Polymer solution, photosensitive resin composition, and uses thereof

Abstract

To provide a photosensitive resin composition excellent in sensitivity while having high alkali solubility, thereby excellent in developability with reduced yellow hue and also to provide a polymer solution to be used for the same.SOLUTION: A polymer solution includes: a polymer including both of, a structural unit obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of a structural unit derived from an unsaturated carboxylic acid, and a structural unit obtained by binding, by an ester linkage, a hydroxyalkyl (meth)acrylate to a carboxyl group having a structure derived from an unsaturated carboxylic acid; and a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups. The amount of the polyfunctional (meth)acrylic compound is 1 to 40 mass%, inclusive, with regard to the polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer solution, a photosensitive resin composition containing the polymer solution, and uses thereof. More specifically, the present invention relates to a polymer solution used as a material for a photosensitive resin composition used in the production of films, color filters, black matrices, display devices, and image pickup devices. [Background technology]

[0002] Liquid crystal display devices and solid-state imaging devices typically include color filters and black matrices. Color filters and black matrices are constructed by forming structures such as colored patterns and protective films on a substrate. Among these structures, photolithography using a photosensitive resin composition is the mainstream method for forming the colored 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 of 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 and black matrices use resins that undergo a polymerization reaction when exposed to light and harden. Color filters and black matrices are produced by patterning a photosensitive resin composition through exposure and development, followed by hardening. While "high sensitivity" is considered a common challenge for photosensitive resin compositions, ever-higher levels of sensitivity are required as display devices and imaging devices become more complex and widespread. The higher the sensitivity of a photosensitive resin composition, the shorter the time required for exposure, improving productivity.

[0005] Furthermore, when forming a color filter or a black matrix, particularly when the pigment content in the photosensitive resin composition is high, the solubility of the pigment in a basic developer is low, which increases the time required for developing the photosensitive resin composition. Therefore, it is necessary to use a strongly basic developer that has a faster development rate than conventional basic developers. However, if the polymer has high alkaline solubility, the alkaline dissolution rate of the photosensitive resin composition containing the pigment and photopolymerization initiator may be too fast, or the difference in dissolution rate between the pigment and the resin composition may be too large, which may result in a pattern after exposure and development that does not have the designed shape.

[0006] Furthermore, when a pattern is formed by applying a photosensitive resin composition to a substrate or the like, exposing the resulting coating film, and developing it, the composition must have excellent adhesion to the substrate or the like from the viewpoint of product yield and product reliability. In addition, if the resolution of the photosensitive resin composition is too low, when patterning is performed by exposure and development, the fine line pattern of a color filter, black matrix, or the like will not be formed as designed, and undissolved portions will remain near the pattern, resulting in a reduced aperture and blocking light transmission, resulting in the formation of dots with poor color reproducibility and reduced panel yield. This problem is particularly pronounced when forming a black matrix, which requires a finer fine line pattern, or when patterning a thick film with a thickness of about 10 to 20 μm. [Means for solving the problem]

[0007] The present inventors have found that, when a strongly basic developer is used, in order to obtain a pattern having a designed shape after exposure and development, it is necessary to adjust the alkaline solubility of the polymer contained in the photosensitive resin composition while maintaining and improving sensitivity, and further to suppress undissolved residues near the pattern after development and achieve excellent adhesion to the substrate. Furthermore, the present inventors have found that these problems can be solved by improving the polymer structure, and have completed the present invention.

[0008] According to the present invention, The following general formula (1) and structural units represented by the following general formula: (2) A polymer comprising a structural unit represented by a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups, The polyfunctional (meth)acrylic compound is contained in an amount of 1% by mass or more and 40% by mass or less relative to the polymer. A polymer solution is provided.

[0009] [ka] (General formula (1) Inside, 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. Ku, R D is a group containing two or more (meth)acryloyl groups. )

[0010] [ka] (In general formula (2), R 1、R 2 、R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, 1 is 0, 1, or 2.)

[0011] The present invention also provides a photosensitive resin composition containing the polymer solution and a photopolymerization initiator.

[0012] The present invention also provides a cured product formed from the above photosensitive resin composition.

[0013] The present invention also provides a film comprising the above cured product. [Effects of the Invention]

[0014] According to the present invention, there are provided a photosensitive resin composition having good sensitivity and high alkali solubility, and therefore excellent developability and reduced yellowing, and a polymer solution for use therein. [Brief explanation of the drawings]

[0015] [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

[0016] 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 notation "a to b" in the description of a numerical range means a to b, unless otherwise specified. For example, "5 to 90%" means "5% to 90%."

[0017] 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).

[0018] 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.

[0019] [Polymer solution] The polymer solution of this embodiment contains a polymer having a specific structure and a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups. In the polymer solution of this embodiment, the polyfunctional (meth)acrylic compound is contained in an amount of 1% by mass or more and 40% by mass or less relative to the polymer.

[0020] (Polymer P) The polymer used in the polymer solution of this embodiment (referred to herein as "polymer P") contains a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2).

[0021] The polymer P used in the polymer solution of this embodiment contains a structural unit represented by general formula (1-1) and a structural unit represented by general formula (1-2), and therefore has excellent sensitivity and alkaline solubility, making it suitable for use as a polymer for forming a color filter or black matrix. This is thought to be because the (meth)acryloyl group contained in the structural unit represented by formula (1-1) or formula (1-2) promotes the curing reaction (polymerization reaction). In particular, the polymer P used in the polymer solution of this embodiment has adjusted alkaline solubility and excellent sensitivity, and therefore, when a strongly basic developer such as a tetramethylammonium hydroxide (TMAH) solution is used, the pattern after exposure and development can be formed into the designed shape.

[0022] In general formula (1-1), Z is not particularly limited as long as it is a group containing one or more (meth)acryloyl groups, but is more preferably a group containing 1 to 4 (meth)acryloyl groups, and even more preferably a group containing 1 to 3 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in Z, the polymer P will have excellent sensitivity and excellent alkali solubility (developability), in other words, an excellent balance of these.

[0023] [ka]

[0024] [ka]

[0025] In general formula (1-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q may be bonded to any carbon atom of the alkylene group of X to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, and a naphthalene ring.

[0026] 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 general formula (1a), or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group, is preferably used.

[0027] [ka]

[0028] In general formula (1a), R is a hydrogen atom or a methyl group.

[0029] In general formula (1-2), R D is a group containing two or more (meth)acryloyl groups. Preferably, R Dis a group containing 2 to 9 (meth)acryloyl groups, and more preferably a group containing 3 to 6 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups, the sensitivity of the resulting polymer P in photolithography can be increased. Furthermore, a better balance between sensitivity and developability can be achieved, and heat resistance can also be improved.

[0030] R D is preferably a group represented by the following general formula (1b), (1c) or (1d): When such a group is used, the above-mentioned various effects tend to be easily obtained.

[0031] [ka]

[0032] 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.

[0033] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When is an alkylene group having 1 to 6 carbon atoms, f 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).

[0034] 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)-.

[0035] 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.

[0036] X 2 The k+1-valent organic group having 1 to 12 carbon atoms can be any group obtained by removing k+1 hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a 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).

[0037] [ka]

[0038] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (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.

[0039] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of the formula (1b) are the same as those explained for the 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.

[0040] [ka]

[0041] 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 relation to general formula (1b).

[0042] The proportion of the structural units represented by general formula (1-1) in all structural units of polymer P is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %, and the proportion of the structural units represented by general formula (1-2) is preferably 1 to 30 mol %, more preferably 2 to 20 mol %.

[0043] The polymer P can contain a structural unit represented by the following general formula (1), which is composed of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-2).

[0044] [ka]

[0045] In the general formula (1), Q, X, and Z are the same as those in the general formula (1-1), and R D has the same meaning as general formula (1-2). The proportion of the structural units represented by general formula (1) in all structural units of the polymer P is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0046] The polymer P may also contain, as a structural unit containing the structural unit represented by the general formula (1-1), a structural unit represented by the general formula (3), a structural unit represented by the general formula (5), or a structural unit represented by the general formula (6), which will be described later. These structural units will be described later. Furthermore, the polymer P may also contain a structural unit represented by the general formula (8) described below as a structural unit containing the structural unit represented by the general formula (1-2). This structural unit will be described later.

[0047] The polymer P may further contain a structural unit represented by the following general formula (2).

[0048] [ka]

[0049] In general formula (2), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0050] The structural unit represented by general formula (2) is chemically robust. Therefore, polymer P containing this structural unit undergoes little weight loss when subjected to heat treatment and is stable. Therefore, photosensitive resin compositions containing polymer P can be suitably used to produce films and filters for use in liquid crystal displays and solid-state imaging devices, which require heat resistance.

[0051] R in general formula (2) 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, straight-chain or branched-chain alkyl groups having 1 to 30 carbon atoms, and more specific examples include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0052] 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. 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.

[0053] 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. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0054] 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.

[0055] In the structural unit represented by general formula (2), R 1 , R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, more preferably hydrogen.

[0056] In addition, R in general formula (2) 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected. In the structural unit represented by the general formula (2), a1 is preferably 0 or 1, and more preferably 0.

[0057] The proportion of the structural units represented by formula (2) in all structural units of the polymer P is preferably 10 to 90 mol %, more preferably 30 to 70 mol %, and even more preferably 40 to 60 mol %.

[0058] The polymer P may further contain a structural unit represented by the following general formula (3-1).

[0059] [ka]

[0060] In general formula (3-1), 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 further contains a structural unit represented by general formula (3-1), which allows a good balance between sensitivity and developability.

[0061] R S is, for example, a group represented by the following general formula (3a).

[0062] [ka]

[0063] In general formula (3a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0064] 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.

[0065] 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 general formula (3-1), the structural unit represented by general formula (3-1) can be more easily involved in the crosslinking reaction, thereby increasing the sensitivity.

[0066] 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.

[0067] 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.

[0068] The proportion of the structural units represented by general formula (3-1) in all structural units of the polymer P is preferably 5 to 40 mol %, more preferably 10 to 30 mol %.

[0069] The polymer P can contain a structural unit represented by the following general formula (3), which is composed of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (3-1).

[0070] [ka]

[0071] In the general formula (3), Z, Q, and X are the same as those in the general formula (1-1), and R Shas the same meaning as general formula (3-1).

[0072] When polymer P contains a structural unit represented by general formula (3), the proportion of the structural unit represented by general formula (3) in all structural units of polymer P is preferably 3 to 35 mol %, more preferably 7 to 25 mol %.

[0073] The polymer P may also contain a structural unit represented by the general formula (8) described below as a structural unit containing the structural unit represented by the general formula (3-1). This structural unit will be described later.

[0074] The polymer P may further contain a structural unit represented by the following general formula (4).

[0075] The polymer P contains the structural unit represented by general formula (4) in addition to the structural unit represented by general formula (1-1) and the structural unit represented by general formula (1-2), thereby adjusting the alkali solubility. As a result, the photosensitive resin composition containing the polymer P exhibits an excellent balance between sensitivity and developability even when subjected to photolithography using a strongly basic developer.

[0076] [ka]

[0077] When polymer P contains a structural unit represented by general formula (4), the proportion of the structural unit represented by general formula (4) in all structural units of polymer P is preferably 1 to 15 mol %, more preferably 2 to 10 mol %.

[0078] The polymer P may further contain a structural unit represented by the following general formula (5), which contains a structural unit represented by general formula (1-1). By containing this structural unit, both sensitivity and developability can be achieved in a better balance.

[0079] [ka]

[0080] In the general formula (5), Z, X, and Q have the same meanings as in the general formula (1-1). When polymer P contains a structural unit represented by general formula (5), the proportion of the structural unit represented by general formula (5) in all structural units of polymer P is preferably 1 to 12 mol %, more preferably 1 to 9 mol %.

[0081] From the viewpoint of the effects of the present invention, the polymer P may further contain a structural unit represented by the following general formula (6) which is composed of two structural units represented by the general formula (1-1). By containing this structural unit, sensitivity can be further improved.

[0082] [ka]

[0083] In the general formula (6), Z, X, and Q have the same meanings as in the general formula (1-1). A plurality of Zs, a plurality of Qs, and a plurality of Xs may be the same or different.

[0084] When polymer P contains a structural unit represented by general formula (6), the proportion of the structural unit represented by general formula (6) in all structural units of polymer P is preferably 1 to 10 mol %, more preferably 1 to 8 mol %.

[0085] From the viewpoint of the effects of the present invention, the polymer P of this embodiment may further contain a structural unit represented by the following general formula (7) and / or a structural unit represented by the following general formula (8).

[0086] [ka]

[0087] In general formula (7), R D has the same meaning as general formula (1-2). When polymer P contains a structural unit represented by general formula (7), the proportion of the structural unit represented by general formula (7) in all structural units of polymer P is preferably 0.5 to 25 mol %, more preferably 1 to 18 mol %.

[0088] [ka]

[0089] In the general formula (8), Q, X and Z have the same meanings as in the general formula (3-1). When polymer P contains a structural unit represented by general formula (8), the proportion of the structural unit represented by general formula (8) in all structural units of polymer P is preferably 0.5 to 35 mol %, more preferably 2 to 25 mol %.

[0090] In addition to the above structural units, polymer P may contain a structural unit represented by general formula (MA). The structural unit represented by general formula (MA) undergoes ring-opening in an alkaline developer to generate two carboxyl groups. Therefore, polymer P containing such a structural unit has excellent developability. When polymer P contains a structural unit represented by general formula (MA), the structural unit represented by general formula (MA) preferably accounts for 1 to 35 mol %, more preferably 2 to 30 mol %, of all structural units of polymer P.

[0091] [ka]

[0092] The polymer P may contain an organic group having a thioether group (—S—). The thioether group in the polymer P provides excellent sensitivity in photolithography and higher alkali solubility, thereby providing a cured resin product with excellent developability, reduced yellowing, and excellent transparency.

[0093] When polymer P contains an organic group having a thioether group, the organic group having the thioether group is preferably a monovalent to hexavalent thioether-containing organic group having 1 to 30 carbon atoms and derived from a difunctional or higher functional thiol group-containing compound (referred to as a "thioether group-containing organic group (i)" in this specification). Here, the number of functional groups in the "difunctional or higher functional thiol group-containing compound" refers to the number of thiol groups. In other words, this thiol group-containing compound refers to a compound containing two or more thiol groups. When polymer P contains thioether group-containing organic group (i), polymer P has a structure in which the above structural units are bonded via 1 to 6 thioether groups derived from the thiol groups of the thiol group-containing compound. The thioether group-containing organic group (i) derived from this thiol group-containing compound may have a thiol group that is not involved in the bond with the above structural unit, and polymer P may be a mixture of polymers in which different numbers of the above structural units are bonded to a monovalent to hexavalent thioether-containing organic group having 1 to 30 carbon atoms and derived from a difunctional or higher functional thiol group-containing compound.

[0094] The thioether group-containing organic group (i) is bifunctional or more, preferably trifunctional or more, and although there is no particular upper limit, it is hexafunctional or less. From the viewpoint of the effects of the present invention, the valence of the thioether group-containing organic group (i) is monovalent to hexavalent, preferably divalent to hexavalent, and more preferably trivalent to hexavalent.

[0095] The thioether group-containing organic group (i) 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)).

[0096] 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.

[0097] 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.

[0098] 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.

[0099] Specific examples of the bifunctional or higher thiol group-containing compound from which the thioether group-containing organic group (i) can be derived include, but are not limited to, the following formulae (s-1) to (s-21).

[0100] [ka]

[0101] [ka]

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[0120] [ka]

[0121] In the present embodiment, from the viewpoint of the effects of the present invention, the bifunctional or higher thiol group-containing compound preferably includes a trifunctional or higher thiol group-containing compound, and more preferably includes an ester structure. In this embodiment, the bifunctional or higher functional thiol group-containing compound preferably includes, among the compounds represented by chemical formulas (s-1) to (s-21), compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10), and particularly preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-9).

[0122] The bifunctional or higher functional thiol group-containing compound may be used alone or in combination of two or more. The monovalent to hexavalent thioether group-containing organic group (i) has a terminal thioether group (-S-* (* represents a bond)) derived from the thiol group of the thiol group-containing compound, and bonds to the above-mentioned structural unit via this thioether group. The thioether group-containing organic group (i) may have a thiol group that is not involved in bonding to the above-mentioned structural unit.

[0123] The polymer P may contain additional structural units derived from monomers polymerizable with norbornene monomers and maleic anhydride. Examples of such structural units include those derived from substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (e.g., cyclohexene, etc.), cyclododecatriene, tricycloundecene, dialkyl fumarates (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, and vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.). Substituents that these monomers may have include alkyl groups, aryl groups, etc. More specifically, substituted indenes include methylindene, etc. Substituted maleimides include cyclohexylmaleimide, phenylmaleimide, etc. Examples of the substituted styrene include methylstyrene and vinyltoluene.

[0124] Among these, the structural unit preferably includes a structural unit represented by general formula (IN) (a divalent structural unit derived from substituted or unsubstituted indene), a structural unit represented by general formula (MI) (a divalent structural unit derived from substituted or unsubstituted maleimide), a structural unit represented by general formula (ST) (a divalent structural unit derived from substituted or unsubstituted styrene), or a structural unit represented by general formula (NBD) (a divalent structural unit derived from substituted or unsubstituted norbornadiene).

[0125] [ka]

[0126] In general formula (IN), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group. 3 represents a hydrogen atom, an alkyl group, or an aryl group. 4 ~R 6 each independently represents a hydrogen atom, an alkyl group, or an aryl group. 7 ~R 10 each independently represents a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

[0127] 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 polymer P, 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.

[0128] The weight-average molecular weight Mw of the polymer P is, for example, 2,000 to 200,000, preferably 3,000 to 150,000, more preferably 5,000 to 100,000, and still more preferably 8,000 to 80,000. By appropriately adjusting the weight-average molecular weight, it is possible to adjust the sensitivity and solubility in an alkaline developer.

[0129] The dispersity of the polymer P (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 8.0, more preferably 1.5 to 7.0, and even more preferably 2.0 to 6.0. 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.

[0130] (Method of manufacturing polymer P) The polymer P of this embodiment can be produced (synthesized) by any method. The production methods of the polymer P will be explained in the first, second, and third embodiments. In the first and second embodiments, the polymer precursor P′ is exemplified as containing a structural unit represented by general formula (8), but the structural unit is optional, and the polymer P of the present embodiment may contain a structural unit represented by general formula (8) and a structural unit represented by general formula (3).

[0131] (First embodiment) The method for producing the polymer P of this embodiment is as follows: (I) a first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), and a structural unit represented by the following general formula (MA); and [ka]

[0132] (II) A second step of reacting the polymer precursor P' obtained in the first step with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P containing a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (3), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), and optionally a structural unit represented by the following general formula (MA).

[0133] [ka]

[0134] Hereinafter, a method for producing (synthesizing) the polymer P of this embodiment through these steps will be described. The first step (I) of preparing the polymer precursor P' comprises: (Ii) preparing a raw material polymer containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (MA); [ka]

[0135] (I-ii) a step of reacting the raw material polymer obtained in step (Ii) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a first polymer precursor containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), and a structural unit represented by the following general formula (MA); and

[0136] [ka]

[0137] (I-iii) Preferably, the method includes a step of reacting the first polymer precursor obtained in step (I-ii) with a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a second polymer precursor containing structural units represented by the following general formula (2), the following general formula (7), the following general formula (8), and the following general formula (MA). Here, the second polymer precursor obtained in step (I-iiii) corresponds to the polymer precursor P' described in the above step (I).

[0138] [ka]

[0139] (Process (I-i)) In step (Ii), a raw polymer containing a structural unit represented by general formula (2) and a structural unit represented by general formula (MA) can be prepared by polymerizing (addition polymerization) a monomer represented by general formula (NBm) with maleic anhydride. 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that of general formula (2), and the same applies to preferred embodiments.

[0140] [ka]

[0141] Examples of the monomer represented by general formula (NBm) include bicyclo[2.2.1]-hept-2-ene (trivial name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride. In the polymerization, the monomer represented by general formula (NBm) may be used alone or in combination of two or more.

[0142] 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.

[0143] Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0144] 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.

[0145] As the polymerization solvent, 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.

[0146] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by the general formula (NBm), maleic anhydride, and a polymerization initiator in a solvent and charging the resulting solution into a reaction vessel, followed by heating 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.

[0147] When charging the monomer represented by general formula (NBm) to maleic anhydride into a reaction vessel, the molar ratio is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. Through such a process, a "raw polymer" can be obtained.

[0148] The raw polymer may be a random copolymer, an alternating copolymer, a block copolymer, or a periodic copolymer. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability. 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.

[0149] Specifically, the organic phase containing the synthesized raw polymer and low-molecular-weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried, thereby increasing the purity of the raw polymer.

[0150] (Process (I-ii)) The raw polymer obtained in step (Ii) is reacted with a polyfunctional (meth)acrylic compound in the presence of a basic catalyst, whereby some of the structural units represented by general formula (MA) contained in the raw polymer are ring-opened to form structural units represented by general formula (7), thereby obtaining a first polymer precursor containing structural units represented by general formula (2), structural units represented by general formula (MA), and structural units represented by general formula (7).

[0151] 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. Next, a polyfunctional (meth)acrylic compound is added to the above solution, followed by a basic catalyst, and the solution is mixed appropriately to obtain a homogeneous solution.

[0152] Examples of the polyfunctional (meth)acrylic compound include a compound represented by general formula (1b-m), a compound represented by general formula (1c-m), and a compound represented by general formula (1d-m). 1 , X 1 ' and X 2 The definitions and specific embodiments of k, R, and X in general formula (1c-m) are the same as those in general 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 general formula (1c). The definition of n in the general formula (1d-m) is the same as those in the above general formula (1d).

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] As the basic catalyst, amine compounds or nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as the catalyst. 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.

[0157] The solution is heated, preferably at 60 to 80°C, for about 3 to 9 hours, to open a portion of the structural units of general formula (MA) contained in the raw polymer and form structural units of general formula (7), thereby producing a first polymer precursor containing structural units represented by general formula (2), structural units represented by general formula (MA), and structural units represented by general formula (7).

[0158] (Process (I-iii)) Next, the first polymer precursor obtained in step (I-ii) is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst, whereby some of the structural units represented by general formula (MA) contained in the first polymer precursor are ring-opened to form structural units represented by general formula (8). As a result, a second polymer precursor containing structural units represented by general formula (2), structural units represented by general formula (MA), structural units represented by general formula (7), and structural units represented by general formula (8), i.e., polymer precursor P', is obtained.

[0159] The step (I-iii) is preferably carried out by adding a monofunctional (meth)acrylic compound to a reaction system containing the first polymer precursor obtained in the step (I-ii). Note that, due to steric hindrance of the reaction, monofunctional (meth)acrylic compounds tend to react more easily with the raw material polymer than polyfunctional (meth)acrylic compounds. Therefore, the step (I-ii) of reacting the monofunctional (meth)acrylic compound and the step (I-iii) of reacting the monofunctional (meth)acrylic compound are preferably not carried out simultaneously but are carried out sequentially in this order.

[0160] The reaction between the monofunctional (meth)acrylic compound and the first polymer precursor proceeds in the presence of a basic catalyst. The basic catalyst remaining in the reaction system obtained in step (I-ii) can be used as is. Therefore, step (I-iii) is preferably carried out in situ by adding the monofunctional (meth)acrylic compound to the reaction mixture containing the first polymer precursor obtained in step (I-ii) without isolating and purifying the first polymer precursor from the reaction mixture containing the first polymer precursor obtained in step (I-ii) or neutralizing the basic catalyst contained in the mixture.

[0161] Specifically, a reaction solution obtained by adding a monofunctional (meth)acrylic compound to a reaction mixture containing a first polymer precursor is heated, preferably at 60 to 80°C, for about 1 to 9 hours, whereby some of the structural units represented by general formula (MA) contained in the first polymer precursor undergo ring-opening, forming structural units represented by general formula (8), and producing polymer precursor P'.

[0162] The monofunctional (meth)acrylic compound used in step (I-iii) may be, for example, a compound represented by the following general formula (3a-m): 10 and R are defined as in general formula (3a).

[0163] [ka]

[0164] Specific examples of the compound represented by general formula (3a-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.

[0165] (Process II)) The polymer precursor P' obtained in the first step (I) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, and the carboxyl group of the polymer precursor P' reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound to form structural units represented by general formula (1) and structural units represented by general formula (3), thereby preparing a polymer P containing structural units represented by general formula (1), structural units represented by the above-mentioned general formula (2), structural units represented by the above-mentioned general formula (3), structural units represented by the above-mentioned general formula (7), structural units represented by the above-mentioned general formula (8), and in some cases structural units represented by the above-mentioned general formula (MA).

[0166] The step (II) is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor P' obtained in the step (I-iii).

[0167] The reaction between the polymer precursor P' and the 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 (I-iii) can be used as is. Therefore, step (II) is preferably carried out in situ by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor P' obtained in step (I-iii), without isolating and purifying the polymer precursor P' from the reaction mixture containing the polymer precursor P' obtained in step (I-iii) or neutralizing the basic catalyst contained in the mixture.

[0168] Specifically, an epoxy group-containing (meth)acrylic compound is further added to a reaction mixture containing a polymer precursor P', and the resulting reaction solution is heated preferably at 60 to 80°C for about 1 to 9 hours. As a result, the carboxyl groups of the polymer precursor P' react with the epoxy groups of the epoxy group-containing (meth)acrylic compound to form structural units represented by general formula (1) and structural units represented by general formula (3), thereby producing a polymer P.

[0169] 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.

[0170] 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 P'.

[0171] After the step (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.

[0172] 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.

[0173] 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). After washing with ion-exchanged water, the polymer powder is dried, for example, at 30 to 60° C. for 16 hours or more, whereby a highly pure polymer P can be obtained.

[0174] (Second embodiment) The method for producing the polymer P of this embodiment is as follows: (a) a first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), and a structural unit represented by the following general formula (MA);

[0175] [ka]

[0176] (b) a second step of treating the polymer precursor P′ obtained in the first step with water in the presence of a catalyst to prepare a polymer precursor (hereinafter referred to as “polymer precursor P”) containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (4), a structural unit represented by the following general formula (7), and a structural unit represented by the following general formula (8), and optionally containing a structural unit represented by the following general formula (MA); and [ka]

[0177] (c) A third step of reacting the polymer precursor P" obtained in the second step with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer containing a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (3), a structural unit represented by the following general formula (4), a structural unit represented by the following general formula (5), a structural unit represented by the following general formula (6), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), and optionally a structural unit represented by the following general formula (MA). [ka]

[0178] The following describes a method for producing (synthesizing) the polymer P through these steps. Note that the first step (a) of preparing the polymer precursor is the same as the first step (I) of this embodiment, and therefore a description thereof will be omitted.

[0179] (Step (b)) By treating the polymer precursor P' obtained in step (a) with water in the presence of a catalyst, the structural units represented by general formula (MA) contained in the polymer precursor P' undergo ring-opening to form structural units represented by general formula (4), thereby producing a polymer precursor P" containing structural units represented by general formula (2), structural units represented by general formula (4), structural units represented by general formula (7), and structural units represented by general formula (8). When some of the structural units represented by general formula (MA) undergo ring-opening and some of the structural units of general formula (MA) remain without ring-opening, the polymer contains structural units represented by general formula (MA) in addition to the structural units of general formula (2), general formula (4), general formula (7), and general formula (8).

[0180] Step (b) is preferably carried out by adding water to the reaction system containing the polymer precursor P' obtained in step (I-iii) above. A basic catalyst can be used as the catalyst used in step (b), and the same catalyst as the basic catalyst used in step (I-ii) or step (I-iii) above can be used. Specific examples of basic catalysts include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0181] In step (b), water is added to a reaction system containing the polymer precursor P' obtained in step (I-iii) above, and the resulting reaction solution is heated, preferably at 60 to 80°C for approximately 0.25 to 6 hours, to open the structural unit of general formula (MA) contained in the polymer precursor P' and produce a structural unit represented by general formula (4). This reaction proceeds in the presence of a basic catalyst. The basic catalyst remaining in the reaction system obtained in step (I-iii) can be used as is. Therefore, step (b) is preferably carried out in situ by adding water to the reaction mixture containing the polymer precursor P' obtained in step (I-iii), without isolating and purifying the polymer precursor P' from the reaction mixture containing the polymer precursor P' obtained in step (I-iii) or neutralizing the basic catalyst contained in the mixture.

[0182] In the third step (c), the polymer precursor P" obtained in the second step (b) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P. The reaction conditions for the third step (c) are the same as those for the second step (ii) of the first embodiment, and therefore will not be described here. After the third step (c), in order to remove unnecessary components other than the desired polymer P, it is preferable to carry out a washing step or the like as appropriate, as in the first embodiment.

[0183] (Third embodiment) The method for producing the polymer P of this embodiment is as follows: (A) a first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), a monovalent to hexavalent thioether-containing organic group (i) having 1 to 30 carbon atoms (thioether-containing organic group (i)) derived from a difunctional or higher functional thiol group-containing compound, and a structural unit represented by the following general formula (MA); and [ka]

[0184] (B) a second step of reacting the polymer precursor P' obtained in the first step with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P containing a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (3), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), a thioether-containing organic group (i), and optionally a structural unit represented by the following general formula (MA):

[0185] [ka]

[0186] Hereinafter, a method for producing (synthesizing) the polymer P of this embodiment through these steps will be described. Note that the third embodiment differs from the first step (I) of preparing the polymer precursor in the first embodiment only in the first step (A) of preparing the polymer precursor. Therefore, a description of step (B) will be omitted.

[0187] The first step (A) of preparing the polymer precursor P' comprises: (Ai) preparing a raw material polymer containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (MA), and a thioether-containing organic group (i); [ka]

[0188] (A-ii) a step of reacting the raw material polymer obtained in step (Ai) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a first polymer precursor containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a thioether-containing organic group (i), and a structural unit represented by the following general formula (MA); and

[0189] [ka]

[0190] (A-iii) It is preferable to include a step of reacting the first polymer precursor obtained in step (A-ii) with a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a second polymer precursor containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), a thioether-containing organic group (i), and a structural unit represented by the following general formula (MA).

[0191] [ka]

[0192] (Process (A)) In step (Ai), the step of preparing a raw polymer containing the structural unit represented by general formula (2), the structural unit represented by general formula (MA), and the thioether-containing organic group (i) can be carried out by polymerizing (addition polymerization) a monomer represented by general formula (NBm) and maleic anhydride in the presence of the bifunctional or higher thiol group-containing compound. 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that in general formula (2). The same applies to preferred aspects. The polymerization conditions are also the same as those in step (Ii) of the first embodiment.

[0193] [ka]

[0194] The bifunctional or higher thiol group-containing compound includes compounds represented by the above chemical formula (s-1) to (s-21)Examples of the bifunctional or higher functional thiol group-containing compound include, but are not limited to, compounds represented by the following formula: One type of compound may be used alone, or two or more types may be used in combination.

[0195] Step (A-ii) and step (A-iii) of this embodiment can be carried out using conditions similar to those in step (I-ii) and step (I-iii) of the first embodiment, respectively.

[0196] In this embodiment as well, it is preferable to appropriately carry out a washing step or the like after the step (B) in order to remove unnecessary components other than the desired polymer P, as in the first embodiment.

[0197] (Polyfunctional (meth)acrylic compound) The polymer solution of this embodiment contains a polyfunctional (meth)acrylic compound. By including the polyfunctional (meth)acrylic compound, the alkali solubility of the photosensitive resin composition is improved, and further yellowing of the photosensitive resin composition is reduced, making it possible to obtain a cured product with excellent transparency. Furthermore, by including the polyfunctional (meth)acrylic compound, when the polymer solution is used to manufacture a color filter, a black matrix, or the like, the occurrence of undissolved residue near the pattern of a fine line pattern is further suppressed, and the desired shape is obtained, thereby further improving yield, and further reducing yellowing of the fine line pattern and improving transparency.

[0198] Examples of the polyfunctional (meth)acrylic compound to be blended in the polymer solution of this embodiment include, but are not limited to, compounds represented by the following formulas (1b-p), (1c-p), and (1d-p). 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 X6 The definition and specific embodiments of are the same as those in the above formula (1c). n and R in formula (1d-p) are the same as those in the above formula (1d). Y in formulas (1b-p), (1c-p) and (1d-p) is a hydrogen atom or a (meth)acryloyl group, or a combination thereof.

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] Specific examples of polyfunctional (meth)acrylic compounds represented by general formula (1b-p) include, but are not limited to, compounds having the following structures: In the following compounds, Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1c-p) include, but are not limited to, the following compounds.

[0207] [ka]

[0208] [ka]

[0209] [ka]

[0210] In the polymer solution of this embodiment, the polyfunctional (meth)acrylic compound is blended in an amount of 1% by mass to 40% by mass, more preferably 4% by mass to 30% by mass, even more preferably 5% by mass to 25% by mass, and even more preferably 5.5% by mass to 20% by mass, relative to the polymer P. As a result, when the polymer solution is used to manufacture a color filter, black matrix, or the like, the occurrence of undissolved residue near the fine line pattern is further suppressed, and the desired shape is achieved, thereby further improving yield, and further reducing yellowing of the fine line pattern and improving transparency.

[0211] (Monofunctional (meth)acrylic compound) The polymer solution of this embodiment may contain a compound having one (meth)acryloyl group (monofunctional (meth)acrylic compound). By containing the monofunctional (meth)acrylic compound, the alkali solubility of the resulting polymer solution is improved, and further yellowing is reduced.

[0212] Examples of monofunctional (meth)acrylic compounds that may be used in the photosensitive resin composition of this embodiment include compounds represented by the following formula (3a-m): 10 and R are defined as above. [ka]

[0213] Specific examples of the compound represented by general formula (3a-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.

[0214] When the polymer solution of this embodiment contains a monofunctional (meth)acrylic compound, the amount thereof relative to the polymer P is, for example, in the range of 1% by mass to 5% by mass.

[0215] 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.

[0216] 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 becomes, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0217] [Method of manufacturing 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.

[0218] [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.

[0219] (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 the polymer.

[0220] 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.

[0221] (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.

[0222] 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.

[0223] 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.).

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] (surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0229] 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.

[0230] 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.

[0231] (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.

[0232] 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 becomes, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0233] (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.

[0234] 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.

[0235] (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 (can chemically bond with the polymer) through the action of the 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.

[0236] 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 (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0237] 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:

[0238] 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.

[0239] 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.

[0240] (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.

[0241] [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 applicable to color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Also, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-blocking agent. Then, a liquid crystal display device or a solid-state imaging device equipped with a color filter or black matrix can be manufactured. A typical procedure for forming a pattern will now be described.

[0242] (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.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] (exposure) Exposure is typically carried out by irradiating the photosensitive resin film with actinic rays through an appropriate photomask.

[0248] 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.

[0249] 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.

[0250] (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.

[0251] 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.

[0252] 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.

[0253] 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 a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

[0254] 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 0.1 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.

[0255] For example, after development, the pattern and substrate may be washed with a rinse solution. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

[0256] 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. FIG. 1 shows a schematic diagram of an example of the structure of a liquid crystal display device and / or a solid-state imaging device that includes a color filter and / or a black matrix.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0261] EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0262] The compounds used in the examples may be indicated by the following abbreviations or trade names. MA: Maleic anhydride NB: 2-Norbornene MEK: Methyl ethyl ketone PEMP: pentaerythritol tetrakis(3-mercaptopropionate), a compound represented by the following formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) [ka] TMMP: Trimethylolpropane tris(3-mercaptopropionate), a compound represented by the following formula (s-1) (manufactured by SC Organic Chemical Co., Ltd.) [ka] DPMP: Dipentaerythritol hexakis(3-mercaptopropionate), a compound represented by the following formula (s-3) (manufactured by SC Organic Chemical Co., Ltd.) [ka] 4-HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate GMA: Glycidyl methacrylate 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]

[0263] A-9550: A mixture of the following two compounds. The amount of the compound on the left in the mixture estimated from the hydroxyl value is approximately 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0264] [ka]

[0265] <Synthesis of raw polymer> (Synthesis of raw polymer 1) 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and 41.45 g (0.180 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser, and dissolved in a solvent mixture consisting of 578.98 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 63°C for 9.5 hours with stirring to polymerize maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was diluted with 712.92 g of methyl ethyl ketone and then added dropwise to 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum dried at a temperature of 120°C to obtain 550.4 g of a polymer (raw polymer 1) having structural units derived from 2-norbornene and structural units derived from maleic anhydride. The resulting polymer was subjected to GPC measurement, and as a result, the weight average molecular weight Mw was 11,600, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.79.

[0266] (Synthesis of raw polymer 2) 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 in terms of NB), maleic anhydride (MA, 470.69 g, 4.8 mol), and 2238.50 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, 44.21 g, 0.19 mol of dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601) and 140.73 g, 0.29 mol of PEMP (pentaerythritol tetrakis(3-mercaptopropionate)) dissolved in 189.74 g of MEK were 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 908.1 g of a polymer (raw polymer 2) having structural units derived from 2-norbornene 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 2700 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.57.

[0267] [Structural analysis of raw polymer 2] The synthesis of raw polymer 2 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, and then the reaction progresses to produce the polymer. The reaction solution and the resulting polymer were analyzed, and the following results were obtained.

[0268] (a) Analysis of the reaction solution GPC measurement of the reaction solution before reprecipitation purification showed no peaks for PEMP alone. In other words, it was confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) measurement of the reaction solution before reprecipitation purification showed that the peaks for 2-norbornene alone and maleic anhydride alone in the reaction solution after the reaction were reduced compared to before the reaction, confirming that 2-norbornene and maleic anhydride had reacted to form a polymer. The measurement conditions for the gas chromatography measurement were 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

[0269] (b) Polymer analysis GPC analysis of the polymer after reprecipitation purification showed no peaks corresponding to PEMP alone, 2-norbornene alone, or maleic anhydride alone, confirming that no PEMP, 2-norbornene alone, or maleic anhydride remained in the polymer.

[0270] The amount of sulfur in the obtained raw polymer 2 was confirmed by flask combustion and elemental analysis by ion chromatography, confirming the presence of elemental sulfur in raw polymer 2. 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 2.

[0271] The elemental analysis method is as follows. -Test items Determination of total sulfur by flask combustion-ion chromatography. -Test Method Flask combustion - ion chromatography (1) Approximately 50 mg of sample is completely combusted in a sealed flask with the atmosphere replaced with oxygen. (2) The gas generated is collected in the hydrogen peroxide absorbent solution that has been added beforehand in the flask, and the solution is made into a constant volume of 50 ml, which is used as the test solution. (3) The test solution and the standard solution are introduced into the ion chromatograph, and the concentration of sulfate ions is determined using the calibration curve method, and the amount of sulfur contained in the sample is calculated. -Equipment used Dionex ICS-3000 Ion Chromatograph

[0272] [Confirmation of the thioether structure contained in raw polymer 2] In the 13C-NMR measurement of PEMP alone, which is represented by the following chemical formula, peak a derived from carbon a was confirmed at around 19.0 ppm, and peak b derived from carbon b was confirmed at around 62.0 ppm.

[0273] [ka] Raw polymer 1 synthesized using PEMP 13 In 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. 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 62.0 ppm thioether (RS-R') appeared around 28 ppm. The integral value of this peak c was approximately twice the integral value of peak b, indicating that raw polymer 2 had a skeleton with a thioether group as shown below, and the thiol group had disappeared. It is believed that the polymers of the examples synthesized using raw polymer 2 also had a similar skeleton.

[0274] [ka] 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)

[0275] (Synthesis of raw polymer 3) 900.1 g of a polymer (raw polymer 3) having structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained in the same manner as for raw polymer 2, except that TMMP (101.99 g, 0.25 mol) was used instead of PEMP. The obtained raw polymer 3 was measured by gel permeation chromatography (GPC) to find that the weight average molecular weight Mw was 3,100 and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.74. In the GPC measurement of the reaction solution, no peak of TMMP alone was observed, and no unreacted TMMP remained, confirming that TMMP was incorporated into Raw Material Polymer 3. In addition, raw polymer 3 13 C-NMR measurement confirmed that TMMP was incorporated into the starting polymer 3. The amount of sulfur in the obtained Raw Material Polymer 3 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in Raw Material Polymer 3.

[0276] (Synthesis of raw material polymer 4) In the same manner as in the preparation of Raw Polymer 2, except that DPMP (100.23 g, 0.13 mol) was used instead of PEMP, 890.2 g of a polymer (Raw Polymer 4) having structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained. The resulting Raw Material Polymer 4 was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,600 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 2.02. GPC measurement of the reaction solution showed no peak of DPMP alone, and no unreacted DPMP remained, confirming that DPMP was incorporated into Raw Material Polymer 4. In addition, raw material polymer 4 13 C-NMR measurement confirmed that DPMP was incorporated into the starting polymer 4. The amount of sulfur in the obtained Raw Material Polymer 4 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in Raw Material Polymer 4.

[0277] <Synthesis of Polymer P> (Preparation Example 1: Preparation of Polymer P1) The MA units of raw polymer 1 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (HEMA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P1. Details are described below. First, 102.26 g of MEK was added to 60 g of raw polymer 1 (0.312 mol of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70°C for 2 hours. 50.78 g (0.390 mol) of HEMA was then added, and the mixture was allowed to react at 70°C for 4 hours. 26.62 g (0.187 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, the structural units derived from maleic anhydride in the raw polymer 1 were ring-opened with A-TMM-3LM-N and HEMA, and reacted with GMA to obtain polymer P1. GPC analysis of polymer P1 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used, confirming that the obtained polymer P1 does not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0278] (Preparation Example 2: Preparation of Polymer P2) The MA units of raw polymer 1 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), and then water was added to further open the ring, followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P2. Details are explained below. First, 103.92 g of MEK was added to 60 g of raw polymer 1 (0.312 mol of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70°C for 2 hours. 1.50 g (0.083 mol) of water was then added, and the mixture was allowed to react at 70°C for 2 hours. 26.62 g (0.187 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, the structural unit derived from maleic anhydride in the raw polymer 1 was ring-opened with A-TMM-3LM-N and water, and reacted with GMA to obtain polymer P2. GPC analysis of polymer P2 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used, confirming that the obtained polymer P4 did not contain any unreacted (meth)acrylic compound, (meth)acrylic compound without a hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0279] (Preparation Example 3: Preparation of Polymer P3) The MA units of raw polymer 1 were ring-opened with a pentafunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P3. Details are described below. First, 102.36 g of MEK was added to 60 g of raw polymer 1 (0.312 mol of MA) to prepare a solution. Next, 52.54 g of A-9550 was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70°C for 2 hours. 56.27 g (0.390 mol) of 4-HBA was then added, and the mixture was allowed to react at 70°C for 4 hours. 26.62 g (0.187 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, the structural units derived from maleic anhydride in the raw polymer 1 were ring-opened with A-9550 and 4-HBA, and reacted with GMA to obtain polymer P3. GPC measurement of polymer P3 confirmed the disappearance of peaks of the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used, which confirmed that the obtained polymer P3 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without a hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0280] (Preparation Example 4: Preparation of Polymer P4) The MA units of raw polymer 2 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P4. Details are described below. First, 100.54 g of MEK was added to 60 g of raw polymer 2 (0.312 mol of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70°C for 2 hours. 40.51 g (0.281 mol) of 4-HBA was then added, and the mixture was allowed to react at 70°C for 4 hours. 26.62 g (0.187 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and 4-HBA, and reacted with GMA to obtain polymer P4. GPC measurement of polymer P4 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used, confirming that the obtained polymer P4 did not contain any unreacted (meth)acrylic compound, (meth)acrylic compound without a hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0281] (Preparation Example 5: Preparation of Polymer P5) Polymer P5 was prepared in the same manner as in Preparation Example 4, except that the amounts of 4-HBA added were changed to 54.02 g, GMA to 33.28 g, and MEK to 100.91 g.

[0282] (Preparation Example 6: Preparation of Polymer P6) The MA unit of raw polymer 2 was ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P13. Details are described below. First, 100.57 g of MEK was added to 60 g of raw polymer 1 (0.312 mol of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70°C for 2 hours. 13.31 g (0.094 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N, and reacted with GMA to obtain polymer P6. GPC analysis of polymer P6 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used, confirming that the obtained polymer P6 does not contain unreacted (meth)acrylic compound, (meth)acrylic compound without a hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0283] (Preparation Example 7: Preparation of Polymer P7) The MA units of raw polymer 1 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P7. Details are described below. First, 100.14 g of MEK was added to 60 g of raw polymer 1 (0.312 mol of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was allowed to react at 70 ° C for 2 hours. 56.27 g (0.390 mol) of 4-HBA was then added, and the mixture was allowed to react at 70 ° C for 4 hours. 26.62 g (0.187 mol) of GMA was then added, and the mixture was allowed to react 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 an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As described above, the MA units of raw polymer 3 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to prepare polymer P7.

[0284] (Preparation Example 8: Preparation of Polymer P8) Polymer P8 was prepared in the same manner as in Preparation Example 7, except that raw polymer 3 was replaced with raw polymer 4. The MA units of raw polymer 4 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA).

[0285] Table 1 shows the components used in each preparation example, the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%). 1 The values ​​were calculated by 1 H-NMR integral analysis and expressed in terms of maleic anhydride (MA).

[0286] (Physical properties of polymer P) The following physical properties of the polymer P obtained in each preparation example were measured, and the results are shown in Table 1.

[0287] (Weight average molecular weight (Mw) / molecular weight distribution (PDI)) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (PDI: Mw / Mn) are calculated using polystyrene equivalent values ​​obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions are as follows. The results are shown in Table 1. Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0288] (acid number) The acid value of the polymer 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 1. 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.

[0289] (double bond equivalent) 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 group (5.6-5.8 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 group (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 group 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 1. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer. A double bond equivalent of 450 g / mol or less can be considered to indicate that the polymer contains double bonds at a density sufficient for achieving high sensitivity.

[0290] [Table 1]

[0291] (Examples 1 to 8, Comparative Examples 1 to 9) (Preparation of polymer solution) The obtained polymers P1 to P8 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare polymer solutions with a solid content of 30% by mass. In Examples 1 to 8 and Comparative Example 1, a polyfunctional (meth)acrylic compound (A-TMM-3LM-N) was added in the amount shown in Table 2.

[0292] (Alkaline dissolution rate of polymer solution) The alkaline dissolution rate of the polymer solution of each of the Examples and Comparative Examples was measured using the following method. The above polymer solution was spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at 100° C. for 2 minutes to prepare a resin film with a thickness of approximately 2 μm. This resin film was immersed together with the wafer in a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) at a temperature of 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 2. If the alkali dissolution rate is 200 nm / s or more and 2200 nm / s or less, the developability can be considered good.

[0293] (Preparation of Photosensitive Resin Composition) A photosensitive resin composition was prepared by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids concentration was 30% by mass. Solid content in polymer solution (total amount of polymer P and polyfunctional (meth)acrylic compound when polyfunctional (meth)acrylic compound is contained): 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 The obtained photosensitive resin composition was filtered, if necessary, through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matter.

[0294] The photosensitive resin compositions thus obtained were evaluated for the following items.

[0295] [Developability evaluation (dissolution rate of photosensitive resin composition in alkaline developer)] The photosensitive resin compositions obtained in the examples and comparative examples were spin-coated onto wafers, the PGMEA was dried, and the wafers were pre-baked at 100°C for 2 minutes to produce resin films with a thickness of 2 μm±0.2 μm. The resin film was immersed together with the wafer in a 0.5% TMAH aqueous solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 2. If the alkali dissolution rate is 200 nm / s or more and 3000 nm / s or less, the developability can be considered good.

[0296] [Sensitivity evaluation of photosensitive resin composition (0.5% TMAH aqueous solution)] (Exposure amount that results in a film remaining rate of 90% or more) The photosensitive resin compositions obtained in the examples and comparative examples were spin-coated onto a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film 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 was developed (immersed with the wafer) in a 0.5 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for the development time listed in Table 2, resulting in an exposure 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 residual film rate was 90% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. The exposure dose at which the residual film rate was 90% or more was 50 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 If the sensitivity is below this, it can be considered as good.

[0297] (Exposure amount that results in a film remaining rate of 95% or more) The exposure dose at which the film remaining rate is 95% or more was measured using the same method as described above (exposure dose at which the film remaining rate is 90% or more). The results are shown in Table 2. The exposure dose at which the film remaining rate is 95% or more was 50 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 If the sensitivity is below this, it can be considered as good.

[0298] [Adhesion during development] (Adhesion to line patterns) The photosensitive resin composition was spin-coated onto Eagle XG glass (manufactured by Corning, thickness 0.5 mm) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film approximately 3.0 μm thick (±0.1 μm). This thin film was then irradiated with 18 mJ / cm using a Canon g+h+i-line mask aligner (PLA-501F) through a photomask with five glass sections (exposed sections) alternating between glass sections (exposed sections) 40 μm wide and 400 μm long and chrome sections (light-shielding sections) 40 μm wide and 400 μm long. 2The thin film was exposed to g+h+i rays at an exposure dose of 18 mJ / cm. This exposure allowed the glass portion of the photomask to transmit light and was therefore exposed at the specified exposure dose, while the chrome portion did not transmit light and remained unexposed, resulting in a line pattern with alternating exposed and unexposed areas. After exposure, the thin film was developed in a 0.5 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersion of the entire wafer), resulting in a line pattern of 18 mJ / cm. 2 After exposure and development, a total of five line patterns, each 40 μm wide and 400 μm long, were observed under a microscope to see if any peeling occurred. (Judgment criteria) Adhesion: After development, the line pattern was adhered to the substrate, and no peeling was observed. Peeling: In the line pattern after development, some areas were found to be peeled off from the substrate.

[0299] (Adhesion to dot patterns) The photosensitive resin composition was spin-coated onto Eagle XG glass (manufactured by Corning, thickness 0.5 mm) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film approximately 3.0 μm thick (±0.1 μm). This thin film was patterned with a total of three 50 μm wide and 50 μm long glass sections (exposed sections) and a chrome section (light-shielding section) around the glass section. The pattern was then applied to the thin film using a Canon g+h+i line mask aligner (PLA-501F) at 18 mJ / cm. 2 The thin film was exposed to g+h+i rays at an exposure dose of 18 mJ / cm. This exposure allowed the glass portion of the photomask to transmit light and was therefore exposed at the specified exposure dose, while the chrome portion did not transmit light and remained unexposed, resulting in a dot pattern with an exposed area of ​​50 μm in width and 50 μm in length. After exposure, the thin film was developed in a 0.5 mass % TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersion of the entire wafer), resulting in a dot pattern of 18 mJ / cm. 2 After exposure and development, a total of three dot patterns, each 50 μm wide and 50 μm long, were observed under a microscope to see if the pattern had peeled off. Furthermore, using the same procedure as above, dot patterns with widths and heights of 40 μm, 30 μm, 20 μm, 10 μm, 8 μm, 6 μm, 4 μm, 2 μm, and 1 μm, respectively, were observed under a microscope to see if the patterns had peeled off. The smallest dot pattern width in which no peeling was observed after development was defined as an adhesive dot pattern. Here, a dot pattern with a width of 50 μm and a length of 50 μm after development in which peeling from the substrate was observed was defined as "peeling."

[0300] (Check for unmelted areas near the pattern) A fine line pattern was formed using the photosensitive resin composition according to the following procedure, and the occurrence of undissolved residue near the fine line pattern was confirmed. The results are shown in Table 3. In each of the Examples and Comparative Examples, the photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass. 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 3.0 µm (±0.3 µm). This thin film A was irradiated with 2 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having alternating 20 μm wide glass areas (exposed areas) and 20 μm wide chrome areas (light-shielding areas). 2 2 to 24 mJ / cm at intervals of 2 Exposure to g+h+i rays at each exposure dose of 2 to 24 mJ / cm 2 A total of 12 patterns were obtained, each with an exposure dose of 2 to 24 mJ / cm. The glass part of the photomask transmits light and is therefore exposed to the specified exposure dose, while the chrome part does not transmit light and remains unexposed. 2 After exposure, the thin film was developed in a 0.5% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersion of the wafer), resulting in a pattern with an exposure dose of 2 to 24 mJ / cm. 2After exposure at each exposure dose of 2 to 24 mJ / cm , a thin film B containing a total of 12 developed patterns was obtained. 2 Of the 12 patterns exposed at an exposure dose of 1.0 μm, the pattern exposed at an exposure dose that resulted in a pattern width of 20.0±1.0 μm was observed under a microscope to see if any undissolved residue was present near the pattern. (Judgment criteria) Present: Undissolved residue was observed near the pattern. None: No undissolved residue was observed near the pattern.

[0301] [Table 2]

[0302] The photosensitive resin compositions of the Examples had a good alkali dissolution rate and therefore excellent developability. The photosensitive resin compositions of the Examples had an exposure dose of 20 mJ / cm at which the residual film ratio was 90% or 95% or more. 2 or less, in other words, it can be said that it cures with a low exposure dose and has high sensitivity. Therefore, the photosensitive resin compositions of the Examples had a good balance of high developability, high sensitivity, and a low yellow index. Furthermore, the photosensitive resin compositions of the Examples suppressed the occurrence of undissolved residues near the pattern, allowing the desired shape to be formed, allowing for adhesion of finer dot patterns, suppressing pattern peeling, and also exhibiting excellent adhesion.

[0303] <Production of color filters> 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 6 to prepare colored photosensitive resin compositions. This was then deposited on a substrate, and a green color filter was formed by exposure and alkaline development. 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.

[0304] <Fabrication of black matrix> A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 6. This was applied to a substrate, and a black matrix was formed by exposure and alkaline development. [Explanation of symbols]

[0305] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups, The polyfunctional (meth)acrylic compound is contained in an amount of 1% by mass or more and 40% by mass or less relative to the polymer. Polymer solution. 【Chemistry 1】 (In general formula (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; R Ｄ is a group containing two or more (meth)acryloyl groups. 【Chemistry 2】 (In general formula (2), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a 1 is 0, 1 or 2.)

2. The polymer solution according to claim 1, wherein the polyfunctional (meth)acrylic compound comprises at least one selected from the group consisting of a compound represented by general formula (1b-p), a compound represented by general formula (1c-p), and a compound represented by general formula (1d-p). 【Transformation 3】 (In general formula (1b-p), 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- (wherein Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (wherein 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, Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof. 【Chemistry 4】 (In general formula (1c-p), 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- (wherein Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X ２ is a (k+1)-valent organic group having 1 to 12 carbon atoms, 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, Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof. 【Transformation 5】 (In general formula (1d-p), n is an integer from 2 to 5, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different; Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

3. The polymer solution according to claim 1 or 2, wherein in the structural unit represented by general formula (1), Z contains a (meth)acryloyloxy group represented by general formula (1a). 【Transformation 6】 (In general formula (1a), R is a hydrogen atom or a methyl group.)

4. In the structural unit represented by general formula (1), R Ｄ The polymer solution according to any one of claims 1 to 3, wherein the polymer solution contains at least one group represented by the following general formulas (1b), (1c), and (1d): 【Transformation 8】 (In general 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- (wherein Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (wherein 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 9】 (In general formula (1c), 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- (wherein Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X ２ is a (k+1)-valent organic group having 1 to 12 carbon atoms, 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. 【Chemistry 10】 (In general formula (1d), n is an integer of 2 to 5, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different.)

5. The polymer solution according to any one of claims 1 to 4, wherein the polymer further contains a structural unit represented by general formula (3): 【Chemistry 11】 (In general formula (3), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group; R Ｓ is a group containing a single (meth)acryloyl group.

6. The polymer solution according to any one of claims 1 to 5, wherein the polymer further contains a structural unit represented by general formula (4): 【Chemistry 12】

7. The polymer solution according to any one of claims 1 to 6, wherein the polymer contains a structural unit represented by general formula (5): 【Chemistry 13】 (In general formula (5), Q, X, and Z have the same meanings as in general formula (1).)

8. The polymer solution according to any one of claims 1 to 7, wherein the polymer further contains a structural unit represented by general formula (6): 【Chemistry 14】 (In general formula (6), Q, X, and Z have the same meanings as in general formula (1).)

9. The polymer solution according to any one of claims 1 to 8, wherein the polymer further comprises a structural unit represented by general formula (MA). 【Chemistry 15】

10. the polymer further comprises an organic group having a thioether group; The polymer solution according to any one of claims 1 to 9, wherein the organic group having a thioether group is a monovalent to hexavalent organic group derived from at least one selected from difunctional or higher functional thiol group-containing compounds represented by the following chemical formulas (s-1) to (s-21), and the organic group having a thioether group is bonded to the structural unit represented by the general formula (1) or the structural unit represented by the general formula (2) via a thioether group (-S-* (* is a bond)) derived from the thiol group-containing compound. 【Chemistry 16】

11. The polymer solution according to claim 10, wherein the bifunctional or higher functional thiol group-containing compound comprises at least one selected from the group consisting of compounds represented by the following chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10): 【Chemistry 17】

12. The polymer solution according to any one of claims 1 to 11, which is used for forming a color filter or a black matrix.

13. A polymer solution according to any one of claims 1 to 11, a photopolymerization initiator; Photosensitive resin composition.

14. A cured product formed from the photosensitive resin composition according to claim 13.

15. A film comprising the cured product according to claim 14.

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