Polymer, polymer solution, photosensitive resin composition and use thereof

Abstract

To provide a polymer excellent in alkali solubility.SOLUTION: The polymer includes structural units of the general formulas (1-1) and (1-2) in the figure. In the formulas, Z comprises one or more (meth)acryloyl groups; Q is H or a C1-6 alkyl group; X is a divalent linking group; and RD is a group including a (meth)acryloyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer, a polymer solution, a photosensitive resin composition, and uses thereof. [Background technology]

[0002] Liquid crystal display devices and solid-state imaging devices usually include a color filter and a black matrix, and photosensitive resin compositions are often used to form the color filter and the black matrix.

[0003] For example, claim 1 of Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin having at least a group having an acidic group and two or more different polymerizable unsaturated groups in at least a side chain, a polymerizable compound, and a photopolymerization initiator. In addition, an example of Patent Document 1 describes that a methacrylic acid / allyl methacrylate / glycidyl adduct was synthesized as the alkali-soluble resin, and used to prepare a photosensitive resin composition.

[0004] Patent Document 2 describes a resin composition containing a resin containing an epoxy group and an acid group, a polybasic acid monoester of a hydroxyl group-containing polyfunctional (meth)acrylate, and a solvent, characterized in that the amount of epoxy groups is 0.5 to 3.0 mol per mol of acid groups in the resin containing an epoxy group and an acid group.

[0005] Patent Document 3 discloses a method for producing a polymer, which includes a step of reacting a precursor polymer in which the maleic anhydride moiety has been ring-opened with a compound having an epoxy group. As the compound having an epoxy group, glycidyl methacrylate is described. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2012 / 147706 [Patent Document 2] International Publication No. 2016 / 103844 [Patent Document 3] International Publication No. 2017 / 154439 Summary of the Invention [Problem to be solved by the invention]

[0007] Photosensitive resin compositions for forming color filters and black matrices use polymers that undergo a polymerization reaction and harden when exposed to light. Color filters and black matrices are produced by patterning the photosensitive resin composition through exposure and development, and then hardening the pattern.

[0008] Although "higher sensitivity" is considered a common issue for photosensitive resin compositions, 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 better the sensitivity), the shorter the time required for exposure, which can improve productivity.

[0009] On the other hand, when forming a color filter or a black matrix, the time required for developing the photosensitive resin composition is long, especially when the content of the pigment in the photosensitive resin composition is high, because the solubility of the pigment in the basic developer is low. Therefore, it is necessary to use a strong basic developer having a faster development speed than conventional basic developers. However, when the alkaline solubility of the polymer is high, the alkaline dissolution rate of the photosensitive resin composition containing the pigment and the photopolymerization initiator is too fast, or the difference in the dissolution rate between the pigment and the resin composition becomes large, so that the pattern after exposure and development may not have the shape as designed. In Patent Documents 1 to 3, there is room for improvement in these characteristics. [Means for solving the problem]

[0010] The present inventors have found that when a strongly basic developer is used, in order to obtain a pattern after exposure and development in a designed shape, it is necessary to maintain and improve the sensitivity while adjusting the alkaline solubility of the polymer contained in the photosensitive resin composition. Furthermore, the present inventors have found that the problem can be solved by improving the polymer structure, and have completed the present invention. That is, the present invention can be shown as follows.

[0011] According to the present invention, A structural unit represented by the following general formula (2): It is possible to provide a polymer including a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2). [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, and a1 is 0, 1 or 2. [ka] (In the 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. X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. In the general formula (1-2), R D is a group containing a polyfunctional (meth)acryloyl group. According to the present invention, A polymer solution can be provided that includes the polymer. According to the present invention, The polymer solution; A polyfunctional (meth)acrylate monomer; A photopolymerization initiator; It is possible to provide a photosensitive resin composition comprising: According to the present invention, A cured product of the photosensitive resin composition can be provided. According to the present invention, It is possible to provide a film made of the cured product. Effect of the Invention

[0012] According to the present invention, a polymer having excellent sensitivity and excellent alkali solubility can be provided, and can be suitably used as a polymer for forming a color filter or a black matrix. In other words, the polymer of the present invention has an excellent balance of these properties. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a diagram (cross-sectional view) illustrating a schematic example of the structure of a liquid crystal display device and / or a solid-state imaging device. [Diagram 2] 1 is a 1H-NMR chart of polymer P3 obtained in Example 1. [Diagram 3] This is an enlarged view of the peak near 6.0 ppm in the 1H-NMR chart of FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In all drawings, similar components are given similar symbols and their explanations are omitted as appropriate. In addition, all drawings are for explanatory purposes only. The shapes and dimensional ratios of each member in the drawings do not necessarily correspond to actual objects. In this specification, the expression "a~b" in the explanation of a numerical range means a or more and b or less, unless otherwise specified. For example, "5~90%" means "5% or more and 90% or less."

[0015] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, the term "alkyl group" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0016] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0017] In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0018] [Polymer P] The polymer P of this embodiment contains a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2). The polymer P containing these structural units is excellent in sensitivity and alkali solubility. In other words, it has a good balance of these properties, and is particularly excellent in sensitivity.

[0019] [ka]

[0020] 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. X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. In general formula (1-2), R D is a group containing a polyfunctional (meth)acryloyl group.

[0021] The polymer P 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, and can be suitably used as a polymer for forming a color filter or a black matrix. In particular, the polymer P of this embodiment has an adjusted alkaline solubility and excellent sensitivity, so that when a strong basic developer such as a tetramethylammonium hydroxide (TMAH) solution is used, the pattern after exposure and development can have a designed shape.

[0022] In the 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 sensitivity is excellent and the alkali solubility (developability) is excellent, in other words, a good balance between these is achieved.

[0023] From the viewpoint of these properties, Z is preferably a group containing one (meth)acryloyl group, and more preferably a group represented by the following general formula (1a).

[0024] [ka]

[0025] In general formula (1a), R is a hydrogen atom or a methyl group.

[0026] In general formula (1-1), 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.

[0027] In general formula (1-1), X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group 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.

[0028] In general formula (1-1), the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, and a naphthalene ring.

[0029] In general formula (1-2), R D is not particularly limited as long as it is a group containing two or more (meth)acryloyl groups, but is more preferably a group containing 2 to 6 (meth)acryloyl groups, and even more preferably a group containing 3 to 5 (meth)acryloyl groups. D By optimizing the number of (meth)acryloyl groups contained in the toner, it is possible to further increase the sensitivity. It is also possible to more easily achieve a high compatibility between sensitivity and developability. Furthermore, it is also possible to more easily increase the heat resistance.

[0030] In order to further improve the sensitivity, R D It is preferable that the alkyl group contains two or more acryloyl groups (groups represented by -C(=O)-CH=CH2).

[0031] R D is preferably a group represented by the following general formula (1b), (1c) or (1d): By using such a group, it tends to be easier to obtain the various effects described above.

[0032] [ka]

[0033] In general formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -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.

[0034] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

[0035] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched.

[0036] The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-. 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 described above.

[0037] 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.

[0038] X 2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon.

[0039] In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0040] [ka]

[0041] In general formula (1c), k, R, X 1 and X 2respectively represent R, k and X in the above general formula (1b). 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms. R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for general formula (1b).

[0042] 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.

[0043] X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0044] [ka]

[0045] In the general formula (1d), n is an integer of 2 to 5, and preferably 2 or 3.

[0046] The proportion of the structural units represented by formula (1-1) in all structural units of the polymer P of this embodiment is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %, and the proportion of the structural units represented by formula (1-2) is preferably 1 to 30 mol %, more preferably 2 to 20 mol %.

[0047] The polymer P of this embodiment may 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). The polymer P containing the structural unit represented by the following general formula (1) is excellent in sensitivity and alkali solubility. In other words, it has a better balance of these properties, and is particularly excellent in sensitivity.

[0048] [ka]

[0049] 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 formula (1) in all structural units of the polymer P of this embodiment is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %. The polymer P of the present embodiment may also contain 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) as a structural unit including the structural unit represented by the general formula (1-1). These structural units will be described later. Furthermore, the polymer P of the present embodiment 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.

[0050] The polymer P of the present embodiment may further include a structural unit represented by the following general formula (2).

[0051] [ka]

[0052] In general formula (2), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0053] The structural unit represented by the general formula (2) is chemically robust. Therefore, the polymer P containing this structural unit undergoes little weight loss when subjected to heat treatment and is stable. Therefore, the photosensitive resin composition containing the polymer P can be suitably used for producing films and filters for use in liquid crystal displays and solid-state imaging devices that require heat resistance.

[0054] R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] In the structural unit represented by the general formula (2), R 1 , R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, and more preferably hydrogen.

[0059] In addition, R 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, or the like. 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 formula (2), a1 is preferably 0 or 1, and more preferably 0.

[0060] The proportion of the structural units represented by formula (2) in all structural units of the polymer P is preferably from 10 to 90 mol %, more preferably from 30 to 70 mol %, and further preferably from 40 to 60 mol %.

[0061] The polymer P of the present embodiment may further include a structural unit represented by the following general formula (3-1). [ka]

[0062] In general formula (3-1), R S is a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while when the developability is improved, the curing tends to be insufficient, so that the polymer P preferably further contains a structural unit represented by the general formula (3-1), which allows both the sensitivity and the developability to be compatible in a good balance.

[0063] R S is, for example, a group represented by the following general formula (3a).

[0064] [ka]

[0065] In the 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 further preferably 1 to 10. In the 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 further preferably 1 to 10.

[0066] X 10As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0067] 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.

[0068] 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.

[0069] Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

[0070] The proportion of the structural units represented by formula (3-1) in all structural units of the polymer P of this embodiment is preferably from 5 to 40 mol %, more preferably from 10 to 30 mol %.

[0071] The polymer P of the present embodiment can contain a structural unit represented by the following general formula (3) which is composed of a structural unit represented by general formula (1-1) and a structural unit represented by general formula (3-1).

[0072] [ka]

[0073] In the general formula (3), Z, Q, and X are the same as those in the general formula (1-1), and RS has the same meaning as general formula (3-1).

[0074] 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 %. The polymer P of the present embodiment may also contain a structural unit represented by the below-described general formula (8) as a structural unit including the structural unit represented by the general formula (3-1). This structural unit will be described later.

[0075] The polymer P of the present embodiment may further include a structural unit represented by the following general formula (4).

[0076] By containing 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), the alkali solubility of polymer P can be adjusted. As a result, the photosensitive resin composition containing polymer P has an excellent balance between sensitivity and developability even when subjected to photolithography processing using a strongly basic developer.

[0077] [ka]

[0078] 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 %.

[0079] The polymer P of the present embodiment may further include a structural unit represented by the following general formula (5) which contains a structural unit represented by general formula (1-1). By including this structural unit, both the sensitivity and the developability can be achieved in a better balance.

[0080] [ka]

[0081] In formula (5), Z, X, and Q have the same meanings as in 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 %.

[0082] From the viewpoint of the effects of the present invention, the polymer P of the present embodiment may further contain a structural unit represented by the following general formula (6) consisting of two structural units represented by the general formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0083] [ka]

[0084] In the general formula (6), Z, X, and Q have the same meanings as in the general formula (1-1). A plurality of Z's, a plurality of Q's, and a plurality of X's may be the same or different.

[0085] 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 %.

[0086] 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).

[0087] [ka]

[0088] 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 %.

[0089] From the viewpoint of the effects of the present invention, the polymer P of the present embodiment may further contain a structural unit represented by the following general formula (8).

[0090] [ka]

[0091] In formula (8), Q, X and Z have the same meanings as in 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 3 to 35 mol %, more preferably 5 to 25 mol %.

[0092] In this embodiment, the polymer P may contain a structural unit represented by general formula (MA) in addition to the above structural units. The structural unit represented by general formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P containing this structural unit has excellent developability. When the polymer P contains a structural unit represented by general formula (MA), the structural unit represented by general formula (MA) preferably accounts for 1 to 30 mol %, more preferably 2 to 25 mol %, of all the structural units of the polymer P.

[0093] [ka]

[0094] The content (ratio) of each structural unit contained in polymer P can be determined by the amount (molar amount) of the raw material used in synthesizing polymer P, the amount of the raw material remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0095] 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 further preferably 8,000 to 80,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer.

[0096] 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 further 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.

[0097] The glass transition temperature of the polymer P is preferably 150 to 250° C., more preferably 170 to 230° C. The polymer P has a relatively high glass transition temperature due to the inclusion of a structural unit represented by general formula (2). This is preferable in that a pattern formed on a substrate can be stably present in the manufacture of a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0098] The acid value of the polymer P is 70 mgKOH / g or more and 150 mgKOH / g or less, preferably 80 mgKOH / g or more and 140 mgKOH / g or less. When the acid value is within this range, the sensitivity and the alkali solubility are excellent, in other words, these properties are well balanced.

[0099] The acid value can be measured by the following method. in particular, 1Using the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as a reference, the amount of carboxyl groups is calculated from the integral value of the H peak (near 12.4 ppm) of the carboxyl group (-COOH) of polymer P. The acid value (mgKOH / g) can then be calculated from that amount.

[0100] (Production of Polymer P) The polymer P of this embodiment can be produced (synthesized) by any method. The production method of the polymer P will be described with reference to a first embodiment and a second embodiment. In the first and second embodiments, the polymer precursor P' is shown as including a structural unit represented by general formula (8) by way of example, but the structural unit is optional, and the polymer P of the present embodiment may include a structural unit represented by general formula (8) and a structural unit represented by general formula (3).

[0101] (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'") including 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);

[0102] [ka]

[0103] (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); Includes.

[0104] [ka]

[0105] Hereinafter, the 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 including a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (MA);

[0106] [ka]

[0107] (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 including 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);

[0108] [ka]

[0109] (I-iii) The first polymer precursor obtained in step (I-ii) is reacted 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), and a structural unit represented by 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).

[0110] [ka]

[0111] (Process (I-i)) In the step (Ii), the step of preparing a raw material polymer containing a structural unit represented by the general formula (2) and a structural unit represented by the general formula (MA) can be produced by polymerizing (addition polymerization) a monomer represented by the general formula (NBm) and maleic anhydride. 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that in formula (2), and the preferred embodiments are the same.

[0112] [ka]

[0113] Examples of the monomer represented by the general formula (NBm) include norbornene, norbornadiene, 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 the general formula (NBm) may be used alone or in combination of two or more kinds.

[0114] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used.

[0115] Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0116] Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more kinds.

[0117] 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.

[0118] 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 solution into a reaction vessel, and then heating the solution to cause addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

[0119] The molar ratio of the monomer represented by the general formula (NBm) to maleic anhydride when they are charged into a reaction vessel 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.

[0120] The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability. 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.

[0121] Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

[0122] (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 a portion 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).

[0123] More specifically, first, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), etc. can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used. Next, a polyfunctional (meth)acrylic compound is added to the above solution, and a basic catalyst is further added, and the solution is mixed appropriately to obtain a homogeneous solution.

[0124] 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 are the same as those in the above general formula (1b). 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiment of are the same as those in the above-mentioned general formula (1c). The definition of n in the general formula (1d-m) is the same as that in the above-mentioned general formula (1d).

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1b-m) include, but are not limited to, the following compounds.

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1c-m) include, but are not limited to, the following compounds.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] 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, dimethylaminopyridine can be used as catalysts. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass relative to 100 parts by mass of the raw material polymer.

[0137] The above solution is heated, preferably at 60 to 80°C, for about 3 to 9 hours, whereby some of the structural units of general formula (MA) contained in the raw material polymer are ring-opened and structural units of general formula (7) are formed, 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).

[0138] (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 a portion 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), thereby obtaining a second polymer precursor comprising 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'.

[0139] It is preferable to carry out the step (I-iii) by adding a monofunctional (meth)acrylic compound to the reaction system containing the first polymer precursor obtained in the step (I-ii). In addition, from the viewpoint of steric hindrance of the reaction, the monofunctional (meth)acrylic compound tends to react more easily with the raw material polymer than the polyfunctional (meth)acrylic compound. Therefore, it is preferable to carry out the step (I-ii) of reacting the monofunctional (meth)acrylic compound and the step (I-iii) of reacting the monofunctional (meth)acrylic compound in the order of succession, rather than simultaneously.

[0140] The reaction between the monofunctional (meth)acrylic compound and the first polymer precursor proceeds in the presence of a basic catalyst. The basic catalyst may be the catalyst remaining in the reaction system obtained in step (I-ii) as it is. Therefore, it is preferable to carry out step (I-iii) 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.

[0141] 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 a portion of the structural units represented by general formula (MA) contained in the first polymer precursor undergoes ring-opening, forming structural units represented by general formula (8), and polymer precursor P' is produced.

[0142] The monofunctional (meth)acrylic compound used in step (I-iii) may be, for example, a compound represented by the following general formula (3a-m). In general formula (3a-m), X 10 and R is defined as the same as in general formula (3a).

[0143] [ka]

[0144] 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.

[0145] (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 a structural unit represented by general formula (1) and a structural unit represented by general formula (3) are formed by the reaction between the carboxyl group of the polymer precursor P' and the epoxy group of the epoxy group-containing (meth)acrylic compound, thereby preparing a polymer P containing the structural unit represented by general formula (1), the structural unit represented by the above general formula (2), the structural unit represented by the above general formula (3), the structural unit represented by the above general formula (7), the structural unit represented by the above general formula (8), and in some cases the structural unit represented by the above general formula (MA).

[0146] 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).

[0147] 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 may be the catalyst remaining in the reaction system obtained in step (I-iii) as it is. Therefore, it is preferable to carry out step (II) 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.

[0148] Specifically, an epoxy group-containing (meth)acrylic compound is added to a reaction mixture containing a polymer precursor P' to obtain a reaction solution, which is then heated, preferably at 60 to 80°C, for about 1 to 9 hours. The carboxyl group of the polymer precursor P' reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound to form a structural unit represented by general formula (1) and a structural unit represented by general formula (3), thereby producing a polymer P.

[0149] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, and the like, and one or more selected from these can be used.

[0150] The amount of the epoxy group-containing (meth)acrylic compound added is desirably 0.1 to 3.0 moles per mole of the carboxyl group of the polymer precursor P'.

[0151] After the step (II), in order to remove unnecessary components other than the desired polymer P, it is preferable to further carry out the following steps as appropriate.

[0152] First, the reaction solution diluted with an organic solvent and to which an acid (e.g., formic acid, citric acid, etc.) has been added is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of polymer P is obtained.

[0153] An excess amount of toluene is added to the obtained organic solution of polymer P to reprecipitate polymer P. Furthermore, the polymer powder obtained by reprecipitation is further washed several times (for example, twice) with toluene. Furthermore, in order to remove the acid or basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (for example, three times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more, to obtain a high-purity polymer P of this embodiment.

[0154] 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'") including 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);

[0155] [ka]

[0156] (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);

[0157] [ka]

[0158] (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); Includes.

[0159] [ka]

[0160] Hereinafter, the method for producing (synthesizing) the polymer of this embodiment by these steps will be described. Note that the first step (a) of preparing the polymer precursor is the same as the first step (I) of this embodiment, so the description will be omitted.

[0161] (Step (b)) The polymer precursor P' obtained in step (a) is treated with water in the presence of a catalyst, whereby the structural unit represented by general formula (MA) contained in the polymer precursor P' undergoes ring-opening to form a structural unit 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 being ring-opened, the polymer contains the structural unit 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).

[0162] The step (b) is preferably carried out by adding water to the reaction system containing the polymer precursor P' obtained in the above step (I-iii). A basic catalyst can be used as the catalyst used in the step (b), and the same catalyst as the basic catalyst used in the above step (I-ii) or step (I-iii) can be used. Specific examples of the basic catalyst include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0163] In step (b), water is added to the reaction system containing the polymer precursor P' obtained in the above-mentioned step (I-iii), and the resulting reaction solution is heated, preferably at 60 to 80°C, for about 0.25 to 6 hours, to open the structural unit of general formula (MA) contained in the polymer precursor P', and generate the 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 it 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.

[0164] 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. Note that the reaction conditions in the third step (c) are the same as those in the second step (ii) of the first embodiment, and therefore a description thereof will be omitted. After the third step (c), in order to remove unnecessary components other than the desired polymer P, it is preferable to appropriately carry out a washing step or the like as in the first embodiment.

[0165] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. Furthermore, the polymer P may contain at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, as long as the effect of the present invention is not adversely affected.

[0166] [Polyfunctional (meth)acrylic compounds] As the polyfunctional (meth)acrylate compound, which is a compound having two or more (meth)acryloyl groups, any conventionally known compound can be used as long as it can exert the effects of the present invention. Examples of polyfunctional (meth)acrylic compounds include, but are not limited to, compounds represented by the following general formula (1b-p), compounds represented by general formula (1c-p), and compounds represented by general formula (1d-p).

[0167] k, R, and X in general formula (1b-p) 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above 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).

[0168] In general formulae (1b-p), (1c-p) and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof. The compounds in which Y is a hydrogen atom in general formula (1b-p), general formula (1c-p) and general formula (1d-p) may be unreacted monomers (i.e., compounds represented by general formula (1b-p), general formula (1c-p) and general formula (1d-p)) or may be added separately.

[0169] In the general formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1b-p) include, but are not limited to, compounds having the following structures, in which Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1c-p) include, but are not limited to, the following compounds.

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] In the polymer solution of the present embodiment, the polyfunctional (meth)acrylic compound can be blended in an amount that does not affect the effects of the present invention, and can be blended in an amount such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the resin composition is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​the resin.

[0182] [Monofunctional (meth)acrylic compounds] The polymer solution of the present embodiment may contain a monofunctional (meth)acrylic compound, which is a compound having one (meth)acryloyl group.

[0183] Examples of the monofunctional (meth)acrylic compound include compounds represented by the following general formula (2a-m): The monofunctional (meth)acrylic compound may be an unreacted monomer, or may be added separately. In general formula (2a-m), X 10 The definition of R is the same as that in general formula (2a).

[0184] [ka]

[0185] Specific examples of the compound represented by general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

[0186] In the polymer solution of the present embodiment, the monofunctional (meth)acrylic compound may be blended within a range that does not affect the effects of the present invention, and may be blended in an amount such that the peak area attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the resin composition is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​the resin.

[0187] The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. The organic solvent may be one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc.

[0188] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0189] (Preparation of polymer solution) The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

[0190] <Photosensitive resin composition> The photosensitive resin composition of the present embodiment includes the above-mentioned polymer, a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound added as necessary, and a photosensitizer. That is, the photosensitive resin composition of the present embodiment includes the above-mentioned polymer solution (varnish, resin composition) of the present embodiment and a photosensitizer. Each component will be described below.

[0191] [Photosensitizer] The photosensitizer used in the photosensitive resin composition of the present embodiment includes a photoradical polymerization initiator. As the photoradical polymerization initiator, a known compound can be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl ... -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, etc.; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc.; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer.

[0192] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in photolithography. In addition, since yellowing of the photosensitive resin composition is suppressed, an article obtained by curing the photosensitive resin composition has transparency.

[0193] In the photosensitive resin composition of the present embodiment, the polyfunctional (meth)acrylic compound is preferably blended in an amount such that the peak area derived from the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5 to 50% of the peak area of ​​the polymer, more preferably 10 to 35%. By blending the polyfunctional (meth)acrylic compound in the above range, the resulting photosensitive resin composition has excellent alkali solubility.

[0194] The photosensitive resin composition of the present embodiment may contain a compound having one (meth)acryloyl group (monofunctional (meth)acrylic compound) in addition to the above-mentioned polymer, polyfunctional (meth)acrylic compound, and photosensitizer. The monofunctional (meth)acrylic compound is the same as that described above. By containing the monofunctional (meth)acrylic compound, the alkali solubility of the obtained photosensitive resin composition is further improved and yellowing is reduced.

[0195] When the photosensitive resin composition of the present embodiment contains a monofunctional (meth)acrylic compound, the amount of the compound is preferably such that the peak area derived from the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5 to 50% of the peak area of ​​the polymer, more preferably 10 to 35%. By adding the monofunctional (meth)acrylic compound in the above range, the obtained photosensitive resin composition has excellent alkali solubility.

[0196] In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0197] Examples of organic pigments that can be used include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, and dye lake pigments.

[0198] Examples of inorganic pigments that can be used include white pigments and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0199] As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

[0200] Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. When transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0201] Depending on the purpose and use, the colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc.

[0202] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and use. In order to achieve a balance between the coloring concentration and the dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

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

[0204] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied onto a substrate to obtain a resin film, making it possible to obtain a coating film of uniform thickness, and also makes it possible to prevent residues and pattern lifting during development of the coating film.

[0205] The nonionic surfactant is, for example, a compound containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorine-based surfactants include, but are not limited to, Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited. When a surfactant is used, the amount of the surfactant added is preferably 0.01 to 10% by weight based on 100 parts by weight of the resin.

[0206] (solvent) The photosensitive resin composition may typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. may be used.

[0207] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof. The amount of the solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0208] (Light blocking agent) The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

[0209] When the photosensitive resin composition contains a light-shielding agent, the amount of the light-shielding agent may be appropriately set depending on the purpose and use. In order to achieve a balance between the light-shielding performance and the dispersion stability of the light-shielding agent, the amount of the light-shielding agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0210] (Crosslinking agent) The photosensitive resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking a polymer (capable of chemically bonding with a polymer) by the action of an active chemical species generated from a photopolymerization initiator. The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

[0211] The crosslinking agent is preferably, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

[0212] Specific examples of crosslinking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene polyfunctional (meth)acrylates such as ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether; vinyl ether group-containing (meth)acrylic acid esters, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

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

[0214] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount of the crosslinking agent may be appropriately set according to the purpose and use. As an example, the amount of the crosslinking agent may be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, relative to 100 parts by mass of the photosensitive resin.

[0215] The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0216] [Films, color filters, black matrices, liquid crystal displays and solid-state imaging devices] A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, and then exposing and developing the film to form a pattern. This film is applied to color filters, 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-shielding agent. Then, a liquid crystal display device or a solid-state imaging device equipped with a color filter or a black matrix can be manufactured. A typical procedure for forming a pattern will now be described.

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

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

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

[0220] The photosensitive resin composition applied onto 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., and preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, and preferably about 30 to 300 seconds.

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

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

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

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

[0225] (developing) The exposed photosensitive resin film can be developed with an appropriate developer to obtain a pattern, and a substrate having a pattern can be produced.

[0226] In the development step, development can be carried out using an appropriate developer, for example, by a dipping method, a paddle 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 is no particular limitation on the type of developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used.

[0227] Specific examples of the alkaline aqueous solution include: (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous organic amine solutions 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 into a designed shape.

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

[0229] In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the aqueous alkaline 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.

[0230] For example, after development, the pattern and the 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.

[0231] The pattern thus obtained may be heated to be sufficiently cured. 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 performed 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 performed 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.

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

[0233] The substrate 10 is usually made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, a polymer of a cyclic olefin, etc. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical treatment, etc., as necessary. 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-shielding agent.

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

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

[0236] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0237] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·MA: Maleic anhydride ·NB: 2-Norbornene MEK: Methyl ethyl ketone 4-HBA: 4-Hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate ·GMA: Glycidyl methacrylate 4HBAGE: 4-Hydroxybutyl acrylate glycidyl ether A-TMM-3LM-N: A mixture of the following two compounds. The amount of the compound on the left in the mixture based on gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0238] [ka]

[0239] 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 about 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0240] [ka]

[0241] <Synthesis of raw polymer> (Synthesis of raw polymer 1) In a suitable sized reaction vessel equipped with a stirrer and a condenser, 353.02g (3.6mol) of maleic anhydride, 338.94g (3.6mol) of 2-norbornene, and 41.45g (0.180mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed out and dissolved in a mixed solvent of 578.98g of methyl ethyl ketone and 113.0g 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 3) having a structural unit derived from 2-norbornene and a structural unit 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.

[0242] (Synthesis of raw polymer 2) 353.02g (3.6 mol) of maleic anhydride, 338.94g (3.6 mol) of 2-norbornene, and 33.16g (0.144 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed into a suitable sized reaction vessel equipped with a stirrer and a condenser, and dissolved in a mixed solvent of 1030.1g of methyl ethyl ketone and 113.0g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to polymerize the maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was dropped into 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 607.5 g of a polymer (raw polymer 2) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,000 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.82.

[0243] [Comparative Example 1] (Polymer synthesis) Polymer P1 was prepared by ring-opening the MA unit of raw material polymer 1 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA). Details are described below. First, 100.30g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, polymer P1 was obtained in which the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and 4-HBA. By GPC measurement of the polymer P1, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared, and it was confirmed that the obtained polymer P1 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound not having a hydroxyl group. Table 1 shows the components used in the synthesis examples, 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 the maleic anhydride (MA) used. 1 H-NMR measurement confirmed that polymer P1 had a structure ring-opened with A-TMM-3LM-N and 4-HBA.

[0244] (Preparation of polymer solution) The obtained polymer P1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution having a solid content concentration of 30 mass %.

[0245] (Preparation of Photosensitive Resin Composition) The following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids concentration was 30% by mass, to prepare a photosensitive resin composition. Polymer P1: 100 parts by weight Multifunctional acrylate (dipentaerythritol hexaacrylate): 50 parts by mass Photopolymerization initiator (BASF, Ingacure OXE01): 5 parts by weight Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight Surfactant (DIC Corporation, F-556): 0.5 parts by weight The obtained photosensitive resin composition was filtered, if necessary, through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matters.

[0246] [Comparative Example 2] (Polymer synthesis) The MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth)acrylic compound (HEMA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce the polymer P2. The details are described below. First, 111.43g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 25.38g (0.195 moles) of HEMA was added to this solution, and then 6.00g (0.059 moles) of triethylamine was added and reacted at 70°C for 6 hours. After that, 13.31g (0.094 moles) of GMA was added and reacted at 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified as follows: The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of water. 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 HEMA, and polymer P2 was obtained by reacting with GMA. The GPC measurement of the polymer P2 confirmed the disappearance of the peaks of the monofunctional (meth)acrylic compound used, and confirmed that the obtained polymer P2 did not contain any unreacted (meth)acrylic compound or epoxy group-containing (meth)acrylic compound. Table 1 shows the components used in the synthesis examples, the amounts of each component charged in terms of maleic anhydride (MA), and the amounts 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). 1 H-NMR measurement confirmed that polymer P2 had a structure in which it had been ring-opened with HEMA and reacted with GMA. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0247] [Example 1] (Polymer synthesis) The MA unit of the raw material polymer 1 was 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 produce the polymer P3. Details are described below. First, 102.63g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 27.12g (0.187 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours. After that, 13.31g (0.094 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P3 was obtained by reacting with GMA. 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 hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. Table 1 shows the components used in the synthesis examples, the amounts of each component charged in terms of maleic anhydride (MA), and the amounts 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). Figure 2 shows the structure of polymer P3. 1 The H-NMR chart is shown in FIG. 3, and a partially enlarged view of the peak near 6.0 ppm is shown in FIG.

[0248] Polymer P3 in Figure 3 1 In addition to the peak corresponding to the 3H of the acryloyl group (-CH=CH2) at 5.8-6.7 ppm shown in the H-NMR chart, peaks corresponding to the 2H of the methacryloyl group (-C(CH3)=CH2 (CH2 of -C(CH3)=CH2) appeared at 5.6-5.8 ppm and 6.0-6.1 ppm, indicated by x. In the GPC measurement of polymer P3, no peaks were observed for the unreacted trifunctional (meth)acrylic compound (A-TMM-3LM-N), monofunctional (meth)acrylic compound (4-HBA), or epoxy group-containing (meth)acrylic compound (GMA), indicating that the acryloyl group and the methacryloyl group derived from GMA had been introduced into the polymer. In addition, in the GPC measurements of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, the peak derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) decreased before and after the ring-opening reaction, and the peak derived from GMA decreased before and after the GMA addition reaction, which indicates that A-TMM-3LM-N and GMA were introduced into the polymer.

[0249] [Example 2] (Polymer synthesis) The MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), and then water was added to further open the ring, and the polymer was then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce the polymer P4. Details are described below. First, 103.92g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 1.50g (0.083 moles) of water was added and reacted at a temperature of 70°C for 2 hours. After that, 26.62g (0.187 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and water, and reacted with GMA to obtain polymer P4. GPC measurement of polymer P3 confirmed the disappearance of peaks of the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used, which confirmed that the obtained polymer P4 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0250] [Example 3] Polymer P5 was produced in the same manner as in Example 2 except that the amounts of the raw materials added were changed as shown in Table 1. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1. By GPC measurement of the prepared polymer P5, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound used disappeared, and it was confirmed that the obtained polymer P5 did not contain any unreacted (meth)acrylic compound, any (meth)acrylic compound without a hydroxyl group, or any unreacted epoxy group-containing (meth)acrylic compound.

[0251] [Example 4] (Polymer synthesis) The MA unit of the raw material polymer 1 was 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 the polymer P6. Details are described below. First, 102.36g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 52.54g of A-9550 was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours. After that, 26.62g (0.187 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-9550 and 4-HBA, and polymer P6 was obtained by reacting with GMA. GPC measurement of polymer P6 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 P6 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0252] [Example 5] Polymer P7 was produced in the same manner as in Example 4 except that the amounts of the raw materials added were changed as shown in Table 1. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0253] [Example 6] (Polymer synthesis) The MA unit of the raw material polymer 1 was 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 the polymer P8. Details are described below. First, 102.26g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 50.78g (0.390 moles) of HEMA was added and reacted at a temperature of 70°C for 4 hours. After that, 26.62g (0.187 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and HEMA, and reacted with GMA to obtain polymer P8. GPC measurement of polymer P8 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 P8 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0254] [Example 7] Polymer P9 was produced in the same manner as in Example 6 except that the amounts of the raw materials added were changed as shown in Table 1. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1. GPC measurement of polymer P9 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 P9 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0255] [Example 8] (Polymer synthesis) The MA unit of the raw material polymer 1 was 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 (4HBAGE) to produce the polymer P10. Details are described below. First, 99.49g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours. After that, 28.13g (0.140 moles) of 4HBAGE was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P10 was obtained by reacting with 4HBAGE. GPC measurement of polymer P10 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 P10 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0256] [Example 9] (Polymer synthesis) The MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce the polymer P11. Details are described below. First, 100.57g of MEK was added to 60g of raw polymer 2 (0.312 moles of MA) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 13.31g (0.094 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous 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, the structural unit derived from maleic anhydride in the raw polymer was ring-opened with A-TMM-3LM-N and reacted with GMA to obtain polymer P11. GPC measurement of polymer P11 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 P11 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound. The polymer solution and the photosensitive resin composition were prepared in the same manner as in Comparative Example 1.

[0257] <Evaluation method> The polymers, polymer solutions, and photosensitive resin compositions synthesized in the Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1 and 2.

[0258] (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 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

[0259] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were carried out. 1 The amount of carboxyl groups is calculated from the integral value of the H peak (around 12.4 ppm) of the polymer's carboxyl group (-COOH) using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as the standard. The acid value (mgKOH / g) can then be calculated from this amount. The higher the acid value, the greater the amount of carboxyl groups per unit mass of polymer. The results are shown in Table 1. When the acid value is 70 gKOH / g or more, it can be considered that the polymer has a carboxy group necessary for the polymer to have sufficient developability.

[0260] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. As with the above method for measuring acid value, 1 H-NMR was measured. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 3H) derived from the acryloyl group in the obtained spectrum chart to the signal (8.1 ppm, 4H) derived from the phenyl group of the internal standard substance, and the amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 2H) derived from the phenyl group of the internal standard substance to the signal (8.1 ppm, 4H). Here, the signal derived from the methacryloyl group at 6.0-6.1 ppm was small and overlapped with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The amount of double bonds (mol / g) was calculated from the sum of the amount of acryloyl groups (mol / g) and the amount of methacryloyl groups (mol / g) in the calculated polymer, and the double bond equivalent (g / mol) was calculated from the amount of double bonds. The results are shown in Table 1. The smaller the double bond equivalent value, the greater the 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 high sensitivity.

[0261] (Developability evaluation (dissolution rate of polymer (or photosensitive resin composition) in alkaline developer)) The polymer solutions (or photosensitive resin compositions) obtained in the Examples and Comparative Examples were spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at 100°C for 2 minutes to produce a resin film having a thickness of 2 μm±0.2. This resin film was immersed together with the wafer in a 2.38 mass % 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 until the resin film dissolved and the interference pattern disappeared, and dividing the film thickness by that time. The results are shown in Table 1. If the alkaline dissolution rate of the polymer solution is 200 nm / s or more and 2000 nm / s or less, the developability and reproducibility of the pattern shape can be considered good. If the alkaline dissolution rate of the photosensitive resin composition is 200 nm / s or more and 2500 nm / s or less, the developability and reproducibility of the pattern shape can be considered good.

[0262] [Sensitivity evaluation of photosensitive resin composition (2.38% by mass TMAH aqueous solution)] (Exposure level at which the remaining film rate is 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 light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 100 nm. After exposure, the thin film was developed in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (only in Example 1 was it developed for 5 seconds, with the entire wafer immersed), resulting in a radiation dose of 1 to 100 mJ / cm. 2 Thin film B was obtained by exposure and development at each exposure dose. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The exposure dose at which the residual film ratio was 90% or more was determined as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. The exposure dose at which the residual film ratio was 90% or more was 20 mJ / cm 2 If it is within the range below, it can be used as a photosensitive composition without any problem.

[0263] (Exposure amount at which the remaining film rate is 95% 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 light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film was developed in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (only in Example 1 was it developed for 5 seconds, with the entire wafer immersed), resulting in a radiation dose of 1 to 100 mJ / cm. 2 Thin film B was obtained by exposure and development at each exposure dose. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The exposure dose at which the residual film ratio was 95% or more was determined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which the residual film ratio was 95% or more was 20 mJ / cm 2 If it is within the range below, it can be used as a photosensitive composition without any problem.

[0264] [Table 1]

[0265] [Table 2]

[0266] The polymers synthesized in Examples 1 to 9 all had a structural unit represented by general formula (1-1) and a structural unit represented by general formula (1-2) in the polymer structure, and had a good alkali dissolution rate and therefore excellent developability. Furthermore, the polymers had excellent sensitivity. Therefore, it was estimated that the photosensitive resin compositions containing the polymers synthesized in Examples 1 to 9 had a good balance between developability and sensitivity, and that even when a strongly basic developer was used, the patterns after exposure and development would have the designed shape.

[0267] <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 9 to prepare colored photosensitive resin compositions. This was formed into a film on a substrate, and then exposed to light and developed with an alkali to form a green color filter.

[0268] 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.

[0269] <Preparation of black matrix> A suitable amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 9 to prepare black photosensitive resin compositions. This was applied to a substrate as a film, and then exposed to light and developed with an alkaline solution to form a black matrix. [Explanation of symbols]

[0270] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer comprising a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (1-1), and a structural unit represented by the following general formula (1-2): 【Chemistry 1】 (In general formula (2), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.) 【Chemistry 2】 (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. X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. In general formula (1-2), R Ｄ is a group containing a polyfunctional (meth)acryloyl group.

2. The polymer according to claim 1 , wherein Z comprises a group represented by the following general formula (1a): 【Chemistry 4】 (In general formula (1a), R is a hydrogen atom or a methyl group.)

3. The R Ｄ The polymer according to claim 1 or 2, wherein the at least one group contains 2 to 6 (meth)acryloyl groups.

4. The R Ｄ The polymer according to any one of claims 1 to 3, which contains at least one group represented by the following general formula (1b), (1c) or (1d): 【Chemistry 5】 (In general formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' represents an alkylene group having 1 to 6 carbon atoms, and Z' represents -O- or -COO-), X ２ is a k+1 valent organic group having 1 to 12 carbon atoms. 【Chemistry 6】 (In general formula (1c), k, R, X １ and X ２ respectively represent R, k and X in the general formula (1b). １ and X ２ Each R may be the same or different; each X may be the same or different. １ may be the same or different, X ３ is a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is a divalent organic group having 1 to 6 carbon atoms. 【Chemistry 7】 (In general formula (1d), n is an integer of 2 to 5.)

5. The polymer according to any one of claims 1 to 4, comprising a structural unit represented by the following general formula (1): 【Chemistry 8】 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).

6. The polymer according to any one of claims 1 to 5, further comprising a structural unit represented by the following general formula (3-1): 【Chemistry 9】 (In general formula (3-1), R Ｓ is a group containing only one (meth)acryloyl group.

7. The polymer according to any one of claims 1 to 6, further comprising a structural unit represented by the following general formula (4): 【Chemistry 10】

8. The polymer according to any one of claims 1 to 7, further comprising a structural unit represented by the following general formula (5): 【Chemistry 11】 (In formula (5), Q, X and Z are the same as those in formula (1-1).)

9. The polymer according to any one of claims 1 to 8, further comprising a structural unit represented by the following general formula (6): 【Chemistry 12】 (In the general formula (6), Q, X, and Z have the same meanings as in the general formula (1-1). A plurality of Z's, a plurality of Q's, and a plurality of X's may be the same or different.)

10. The polymer according to any one of claims 1 to 9, further comprising a structural unit represented by the following general formula (MA): 【Chemistry 13】

11. The polymer according to any one of claims 1 to 10, having an acid value of 70 mg KOH / g or more and 150 mg KOH / g or less.

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

13. The polymer solution according to claim 12, which is used to form a color filter or a black matrix.

14. A polymer solution according to claim 12; A polyfunctional (meth)acrylate monomer; A photopolymerization initiator; A photosensitive resin composition comprising:

15. The photosensitive resin composition according to claim 14, further comprising a surfactant.

16. A cured product of the photosensitive resin composition according to claim 14 or 15.

17. A film comprising the cured product of claim 16.

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