Polymer, polymer solution, photosensitive resin composition and use thereof

Abstract

To provide a polymer having high sensitivity and high developability.SOLUTION: A polymer contains a constitutional unit represented by general formula (1-1). (In the general formula (1-1), Z is a group having one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted C1-6 alkyl group, X is an oxygen atom, or a substituted or unsubstituted C1-4 alkylene).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Display devices (such as liquid crystal displays) and image pickup devices (such as CCDs and CMOSs) usually include color filters and black matrices. A photosensitive resin composition is often used to form a color filter or a black matrix. Specifically, a photosensitive resin film is formed on a substrate using a photocurable photosensitive resin composition, and the film is exposed to light and developed to form a pattern such as a color filter or a black matrix on the substrate.

[0003] Patent Document 1 describes a curable polymer that contains an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in the molecule, has an acid value of 20 to 300 mgKOH / g, an unsaturated group equivalent of 100 to 4,000 g / mol, and a blocked isocyanate group equivalent of 400 to 6,000 g / mol, and also describes the use of this curable polymer to form a color filter.

[0004] Patent Document 2 describes the formation of a black matrix using a binder resin having a weight average molecular weight of 1,000 to 6,000, an acid value of 80 to 200 mgKOH / g, and an ethylenically unsaturated bond equivalent of 500 or less.

[0005] Patent Document 3 describes a photosensitive resin obtained by reacting 0.2 to 0.9 mol of an epoxy group in an epoxy group-containing ethylenically unsaturated monomer with 1 mol of a carboxyl group in a copolymer obtained by radical polymerization of an ethylenically unsaturated monomer having a formula weight of 70 to 120 and an ethylenically unsaturated monomer containing a carboxyl group. It also describes a photosensitive composition containing the photosensitive resin. It also describes the formation of a color filter using the photosensitive composition. In Patent Document 3, it is described that the acid value of the photosensitive resin is preferably 20 to 200 mgKOH / g, and the double bond equivalent of the photosensitive resin is preferably 300 to 1,000.

[0006] Patent Document 4 describes an alkali-soluble resin obtained by reacting a carboxyl group-containing polymer represented by a specific general formula with (i) a compound having a group reactive with carboxylic acid and an ethylenically unsaturated group, or (ii) a compound having a group reactive with carboxylic acid and a silicon-based functional group, and also describes a photosensitive resin composition containing the alkali-soluble resin. It also describes the formation of a color filter using the photosensitive resin composition. Patent Document 4 describes that the acid value of the alkali-soluble resin is preferably 25-100 mgKOH / g, and the ethylenically unsaturated group equivalent is preferably 50-400. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2014 / 141731 [Patent Document 2] JP 2015-197619 A [Patent Document 3] JP 2011-33951 A [Patent Document 4] JP 2007-264433 A Summary of the Invention [Problem to be solved by the invention]

[0008] When a pattern is formed using a photosensitive resin composition, particularly a negative-type photosensitive resin composition, there tends to be a trade-off between the ease of photocuring the exposed area (i.e., sensitivity) and the ease of dissolving the unexposed area in a developer (developability). In particular, in recent years, with the background of further increasing sophistication and miniaturization of liquid crystal display devices and solid-state imaging devices, there has been a demand for achieving both high levels of sensitivity and developability.

[0009] On the other hand, when forming a color filter or a black matrix, the solubility of the pigment in a basic developer is low, particularly when the content of the pigment in the photosensitive resin composition is high, so that the time required for developing the photosensitive resin composition is long. Therefore, it is necessary to use a strong basic developer having a faster development speed than conventional basic developers. However, if the alkaline solubility of the polymer is too high, the alkaline dissolution rate of the photosensitive resin composition containing the pigment and the photopolymerization initiator is too high, or the difference in 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.

[0010] The present inventors have carried out studies with the aim of providing a polymer that can be used to produce a photosensitive resin composition in which the sensitivity is maintained and improved while adjusting the alkali solubility of the polymer contained in the photosensitive resin composition, in order to obtain a pattern having a designed shape after exposure and development, particularly when a strongly basic developer is used. [Means for solving the problem]

[0011] As a result of extensive investigations, the present inventors have completed the invention provided below.

[0012] According to the present invention, At least one structural unit selected from the structural unit represented by general formula (2) and the structural unit represented by general formula (IN), and A polymer comprising a structural unit represented by general formula (5): [ka] (In general formula (2), R 1 , R 2 , R 3 and R 4are 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 (IN), R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] (In general formula (5), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. Acid value: 50mg KOH / g or more, 120mg KOH / g or less, Polymers are provided having a double bond equivalent weight of 280 g / mol or more and 500 g / mol or less. Further, according to the present invention, At least one structural unit selected from a structural unit represented by general formula (2) and a structural unit represented by general formula (IN), A structural unit represented by general formula (1), and A structural unit represented by general formula (7) is included, A polymer comprising: [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 (IN), R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] (In general formula (1), R D represents a group containing two or more (meth)acryloyl groups, Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. [ka] (In general formula (7), R D represents a group containing two or more (meth)acryloyl groups. Acid value: 50mg KOH / g or more, 120mg KOH / g or less, Polymers are provided having a double bond equivalent weight of 280 g / mol or more and 500 g / mol or less.

[0013] The present invention also provides a polymer solution containing the above polymer.

[0014] According to the present invention, there is also provided a photosensitive resin composition comprising the above polymer solution, a polyfunctional (meth)acrylic compound, and a photopolymerization initiator.

[0015] According to the present invention, there is also provided a cured product formed from the above photosensitive resin composition.

[0016] Furthermore, according to the present invention, there is provided a film comprising the above-mentioned cured product. Effect of the Invention

[0017] According to the present invention, there is provided a polymer that can be suitably used for producing a photosensitive resin composition that has both high sensitivity and developability. [Brief description of the drawings]

[0018]

Figure 1

[0019] 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 to b" in the explanation of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less".

[0020] 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).

[0021] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0022] [Polymer P] The polymer of this embodiment (referred to as "polymer P" in this specification) contains a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-3). In this embodiment, the acid value of polymer P is 50 mg KOH / g or more, 120mg KOH / g or less, and the double bond equivalent of polymer P is 280 g / mol or more and 500 g / mol or less.

[0023] [ka]

[0024] 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. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a mercapto group. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q may be bonded to any carbon atom of the alkylene group of X to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, and a naphthalene ring. In the formula (1-1), an embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0025] An embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following general formula (1a), or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0026] [ka]

[0027] In general formula (1a), R is a hydrogen atom or a methyl group.

[0028] [ka]

[0029] By producing a photosensitive resin composition using the above-mentioned polymer, it is possible to obtain a photosensitive resin composition that has both sensitivity and developability. The reason for this can be explained as follows. Note that the following explanation should not be construed as limiting the present invention.

[0030] The polymer P has a structural unit containing a (meth)acryloyl group (the "-Z" group in formula (1-1)) represented by the general formula (1-1). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. The polymer P also has a structural unit containing a carboxyl group represented by the general formula (1-3). Thus, the polymer P has "both" a (meth)acryloyl group and a carboxyl group. Furthermore, the polymer P has both a polymerizable group and a carboxyl group in an amount such that the acid value and double bond equivalent of the polymer P as a whole are in a specific range. The polymer P can be designed to have both a polymerizable group and a carboxyl group in a relatively large value because the polymerizable group and the carboxyl group are present in the same polymer molecule. It is difficult to increase the content of both the polymerizable group and the carboxyl group in other resins such as (meth)acrylic resins. The polymer P can achieve both high sensitivity and developability by having such a structure.

[0031] In this embodiment, the acid value of the polymer P is 50 to 120 mgKOH / g, and the double bond equivalent is 280 to 500 g / mol. This allows the photosensitive resin composition containing the polymer P to have high levels of sensitivity and developability. That is, when the acid value of the polymer P is 70 mgKOH / g or more, good developability can be obtained. In addition, when the double bond equivalent is 500 g / mol or less, the sensitivity of the composition can be improved.

[0032] If the acid value is too large, the exposed portion may be easily dissolved during development with an alkaline developer, and the amount of exposure required for photocuring may be large, or the pattern shape may be insufficient. Therefore, in this embodiment, the upper limit of the acid value is set to 120 mgKOH / g. Also, if the double bond equivalent is too small (i.e., if the density of double bonds in the polymer is too large), the unexposed portion or the low-exposed portion may be difficult to dissolve during development with an alkaline developer, and a residual film may be generated during development. Also, if the double bond equivalent is too small, the molecular weight may be excessively increased by crosslinking, and there is a concern that the solubility may be excessively reduced. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 500 g / mol.

[0033] The acid value of the polymer P is from 50 to 120 mgKOH / g, preferably from 60 to 110 mgKOH / g, and more preferably from 70 to 100 mgKOH / g. The double bond equivalent of the polymer is 280 to 500 g / mol, preferably 300 to 470 g / mol, and more preferably 310 to 440 g / mol. By adjusting the acid value and / or double bond equivalent of the polymer, it is possible to achieve both sensitivity and developability at a higher level.

[0034] The acid value and double bond equivalent can be determined by spectrum measurement or the like. For example, they can be determined by the following procedure. For more details, see the Examples. (1) Polymer 1 From the H-NMR chart, the areas (integral values) of the peaks corresponding to the hydrogen atoms of the carboxyl group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond are determined. (2) From the area determined in (1) and the area of ​​the peak derived from the standard substance, the amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated. (3) Convert the amount of carboxyl groups obtained in (2) into an acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) into a double bond equivalent (g / mol).

[0035] The acid value and double bond equivalent of polymer P can be adjusted to desired values ​​by adjusting the ratio of the structural units of formula (1-1) and the structural units of formula (1-3) that constitute polymer P, and the structure and valence of (meth)acryloyl groups that can be introduced into polymer P in addition to these structural units.

[0036] The proportion of the structural units represented by formula (1-1) in all structural units of polymer P is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %, and the proportion of the structural units represented by formula (1-3) is preferably 1 to 15 mol %, more preferably 2 to 10 mol %.

[0037] In one embodiment, the polymer P may further include a structural unit represented by the following general formula (1-2).

[0038] [ka]

[0039] In general formula (1-2), R D is a group containing two or more (meth)acryloyl groups. D is a group containing 2 to 9 (meth)acryloyl groups, and more preferably a group containing 3 to 6 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups, the sensitivity of the obtained polymer P in photolithography can be increased. In addition, it is possible to achieve a higher balance between sensitivity and developability, and further improve heat resistance.

[0040] When the polymer P contains a structural unit represented by general formula (1-2), the proportion of the structural unit represented by general formula (1-2) in all structural units of the polymer P is preferably 1 to 30 mol %, more preferably 2 to 20 mol %.

[0041] 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.

[0042] [ka]

[0043] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X 1is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a k+1 valent organic group having 1 to 12 carbon atoms. 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.

[0044] 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).

[0045] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0046] X 1 When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X described above.

[0047] X 2 The k+1 valent organic group having 1 to 12 carbon atoms can be any group obtained by removing k+1 hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0048] [ka]

[0049] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6is a divalent organic group having 1 to 6 carbon atoms.

[0050] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for general formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0051] [ka]

[0052] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. Specific embodiments and preferred embodiments of R are the same as those explained in relation to general formula (1b).

[0053] In one embodiment, the polymer P may include a structural unit represented by general formula (2) and / or a structural unit represented by general formula (IN).

[0054] [ka]

[0055] In general formula (2), R 1 , R 2 , R 3 and R 4each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0056] 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.

[0057] R in general formula (2) 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] In addition, R in the general formula (2) 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, 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.

[0063] [ka]

[0064] In the general formula (IN), R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0065] R in the general formula (IN) 1 and R 2 The organic group having 1 to 30 carbon atoms constituting the above general formula (2) is R 1 ~R 4 The same applies to the organic group having 1 to 30 carbon atoms in the above, and the preferred embodiments are also the same.

[0066] The structural unit represented by the general formula (2) and the structural unit represented by the general formula (IN) are chemically robust. Therefore, the polymer P containing them as structural units has a small weight loss and is stable when subjected to heat treatment. 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.

[0067] The proportion of the structural unit represented by general formula (2) or the structural unit represented by general formula (IN) in all structural units of polymer P is preferably 10 to 90 mol %, more preferably 30 to 70 mol %, and further preferably 40 to 60 mol %. When polymer P contains both the structural unit represented by general formula (2) and the structural unit represented by general formula (IN), the total amount thereof is preferably within the above range.

[0068] In one embodiment, the polymer P may further include a structural unit represented by the following general formula (3-1).

[0069] [ka]

[0070] In general formula (3-1), R Sis a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while when the developability is improved, the curing tends to be insufficient, 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.

[0071] R S is, for example, a group represented by the following general formula (3a).

[0072] [ka]

[0073] 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.

[0074] X 10 As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0075] 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.

[0076] X 10The 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.

[0077] 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.

[0078] When polymer P contains a structural unit represented by general formula (3-1), the proportion of the structural unit represented by general formula (3-1) in all structural units of polymer P is preferably 5 to 40 mol %, more preferably 10 to 30 mol %.

[0079] The polymer P may further contain a structural unit represented by the following general formula (4).

[0080] 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 (1-3), 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.

[0081] [ka]

[0082] 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 %.

[0083] The polymer P may contain a structural unit represented by the following general formula (5), which is composed of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-3). By containing this structural unit, both sensitivity and developability can be achieved in a better balance.

[0084] [ka]

[0085] 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 %.

[0086] From the viewpoint of the effects of the present invention, the polymer P may further contain a structural unit represented by the following general formula (6) consisting of two structural units represented by the general formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0087] [ka]

[0088] 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.

[0089] 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 %.

[0090] In addition to the above structural units, the polymer P may contain a structural unit represented by general formula (MA). 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 structural units of the polymer P.

[0091] [ka]

[0092] 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).

[0093] [ka]

[0094] 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 %.

[0095] [ka]

[0096] In formula (8), Q, X and Z have the same meanings as in formula (3-1). When the polymer P contains a structural unit represented by general formula (3-1), the proportion of the structural unit represented by general formula (3-1) in all structural units of the polymer P is preferably 3 to 35 mol %, more preferably 5 to 25 mol %.

[0097] The polymer P 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).

[0098] [ka]

[0099] 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). When polymer P contains a structural unit represented by general formula (1), the proportion of the structural unit represented by general formula (1) in all structural units of polymer P is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0100] The polymer P may contain a structural unit represented by the following general formula (3) which is composed of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (3-1).

[0101] [ka]

[0102] In the general formula (3), Z, Q, and X are the same as those in the general formula (1-1), and R S has the same meaning as general formula (3-1).

[0103] 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 %.

[0104] The polymer P may have a thioether group (-S-). By having the thioether group, the polymer P has excellent sensitivity in photolithography and higher alkali solubility, and therefore it is possible to provide a cured resin product that has excellent developability, reduced yellowing, and excellent transparency.

[0105] When the polymer P has a thioether group, the polymer P has a structure in which the above structural units are bonded via an organic group having a thioether group (-S-) derived from a di- or higher functional thiol group-containing compound.

[0106] Examples of bifunctional or higher thiol group-containing compounds capable of inducing an organic group having a thioether group include, but are not limited to, the following formulas (s-1) to (s-20).

[0107] [ka]

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[0124] [ka]

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[0126] [ka]

[0127] The polymer P may contain further structural units derived from norbornene or indene monomers and monomers polymerizable with maleic anhydride. Such structural units include structural units derived from substituted or unsubstituted maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (e.g., cyclohexene, etc.), cyclododecatriene, tricycloundecene, dialkyl fumarates (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.). Substituents that these monomers may have include alkyl groups, aryl groups, etc. More specifically, substituted maleimides include cyclohexylmaleimide, phenylmaleimide, etc. Substituted styrenes include methylstyrene, vinyltoluene, and the like.

[0128] Among these, the structural unit preferably includes a structural unit represented by general formula (MI) (a divalent structural unit derived from a substituted or unsubstituted maleimide), a structural unit represented by general formula (ST) (a divalent structural unit derived from a substituted or unsubstituted styrene), or a structural unit represented by general formula (NBD) (a divalent structural unit derived from a substituted or unsubstituted norbornadiene).

[0129] [ka]

[0130] In general formula (MI), R 3 represents a hydrogen atom, an alkyl group, or an aryl group. 4 ~R 6 Each of R independently represents a hydrogen atom, an alkyl group, or an aryl group. 7 ~R 10 each independently represents a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

[0131] 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, 13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0132] The weight average molecular weight Mw of the polymer P is, for example, 2,000 to 50,000, preferably 3,000 to 45,000, more preferably 5,000 to 40,000, and further preferably 6,000 to 38,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer.

[0133] 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.

[0134] [Method of manufacturing polymer P] The polymer P of this embodiment can be produced (synthesized) by any method. The production methods of the polymer P will be described with reference to the first embodiment, the second embodiment, and the third embodiment. In the first to third embodiments, the polymer precursor P' is shown by way of example to contain a structural unit represented by general formula (8), but the structural unit is optional, and the polymer P of this embodiment may contain a structural unit represented by general formula (8) and a structural unit represented by general formula (3). In the first to third embodiments, the polymer P is shown by way of example to contain a structural unit represented by general formula (2), but instead of or in addition to the structural unit represented by general formula (2), the polymer P may contain a structural unit represented by the above general formula (IN).

[0135] (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); and

[0136] [ka]

[0137] (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).

[0138] [ka]

[0139] 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 containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (MA);

[0140] [ka]

[0141] (I-ii) a step of reacting the raw material polymer obtained in the 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); and

[0142] [ka]

[0143] (I-iii) It is preferable to include a step of reacting the first polymer precursor obtained in step (I-ii) with a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a second polymer precursor containing 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-iii) corresponds to the polymer precursor P' described in the above step (I).

[0144] [ka]

[0145] (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.

[0146] [ka]

[0147] 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.

[0148] When the polymer P contains a structural unit represented by the above general formula (IN), a raw polymer containing a structural unit represented by the general formula (IN) and a structural unit represented by the general formula (MA) is prepared. Such a raw polymer can be produced by polymerizing (addition polymerization) a monomer represented by the following general formula (INm) with maleic anhydride. 1 and R 2 The definition of is the same as that of the general formula (IN). The same also applies to the preferred embodiments.

[0149] [ka]

[0150] 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.

[0151] Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] (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).

[0159] 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.

[0160] 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 , X1 ' 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).

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] 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.

[0165] 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).

[0166] (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'.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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).

[0171] [ka]

[0172] 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.

[0173] (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).

[0174] 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).

[0175] 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.

[0176] 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.

[0177] 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, etc., and one or more types selected from these can be used.

[0178] 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'.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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);

[0183] [ka]

[0184] (b) a second step of treating the polymer precursor P' obtained in the first step with water in the presence of a catalyst to prepare a polymer precursor (hereinafter referred to as "polymer precursor P") containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (4), a structural unit represented by the following general formula (7), and a structural unit represented by the following general formula (8), and optionally containing a structural unit represented by the following general formula (MA); and

[0185] [ka]

[0186] (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 in some cases a structural unit represented by the following general formula (MA).

[0187] [ka]

[0188] Hereinafter, a method for producing (synthesizing) the polymer P through these steps will be described. Note that the first step (a) of preparing a polymer precursor is the same as the first step (I) of this embodiment, and therefore a description thereof will be omitted.

[0189] (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).

[0190] 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.

[0191] 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.

[0192] 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.

[0193] (Third embodiment) The method for producing the polymer P of this embodiment is as follows: (A) a first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") 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), a monovalent to hexavalent thioether-containing organic group (i) having 1 to 30 carbon atoms derived from a difunctional or higher thiol group-containing compound (simply referred to as "thioether-containing organic group (i)" in this specification), and a structural unit represented by the following general formula (MA); and

[0194] [ka]

[0195] (B) a second step of reacting the polymer precursor P' obtained in the first step with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P containing a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (3), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), a thioether-containing organic group (i), and optionally a structural unit represented by the following general formula (MA).

[0196] [ka]

[0197] Hereinafter, the method for producing (synthesizing) the polymer P of this embodiment by these steps will be described. Note that the third embodiment differs from the first step (I) of preparing the polymer precursor of the first embodiment only in the first step (A) of preparing the polymer precursor. Therefore, the description of step (B) will be omitted.

[0198] The first step (A) of preparing the polymer precursor P' comprises: (Ai) preparing a raw material polymer including a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (MA), and a thioether-containing organic group (i);

[0199] [ka]

[0200] (A-ii) a step of reacting the raw material polymer obtained in the step (Ai) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a first polymer precursor including a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a thioether-containing organic group (i), and a structural unit represented by the following general formula (MA); and

[0201] [ka]

[0202] (A-iii) It is preferable to include a step of reacting the first polymer precursor obtained in the step (A-ii) with a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") in the presence of a basic catalyst to prepare a second polymer precursor containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), a thioether-containing organic group (i), and a structural unit represented by the following general formula (MA).

[0203] [ka]

[0204] (Process (A)) In the step (Ai), the step of preparing a raw polymer containing the structural unit represented by the general formula (2), the structural unit represented by the general formula (MA), and the thioether-containing organic group (i) can be carried out by polymerizing (addition polymerizing) the monomer represented by the general formula (NBm) and maleic anhydride in the presence of the bifunctional or higher thiol group-containing compound. 1 , R 2 , R 3 and R 4The definition of a1 is the same as that of the general formula (2). The same applies to the preferred aspects. The polymerization conditions are also the same as those in the step (Ii) of the first embodiment.

[0205] [ka]

[0206] Examples of bifunctional or higher thiol group-containing compounds include, but are not limited to, the compounds represented by the above chemical formulas (s-1) to (s-20). The bifunctional or higher thiol group-containing compounds may be used alone or in combination of two or more.

[0207] Step (A-ii) and step (A-iii) of this embodiment can be carried out using conditions similar to those in step (I-ii) and step (I-iii) of the first embodiment, respectively.

[0208] In this embodiment as well, in order to remove unnecessary components other than the desired polymer P after the step (B), a washing step or the like is preferably carried out as appropriate, as in the first embodiment.

[0209] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. 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.

[0210] 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.

[0211] [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.

[0212] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment contains the above-mentioned polymer P and a photopolymerization initiator. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution of the present embodiment and a photopolymerization initiator. Each component will be described below.

[0213] (Photopolymerization initiator) The photopolymerization initiator used in the photosensitive resin composition of the present embodiment may be a photoradical polymerization initiator. As the photoradical polymerization initiator, a known compound may be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl ... -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, etc.; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc.; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer.

[0214] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, and therefore has excellent developability and processability in photolithography.

[0215] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0216] 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.

[0217] 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.).

[0218] As the dye, for example, known dyes described in JP-A Nos. 2003-270428, 9-171108, and 2008-50599 can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0223] 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.

[0224] 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.

[0225] (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.

[0226] 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.

[0227] (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.

[0228] 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.

[0229] (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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] (Other additives) The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0235] [Application] A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, and then exposing and developing the film to form a pattern. This film is applied to color filters, 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.

[0236] (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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] (exposure) Exposure is typically carried out by applying actinic rays to the photosensitive resin film through an appropriate photomask.

[0242] 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.

[0243] 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.

[0244] (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. A photosensitive resin film made of a photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to a substrate, and therefore peeling of the pattern is suppressed during the development process.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above steps, a pattern can be obtained / a substrate having a pattern can be manufactured, but various treatments may be carried out after development.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] 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.

[0254] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. EXAMPLES

[0255] EXAMPLES Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these.

[0256] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·MA: Maleic anhydride ·NB: 2-Norbornene ·IN: Inden MEK: Methyl ethyl ketone ·PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) 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.)

[0257] [ka]

[0258] 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.)

[0259] [ka]

[0260] <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 1) 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.

[0261] (Synthesis of raw polymer 2) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (NB equivalent: 451.92 g, 4.8 mol), maleic anhydride (MA, 470.69 g, 4.8 mol), and 2238.50 g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyrate dimethyl (Wako Pure Chemical Industries, trade name: V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 140.73 g, 0.29 mol) dissolved in MEK 189.74 g was added over 1 hour. The mixture was then further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 3686.4 g of methanol to precipitate a white solid. The obtained white solid was washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 908.1 g of a polymer (raw polymer 2) having 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 2700 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.57. The amount of sulfur in the obtained raw polymer 2 was confirmed by flask combustion and elemental analysis by ion chromatography, confirming the presence of elemental sulfur in raw polymer 1. In addition, GPC measurement of the reaction solution showed no peak for PEMP alone, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw polymer 2.

[0262] The elemental analysis method is as follows. -Test items Determination of total sulfur by flask combustion-ion chromatography. -Test Method Flask combustion - ion chromatography method (1) Approximately 50 mg of a sample is completely combusted in a sealed flask with oxygen replaced inside. (2) The gas generated is collected in the hydrogen peroxide absorbing solution that has already been added to the flask, and the test liquid is adjusted to 50 ml. (3) The test solution and the standard solution are introduced into the ion chromatography analyzer, the concentration of sulfate ions is determined using the calibration curve method, and the amount of sulfur contained in the sample is calculated. -Equipment used Dionex ICS-3000 ion chromatograph

[0263] (Confirmation of the thioether structure contained in raw polymer 2) PEMP alone, as shown in the following chemical formula: 13 By C-NMR measurement, peak a derived from carbon a was confirmed at about 19.0 ppm, and peak b derived from carbon b was confirmed at about 62.0 ppm.

[0264] [ka]

[0265] Raw polymer 2 synthesized using PEMP 13 In the C-NMR measurement, the appearance of peak b derived from carbon b was confirmed at around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw material polymer 2.

[0266] In addition, raw polymer 2 13 In the C-NMR measurement, the peak a derived from carbon a was not confirmed, and instead, a peak c corresponding to thioether (RS-R') appeared at about 28 ppm. The integral value of this peak c is approximately twice the integral value of peak b, so that the raw material polymer 2 has a skeleton having a thioether group as shown below, and the thiol group has disappeared. It is considered that the polymer of the example synthesized using the raw material polymer 2 also has a similar skeleton.

[0267] [ka]

[0268] 13 The conditions for C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding a measurement solvent to a weighed sample to adjust its concentration, and then pouring a specified amount into a sample tube for NMR measurement. Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR equipment ·Resonance frequency: 100.53MHz Measurement nucleus: 13 C Measurement method: NNE measurement (inverse gate decoupling method) Pulse width: 3.83μsec Pulse repetition time: 30s Number of times accumulated: 4096 ·Measurement temperature: room temperature Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) Sample concentration: 20% (w / v)

[0269] (Synthesis of raw polymer 3) In a reaction vessel of suitable size equipped with a stirrer and a cooling tube, 122.4g (1.05 mol) of indene, 1376.7g of methyl ethyl ketone, and 9.70g (0.042 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in the vessel, and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the vessel was heated. When the internal temperature reached 80°C, 103.2g (1.05 mol) of maleic anhydride was dissolved in 741.30g of MEK, and the solution in which the dissolved oxygen in the system was removed by nitrogen bubbling was added over 3 hours. After that, the vessel was heated at 80°C for 4 hours to polymerize maleic anhydride and indene, and a polymerized solution was produced. The polymerization solution obtained above was dropped into 2047.94 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2047.94 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 320.1 g of a polymer (raw polymer 3) having a structural unit derived from indene 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 9248 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 2.31.

[0270] (Synthesis of raw polymer 4) 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.

[0271] <Preparation of Polymer P (Polymer Solution)> In each preparation example, polymer P was prepared. Table 1 shows the components used in the preparation 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 maleic anhydride (MA).

[0272] (Preparation Example 1: Preparation of Polymer P1) 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. 1 H-NMR measurement confirmed that polymer P1 had a structure ring-opened with A-TMM-3LM-N and 4-HBA.

[0273] (Preparation Example 2: Preparation of Polymer P2) 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. 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. 1 H-NMR measurement confirmed that polymer P2 had a structure in which it had been ring-opened with HEMA and reacted with GMA.

[0274] (Preparation Example 3: Preparation of Polymer P3) The MA unit of the raw material polymer 1 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 P3. Details are described below. First, 255.91g 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 36.00g (0.356 moles) of triethylamine was added and reacted at 70°C for 5 hours. After that, 5.47g (0.390 moles) of GMA was added and reacted at 70°C for 5 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 of the above, 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 P3. 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 P3 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0275] (Preparation Example 4: Preparation of Polymer P4) The MA units of the raw polymer 1 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then water was added to further open the rings, 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, 106.67g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 15.50g 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. After that, 6.00g (0.333 moles) of water was added and reacted at a temperature of 70°C for 2 hours. After that, 4.44g (0.031 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 of the above, the structural unit derived from maleic anhydride in the raw material polymer 1 was ring-opened with A-TMM-3LM-N, 4-HBA and water, and reacted with GMA to obtain polymer P4. GPC measurement of polymer P4 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 P4 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0276] (Preparation Example 5: Preparation of Polymer P5) 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 P5. 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 reacted with GMA to obtain polymer P5. GPC measurement of polymer P5 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 P5 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0277] (Preparation Example 6: Preparation of Polymer P6) 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 P6. 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, 0.90g (0.050 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 of the above, the structural unit derived from maleic anhydride in the raw material polymer 1 was ring-opened with A-TMM-3LM-N and water, and reacted with GMA to obtain polymer P6. GPC measurement of polymer P6 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 P6 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0278] (Preparation Example 7: Preparation of Polymer P7) The MA unit of the raw material polymer 1 was ring-opened with a pentafunctional (meth)acrylic compound (A-9550) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce the polymer P7. Details are described below. First, 100.91g 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, 19.97g (0.140 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 1 were ring-opened with A-9550 and 4-HBA, and reacted with GMA to obtain polymer P7. GPC measurement of polymer P7 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 P7 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0279] (Preparation Example 8: Preparation of Polymer P8) 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 unit derived from maleic anhydride in the raw polymer 1 was 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.

[0280] (Preparation Example 9: Preparation of Polymer P9) The MA unit of the raw 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 P9. 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 unit derived from maleic anhydride in the raw polymer 1 was ring-opened with A-TMM-3LM-N and 4-HBA, and reacted with 4HBAGE to obtain polymer P9. 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.

[0281] (Preparation Example 10: Preparation of Polymer P10) 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 P10. Details are described below. First, 100.14g 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, 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 4-HBA, and polymer P10 was obtained by reacting with GMA. 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.

[0282] (Preparation Example 11: Preparation of Polymer P11) The MA unit of the raw material polymer 2 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 P11. Details are described below. First, 100.54g 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, 40.51g (0.281 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-TMM-3LM-N and 4-HBA, and polymer P11 was obtained by reacting with GMA. 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.

[0283] (Preparation Example 12: Preparation of Polymer P12) Raw Polymer3 The MA unit 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 polymer P12. Details are described below. First, the raw polymer 3 To 60g (0.312 moles in terms of MA), 102.63g of MEK was added 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 the mixture was reacted at a temperature of 70°C for 2 hours. After that, 27.01g (0.187 moles) of 4-HBA was added, and the mixture was reacted at a temperature of 70°C for 4 hours. After that, 13.31g (0.094 moles) of GMA was added, and the mixture was 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 by the following procedure. 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 raw polymer 3 The structural units derived from maleic anhydride in the copolymer were ring-opened with A-TMM-3LM-N and 4-HBA, and reacted with GMA to obtain 32.0 g of polymer 12. GPC measurement of polymer P12 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 P12 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0284] (Preparation Example 13: Preparation of Polymer P13) 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 P13. Details are described below. First, 100.57g 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 70°C for 2 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 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 P13. GPC measurement of polymer P13 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 P13 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0285] (Preparation Example 14: Preparation of Polymer P14) Polymer P14 was obtained in the same manner as in Preparation Example 13, except that raw polymer 4 was used instead of raw polymer 2. GPC measurement of polymer P14 confirmed the disappearance of peaks of the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P14 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

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

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

[0288] (Acid 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 performed. 1The 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 50 gKOH / g or more, it can be considered that the polymer has a carboxy group necessary for the polymer to have sufficient developability.

[0289] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. As with the above 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 500 g / mol or less can be considered to indicate that the polymer contains double bonds at a density sufficient for high sensitivity.

[0290] [Table 1]

[0291] (Examples 1 to 10, Comparative Examples 1 to 4) (Preparation of polymer solution) The obtained polymers P1 to P14 were each dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution having a solid content concentration of 30 mass %.

[0292] (Alkaline dissolution rate of polymer solution) The alkaline dissolution rate of the polymer solution of each of the Examples and Comparative Examples was measured using the following method. The above polymer solution was spin-coated on a wafer, the PGMEA was dried, and the wafer was pre-baked at 100° C. for 2 minutes to prepare a resin film with a thickness of about 2 μm. This resin film was immersed together with the wafer in a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 2. If the alkali dissolution rate is between 200 nm / s and 2400 nm / s, the material can be used without problems as a photosensitive material. In particular, if it is between 600 nm / s and 2000 nm / s, it can be considered to be particularly good.

[0293] (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. Solid content in polymer solution: 100 parts by weight Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 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.

[0294] The resulting photosensitive resin composition was evaluated for the following items.

[0295] [Developability evaluation (dissolution rate of photosensitive resin composition in alkaline developer)] The photosensitive resin compositions obtained in the Examples and Comparative Examples were spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to produce a resin film having a thickness of 2 μm±0.2 μm. This resin film was immersed together with the wafer in a 2.38% TMAH aqueous solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 2. If the alkali dissolution rate is 300 nm / s or more and 2500 nm / s or less, the developability can be considered good.

[0296] [Sensitivity evaluation of photosensitive resin composition (2.38% TMAH aqueous solution)] (Exposure amount 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 (immersed with the wafer) in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for the development time shown in Table 2, resulting in an exposure 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 18 mJ / cm 2 If it is below this, the sensitivity can be considered to be good.

[0297] (Exposure amount at which the remaining film rate is 95% or more) The exposure dose at which the film remaining ratio is 95% or more was measured using the same method as described above (Exposure dose at which the film remaining ratio is 90% or more). The results are shown in Table 2. The exposure dose at which the film remaining ratio is 95% or more was 18 mJ / cm 2 If it is below this, the sensitivity can be considered to be good.

[0298] [Table 2]

[0299] As shown in Table 2, the polymers of Examples 1 to 10 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 10 have a good balance between developability and sensitivity, and that even when a strong basic developer is used, the patterns after exposure and development will have the designed shape.

[0300] <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 10 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.

[0301] 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.

[0302] <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 10 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]

[0303] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. At least one structural unit selected from the structural unit represented by general formula (2) and the structural unit represented by general formula (IN), and A polymer comprising a structural unit represented by general formula (5): 【Chemistry 1】 (In general formula (2), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; １ is 0, 1 or 2.) 【Chemistry 2】 (In the general formula (IN), R １ and R ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Chemistry 3】 (In general formula (5), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. The acid value is 50 mgKOH / g or more and 120 mgKOH / g or less, A polymer having a double bond equivalent weight of 280 g / mol or more and 500 g / mol or less.

2. The polymer according to claim 1 , further comprising a structural unit represented by general formula (7): 【Chemistry 5】 (In general formula (7), R Ｄ represents a group containing two or more (meth)acryloyl groups.

3. In the structural unit represented by the general formula (7), R Ｄ The polymer according to claim 2, which contains at least one group represented by the following general formulas (1b), (1c) and (1d): 【Chemistry 8】 (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 having 1 to 6 carbon atoms, or a group represented by -Z-X- (wherein Z is -O- or -OCO-, and X is an alkylene having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (wherein X' represents an alkylene having 1 to 6 carbon atoms, and Z' represents -O- or -COO-), X ２ is a (k+1) valent organic group having 1 to 12 carbon atoms. 【Chemistry 9】 (In general formula (1c), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X １ is a single bond, an alkylene having 1 to 6 carbon atoms, or a group represented by -Z-X- (wherein Z is -O- or -OCO-, and X is an alkylene having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X ２ is a (k+1)-valent organic group having 1 to 12 carbon atoms, X ３ is a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ 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 10】 (In general formula (1d), n is an integer from 2 to 5, R is a hydrogen atom or a methyl group, and multiple R may be the same or different.

4. The polymer according to any one of claims 1 to 3, further comprising a structural unit represented by general formula (8): 【Chemistry 11】 (In general formula (8), R Ｓ is a group containing a single (meth)acryloyl group.

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

6. The polymer according to any one of claims 1 to 5, further comprising a structural unit represented by general formula (6): 【Chemistry 14】 (In the general formula (6), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group.

7. The polymer according to any one of claims 1 to 6, further comprising a structural unit represented by general formula (MA): 【Chemistry 15】

8. The polymer according to any one of claims 1 to 7, further comprising an organic group having a thioether group.

9. The polymer according to any one of claims 1 to 8, having a weight average molecular weight of 2,000 or more and 50,000 or less.

10. At least one structural unit selected from a structural unit represented by general formula (2) and a structural unit represented by general formula (IN), A structural unit represented by general formula (1), and A structural unit represented by general formula (7): A polymer comprising: 【Chemistry 16】 (In general formula (2), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; １ is 0, 1 or 2.) 【Chemistry 17】 (In the general formula (IN), R １ and R ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Chemistry 18】 (In general formula (1), R Ｄ represents a group containing two or more (meth)acryloyl groups, Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms; When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. 【Chemistry 19】 (In general formula (7), R Ｄ represents a group containing two or more (meth)acryloyl groups. The acid value is 50 mgKOH / g or more and 120 mgKOH / g or less, A polymer having a double bond equivalent weight of 280 g / mol or more and 500 g / mol or less.

11. In the structural unit represented by the general formula (1), R Ｄ The polymer according to claim 10, wherein the polymer comprises at least one of groups represented by the following general formulas (1b), (1c) and (1d): 【Chemistry 23】 (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 having 1 to 6 carbon atoms, or a group represented by -Z-X- (wherein Z is -O- or -OCO-, and X is an alkylene having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (wherein X' represents an alkylene 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 24】 (In general formula (1c), 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 having 1 to 6 carbon atoms, or a group represented by -Z-X- (wherein Z is -O- or -OCO-, and X is an alkylene having 1 to 6 carbon atoms), and when there are a plurality of X １ may be the same or different, X ２ is a (k+1)-valent organic group having 1 to 12 carbon atoms, X ３ is a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ 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 25】 (In general formula (1d), n is an integer from 2 to 5, R is a hydrogen atom or a methyl group, and multiple R may be the same or different.

12. The polymer according to claim 10 or 11, further comprising a structural unit represented by general formula (8): 【Chemistry 26】 (In general formula (8), R Ｓ is a group containing a single (meth)acryloyl group.

13. The polymer according to any one of claims 10 to 12, further comprising a structural unit represented by general formula (4): 【Chemistry 27】

14. The polymer according to any one of claims 10 to 13, further comprising a structural unit represented by general formula (MA): 【Chemistry 30】

15. The polymer according to any one of claims 10 to 14, further comprising an organic group having a thioether group.

16. The polymer according to any one of claims 10 to 15, having a weight average molecular weight of 2,000 or more and 50,000 or less.

17. A polymer solution comprising the polymer according to any one of claims 1 to 16.

18. The polymer solution according to claim 17, which is used to form a color filter or a black matrix.

19. A polymer solution according to claim 17; A polyfunctional (meth)acrylic compound, A photopolymerization initiator, Photosensitive resin composition.

20. A cured product formed from the photosensitive resin composition according to claim 19.

21. A film comprising the cured product according to claim 20.

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