount of the epoxy group-containing (meth)acrylic compound added is preferably 0.1 to 3.0 moles per mole of the carboxyl group of the polymer precursor (a) or (b).

[0172] When the polymer P is a polymer obtained via the polymer precursor (a), the polymer P contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; a structural unit represented by formula (ST); a structural unit represented by formula (8); a structural unit represented by formula (9); a structural unit represented by formula (1); and a structural unit represented by formula (2).

[0173] When the polymer P is a polymer obtained via the polymer precursor (b), the polymer P contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; a structural unit represented by formula (ST); 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).

[0174] After step III-ii, it is preferable to further carry out the following steps as appropriate in order to remove unnecessary components other than the desired polymer P.

[0175] First, the reaction solution diluted with the 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 then left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is then removed. In this way, an organic solution of polymer P is obtained.

[0176] An excess amount of toluene is added to the obtained organic solution of polymer P to reprecipitate polymer P. The polymer powder obtained by reprecipitation is further washed several times (for example, 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 highly pure polymer P of this embodiment.

[0177] [Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P. The polymer solution of this embodiment may contain, in addition to the polymer P, at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound.

[0178] (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 II in the production of polymer P, or may be one that is added separately.

[0179] 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):

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] 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). 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).

[0184] Y in the formulae (1b-p), (1c-p) and (1d-p) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0185] The compounds of 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.

[0186] When a polyfunctional (meth)acrylic compound is blended into the polymer solution of this embodiment in addition to the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P, 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 ​​polymer P.

[0187] (Monofunctional (meth)acrylic compound) The monofunctional (meth)acrylic compound to be blended in the polymer solution of this embodiment includes compounds represented by the following formula (2a-m): 10 and R are defined as in formula (2a).

[0188] [ka]

[0189] When a monofunctional (meth)acrylic compound is blended into the polymer solution of this embodiment in addition to the unreacted monofunctional (meth)acrylic compound used in the production of polymer P, 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 ​​polymer P.

[0190] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish, which 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.

[0191] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyl lactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of organic solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0192] [Preparation of polymer solution] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material for the photosensitive resin composition described below.

[0193] [Photosensitive resin composition] The photosensitive resin composition of this embodiment contains the above-mentioned polymer P and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment contains the above-mentioned polymer solution of this embodiment and a photopolymerization initiator. Each component will be described below.

[0194] (Photopolymerization initiator) The photopolymerization initiator used in the photosensitive resin composition of this embodiment may be a photoradical polymerization initiator. Known compounds may be used as the photoradical polymerization initiator, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and the like. -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 ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-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 suitable photo-radical polymerization initiators 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-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photo-radical polymerization initiator may be used alone or in combination of two or more. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of polymer P.

[0195] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, thereby providing excellent developability and processability in photolithography.

[0196] (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 imaging device. As the colorant, various pigments or dyes can be used. As the pigment, organic pigments and inorganic pigments can be used.

[0197] 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.

[0198] Examples of inorganic pigments that can be used include white extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellowing 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.), lustrous pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0199] As the dye, known dyes described in, for example, JP-A Nos. 2003-270428, 9-171108, and 2008-50599 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.

[0200] 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, and when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0201] Depending on the purpose and application, the colorant may be surface-treated, such as with rosin, surfactant, resin-based dispersant, pigment derivative, oxide film, silica coating, or wax coating.

[0202] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and application. In order to achieve both coloring concentration and 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.

[0203] (surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0204] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied to a substrate to obtain a resin film, enabling a coating film of uniform thickness to be obtained, and also prevents residues and pattern lift-up when the coating film is developed.

[0205] 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 its 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 to be added is preferably 0.01 to 10% by weight relative to 100 parts by weight of the resin.

[0206] (solvent) The photosensitive resin composition may typically contain a solvent. An organic solvent is preferably used as the solvent. 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.

[0207] 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 solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0208] (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.

[0209] When the photosensitive resin composition contains a light-blocking agent, the amount thereof may be appropriately set depending on the purpose and application. In order to achieve both light-blocking performance and dispersion stability of the light-blocking agent, the amount 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.

[0210] (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 can crosslink the polymer P (can chemically bond with the polymer P) through the action of activated chemical species generated from the photopolymerization initiator. The crosslinking agent may not only chemically bond with the polymer, but may also react with itself to form a bond.

[0211] 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 category of the aforementioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group (polymerizable double bond) as 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, preferably 6 or less.

[0212] 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-adduct tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-adduct 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; The following can be mentioned:

[0213] Among these, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0214] 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. When the photosensitive resin composition contains a crosslinking agent, the amount thereof may be appropriately set depending on the purpose and application. For example, the amount of the crosslinking agent may be typically 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, per 100 parts by mass of the photosensitive resin.

[0215] (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.

[0216] [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. This film is applied to color filters, etc. In other words, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Then, a liquid crystal display device or a solid-state imaging device equipped with a color filter can be manufactured. A typical procedure for forming a pattern will now be described.

[0217] (Photosensitive resin film formation) For example, the above-mentioned photosensitive resin composition is applied to any substrate and dried as necessary to first obtain a photosensitive resin film.

[0218] The substrate to which the composition is applied is not particularly limited, and examples thereof include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates. The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on its surface, and may be surface-treated to improve adhesion.

[0219] The method for applying the photosensitive resin composition is not particularly limited, and may be spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, ink jet method, or the like.

[0220] The photosensitive resin composition coated on the substrate is typically dried by heating using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

[0221] The thickness of the photosensitive resin film is not particularly limited and may be adjusted appropriately depending on the pattern to be finally obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, etc.

[0222] (exposure) Exposure is typically carried out by irradiating the photosensitive resin film with actinic rays through an appropriate photomask.

[0223] Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible light. In terms of wavelength, light with a wavelength of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, with the i-line being particularly preferred. Two or more light rays may be used in combination. The exposure device is preferably a contact aligner, a mirror projection, or a stepper. The amount of light for exposure may be adjusted appropriately depending on the amount of photosensitizer in the photosensitive resin film, for example, 100 to 500 mJ / cm 2 That's about it.

[0224] After exposure, the photosensitive resin film may be heated again (post-exposure bake) if necessary. The temperature is, for example, 70 to 150°C, and preferably 90 to 120°C. The time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds. Post-exposure bake promotes the reaction caused by the radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

[0225] (developing) The exposed photosensitive resin film is developed with an appropriate developer to obtain a pattern, and a substrate having the pattern can be produced. A photosensitive resin film made of a photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to a substrate, and therefore peeling of the pattern is suppressed during the development step.

[0226] In the development step, development can be carried out using an appropriate developer by, for example, an immersion method, a puddle method, a rotary spray method, etc. By development, the exposed area (in the case of a positive type) or the unexposed area (in the case of a negative type) of the photosensitive resin film is dissolved and removed, thereby obtaining a pattern. There are no particular restrictions on the developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used.

[0227] Specific examples of alkaline aqueous solutions include: (i) aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous solutions of organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. The polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, and therefore, when a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution is used, a pattern after exposure and development can be formed in the designed shape.

[0228] Specific examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. The developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

[0229] In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above steps, a pattern can be obtained / a substrate having a pattern can be manufactured, but various treatments may be carried out after development.

[0230] For example, after development, the pattern and substrate may be washed with a rinse solution. Examples of rinse solutions include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

[0231] The pattern thus obtained may be heated to sufficiently cure it. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and more preferably 200 to 250°C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be carried out using a hot plate, an oven, a temperature-programmable heating oven, or the like. The atmospheric gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Heating may also be carried out under reduced pressure. An example of the structure of a liquid crystal display device and / or a solid-state imaging device having a color filter and / or a black matrix is ​​shown schematically in Figure 1. Although the black matrix may be a black bank, the following description will be directed to a liquid crystal display device and / or a solid-state imaging device having a color filter and a black matrix.

[0232] A black matrix 11 and a color filter 12 are formed on a substrate 10. A protective film 13 and a transparent electrode layer 14 are provided on top of the black matrix 11 and the color filter 12.

[0233] The substrate 10 is usually made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin polymer, etc. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, etc., as needed. The substrate 10 is preferably made of glass. The black matrix 11 is made of, for example, a cured product of a photosensitive resin composition containing a light-blocking agent.

[0234] There are usually three colors, red, green, and blue, for the color filter 12. The color filter 12 is made of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

[0235] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0236] EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0237] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride ST: Styrene NB: 2-Norbornene MEK: Methyl ethyl ketone 4-HBA: 4-hydroxybutyl acrylate GMA: Glycidyl methacrylate PEMP: pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (azo polymerization initiator) 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 measurement is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka]

[0238] <Synthesis of raw polymer> (Synthesis of raw polymer 1) A reaction vessel equipped with a stirrer, condenser, and dropping funnel was charged with 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g, 4.8 mol equivalent to 2-norbornene), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) and stirred to dissolve. Dissolved oxygen was removed from the system by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyric acid dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries, Ltd., 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) dissolved in 193.4 g of MEK was added over 1 hour. The reaction mixture was then further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120°C to obtain 910.1 g of a polymer (raw polymer 1) having structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained raw polymer 1 was measured by gel permeation chromatography (GPC) to find that the weight average molecular weight Mw was 3,500 and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.62.

[0239] (Confirmation of the thioether structure contained in raw polymer 1) PEMP alone, as shown in the following chemical formula: 13 C-NMR measurement confirmed peak a due to carbon a at around 19.0 ppm and peak b due to carbon b at around 62.0 ppm.

[0240] [ka]

[0241] Raw polymer 1 synthesized using PEMP 13In C-NMR measurement, the appearance of peak b due to carbon b was confirmed at around 62.0 ppm. In GPC measurement of the reaction solution, no peak due to PEMP alone was observed, and no unreacted PEMP remained, confirming that PEMP was incorporated into Raw Material Polymer 1.

[0242] In addition, raw polymer 1 13 In C-NMR measurement, peak a derived from carbon a was not confirmed, and instead peak c corresponding to thioether (RS-R') appeared around 28 ppm. The integral value of this peak c was approximately twice that of peak b, which indicates that raw polymer 1 has a skeleton with thioether groups as shown below, and the thiol groups had disappeared.

[0243] [ka]

[0244] 13 The conditions for C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding a measurement solvent to a weighed sample to adjust its concentration, and then pouring a specified amount into a sample tube for NMR measurement. Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR equipment ·Resonance frequency: 100.53MHz Measurement nuclei: 13 C Measurement method: NNE measurement (inverse gate decoupling method) Pulse width: 3.83μsec Pulse repetition time: 30 seconds Accumulation count: 4096 ·Measurement temperature: room temperature Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) Sample concentration: 20% (w / v). The amount of sulfur in the resulting polymer was confirmed by flask combustion and elemental analysis using ion chromatography, confirming the presence of elemental sulfur in the polymer. In addition, GPC measurement of the reaction solution before the addition of methanol showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the raw polymer 1.

[0245] As a result of elemental analysis, the sulfur content in Raw Material Polymer 1 was found to be 2.4 wt %.

[0246] (Synthesis of raw polymer 2) XIRAN (registered trademark) 1000 (Tomoe Engineering Co., Ltd., styrene-maleic anhydride copolymer, (styrene:maleic acid ratio = 1:1)), a copolymer consisting of structural units derived from styrene and structural units derived from maleic anhydride, was prepared and used as raw polymer 2. The weight average molecular weight Mw of the raw material polymer 1 was 7100, and the polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.53.

[0247] (Synthesis of raw polymer 3) XIRAN (registered trademark) 3000 (Tomoe Engineering Co., Ltd., styrene-maleic anhydride copolymer, (styrene:maleic acid ratio = 3:1)), a copolymer consisting of structural units derived from styrene and structural units derived from maleic anhydride, was prepared and used as raw polymer 3. The weight average molecular weight Mw of the raw material polymer 3 was 10,900, and the polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.62.

[0248] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, styrene (ST, 122.40 g, 1.18 mol), maleic anhydride (MA, 115.24 g, 1.18 mol), methyl ethyl ketone (MEK, 678.89 g), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 11.04 g, 0.047 mol), and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 22.97 g, 0.047 mol) were added and stirred to dissolve. Dissolved oxygen was then removed from the system by nitrogen bubbling, and the mixture was heated until the internal temperature reached 80°C. The reaction mixture was then cooled to room temperature. The resulting polymerization solution was added dropwise to methanol (2640.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (2640.0 g) and then vacuum dried at a temperature of 120°C to obtain 235.1 g of a polymer (raw polymer 4) having structural units derived from styrene and structural units 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 8,300 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.37. The amount of sulfur in the obtained raw polymer 4 was confirmed by flask combustion and elemental analysis by ion chromatography, confirming the presence of elemental sulfur in raw polymer 4. Furthermore, GPC measurement of the reaction solution showed no peak for PEMP alone, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw polymer 4. In addition, raw material polymer 4 13 C-NMR measurement confirmed that PEMP was incorporated into the raw polymer 4.

[0249] (Synthesis of raw polymer 5) A reaction vessel equipped with a stirrer, condenser, and dropping funnel was charged with styrene (ST, 75.32 g, 0.72 mol), maleic anhydride (MA, 23.64 g, 0.24 mol), methyl ethyl ketone (MEK, 282.9 g), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 4.53 g, 0.020 mol), and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 9.42 g, 0.019 mol) and stirred to dissolve. Dissolved oxygen was then removed from the system by nitrogen bubbling, and the mixture was heated until the internal temperature reached 80°C. The reaction mixture was then cooled to room temperature. The resulting polymerization solution was then added dropwise to methanol (1100.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (1100.0 g) and then vacuum dried at a temperature of 120°C to obtain 67.8 g of a polymer (raw polymer 5) having structural units derived from styrene and structural units derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 6,100 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.34. The amount of sulfur in the obtained raw polymer 5 was confirmed by flask combustion and elemental analysis by ion chromatography, confirming the presence of elemental sulfur in raw polymer 5. Furthermore, GPC measurement of the reaction solution showed no peak for PEMP alone, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw polymer 5. In addition, raw polymer 5 13 C-NMR measurement confirmed that PEMP was incorporated into the starting polymer 5.

[0250] (Synthesis of raw material polymer 6) A reaction vessel equipped with a stirrer, condenser, and dropping funnel was charged with styrene (ST, 141.23 g, 1.36 mol), maleic anhydride (MA, 66.48 g, 0.68 mol), methyl ethyl ketone (MEK, 593.70 g), dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 9.55 g, 0.042 mol), and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 19.88 g, 0.041 mol) and stirred to dissolve. Dissolved oxygen was then removed from the system by nitrogen bubbling, and the mixture was heated until the internal temperature reached 80°C. The reaction mixture was then cooled to room temperature. The resulting polymerization solution was added dropwise to methanol (2308.0 g) to precipitate a white solid. The obtained white solid was further washed with methanol (2308.0 g) and then vacuum dried at a temperature of 120°C to obtain 183.6 g of a polymer (raw polymer 6) having structural units derived from styrene and structural units derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 6,700 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.35. The amount of sulfur in the obtained raw polymer 6 was confirmed by flask combustion and elemental analysis by ion chromatography, confirming the presence of elemental sulfur in raw polymer 6. Furthermore, GPC measurement of the reaction solution showed no peak for PEMP alone, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw polymer 6. In addition, raw material polymer 6 13 C-NMR measurement confirmed that PEMP was incorporated into the raw polymer 6.

[0251] For raw polymers 4 to 6, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC), and the consumption amount of each monomer was calculated to calculate the ratio of each monomer introduced into the raw polymer. Table 1 below shows the feed ratio of the monomers used in synthesizing the raw polymer, the ratio of the monomers introduced into the raw polymer, and the weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the raw polymer. The conditions for the gas chromatography measurement are as follows. ·GC device: GC-2030 (Shimadzu Corporation) Carrier gas: N2 Detector: Flame ionization detector (FID), FID temperature: 300°C Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Corporation) Vaporization chamber temperature: 210℃ Column flow rate: 0.64 mL / min Column temperature conditions: 50°C, 5 min hold, 20°C / min increase to 300°C, 300°C, 10 min hold

[0252] [Table 1]

[0253] <Synthesis of Polymer P> Polymer P was prepared using the following method. (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw polymer 1 with a monofunctional (meth)acrylic compound (4-HBA), as described in detail below. First, MEK (18.44 g) was added to raw polymer 1 (10.00 g, calculated from the amount of raw polymer 1 charged, equivalent to 0.052 mol of MA) to prepare a solution. Next, 4-HBA (9.38 g, 0.065 mol) was added to this solution, and then triethylamine (3.00 g, 0.030 mol) was added. The mixture was reacted at 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. 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 twice with an excess amount of water. The resulting reaction product was dried in vacuum at 40°C for 12 hours. As a result of the above, 8.7 g of polymer P1 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the polymer P1 obtained were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of the polymer P1 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound.

[0254] (Preparation Example 2) Polymer P2 was prepared by ring-opening the MA units of raw polymer 2 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that raw polymer 2 (10.00 g, 0.049 mol in terms of MA calculated from the composition ratio of raw polymer 2) was used instead of raw polymer 1, and MEK (44.75 g) and 4-HBA (8.91 g, 0.062 mol) were used. The weight average molecular weight and polydispersity of the obtained polymer P2 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of the polymer P2 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P2 did not contain any unreacted monofunctional (meth)acrylic compound.

[0255] (Preparation Example 3) Polymer P3 was prepared by ring-opening the MA units of Raw Polymer 3 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that Raw Polymer 3 (10.00 g, 0.024 mol in terms of MA calculated from the compositional ratio of Raw Polymer 3) was used instead of Raw Polymer 1, MEK (49.28 g), and 4-HBA (4.39 g, 0.030 mol) were used. The weight average molecular weight and polydispersity of the obtained polymer P3 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of polymer P3 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound.

[0256] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA units of raw polymer 4 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 2, except that raw polymer 4 (10.00 g, 0.049 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 4) was used instead of raw polymer 2. The weight average molecular weight and polydispersity of the obtained polymer P4 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of polymer P4 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P4 did not contain any unreacted monofunctional (meth)acrylic compound.

[0257] (Preparation Example 5) Polymer P5 was prepared by ring-opening the MA units of raw polymer 5 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that raw polymer 5 (10.00 g, 0.026 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 5) was used instead of raw polymer 1, MEK (49.06 g), and 4-HBA (4.60 g, 0.032 mol) were used. The weight average molecular weight and polydispersity of the obtained polymer P5 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of polymer P5 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, confirming that the obtained polymer P5 did not contain any unreacted monofunctional (meth)acrylic compound.

[0258] (Preparation Example 6) Polymer P6 was prepared by ring-opening the MA units of raw polymer 6 with a monofunctional (meth)acrylic compound (4-HBA) in the same manner as in Preparation Example 1, except that raw polymer 6 (10.00 g, 0.036 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 6) was used instead of raw polymer 1, MEK (47.09 g), and 4-HBA (6.58 g, 0.046 mol). The weight average molecular weight and polydispersity of the obtained polymer P6 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of polymer P6 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used, confirming that the obtained polymer P6 did not contain any unreacted monofunctional (meth)acrylic compound.

[0259] (Preparation Example 7) The MA unit of the raw polymer 5 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to prepare polymer P7. Details are described below. First, MEK (48.58 g) was added to raw polymer 5 (10 g, 0.026 moles in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 5) to prepare a solution. Next, 4-HBA (4.39 g, 0.030 moles) was added to this solution, followed by triethylamine (3.00 g, 0.030 moles), and the mixture was allowed to react at 70°C for 3 hours. GMA (0.69 g, 0.005 moles) was then added, and the mixture was allowed to react at 70°C for 4 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. 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 twice with an excess amount of water. The resulting reaction product was dried in vacuum at 40°C for 12 hours. As a result of the above, the structural unit derived from maleic anhydride in Raw Material Polymer 5 was ring-opened with 4-HBA, and reacted with GMA to obtain Polymer P7. The weight average molecular weight and polydispersity of the obtained polymer P7 were measured by GPC. The results are shown in Table 2. Furthermore, GPC measurement of polymer P7 confirmed the disappearance of the peaks of the polymonofunctional (meth)acrylic compound used, confirming that the obtained polymer P7 did not contain any unreacted polyfunctional (meth)acrylic compound.

[0260] Furthermore, GPC measurements of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction showed that the peak derived from the monofunctional (meth)acrylic compound (4-HBA) decreased before and after the ring-opening reaction, and the peak derived from GMA decreased before and after the GMA addition reaction, indicating that 4-HBA and GMA were introduced into the polymer.

[0261] Also 13 C-NMR measurement confirmed that polymer P7 had a structure in which the maleic anhydride-derived structural unit of raw polymer 5 was ring-opened with 4-HBA, and a structure in which GMA was introduced.

[0262] (Preparation Example 8) Polymer P8 was prepared by ring-opening the MA units of raw polymer 5 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA). Details are described below. First, MEK (47.46 g) was added to raw polymer 5 (10 g, 0.026 moles in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 5) to prepare a solution. Next, A-TMM-3LM-N (1.81 g) was added to this solution, followed by triethylamine (3.00 g, 0.030 moles) and reacting at 70°C for 2 hours. Further, 4-HBA (4.39 g, 0.030 moles) was added and reacted at 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with a formic acid solution to remove the aqueous phase. The polymer was then purified as follows: The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed with an excess amount of toluene three times. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried in vacuum at 40°C for 16 hours. As a result of the above, polymer P8 was obtained in which the structural units derived from maleic anhydride in raw polymer 5 were ring-opened with A-TMM-3LM-N and 4-HBA. GPC measurement of polymer P8 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used, confirming that the obtained polymer P8 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P8 had a structure in which the maleic anhydride-derived structural units of raw polymer 5 were ring-opened with A-TMM-3LM-N and 4-HBA.

[0263] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA units of raw polymer 5 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and water. Details are described below. First, MEK (49.86 g) was added to raw polymer 5 (10 g, 0.026 moles in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 5) to prepare a solution. Next, A-TMM-3LM-N (3.81 g) was added to this solution, followed by triethylamine (3.00 g, 0.030 moles), and the mixture was reacted at 70°C for 2 hours. Next, water (0.50 g, 0.028 mol) was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase, followed by further purification as follows: The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed with an excess amount of toluene three times. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried in vacuum at 40°C for 12 hours. As a result, polymer P9 was prepared by ring-opening the MA units of raw polymer 5 with a trifunctional (meth)acrylic compound and water. The weight average molecular weight and polydispersity of the polymer P9 were measured by GPC, and the results are shown in Table 2. Furthermore, GPC measurement of polymer P9 confirmed the disappearance of the peak of the polyfunctional (meth)acrylic compound used, which confirmed that the obtained polymer P9 did not contain any unreacted polyfunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P9 had a structure in which the maleic anhydride-derived structural unit of raw material polymer 5 was ring-opened with A-TMM-3LM-N and water.

[0264] (Physical properties of polymer P) The acid value and double bond equivalent of each of the polymers P prepared in Preparation Examples 6 to 9 were measured by the following methods.

[0265] (acid number) The acid value of the polymer P was measured by the following method. Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were carried out. 1The amount of carboxyl groups is determined from the integral value of the H peak (near 12.4 ppm) of the polymer's carboxyl group (-COOH), using the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurements, as the reference. The acid value (mgKOH / g) can then be calculated from this amount. A higher acid value indicates a greater amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. When the acid value is 50 gKOH / g or more, it can be considered that the polymer has carboxy groups necessary for the polymer to have sufficient developability.

[0266] (double bond equivalent) For each of the polymers P prepared in Preparation Examples 6 to 9, the double bond equivalent of the polymer was measured by the following method. As with the above acid value measurement method, 1 H-NMR measurements were performed. The amount of acryloyl groups in the polymer (mol / g) was calculated from the integral ratio of the signal derived from the acryloyl groups (5.8-6.7 ppm, 3H) to the signal derived from the internal standard phenyl group (8.1 ppm, 4H) in the obtained spectrum chart. The amount of methacryloyl groups in the polymer (mol / g) was calculated from the integral ratio of the signal derived from the methacryloyl groups (5.6-5.8 ppm, 2H) to the signal derived from the internal standard phenyl group (8.1 ppm, 4H). Here, the signal derived from the methacryloyl groups at 6.0-6.1 ppm was weak and overlapped with the signal derived from the acryloyl group, so it was calculated as the signal derived from the acryloyl group. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and the amount of methacryloyl groups (mol / g) in the 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. Polymers P5 to P7 and P9 1 The molar ratio of the reacted compound to the starting polymer in the overall structure was calculated by H-NMR measurement. The results are shown in Table 2.

[0267] [Table 2]

[0268] (Examples 1 to 9, Comparative Examples 1 to 4) In each of the Examples and Comparative Examples, a resin composition was prepared and evaluated for the following items. [Alkaline dissolution rate of resin composition (0.5 wt% TMAH)] In Comparative Examples 1 to 4 and Examples 1 to 5, polymers P1 to P9 obtained in Preparation Examples 1 to 9 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 9 with a solid content concentration of 30 mass %. In Examples 6 and 7, resin compositions 10 and 11 were prepared by adding the polyfunctional (meth)acrylic compound (A-TMM-3LM-N) in the amount shown in Table 2 to the solid content of polymer P. Next, the above-mentioned resin compositions 1 to 11 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 about 2 μm. This resin film was immersed together with the wafer in a 0.5 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer and measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and then dividing that time by the film thickness. The results are shown in Table 3. If the alkali dissolution rate is 150 nm / s or more, the material can be used as a photosensitive material without any problems, if it is 200 nm / s or more, the developability can be considered to be good, if it is 250 nm / s or more, it can be considered to be even better, and if it is 300 nm / s or more, it can be considered to be particularly good.

[0269] [Yellow index (YI) of resin composition] In Comparative Examples 1 to 4 and Examples 1 to 5, polymers P1 to P9 obtained in Preparation Examples 1 to 9 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 9 having a polymer P concentration (RC) of 25% by mass. In Examples 6 and 7, the polyfunctional (meth)acrylic compound (A-TMM-3LM-N) in the amount shown in Table 2 was added to the solid content of polymer P to prepare resin compositions 10 and 11 having a solid content (total concentration of polymer P and polyfunctional (meth)acrylic compound) (RC) of 25% by mass. The obtained resin composition was placed in a quartz cell with an optical path length of 1.0 cm and measured using a spectrophotometer (Konica Minolta's "Colorimeter CR-5"). The measurement type was transmission measurement, and a quartz cell with an optical path length of 1.0 cm containing no solution was used for 100% calibration. If YI is 4.00 or less, it can be said that there is no problem with coloration of the solution; if it is 3.00 or less, it can be said that there is little coloration of the solution; if it is 2.50 or less, it can be said that there is even less coloration of the solution; and if it is 2.00 or less, it can be said that there is especially little coloration of the solution.

[0270] [Sensitivity evaluation of photosensitive resin composition (exposure amount at which the residual film rate is 90% or more / exposure amount at which the residual film rate is 95% or more)] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration was 30% by mass. Polymers P1 to P9 (polymers P in Preparation Examples 1 to 9, respectively) or the above resin compositions 10 and 11: 100 parts by mass (Here, Resin Compositions 10 and 11 were weighed so that the total amount of the solid content (polymer P5) and the polyfunctional (meth)acrylic compound was 100 parts by mass.) Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass Surfactant (DIC Corporation, F-556): 0.5 parts by mass

[0271] The obtained photosensitive resin composition was spin-coated onto a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A having a thickness of approximately 3.0 μm (±0.3 μm). This thin film A was irradiated with 100 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having a gradation of shading rate of 1 to 100%. 2 The film was exposed to g+h+i rays at an exposure dose of . After exposure, the thin film is developed (immersed with the wafer) in 0.5% by mass TMAH (tetramethylammonium hydroxide) at 23°C for a development time 1.5 times the time required for the unexposed area to completely dissolve, resulting in a dose of 1 to 100 mJ / cm. 2 Thin film B was obtained by exposure and development at each exposure dose. The remaining film ratio was calculated from the film thicknesses of Thin Film A and Thin Film B obtained by the above method using the following formula. Residual film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) × 100 The exposure dose at which the film remaining rate was 90% or more was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which the film remaining rate was 90% or more was 20 mJ / cm 2 If the photosensitive composition has a light intensity of 15 mJ / cm or less, it can be used without any problems as a photosensitive composition. 2 Sensitivity can be considered good if it is below 12 mJ / cm 2 Less than 10 mJ / cm can be considered better, and even less than 10 mJ / cm 2 It can be considered particularly good if:

[0272] The exposure dose at which the film remaining rate was 95% or more was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which the film remaining rate was 95% or more was 25 mJ / cm 2 If the photosensitive composition has a light intensity of 20 mJ / cm or less, it can be used without any problems as a photosensitive composition. 2 Sensitivity can be considered good if it is below 15 mJ / cm 2Less than 10 mJ / cm can be considered better, and even less than 10 mJ / cm 2 It can be considered particularly good if:

[0273] [Alkaline dissolution rate of photosensitive resin composition (0.5 wt% TMAH)] The photosensitive resin composition prepared in the sensitivity evaluation described above was spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at 100°C for 2 minutes to produce a resin film with a thickness of approximately 2 μm. This resin film was immersed together with the wafer in a 0.5 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer and measuring the time it took for the resin film to dissolve and the interference pattern to disappear, then dividing that time by the film thickness. The results are shown in Table 3. If the alkaline dissolution rate is 300 nm / s or higher, the material can be used without any problems as a photosensitive material; if it is 470 nm / s or higher, the developability can be considered good; if it is 600 nm / s or higher, the developability can be considered even better; and if it is 800 nm / s or higher, the developability can be considered particularly good.

[0274] [Table 3]

[0275] Polymer P1, which does not contain styrene-derived structural units and is composed of PEMP-derived structures, norbornene-derived structural units, and maleic anhydride-derived structural units (norbornene-derived structure:maleic anhydride-derived structure = approximately 1:1), had a high yellow index in its solution and a high exposure dose at which the residual film rate was 90% or more or 95% or more, resulting in poor sensitivity. Polymer P2 (styrene-derived structure:maleic anhydride-derived structure = approximately 1:1) composed of styrene-derived structural units and maleic anhydride-derived structural units, and polymer P4 (norbornene-derived structure:maleic anhydride-derived structure = approximately 1:1) composed of PEMP-derived structural units, styrene-derived structural units, and maleic anhydride-derived structural units both had high solution yellow indices. In particular, polymer P4, into which PEMP-derived structures had been introduced, had a very high solution yellow index and exhibited a pronounced yellow color. Polymer P3 (norbornene-derived structure:maleic anhydride-derived structure = approximately 3:1), which is composed of PEMP-derived structure, styrene-derived structural units, and maleic anhydride-derived structural units, had low alkali solubility and a slightly high yellow index in the solution. On the other hand, polymers P5 to P9 (styrene-rich polymers) composed of PEMP-derived structures, styrene-derived structural units, and maleic anhydride-derived structural units, and having a higher content of styrene-derived structural units than maleic anhydride-derived structural units, had a low yellow index in their solutions, were nearly colorless and transparent, and had a low exposure dose at which the residual film rate was 90% or more or 95% or more, and had excellent sensitivity.

[0276] <Color filter / spacer fabrication> A suitable amount of pigment dispersion NX-061 (green, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 7 to prepare colored photosensitive resin compositions. This was formed into a film on a substrate, and then exposed to light and developed with an alkaline solution to form a green color filter and spacers. In addition, by using the same company's NX-053 (blue) or NX-032 (red) as the pigment dispersion liquid instead of NX-061, it was possible to form blue or red color filters and spacers.

[0277] <Production of black matrix / black bank / black spacer> A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion liquid NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 7. This was deposited on a substrate, and then exposed to light and developed with an alkaline solution to form a black matrix, black bank, and black spacer. [Explanation of symbols]

[0278] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer having a structure represented by formula (P2): 【Chemistry 1】 In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each of the n polymer chains in the brackets [ ]; p and q may be the same or different for each of the n polymer chains in the brackets [ ]; p+q=1, p is 0 or greater, and q is 0 or greater; The molar contents of the structural units A and B contained in the polymer are respectively represented by p ｔ , and q ｔ Then, p ｔ +q ｔ = 1, and p ｔ is equal to or greater than 0.55 and equal to or less than 0.85, and q ｔ is equal to or greater than 0.15 and equal to or less than 0.45, X is hydrogen or an organic group having 1 to 30 carbon atoms; Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or di- or higher functional thiol group-containing compound, A represents a structural unit represented by formula (ST), B includes at least one structure selected from the structure represented by formula (1-2) and the structure represented by formula (1-3), Multiple A's and multiple B's may be the same or different, 【Chemistry 2】 In the formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ４３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, 【Transformation 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. 10. The polymer of claim 1, The structural unit B includes a structure represented by formula (1-1): 【Transformation 5】 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.

3. 10. The polymer of claim 1, The structural unit B includes a structure represented by formula (1-4): 【Transformation 6】 polymer.

4. 10. The polymer of claim 1, The structural unit B includes at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), 【Transformation 7】 In formula (1), R ｐ is a group having two or more (meth)acryloyl groups, 【Transformation 8】 In formula (2), R ｓ is a group having one (meth)acryloyl group.

5. 10. The polymer of claim 1, The structural unit B includes a structural unit represented by formula (3): 【Chemistry 9】 polymer.

6. 10. The polymer of claim 1, The structural unit B includes a structural unit represented by formula (MA): 【Chemistry 10】 polymer.

7. 10. The polymer of claim 1, The structural unit B includes a structure represented by the 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 11】 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 -Z-X- (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 ' 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 12】 In formula (1c), k, R, X １ and X ２ are k, R, and X in formula (1b), respectively. １ and X ２ and a plurality of R's may be the same or different, and a plurality of X's may be the same or different. １ may be the same or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is a divalent organic group having 1 to 6 carbon atoms, 【Chemistry 13】 In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group. polymer.

8. 10. The polymer of claim 1, The structural unit B includes a structure represented by the formula (1-3), R in the formula (1-3) ｓ is a group represented by formula (2a), 【Chemistry 14】 In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group.

9. 10. The polymer of claim 1, The polymer, wherein the thiol group-containing compound is at least one compound selected from the group consisting of formulas (s-1) to (s-21): 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 【Chemistry 35】

10. 10. The polymer of claim 1, The polymer has a weight average molecular weight of 3,000 or more and 30,000 or less.

11. 10. The polymer of claim 1, A polymer, wherein the yellow index of a 25% by mass solution of the polymer in propylene glycol monomethyl ether acetate is 4.0 or less.

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

13. 13. The polymer solution of claim 12, A polymer solution used to form color filters, black matrices, spacers, partition materials, or optical components.

14. A polymer according to any one of claims 1 to 11; a photoradical polymerization initiator; Photosensitive resin composition.

15. A cured product formed from the photosensitive resin composition according to claim 14.

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