Polymer, composition, cured product, and display element

Abstract

One embodiment of the present invention relates to a polymer, a composition containing a polymer having a structural unit represented by formula (1), a cured product, or a display element. [In formula (1), A is a divalent group having an aromatic heterocyclic ring, B is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having an alkali-soluble group, and X is independently-O-,-NH-or-S-. ] # imgabs0 #

Description

Technical Field

[0001] One embodiment of the present invention relates to a polymer, a composition, a cured product, or a display element. Background Art

[0002] With the increase in integration, the patterns of semiconductor circuit substrates have become increasingly finer in recent years, and the insulating films used in the semiconductor circuit substrates are also required to have patterns corresponding to the fine pitch between electrode pads or between wirings. The composition for forming the resin film such as the insulating film having such a pattern is required to have photolithography properties that can be patterned by exposure and development.

[0003] As compositions having such photolithographic properties, in particular compositions excellent in sensitivity and resolution, various photosensitive compositions have been proposed (for example, see Patent Documents 1 to 3).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2014 / 109143

[0007] Patent Document 2: Japanese Patent Application Publication No. 2005-266049

[0008] Patent Document 3: Japanese Patent Application Publication No. 2000-275842 Summary of the invention

[0009] As display elements and the like have become more advanced in recent years, a large amount of current is required, and therefore resin films such as insulating films used in such display elements and the like are required to have low dielectric properties and heat resistance.

[0010] In addition, regarding the sensitivity, high transmittance of light with a wavelength of 400 nm may be required, and further, resin films such as insulating films used in display elements in recent years may also be required to have flatness, a low linear expansion coefficient, and bending resistance.

[0011] One embodiment of the present invention provides a composition and a polymer capable of forming a cured product (cured film) having excellent and balanced sensitivity, transmittance of light with a wavelength of 400 nm, heat resistance, low relative dielectric constant, flatness, low linear expansion coefficient, and bending resistance.

[0012] Technical means of solving problems

[0013] The structure of the present invention is as follows.

[0014] [1] A composition comprising a polymer having a structural unit represented by the following formula (1).

[0015] [Chemistry 1]

[0016]

[0017] [In formula (1), A is a divalent group having an aromatic heterocyclic ring,

[0018] B is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having an alkali-soluble group,

[0019] X is independently -O-, -NH- or -S-]

[0020] [2] The composition according to [1], wherein the aromatic heterocyclic ring in A is a nitrogen-containing aromatic ring.

[0021] [3] The composition according to [1] or [2], wherein the aromatic heterocyclic ring in A is an aromatic ring having two or more nitrogen atoms.

[0022] [4] The composition according to any one of [1] to [3], wherein X is -O- or -NH-.

[0023] [5] The composition according to any one of [1] to [4], wherein B is a group represented by any one of the following formulas (B1) to (B10).

[0024] [Chemistry 2]

[0025]

[0026] [In formula (B1), C1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y1 and Y2 are each independently an alkali-soluble group, Z1 and Z2 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, Z1 and Z2 may each independently bond to C1 to form a ring, n1 and n3 are each independently an integer of 0 to 2, wherein n1+n3 is an integer of 1 to 4, n2 and n4 are each independently an integer of 0 to 4, and * represents a bond to X]

[0027] [Chemistry 3]

[0028]

[0029] [In formula (B2), D1 is a trivalent organic group not containing an alkali-soluble group, Y3 is independently an alkali-soluble group, Z3 to Z5 are independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, at least one selected from Z3 and Y3 can be bonded to D1 to form a ring, n5 is an integer of 1 to 2, n6 to n8 are independently an integer of 0 to 4, and * represents a bond to X]

[0030] [Chemistry 4]

[0031]

[0032] [In formula (B3), E1 is a tetravalent organic group not containing an alkali-soluble group, Y4 and Y5 are each independently an alkali-soluble group, Z6 to Z9 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, n9 and n11 are each independently an integer of 1 to 2, n10 and n12 to n14 are each independently an integer of 0 to 4, and * represents a bond to X]

[0033] [Chemistry 5]

[0034]

[0035] [In formula (B4), C2 and C3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y6 and Y7 are each independently an alkali-soluble group, and Z 10 and Z 11 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n15 and n16 are independently 0 or 1, wherein n15+n16 is 1 or 2, n17 and n18 are independently an integer of 0 to 3, and * represents a bond to X]

[0036] [Chemistry 6]

[0037]

[0038] [In formula (B5), D2 is a trivalent organic group containing no alkali-soluble group, Z 12 and Z 13 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n19 and n20 are each independently an integer of 0 to 4, and * represents a bond to X]

[0039] [Chemistry 7]

[0040]

[0041] [In formula (B6), D3 and D4 are each independently a trivalent organic group not containing an alkali-soluble group, and Y8 to Y 10 are independently alkali-soluble groups, Z 14 ~Z 17 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n21, n23 and n25 are independently an integer of 0 to 1, wherein n21+n23+n25 is an integer of 1 to 3, n22 and n24 are independently an integer of 0 to 5, n26 and n27 are independently an integer of 0 to 4, and * represents a bond to X]

[0042] [Chemistry 8]

[0043]

[0044] [In formula (B7), C4 and C5 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, and Y 11 ~Y 13 are independently alkali-soluble groups, Z 18 ~Z 20 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n28 and n32 are each independently an integer of 0 to 2, n30 is each independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, n31 is each independently an integer of 0 to 3, m is an integer of 1 to 3, and * represents a bond to X]

[0045] [Chemistry 9]

[0046]

[0047] [In formula (B8), Y 14 are independently alkali-soluble groups, Z 21 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n34 is an integer of 1 to 2, n35 is an integer of 0 to 3, and * represents a bond to X]

[0048] [Chemistry 10]

[0049]

[0050] [In formula (B9), Y1, Y2, Z1, Z2, n1, n3 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3 and * in formula (B1), R 6 are each independently a hydrogen atom or an alkyl group, G1 is each independently a single bond or an oxygen atom, and n is each independently an integer of 0 to 3]

[0051] [Chemistry 11]

[0052]

[0053] [In formula (B10), Y1, Y2, Z1, Z2, n1, n3, n4 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3, n4 and * in formula (B1), R 6 are independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 Each other, R 7 Each other or adjacent R 6 and R 7can be bonded to form a ring, G1 is a single bond or an oxygen atom, and n is an integer from 0 to 3]

[0054] [6] The composition according to any one of [1] to [5], wherein the alkali-soluble group in B is a phenolic hydroxyl group or a carboxyl group.

[0055] [7] The composition according to any one of [1] to [6], further comprising a photosensitive compound.

[0056] [8] The composition according to [7], wherein the photosensitive compound is a photosensitive acid generator.

[0057] [9] A cured product formed using the composition according to any one of [1] to [8].

[0058]

[10] The cured product according to [9], which is an insulating film, a surface protection film or a planarizing film.

[0059]

[11] A display element comprising the cured product according to [9] or

[10] .

[0060]

[12] A polymer having a structural unit represented by the following formula (2).

[0061] [Chemistry 12]

[0062]

[0063] [In formula (2), A is a divalent group having a nitrogen-containing aromatic ring,

[0064] B is a divalent group represented by any one of the following formulas (B1) to (B10),

[0065] X is independently -O-, -NH- or -S-]

[0066] [Chemistry 13]

[0067]

[0068] [In formula (B1), C1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y1 and Y2 are each independently an alkali-soluble group, Z1 and Z2 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, Z1 and Z2 may each independently bond to C1 to form a ring, n1 and n3 are each independently an integer of 0 to 2, wherein n1+n3 is an integer of 1 to 4, n2 and n4 are each independently an integer of 0 to 4, and * represents a bond to X]

[0069] [Chemistry 14]

[0070]

[0071] [In formula (B2), D1 is a trivalent organic group not containing an alkali-soluble group, Y3 is independently an alkali-soluble group, Z3 to Z5 are independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, at least one selected from Z3 and Y3 can be bonded to D1 to form a ring, n5 is an integer of 1 to 2, n6 to n8 are independently an integer of 0 to 4, and * represents a bond to X]

[0072] [Chemistry 15]

[0073]

[0074] [In formula (B3), E1 is a tetravalent organic group not containing an alkali-soluble group, Y4 and Y5 are each independently an alkali-soluble group, Z6 to Z9 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, n9 and n11 are each independently an integer of 1 to 2, n10 and n12 to n14 are each independently an integer of 0 to 4, and * represents a bond to X]

[0075] [Chemistry 16]

[0076]

[0077] [In formula (B4), C2 and C3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y6 and Y7 are each independently an alkali-soluble group, and Z 10 and Z 11 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n15 and n16 are independently 0 or 1, wherein n15+n16 is 1 or 2, n17 and n18 are independently an integer of 0 to 3, and * represents a bond to X]

[0078] [Chemistry 17]

[0079]

[0080] [In formula (B5), D2 is a trivalent organic group containing no alkali-soluble group, Z 12 and Z 13 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n19 and n20 are each independently an integer of 0 to 4, and * represents a bond to X]

[0081] [Chemistry 18]

[0082]

[0083] [In formula (B6), D3 and D4 are each independently a trivalent organic group not containing an alkali-soluble group, and Y8 to Y10 are independently alkali-soluble groups, Z 14 ~Z 17 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n21, n23 and n25 are independently an integer of 0 to 1, wherein n21+n23+n25 is an integer of 1 to 3, n22 and n24 are independently an integer of 0 to 5, n26 and n27 are independently an integer of 0 to 4, and * represents a bond to X]

[0084] [Chemistry 19]

[0085]

[0086] [In formula (B7), C4 and C5 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, and Y 11 ~Y 13 are independently alkali-soluble groups, Z 18 ~Z 20 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n28 and n32 are each independently an integer of 0 to 2, n30 is each independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, n31 is each independently an integer of 0 to 3, m is an integer of 1 to 3, and * represents a bond to X]

[0087] [Chemistry 20]

[0088]

[0089] [In formula (B8), Y 14 are independently alkali-soluble groups, Z 21 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n34 is an integer of 1 to 2, n35 is an integer of 0 to 3, and * represents a bond to X]

[0090] [Chemistry 21]

[0091]

[0092] [In formula (B9), Y1, Y2, Z1, Z2, n1, n3 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3 and * in formula (B1), R 6 are each independently a hydrogen atom or an alkyl group, G1 is each independently a single bond or an oxygen atom, and n is each independently an integer of 0 to 3]

[0093] [Chemistry 22]

[0094]

[0095] [In formula (B10), Y1, Y2, Z1, Z2, n1, n3, n4 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3, n4 and * in formula (B1), R 6 are independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 Each other, R 7 Each other or adjacent R 6 and R 7 can be bonded to form a ring, G1 is a single bond or an oxygen atom, and n is an integer from 0 to 3]

[0096] Effects of the Invention

[0097] According to one embodiment of the present invention, a cured product (cured film) having excellent and balanced sensitivity, transmittance of light with a wavelength of 400 nm, heat resistance, low relative dielectric constant, flatness, low linear expansion coefficient, and bending resistance can be formed. DETAILED DESCRIPTION

[0098] Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the embodiments described below, and it should be understood that various modifications implemented within the scope of the present invention are also included.

[0099] In the present specification, a numerical range described using “to” means that the numerical values ​​described before and after “to” are included as the lower limit and the upper limit.

[0100] 《Compositions and polymers》

[0101] The composition of one embodiment of the present invention (hereinafter also referred to as “the present composition”) contains a polymer (hereinafter also referred to as “polymer (1)”) having a structural unit represented by the following formula (1).

[0102] The polymer (1) contained in the present composition may be one kind or two or more kinds.

[0103] The polymer according to one embodiment of the present invention (hereinafter also referred to as "polymer (2)") has a structural unit represented by the following formula (2).

[0104] Hereinafter, the polymer (1) and the polymer (2) are also collectively referred to as "the present polymer".

[0105] The structural unit represented by the following formula (1) and the structural unit represented by the following formula (2) may be bonded to, for example, the following other structural units. That is, the polymer (1) and the polymer (2) may have other structural units other than the structural unit represented by the following formula (1) or the structural unit represented by the following formula (2).

[0106] <This polymer>

[0107] The polymer (1) is a polymer having a structural unit represented by the following formula (1), and the polymer (2) is a polymer having a structural unit represented by the following formula (2).

[0108] Since the present polymer has a structural unit represented by the following formula (1) or formula (2), it becomes a polymer that exerts the above-mentioned effects, particularly a low relative dielectric constant, excellent alkali solubility, specifically, a polymer with high dP and dH of the Hansen Solubility Parameter (HSP) values, and is easily soluble in alkaline aqueous solutions. In addition, the present polymer has an alkali solubility that is better than expected compared to other polymers containing the same alkali-soluble group in the same amount.

[0109] The structural unit represented by the following formula (1) contained in the polymer (1) may be one type or two or more types. Also, the structural unit represented by the following formula (2) contained in the polymer (2) may be one type or two or more types.

[0110] The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (2).

[0111] The content of the structural units represented by the formula (1) and the formula (2) in the present polymer is preferably 20% to 100% by mass, more preferably 40% to 100% by mass, further preferably 50% to 100% by mass, and particularly preferably 70% to 100% by mass, relative to 100% by mass of all structural units constituting the present polymer.

[0112] When the present polymer contains structural units other than the structural unit represented by the above formula (1) or the structural unit represented by the above formula (2), the upper limit of the content of the structural units represented by the above formula (1) and the above formula (2) in the present polymer is preferably 99% by mass, more preferably 95% by mass, relative to 100% by mass of all the structural units constituting the present polymer.

[0113] [Chemistry 23]

[0114]

[0115] [In formula (1), A is a divalent group having an aromatic heterocyclic ring,

[0116] B is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having an alkali-soluble group,

[0117] X is independently -O-, -NH- or -S-]

[0118] [Chemistry 24]

[0119]

[0120] [In formula (2), A is a divalent group having a nitrogen-containing aromatic ring,

[0121] B is a divalent group represented by any one of the following formulas (B1) to (B10),

[0122] X is independently -O-, -NH- or -S-]

[0123] A is preferably a divalent group derived from a dihalogen compound (a) represented by the following formula (a).

[0124] When the structural unit represented by the formula (1) and the formula (2) contains a plurality of A's, the plurality of A's may be the same or different.

[0125] The aromatic heterocycle in A is preferably a five-membered or six-membered aromatic heterocycle in terms of sensitivity to alkaline solubility, and examples thereof include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, furan, thiophene, and thiazole.

[0126] The nitrogen-containing aromatic ring in A is preferably a five-membered or six-membered nitrogen-containing aromatic ring in terms of sensitivity to alkaline solubility, and examples thereof include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and thiazole.

[0127] As the aromatic heterocyclic ring and nitrogen-containing aromatic ring in A, among these, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine and triazine are preferred, and pyrazine, pyrimidine, pyridazine and triazine are more preferred, in terms of the ease of obtaining a high molecular weight polymer due to high nucleophilic substitution reactivity and the ability to suppress side reactions caused by alkalinity.

[0128] The carbon number of A is preferably 3-48, more preferably 3-24.

[0129] The above-mentioned A may have an alkali-soluble group, but preferably has no alkali-soluble group.

[0130] The alkali-soluble group in the present specification is not particularly limited, and examples thereof include a carboxyl group, a hydroxyl group, a sulfone group, a phosphoric acid group, and an acid anhydride group. Among these, a carboxyl group and a phenolic hydroxyl group are preferred.

[0131] The aromatic heterocyclic ring in A is preferably a nitrogen-containing aromatic ring because a cured product (cured film) exhibiting the above effects and particularly having excellent alkali solubility can be easily obtained and a desired polymer can be easily synthesized.

[0132] As the nitrogen-containing aromatic ring, an aromatic ring having two or more nitrogen atoms is more preferred, and an aromatic ring having two or three nitrogen atoms is particularly preferred.

[0133] The above-mentioned A is preferably any group of the following group (A1).

[0134] [Chemistry 25]

[0135]

[0136] [R in group (A1) is an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms; a bond ("-") in group (A1) in which one of the bonding partners is not specified does not represent a methyl group but represents a bond to X etc.]

[0137] In terms of being able to easily form a cured product (cured film) having a balanced and excellent effect, X is preferably -O- or -NH-, and in terms of being able to easily form a cured product (cured film) having a better transmittance to light of a wavelength of 400 nm and a low relative dielectric constant, X is more preferably -O-.

[0138] Generally, polyethers in which X is -O- often have poor solubility in alkaline aqueous solutions and the like. However, the present polymer is a polymer that has excellent solubility in alkaline aqueous solutions and the like even when X is -O-.

[0139] A plurality of Xs contained in the structural units represented by the formula (1) and the formula (2) may be the same or different, but are preferably the same in terms of ease of synthesis.

[0140] The above-mentioned B is preferably a divalent group derived from an alkali-soluble group-containing compound (b) represented by the following formula (b).

[0141] When the structural unit represented by the formula (1) and the formula (2) contains a plurality of Bs, the plurality of Bs may be the same or different.

[0142] B in the formula (1) is preferably a divalent group having an aromatic ring and an alkali-soluble group.

[0143] The carbon number of B is preferably 5-48, more preferably 6-36.

[0144] In terms of sensitivity, transmittance, heat resistance, flatness, etc., B in the formula (1) is preferably a group represented by any one of the following formulas (B1) to (B10).

[0145] In terms of sensitivity and flatness, B in the formula (1) and the formula (2) is more preferably a group represented by any one of the following formulas (B1) to (B7), and is further preferably a group represented by any one of the following formulas (B1) to (B3) and (B5).

[0146] [Chemistry 26]

[0147]

[0148] [In formula (B1), C1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y1 and Y2 are each independently an alkali-soluble group, Z1 and Z2 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, Z1 and Z2 may each independently bond to C1 to form a ring, n1 and n3 are each independently an integer of 0 to 2, wherein n1+n3 is an integer of 1 to 4, n2 and n4 are each independently an integer of 0 to 4, and * represents a bond to X]

[0149] Preferred examples of C1 are: a single bond, an oxygen atom, a sulfur atom, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO2-, -CH(CH2OH)-; a divalent organic group having 1 to 15 carbon atoms or a divalent halogenated organic group having 1 to 15 carbon atoms which may contain these groups other than single bonds (hereinafter also referred to as "heteroatom-containing substituents"); and a divalent hydrocarbon group having 1 to 15 carbon atoms is more preferred.

[0150] As the organic group (before containing a substituent containing a heteroatom and before halogenation) and the hydrocarbon group, linear or branched alkyl groups and hydrocarbon groups containing alicyclic or aromatic rings can be cited. The following C2 to C5 organic groups (before containing a substituent containing a heteroatom and before halogenation) can also be cited as the same groups.

[0151] The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0152] The number of carbon atoms in the hydrocarbon group containing an alicyclic ring or an aromatic ring is preferably 5 to 15, and more preferably 6 to 12. The alicyclic ring that may be contained in the hydrocarbon group may be a monocyclic ring or a polycyclic ring, and the aromatic ring that may be contained in the hydrocarbon group may be a monocyclic ring or a polycyclic ring. In addition, the hydrocarbon group may contain an alicyclic ring and an aromatic ring.

[0153] Preferred examples of Y1 and Y2 are -OH and -COOH, and -OH is more preferred.

[0154] Preferred examples of Z1 and Z2 are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano, and amino, and more preferably alkyl having 1 to 12 carbon atoms.

[0155] The carbon number of the alkyl group and R' is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. 21 The number of carbon atoms in the alkyl group and R' is also the same.

[0156] The carbon number of the aryl group and the aryloxy group is preferably 6 to 20, more preferably 6 to 14. 21 The number of carbon atoms in the aryl group and the aryloxy group is also the same.

[0157] The carbon number of the aralkyl group and the aralkyloxy group is preferably 7 to 32, and more preferably 7 to 20. 21 The number of carbon atoms in the aralkyl group and the aralkyloxy group is also the same.

[0158] Regarding the structure when Z1 and Z2 are each independently bonded to C1 to form a ring, examples of the structure of the following formula (B1-1) moiety include structures represented by the following group (B1-1-1).

[0159] [Chemistry 27]

[0160]

[0161] [Chemistry 28]

[0162]

[0163] n1 and n3 are preferably 1.

[0164] n2 and n4 are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0165] [Chemistry 29]

[0166]

[0167] [In formula (B2), D1 is a trivalent organic group not containing an alkali-soluble group, Y3 is independently an alkali-soluble group, Z3 to Z5 are independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, at least one selected from Z3 and Y3 can be bonded to D1 to form a ring, n5 is an integer of 1 to 2, n6 to n8 are independently an integer of 0 to 4, and * represents a bond to X]

[0168] Preferred examples of D1 are hydrocarbon groups having 1 to 24 carbon atoms, groups in which a part of the hydrocarbon groups is substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, a phosphorus atom or a phosphine oxide group, and more preferably hydrocarbon groups having 1 to 12 carbon atoms.

[0169] Preferred examples of Y3 are -OH and -COOH, and -OH is more preferred.

[0170] Preferred examples of Z3 to Z5 are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano, and amino, and more preferably alkyl having 1 to 12 carbon atoms.

[0171] n5 is preferably 1.

[0172] n6 to n8 are preferably integers of 0 to 3, more preferably integers of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0173] [Chemistry 30]

[0174]

[0175] [In formula (B3), E1 is a tetravalent organic group not containing an alkali-soluble group, Y4 and Y5 are each independently an alkali-soluble group, Z6 to Z9 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, n9 and n11 are each independently an integer of 1 to 2, n10 and n12 to n14 are each independently an integer of 0 to 4, and * represents a bond to X]

[0176] Preferred examples of E1 are hydrocarbon groups having 1 to 24 carbon atoms, or groups in which a part of the hydrocarbon group is substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, and more preferably hydrocarbon groups having 1 to 20 carbon atoms.

[0177] Examples of the hydrocarbon group include a linear or branched alkyl group and a hydrocarbon group containing an alicyclic ring or an aromatic ring.

[0178] The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0179] The number of carbon atoms in the hydrocarbon group containing an alicyclic ring or an aromatic ring is preferably 5 to 15, and more preferably 6 to 12. The alicyclic ring that may be contained in the hydrocarbon group may be a monocyclic ring or a polycyclic ring, and the aromatic ring that may be contained in the hydrocarbon group may be a monocyclic ring or a polycyclic ring. In addition, the hydrocarbon group may contain an alicyclic ring and an aromatic ring.

[0180] Preferred examples of Y4 and Y5 are -OH and -COOH, and -OH is more preferred.

[0181] Preferred examples of Z6 to Z9 are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano, and amino groups, and more preferably alkyl having 1 to 12 carbon atoms.

[0182] n9 and n11 are preferably 1.

[0183] n10 and n12 to n14 are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0184] [Chemistry 31]

[0185]

[0186] [In formula (B4), C2 and C3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y6 and Y7 are each independently an alkali-soluble group, and Z 10 and Z 11 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n15 and n16 are independently 0 or 1, wherein n15+n16 is 1 or 2, n17 and n18 are independently an integer of 0 to 3, and * represents a bond to X]

[0187] Preferred examples of C2 and C3 are a single bond, an oxygen atom or a sulfur atom, and a single bond is more preferred.

[0188] Examples of divalent organic groups in C2 and C3 that do not contain an alkali-soluble group include: -O-, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO2-, and -CH(CH2OH)-; divalent organic groups having 1 to 15 carbon atoms that may contain these groups (substituents containing heteroatoms) or divalent halogenated organic groups having 1 to 15 carbon atoms.

[0189] Preferred examples of Y6 and Y7 are -OH and -COOH, and -OH is more preferred.

[0190] Z 10 and Z 11 Preferred examples are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano and amino groups, and more preferred are alkyl groups having 1 to 12 carbon atoms.

[0191] n15 and n16 are preferably 1.

[0192] n17 and n18 are preferably integers of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0193] [Chemistry 32]

[0194]

[0195] [In formula (B5), D2 is a trivalent organic group containing no alkali-soluble group, Z 12 and Z 13 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n19 and n20 are each independently an integer of 0 to 4, and * represents a bond to X]

[0196] Preferred examples of D2 are hydrocarbon groups having 1 to 24 carbon atoms, or groups in which a part of the hydrocarbon group is substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, and more preferably hydrocarbon groups having 1 to 12 carbon atoms.

[0197] Z 12 and Z 13 Preferred examples are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano and amino groups, and more preferred are alkyl groups having 1 to 12 carbon atoms.

[0198] n19 and n20 are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0199] [Chemistry 33]

[0200]

[0201] [In formula (B6), D3 and D4 are each independently a trivalent organic group not containing an alkali-soluble group, and Y8 to Y 10 are independently alkali-soluble groups, Z 14 ~Z 17 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n21, n23 and n25 are independently an integer of 0 to 1, wherein n21+n23+n25 is an integer of 1 to 3, n22 and n24 are independently an integer of 0 to 5, n26 and n27 are independently an integer of 0 to 4, and * represents a bond to X]

[0202] Preferred examples of D3 and D4 are hydrocarbon groups having 1 to 24 carbon atoms, or groups in which a part of the hydrocarbon groups is substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, and more preferably hydrocarbon groups having 1 to 12 carbon atoms.

[0203] Y8~Y 10 Preferred examples are -OH and -COOH, and -OH is more preferred.

[0204] Z 14 ~Z 17Preferred examples are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano and amino groups, and more preferred are alkyl groups having 1 to 12 carbon atoms.

[0205] n21, n23 and n25 are preferably 1.

[0206] n22, n24, n26 and n27 are preferably integers of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0207] [Chemistry 34]

[0208]

[0209] [In formula (B7), C4 and C5 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, and Y 11 ~Y 13 are independently alkali-soluble groups, Z 18 ~Z 20 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n28 and n32 are each independently an integer of 0 to 2, n30 is each independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, n31 is each independently an integer of 0 to 3, m is an integer of 1 to 3, and * represents a bond to X]

[0210] Preferred examples of C4 and C5 are: single bond, oxygen atom, sulfur atom, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO2-, -CH(CH2OH)-; divalent organic group having 1 to 15 carbon atoms or divalent halogenated organic group having 1 to 15 carbon atoms which may contain these groups (substituents containing heteroatoms) other than single bonds; more preferably, a divalent hydrocarbon group having 1 to 15 carbon atoms.

[0211] Y 11 ~Y 13 Preferred examples are -OH and -COOH, and -OH is more preferred.

[0212] Z 18 ~Z 20 Preferred examples are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano and amino groups, and more preferred are alkyl groups having 1 to 12 carbon atoms.

[0213] n28 and n32 are preferably 0 or 1.

[0214] n30 is preferably 1.

[0215] n29, n31 and n33 are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0216] m is preferably 1 or 2.

[0217] [Chemistry 35]

[0218]

[0219] [In formula (B8), Y 14 are independently alkali-soluble groups, Z 21 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n34 is an integer of 1 to 2, n35 is an integer of 0 to 3, and * represents a bond to X]

[0220] Y 14 Preferred examples are -OH and -COOH, and -OH is more preferred.

[0221] Z 21 Preferred examples are alkyl, alkoxy (-OR'), acyl (-OCR'), acyloxy (-OOCR'), aryl, aryloxy, aralkyl, aralkyloxy, halogen, nitro, cyano and amino groups, and more preferred are alkyl groups having 1 to 12 carbon atoms.

[0222] n34 is preferably 1.

[0223] n35 is preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0224] [Chemistry 36]

[0225]

[0226] [In formula (B9), Y1, Y2, Z1, Z2, n1, n3 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3 and * in formula (B1),

[0227] R 6 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms,

[0228] G1 is independently a single bond or an oxygen atom, preferably a single bond,

[0229] n is an integer of 0 to 3, preferably 0 or 1, more preferably 0]

[0230] [Chemistry 37]

[0231]

[0232] [In formula (B10), Y1, Y2, Z1, Z2, n1, n3, n4 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3, n4 and * in formula (B1),

[0233] R 6 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms,

[0234] R 7 is a hydrogen atom or an organic group, preferably a hydrogen atom or an organic group having 10 or less carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

[0235] R 6 Each other, R 7 Each other or adjacent R 6 and R 7 can be bonded to form a ring, preferably a five-membered or six-membered ring,

[0236] G1 is a single bond or an oxygen atom, preferably a single bond,

[0237] n is an integer of 0 to 3, preferably 0 or 1, more preferably 0]

[0238] <Other structural units>

[0239] The present polymer may have one or two or more structural units other than the structural unit represented by the above formula (1) or the structural unit represented by the above formula (2).

[0240] Examples of the other structural unit include a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a terminal structure.

[0241] Examples of the terminal structure include a structure derived from a raw material constituting a structural unit represented by the following formula (1) or (2) (for example, a compound represented by the following formula (a) to (d)) or a structure derived from the following terminal blocking agent.

[0242] The content of the other structural units in the present polymer is preferably 60% by mass or less relative to 100% by mass of all structural units constituting the present polymer, and is more preferably 1% by mass to 30% by mass in terms of easily forming a cured product (cured film) having better flatness and a low linear expansion coefficient.

[0243] [Chemistry 38]

[0244]

[0245] [In formula (3), A and X are independently the same as A and X in formula (1), and B' is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having no alkali-soluble group]

[0246] A preferred example of B' is a group obtained by removing an alkali-soluble group from the group described as B. More preferred B' is a group represented by the formula (B1) wherein n1 and n3 are 0.

[0247] The above-mentioned B' is preferably a divalent group derived from a compound (c) represented by the following formula (c).

[0248] [Chemistry 39]

[0249]

[0250] [In formula (4), A' is a divalent group having an aromatic ring (excluding an aromatic heterocyclic ring), and B and X each independently have the same meaning as B and X in formula (1)]

[0251] Preferred examples of A' are phenylenediyl or phenylenediyl having a substituent.

[0252] Examples of the substituent include organic groups having 1 to 12 carbon atoms, and preferably hydrocarbon groups having 1 to 12 carbon atoms.

[0253] The above-mentioned A' is preferably a divalent group derived from a compound (d) represented by the following formula (d).

[0254] <Method for synthesizing the present polymer>

[0255] The synthesis method of the present polymer is not particularly limited and may be a conventionally known method. Preferably, the method comprises a reaction step of reacting a dihalogen compound (a) represented by the following formula (a) with an alkali-soluble group-containing compound (b) represented by the following formula (b).

[0256] In the reaction step, one type of compound (a) may be used or two or more types of compounds (a) may be used, and one type of compound (b) may be used or two or more types of compounds (b) may be used.

[0257] LAL(a)

[0258] [In formula (a), A has the same meaning as A in formula (1), and L is a halogen atom]

[0259] Specific examples of the dihalogen compound (a) include 2,5-dichloropyrrole, 3,4-dichloropyrrole, 2,4-dichloroimidazole, 4,5-dichloroimidazole, 3,5-dichloropyrazole, 2,4-dichloropyridine, 2,6-dichloropyridine, 3,5-dichloropyridine, 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,6-dichloropyrimidine, 4,6-dichloropyrimidine, 3,6-dichloropyridazine, 4,5-dichloropyridazine, 2,4-dichloro-1, 3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,5-dichlorofuran, 3,4-dichlorofuran, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2,4-dichlorothiazole, 4,5-dichlorothiazole, difluoro compounds in which the chlorine atoms of these compounds are substituted with fluorine atoms, and substituted compounds in which at least one hydrogen atom of these compounds is substituted with an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms.

[0260] MBM(b)

[0261] [In formula (b), B has the same meaning as B in formula (1), and M is independently -OH, -SH or -NH2]

[0262] Examples of the alkali-soluble group-containing compound (b) include compounds in which "-*" in the above-mentioned formula (B1) to formula (B10) is replaced by "-M".

[0263] The M is preferably -OH.

[0264] Specific examples of the alkali-soluble group-containing compound (b) include compounds described in the following groups (b1) to (b8).

[0265] [Chemistry 40]

[0266]

[0267] [Chemistry 41]

[0268]

[0269] [Chemistry 42]

[0270]

[0271] [Chemistry 43]

[0272]

[0273] [Chemistry 44]

[0274]

[0275] [Chemistry 45]

[0276]

[0277] [Chemistry 46]

[0278]

[0279] [Chemistry 47]

[0280]

[0281] In the reaction step, at least one selected from the group consisting of a compound (c) represented by the following formula (c), a compound (d) represented by the following formula (d), and a terminal blocking agent may be used.

[0282] In this case, one compound (c) or two or more compounds (c) may be used, one compound (d) or two or more compounds (d) may be used, and one blocking agent or two or more blocking agents may be used.

[0283] M-B'-M(c)

[0284] [In formula (c), B' has the same meaning as B' in formula (3), and M is independently -OH, -SH or -NH2]

[0285] Examples of the compound (c) include compounds in which "-*" in the formula (B1) to (B10) is replaced by "-M" and the alkali-soluble group in the formula (B1) to (B10) is replaced by a hydrogen atom.

[0286] The M is preferably -OH.

[0287] Specific examples of the compound (c) include compounds in which the alkali-soluble group other than M in the compounds described in the above groups (b1) to (b8) is a hydrogen atom, and preferred examples include the compounds described in the following group (c1).

[0288] [Chemistry 48]

[0289]

[0290] L-A'-L(d)

[0291] [In formula (d), A' has the same meaning as A' in formula (4), and L is a halogen atom]

[0292] Specific examples of the compound (d) include 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, difluoro compounds in which the chlorine atoms of these compounds are substituted with fluorine atoms, and substituted compounds in which at least one hydrogen atom of these compounds is substituted with an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms.

[0293] Examples of the end-capping agent include monohalides in which one of the two Ls in the compound (a) and the compound (d) is a hydrogen atom, and compounds in which the other M in the compound (b) and the compound (c) is a hydrogen atom (for example, a monohydroxy compound).

[0294] Specifically, the reaction step can be performed by polymerizing monomers such as the compound (a) and the compound (b) in the presence of an alkali metal compound such as potassium carbonate in an appropriate solvent.

[0295] The present polymer obtained in the reaction step can also be purified by a known method. For example, the present polymer solution obtained by filtration is purified by removing inorganic salts and then the filtered solution is injected into a methanol aqueous solution or the like to precipitate the present polymer.

[0296] The reaction temperature in the reaction step is not particularly limited as long as the polymerization reaction proceeds, but is preferably 30° C. to 250° C., more preferably 40° C. to 180° C., from the perspective of suppressing side reactions. The reaction time is preferably 0.5 to 100 hours, more preferably 1 to 24 hours.

[0297] The amount of the compound (a) used is preferably 40 mol% to 60 mol%, more preferably 45 mol% to 55 mol%, based on 100 mol% of the total of the compounds (a) to (d).

[0298] The amount of the compound (b) used is preferably 20 mol% to 60 mol%, more preferably 30 mol% to 55 mol%, based on 100 mol% of the total of the compounds (a) to (d).

[0299] In terms of the ease of synthesizing a polymer having a structural unit represented by the formula (1) or (2), the molar ratio of the amount of the compound (a) and the compound (d) to the amount of the compound (b) and the compound (c) used [(compound (a) and compound (d)) / (compound (b) and compound (c))] is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0300] The amount of the compound (c) used is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%, based on 100 mol% of the total of the compounds (a) to (d).

[0301] The amount of the compound (d) used is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%, based on 100 mol% of the total of the compounds (a) to (d).

[0302] As the alkali metal compound, for example, there can be listed: alkali metals such as lithium, potassium, and sodium; alkali metal hydrides such as lithium hydride, potassium hydride, and sodium hydride; alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; alkali metal bicarbonates such as lithium bicarbonate, potassium bicarbonate, and sodium bicarbonate; alkali metal alkoxides such as sodium ethoxide; alkali metal acetates such as sodium acetate and potassium acetate; alkali metal oxides such as lithium oxide; alkali metal phosphates such as trilithium phosphate, trisodium phosphate, and tripotassium phosphate; alkali metal fluorides such as cesium fluoride. Among these, potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, and cesium fluoride are preferred.

[0303] The alkali metal compounds may be used alone or in combination of two or more.

[0304] The alkali metal compound is used in an amount such that the amount of the alkali metal atom in the alkali metal compound is generally 2 to 6 equivalents, preferably 2 to 5 equivalents, and more preferably 2.2 to 4 equivalents, relative to the two -Ms in the compounds (b) and (c).

[0305] Examples of the solvent include aprotic solvents such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone, and toluene; and protic solvents such as propylene glycol monomethyl ether, ethyl lactate, and water.

[0306] The solvent may be used alone or in combination of two or more.

[0307] <Physical properties of this polymer>

[0308] In terms of becoming a polymer with excellent heat resistance, the polystyrene-equivalent weight average molecular weight (Mw) of the present polymer is preferably 5,000 to 300,000, more preferably 10,000 to 200,000, and the molecular weight distribution (Mw / Mn) is preferably 2.0 to 7.0, more preferably 2.0 to 5.0.

[0309] The present polymer is alkali-soluble and has excellent solubility in alkaline aqueous solutions.

[0310] Here, as the alkaline aqueous solution, for example, the following alkaline developer can be mentioned.

[0311] Furthermore, the present polymer is said to be alkali-soluble when 1 g or more of the present polymer dissolves in 100 g of a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 25° C. Whether or not the polymer is alkali-soluble can be determined by the presence or absence of a precipitate.

[0312] <Other additives>

[0313] The present composition may contain additives other than the present polymer within the range not impairing the object and characteristics of the present invention.

[0314] Examples of the other additives include photosensitive compounds, crosslinking agents, solvents, alkali-soluble polymers other than the present polymer, monocarboxylic acid compounds, adhesion aids, crosslinked microparticles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers (polymerization inhibitors), pigments, dispersants, antioxidants, and acid amplifiers.

[0315] When other additives are used in the present composition, one type of other additive may be used, or two or more types of other additives may be used.

[0316] 〈Photosensitive compounds〉

[0317] When the present composition is made into a photosensitive composition, the present composition preferably contains a photosensitive compound.

[0318] When a photosensitive compound is used in the present composition, one type of photosensitive compound may be used, or two or more types of photosensitive compounds may be used.

[0319] The photosensitive compound is not particularly limited, but is preferably a photosensitive acid generator that generates an acid upon light irradiation.

[0320] When such a photosensitive acid generator is used, the photosensitive acid generator generates an acid in the exposed portion by exposing the cured product (cured film) formed from the present composition, and the solubility of the exposed portion in the alkaline aqueous solution changes due to the action of the acid.

[0321] The present composition may be either positive or negative, but is preferably positive in terms of further exerting the effects of the present invention.

[0322] The type of the photosensitive compound can be appropriately selected according to the desired properties of the present composition, such as positive or negative type.

[0323] Examples of the photosensitive acid generator include compounds having a quinonediazide group, onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Hereinafter, compounds having a quinonediazide group are also referred to as "quinonediazide compounds", and photosensitive acid generators other than these are also referred to as "other acid generators".

[0324] The quinonediazide compound is a compound that generates a carboxyl group by decomposing a quinonediazide group by light irradiation. By using the present composition containing a quinonediazide compound, for example, a resin film that is insoluble in an alkaline developer (resin film before light irradiation) can be formed. By irradiating the resin film with light, a hardened material (hardened film) that is easily soluble in an alkaline developer can be formed. Therefore, a positive pattern can be formed by this composition containing a quinonediazide compound.

[0325] The other acid generator is a compound that forms an acid by light irradiation. By using the present composition containing other acid generators, for example, a resin film that is easily soluble in an alkaline developer (resin film before light irradiation) can be formed. By irradiating the resin film with light, the acid generated by light irradiation reacts with a cross-linking agent described later to form a cross-linked structure, and a hardened material (hardened film) that is insoluble in an alkaline developer can be formed. Therefore, a negative pattern can be formed by this composition containing other acid generators.

[0326] [Quinonediazide compounds]

[0327] Examples of the quinonediazide compound include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother core") and an o-naphthoquinonediazide compound.

[0328] When a quinonediazide compound is used in the present composition, one type of quinonediazide compound may be used, or two or more types of quinonediazide compounds may be used.

[0329] Examples of the mother core include compounds described in JP-A-2014-186300, and a phenolic compound is preferred.

[0330] The o-naphthoquinonediazide compound is preferably 1,2-naphthoquinonediazidesulfonyl halide.

[0331] Specific examples of the quinonediazide compound include: 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1- Ester compounds of phenolic hydroxyl group-containing compounds among 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride.

[0332] Regarding the ratio of the core to the o-naphthoquinonediazide compound, it is desirable that the amount of the o-naphthoquinonediazide compound used is preferably 30 to 85 mol %, more preferably 50 to 70 mol %, relative to the number of OH groups in the core.

[0333] In the present composition, when a quinonediazide compound is used as the photosensitive compound, the content of the quinonediazide compound is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 30 parts by mass, based on 100 parts by mass of the present polymer.

[0334] When the content of the quinonediazide compound is at least the lower limit, the residual film rate of the non-exposed portion increases, and an image faithful to the mask pattern is easily obtained. When the content of the quinonediazide compound is at most the upper limit, a cured product (cured film) having a desired shape (pattern shape) can be easily obtained, and foaming during film formation tends to be suppressed.

[0335] [Other acid generators]

[0336] Examples of the other acid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.

[0337] When other acid generators are used in the present composition, one type of other acid generator may be used, or two or more types of other acid generators may be used.

[0338] Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.

[0339] Preferred examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate.

[0340] Examples of the halogen-containing compound include halogenated alkyl group-containing hydrocarbon compounds and halogenated alkyl group-containing heterocyclic compounds.

[0341] Preferred examples of halogen-containing compounds include: 1,10-dibromo-n-decane; 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, s-triazine derivatives such as s-triazine, s-triazine, s-triazine, s-triazine, and naphthyl-bis(trichloromethyl)-s-triazine.

[0342] Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds.

[0343] Preferred examples of the sulfone compound include 4-triphenylmethyl sulfone, mesitylphenylmethyl sulfone, and bis(phenacylsulfonyl)methane.

[0344] Examples of the sulfonic acid compound include alkyl sulfonates, halogenated alkyl sulfonates, aryl sulfonates, and imino sulfonates.

[0345] Preferred examples of the sulfonic acid compound include benzoin toluenesulfonate, pyrogallol tris-trifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl p-toluenesulfonate.

[0346] Examples of the sulfonyl imide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, and N-(trifluoromethylsulfonyloxy)naphthyl imide.

[0347] Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane.

[0348] In the present composition, when other acid generators are used as photosensitive compounds, the content of the other acid generators is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the present polymer.

[0349] If the content of the other acid generator is at least the lower limit, the exposure portion is sufficiently cured and heat resistance is easily improved. If the content of the other acid generator is at most the upper limit, transparency to exposure light is not reduced and a pattern with high resolution is easily obtained.

[0350] 〈Crosslinking agent〉

[0351] The present composition may further contain a crosslinking agent in order to improve curability.

[0352] By using a crosslinking agent in the present composition, the strength of the obtained cured product (cured film) and the adhesion to an object (for example, a support described below) on which the obtained cured product (cured film) is to be formed can be improved.

[0353] The crosslinking agent functions as a crosslinking component (hardening component) that reacts with the present polymer or with the crosslinking agent.

[0354] When a cross-linking agent is used in the present composition, one type of cross-linking agent may be used, or two or more types of cross-linking agents may be used.

[0355] The cross-linking agent is preferably a compound having two or more cross-linking groups.

[0356] The crosslinkable group is not particularly limited, but is preferably at least one selected from the group consisting of a hydroxymethyl group, an alkoxymethyl group, and a glycidyl group, and more preferably at least one selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, in terms of high crosslinking reactivity.

[0357] The number of crosslinkable groups contained in one molecule of the crosslinking agent is, for example, 2 to 10, and preferably 2 to 8.

[0358] Specific examples of the cross-linking agent include compounds described in JP-A-2022-67054 and WO-2014 / 109143.

[0359] When the present composition contains a crosslinking agent, the content of the crosslinking agent in the present composition is usually 1 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 40 parts by mass, based on 100 parts by mass of the present polymer.

[0360] When the content of the cross-linking agent is within the above range, a cured product (cured film) excellent in resolution, elongation properties, and heat resistance tends to be easily formed.

[0361] 〈Adhesive agent〉

[0362] The adhesion aid is preferably a component that can improve the adhesion between the resin film formed using the present composition and the adherend (substrate).

[0363] The adhesion aid is preferably a functional silane coupling agent having a reactive functional group.

[0364] Examples of the reactive functional group include a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0365] Specific examples of the functional coupling agent include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0366] When a close contact aid is used in the present composition, the content of the close contact aid in the present composition is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the present polymer contained in the present composition.

[0367] 〈Solvent〉

[0368] The present composition preferably contains a solvent.

[0369] By using a solvent, the handleability of the present composition can be improved, or the viscosity or storage stability can be adjusted.

[0370] When a solvent is used in the present composition, one type of solvent may be used, or two or more types of solvents may be used.

[0371] Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoalkyl ethers such as dipropylene glycol monobutyl ether; carbitols such as butyl carbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-butyrolactone; aromatic hydrocarbons such as toluene and xylene.

[0372] When the present composition contains a solvent, the content of the solvent in the present composition is usually 40 to 900 parts by mass, preferably 60 to 400 parts by mass, based on 100 parts by mass of the total of components other than the solvent in the present composition.

[0373] <Negative type of the present composition>

[0374] The present composition can be preferably used as a positive-type present composition. The present composition is preferably a positive-type composition, but may also be a negative-type composition.

[0375] The negative type present composition is described below. The negative type present composition is not particularly limited as long as it contains the present polymer, and is preferably a resin composition further containing one or more polymerizable monomers and one or more photopolymerization initiators, and may also contain other components.

[0376] 〈Polymerization monomer〉

[0377] The polymerizable monomer is a compound having one or more, preferably two or more polymerizable groups.

[0378] Examples of the polymerizable group include ethylenically unsaturated groups, oxirane groups, oxetanyl groups, and N-alkoxymethylamino groups. Of these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred in terms of high polymerizability, and vinyl-containing groups such as (meth)acryloyl groups, vinyl groups, and vinylphenyl groups are preferred.

[0379] Specifically, the polymerizable monomer is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly preferably a compound having two or more (meth)acryloyl groups.

[0380] The number of polymerizable groups contained in one molecule of the polymerizable monomer is preferably 2 to 10, more preferably 2 to 8.

[0381] Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0382] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the so-called melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and are concepts that also include melamine, benzoguanamine, or condensates thereof.

[0383] Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)acetylene carbamide.

[0384] Among these, the polymerizable monomer is preferably a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a caprolactone-modified polyfunctional (meth)acrylate, a polyfunctional urethane (meth)acrylate, a polyfunctional (meth)acrylate having a carboxyl group, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, or N,N,N',N'-tetra(alkoxymethyl)benzoguanamine; more preferably, a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a polyfunctional urethane (meth)acrylate, or a polyfunctional (meth)acrylate having a carboxyl group; and further preferably, a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid.

[0385] Specific examples of multifunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid include pentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane di(meth)acrylate, and polypentaerythritol poly(meth)acrylate. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferred in terms of increasing the crosslinking density between or within molecules and further improving the curability of the film by low-temperature calcination.

[0386] When a polymerizable monomer is used in the present composition, the content of the polymerizable monomer in the present composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of the present polymer contained in the present composition.

[0387] When the content of the polymerizable monomer is within the above range, sufficient curability and alkali developability can be ensured as a cured film, and generation of stains, film residues, etc. on the substrate or the light shielding layer in the non-exposed portion can be sufficiently suppressed, which is preferred.

[0388] 〈Photopolymerization Initiator〉

[0389] The photopolymerization initiator is preferably a compound that is sensitive to actinic rays having a wavelength of 300 nm or longer (preferably 300 nm to 450 nm) to initiate polymerization of the polymerizable monomer and promote the polymerization.

[0390] Furthermore, when a photopolymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or longer is used, polymerization of the polymerizable monomer may be initiated and accelerated by using it together with a sensitizer to be sensitive to actinic rays having a wavelength of 300 nm or longer.

[0391] As the photopolymerization initiator, known compounds can be used. As specific examples thereof, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryl biimidazole compounds, organic boronic acid compounds, disulfonic acid compounds, α-amino ketone compounds, onium salt compounds, acylphosphine (including acylphosphine oxide) compounds can be listed. Among these, in terms of further improving the sensitivity of the present composition, it is preferably at least one selected from the group consisting of oxime ester compounds, α-amino ketone compounds and hexaaryl biimidazole compounds, and more preferably oxime ester compounds or α-amino ketone compounds.

[0392] When a photopolymerization initiator is used in the present composition, the content of the photopolymerization initiator in the present composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less, relative to 100 parts by mass of the present polymer contained in the present composition.

[0393] 〈Other ingredients〉

[0394] The other components are components other than the polymerizable monomers and the photopolymerization initiator, and specific examples thereof include: a close contact aid, a solvent, a sensitizer, a crosslinking agent, a surfactant (a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, etc.), and an antioxidant.

[0395] These other components may be used alone or in combination of two or more.

[0396] ·Adhesives

[0397] The adhesion aid is preferably a component that can improve the adhesion between a cured film formed using the present composition and an adherend (substrate).

[0398] The adhesion aid is preferably a functional silane coupling agent having a reactive functional group.

[0399] Examples of the reactive functional group include a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0400] Examples of the functional coupling agent include the same compounds as those described in the section of other additives.

[0401] When a close contact aid is used in the negative-type present composition, the content of the close contact aid is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the present polymer contained in the present composition.

[0402] ·Solvent

[0403] The solvent is preferably an organic solvent that dissolves the components prepared in the present composition and does not react with the components. Examples of the solvent include the same solvents as those described in the column of other additives.

[0404] When a solvent is used in the negative-type present composition, the content of the solvent is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, based on 100% by mass of the present composition.

[0405] <Method for preparing the present composition>

[0406] The present composition can be prepared by (uniformly) mixing the formulated components. During the mixing, the components may be added and mixed all at once or in multiple additions.

[0407] The preparation of the present composition can be carried out at room temperature or by heating as appropriate.

[0408] In order to remove slag and the like, after the prepared components are mixed (uniformly), the obtained mixture may be filtered using a filter or the like.

[0409] Hardened

[0410] A cured product according to one embodiment of the present invention (hereinafter also referred to as “the present cured product”) is formed using the present composition.

[0411] By using this composition, the sensitivity, transmittance of light with a wavelength of 400nm, heat resistance, low relative dielectric constant, flatness, low linear expansion coefficient and bending resistance of this cured product are balanced and excellent. Therefore, this cured product can be suitably used as an (interlayer) insulating film, surface protection film, flattening film, etc. used in electronic parts such as circuit boards, high-density mounting substrates, semiconductor elements, semiconductor packages or display elements.

[0412] A preferred example of the present cured product is a cured film, particularly a patterned cured film. A preferred production example of the patterned cured film is shown below.

[0413] A preferred manufacturing example of the patterned cured film includes: a step of coating the present composition on a support to form a resin film (coating step); a step of exposing the resin film through a desired mask pattern (exposure step); and a step of developing the resin film after the exposure step with an alkaline developer, dissolving and removing the exposed portion in the case of a positive type, and dissolving and removing the exposed portion in the case of a negative type, thereby forming a cured film (patterned cured film) of a desired pattern on the support (development step).

[0414] [1] Coating process

[0415] In the coating step, the present composition is applied onto the support so that the film thickness of the patterned cured film finally obtained becomes, for example, 0.1 μm to 100 μm.

[0416] The present composition applied on the support is preferably heated using an oven, a hot plate or the like, usually at 50° C. to 140° C. for 10 seconds to 360 seconds to form a resin film on the support.

[0417] Examples of the support include a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor chip on the surface of these supports.

[0418] Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a screen method, and an inkjet method.

[0419] [2] Exposure process

[0420] In the exposure step, the resin film obtained in the coating step is exposed to light through a desired mask pattern using, for example, a contact aligner, a stepper, or a scanner.

[0421] The shape of the pattern is not particularly limited and may be appropriately selected according to the desired use. Examples thereof include a line and space pattern, a dot pattern, a hole pattern (eg, a square contact hole pattern), and a grid pattern.

[0422] Examples of the exposure light include ultraviolet rays and visible rays, and generally, examples include light having a wavelength of 200 nm to 500 nm (eg, i-rays (365 nm)).

[0423] The exposure dose varies depending on the type and proportion of each component in the composition, the thickness of the resin film, etc. When i-rays are used as exposure light, the exposure dose is usually 10 J / m 2 ~10,000J / m 2 .

[0424] When using the negative type composition of the present invention, heat treatment may be performed after exposure.

[0425] The conditions of the heat treatment are not particularly limited and vary depending on the contents of the components in the present composition and the thickness of the resin film, but are generally performed at 70° C. to 150° C., preferably 80° C. to 120° C. for about 1 minute to 60 minutes.

[0426] [3] Development process

[0427] In the development step, the resin film after the exposure step is developed with an alkaline developer to dissolve and remove the exposed portion in the case of a positive type and the non-exposed portion in the case of a negative type, thereby forming a desired patterned cured film on the support.

[0428] Furthermore, the obtained patterned cured film may be washed with water or the like and dried as necessary.

[0429] Examples of the development method include a shower development method, a spray development method, an immersion development method, and a liquid coating development method.

[0430] The development conditions are usually 20° C. to 40° C. for about 1 minute to 10 minutes.

[0431] As the alkaline developer, for example, there can be mentioned an alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. in water at a concentration of 1% to 10% by mass. To the alkaline aqueous solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount.

[0432] [4] Hardening process

[0433] After the development step, in order to fully develop the characteristics as a patterned cured film, a curing step of sufficiently curing the patterned cured film after the development step by heating or the like may be performed as necessary.

[0434] The conditions of the curing step are not particularly limited and may be appropriately set according to the application of the cured film, and examples thereof include heating at 100° C. to 250° C. for about 30 minutes to 10 hours.

[0435] Display Components

[0436] The display element of one embodiment of the present invention is not particularly limited as long as it has the present cured product, but preferably has the present cured film of one or more selected from the group consisting of an (interlayer) insulating film, a surface protective film, and a planarizing film.

[0437] The display element can be preferably used in display devices such as a liquid crystal display device and an organic electroluminescence (EL) display device.

[0438] The liquid crystal display device may include a backlight unit using a white light emitting diode (LED) as a light source in addition to a cold cathode fluorescent lamp (CCFL).

[0439] Examples of the organic EL display device include organic EL display devices having a top emission structure, a bottom emission structure, and the like.

[0440] The display element can be preferably used for various purposes. As a specific example, it can be used in various display devices such as watches, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital cameras, mobile phones, smart phones, various monitors, liquid crystal televisions, and information displays.

[0441] Example

[0442] Hereinafter, one embodiment of the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.

[0443] [Synthesis Example 1] Synthesis of Polymer P-1

[0444] In a four-necked flask equipped with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube, 100 mol parts of 4,6-dichloropyrimidine as a dihalogen compound, 60 mol parts of 4,4',4"-trihydroxytriphenylmethane as a compound containing an alkali-soluble group, 40 mol parts of 2,2-bis(4-hydroxyphenyl)propane as other compounds, 260 mol parts of potassium carbonate as a polymerization catalyst, N-methyl-2-pyrrolidone as a polymerization solvent (0.5 g relative to 1 mmol of the total amount of the dihalogen compound, the compound containing an alkali-soluble group and other compounds) and toluene (0.25 g relative to 1 mmol of the total amount of the dihalogen compound, the compound containing an alkali-soluble group and other compounds) were placed.

[0445] After nitrogen substitution in the flask, the contents of the flask were heated at 130° C. for 6 hours, and the water generated during heating was removed from the Dean-Stark tube at any time. After the contents of the flask were cooled to room temperature, the precipitated solid matter was filtered and separated. In addition, acetic acid was added, and the acidified filtrate was added to a methanol aqueous solution, and the precipitated solid matter was washed with a methanol aqueous solution. The solid matter after filtration and separation and the solid matter after washing with a methanol aqueous solution were dried to obtain a polymer P-1.

[0446] [Synthesis Examples 2 to 10, 12 and 13] Synthesis of Polymers P-2 to P-10, P-12 and P-13

[0447] Polymers P-2 to P-10, P-12 and P-13 were obtained in the same manner as in Synthesis Example 1, except that the dihalogen compound, alkali-soluble group-containing compound, other compounds and polymerization catalyst described in Table 1 were used in the amounts (molar parts) described in Table 1.

[0448] [Synthesis Example 11] Synthesis of Polymer P-11

[0449] In a three-necked flask equipped with a nitrogen inlet tube, 100 mol parts of 4,6-dichloropyrimidine as a dihalogen compound, 60 mol parts of 2,2-bis(3-amino-4-hydroxyphenyl)propane as a compound containing an alkali-soluble group, 40 mol parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as other compounds, and N-methyl-2-pyrrolidone as a polymerization solvent (0.8 g relative to the total amount of 1 mmol of the dihalogen compound, the compound containing an alkali-soluble group and other compounds) were placed.

[0450] After the flask was purged with nitrogen, the contents of the flask were heated at 150° C. for 8 hours. Thereafter, the contents of the flask were cooled to room temperature and added to a methanol aqueous solution, and the precipitated solid matter was washed with a methanol aqueous solution. The solid matter washed with the methanol aqueous solution was dried to obtain a polymer P-11.

[0451]

[0452] The dihalogen compounds in Table 1 are as follows.

[0453] "DH-1": 4,6-dichloropyrimidine

[0454] "DH-2": 2,4-dichloro-1,3,5-triazine

[0455] "DH-3": 2,6-dichloropyrimidine

[0456] "DH-4": 2,6-dichloropyrazine

[0457] "DH-5": 2,4-dichloro-6-phenyl-1,3,5-triazine

[0458] "DH-6": Bis(4-fluorophenyl)sulfone

[0459] The alkali-soluble group-containing compounds in Table 1 are as follows.

[0460] "AD-1": 4,4',4"-trihydroxytriphenylmethane

[0461] "AD-2": α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene

[0462] "AD-3": 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane

[0463] "AD-4": 1,3,5-trihydroxybenzene

[0464] "AD-5": 1,4-bis(3,4-dihydroxyphenyl)-2,3-dimethylbutane

[0465] "AD-6": 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane

[0466] "AD-7": 3,5-dihydroxybenzoic acid

[0467] "AD-8": 4,4-bis(4-hydroxyphenyl)valeric acid

[0468] "AD-9": 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0469] "AD-10": 3,5-dithiolbenzoic acid

[0470] The other compounds in Table 1 are described below.

[0471] "BP-1": 2,2-bis(4-hydroxyphenyl)propane

[0472] "BP-2": 2,2-bis(4-hydroxyphenyl)hexafluoropropane

[0473] "BP-3": 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane

[0474] "BP-4": α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene

[0475] "BP-5": 9,9-bis(4-hydroxyphenyl)fluorene

[0476] [Synthesis Example 14] Synthesis of polymer P-14 (acrylic resin)

[0477] Under nitrogen, 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, 40 parts by mass of methyl methacrylate and 20 parts by mass of styrene as polymerization monomers, 3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a free radical polymerization initiator and 400 parts by mass of N-methyl-2-pyrrolidone (NMP) as a solvent were added to a 100 mL two-necked flask, and polymerization was carried out at 70° C. for 6 hours.

[0478] After polymerization, the mixture was reprecipitated in methanol, the precipitate obtained was filtered, and the filtrate was vacuum dried at room temperature for 8 hours to obtain a solid substance. In addition, the obtained filtrate was added to methanol, and the precipitated solid substance was washed with a methanol aqueous solution. The vacuum dried solid substance and the solid substance washed with a methanol aqueous solution were dried to obtain a polymer P-14 (acrylic resin).

[0479] [Synthesis Example 15] Synthesis of polymer P-15 (polyimide)

[0480] 100 mol parts of 2,2-bis(3-amino-4-hydroxyphenyl)propane was dissolved in N-methyl-2-pyrrolidone (NMP), 100 mol parts of pyromellitic dianhydride was added thereto, and reacted at 40° C. for 24 hours to obtain a polyamic acid solution containing 20 mass % of polyamic acid.

[0481] Then, NMP was added to the obtained polyamic acid solution to set the concentration of the polyamic acid to 10% by mass, pyridine and acetic anhydride were added thereto, and a dehydration ring-closure reaction was carried out at 90° C. for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new NMP to obtain a polyimide solution containing 15% by mass of polyimide with an imidization rate of about 70%. The obtained polyimide solution was added to methanol, the precipitated solid matter was washed with a methanol aqueous solution, and the obtained solid matter was dried to obtain a polymer P-15 (polyimide).

[0482] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]

[0483] The Mw and Mn of the polymer synthesized in the above synthesis example were measured by gel permeation chromatography (GPC) using the following apparatus and conditions. The molecular weight distribution (Mw / Mn) was calculated from the measured Mw and Mn. The results are shown in Table 2.

[0484] · Equipment: GPC-101 manufactured by Showa Denko Co., Ltd.

[0485] ·GPC column: Combination of GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by SHIMADZU GLC (Co., Ltd.)

[0486] Mobile phase: Tetrahydrofuran

[0487] Column temperature: 40℃

[0488] Flow rate: 1.0mL / min

[0489] Sample concentration: 1.0 mass%

[0490] Sample injection volume: 100μL

[0491] Detector: Differential refractometer

[0492] ·Standard material: monodisperse polystyrene

[0493] <Preparation of evaluation resin solution>

[0494] To 100 parts by weight of the polymer obtained in the above synthesis example, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as solvents to obtain a solution having a solvent composition of NMP / BC = 50 / 50 (mass ratio) and a solid content concentration of 12% by weight.

[0495] The obtained solution was filtered through a filter having a pore size of 0.45 μm to prepare a resin solution for evaluation.

[0496] <Evaluation of transmittance (light transmittance)>

[0497] The prepared evaluation resin solution was applied to the glass substrate using a spinner, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with a film thickness of 3.0 μm. Subsequently, the glass substrate was heated at 230°C for 30 minutes in a clean oven after nitrogen replacement to form a cured film. The transmittance of the formed cured film was measured using a "V-630" UV-visible spectrophotometer manufactured by JASCO Corporation. The transmittance of light with a wavelength of 400 nm is set to "A" for a case of 90% or more, "B" for a case of 80% or more and less than 90%, and "C" for a case of less than 80%, and the transmittance is evaluated. The results are shown in Table 2.

[0498] When the evaluation result was "A" or "B", it was evaluated that the transmittance was good, and when the evaluation result was "C", it was evaluated that the transmittance was poor.

[0499] <Evaluation of heat resistance>

[0500] The prepared evaluation resin solution was applied to the silicon substrate using a spinner, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with a film thickness of 3.0 μm. Subsequently, the silicon substrate was heated at 230°C for 60 minutes in a clean oven after nitrogen substitution to form a cured film. The 5% thermal weight loss temperature of the formed cured film was measured in air using "TG / DTA220U" manufactured by Hitachi High-Tech Science (Hitachi High-Tech Science). The case where the 5% thermal weight loss temperature is above 350°C is set as "A", the case where it is above 300°C and less than 350°C is set as "B", and the case where it is less than 300°C is set as "C" to evaluate the heat resistance. The results are shown in Table 2.

[0501] <Evaluation of relative dielectric constant>

[0502] The prepared evaluation resin solution was applied to a SUS304 substrate that was polished and smoothed using a sisal buff (hemp buff), and then the reaching pressure was set to 100 Pa. The solvent was removed from the applied solution under vacuum, and then pre-baked at 90°C for 2 minutes to form a coating with an average film thickness of 3.0 μm. Subsequently, the substrate was heated at 230°C for 1 hour in a clean oven after nitrogen substitution, thereby forming an insulating film on the substrate. On the insulating film, a Pt / Pd electrode pattern was formed by evaporation to prepare a sample for dielectric constant measurement.

[0503] The relative dielectric constant was measured by the capacitance voltage method (CV method) at a frequency of 10 kHz using the prepared dielectric constant measurement sample and HP16451B electrode and HP4284A precision inductance-capacitance-resistance (LCR) meter manufactured by Hewlett Packard Co., Ltd. of Japan. The relative dielectric constant was evaluated by setting the relative dielectric constant to "A" when the relative dielectric constant was less than 3.3, "B" when the relative dielectric constant was more than 3.3 and less than 3.6, and "C" when the relative dielectric constant was more than 3.6. The results are shown in Table 2.

[0504] When the evaluation result was "A" or "B", it was evaluated that the relative dielectric constant was good, and when the evaluation result was "C", it was evaluated that the relative dielectric constant was poor.

[0505] <Evaluation of Linear Expansion Coefficient (Coefficient of Thermal Expansion, CTE)>

[0506] The polymers obtained in the synthesis examples were dissolved in N-methyl-2-pyrrolidone to prepare a resin composition having a polymer concentration of 20% by mass. The prepared resin composition was applied to a silicon substrate using a bar coater, dried at 70°C for 15 minutes, and then dried at 100°C for 15 minutes to form a film, which was then peeled off from the silicon substrate. Thereafter, the film was fixed to a metal frame and further dried at 230°C for 1 hour to prepare an evaluation film.

[0507] The coefficient of linear expansion of the produced evaluation film was measured using a Thermomechanical Analysis (TMA) SS6100 apparatus (manufactured by Seiko Instruments Co., Ltd.). The measurement was performed as follows.

[0508] Temporarily heat from room temperature to 200°C at 5°C / min, then cool to room temperature, and heat from room temperature to 250°C at 5°C / min again to make a TMA curve. The linear expansion coefficient is obtained from the slope between 50°C and the glass transition temperature (Tg) of the TMA curve. The case where the linear expansion coefficient is less than 70ppm / °C is set to "A", the case where 70ppm / °C or more and less than 100ppm / °C is set to "B", and the case where 100ppm / °C or more is set to "C", and the linear expansion coefficient (CTE) is evaluated. The results are shown in Table 2.

[0509] When the evaluation result was "A" or "B", it was evaluated that the CTE was good, and when the evaluation result was "C", it was evaluated that the CTE was poor.

[0510] [Table 2]

[0511]

[0512] [Example 1] Preparation of positive resist

[0513] 100 parts by mass of polymer P-1, 20 parts by mass of a quinonediazide compound (a condensate of 4,4'-〔1-〔4-〔1-〔4-hydroxyphenyl〕-1-methylethyl〕phenyl〕ethylene〕bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)) as a photosensitive compound, 5 parts by mass of a close contact aid (γ-glycidyloxypropyltrimethoxysilane), and 0.5 parts by mass of a surfactant ("FTX-218" manufactured by NEOS (Co., Ltd.)) were mixed. Furthermore, a mixed solution of diethylene glycol methyl ethyl ether and cyclohexanone as a solvent was added in such a manner that the solid content concentration became 20% by mass. Thereafter, the mixture was filtered using a membrane filter having a pore size of 0.2 μm to prepare a composition (positive resist).

[0514] [Example 2 to Example 17 and Comparative Example 1 to Comparative Example 4]

[0515] Using polymers of the types listed in Table 3, and further, in addition to using the photosensitive compound, adhesion aid, surfactant and solvent used in Example 1, the additives listed in Table 3 are used in the amounts (parts by mass) listed in Table 3, and a composition (positive resist) is prepared in the same manner as in Example 1.

[0516] <Evaluation of sensitivity (radiation sensitivity)>

[0517] The prepared composition (positive resist) was coated on a silicon substrate treated with hexamethyl disilazane (HMDS) at 60°C for 60 seconds using a spinner, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with a film thickness of 3.0 μm. Using an "MPA-600FA" exposure machine manufactured by Canon (Canon) (stock), a pattern mask with a line and space pattern of 10 μm in width was used to irradiate the coating with a specified amount of ultraviolet rays. Subsequently, a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide) was used for development treatment at 25°C for 60 seconds, followed by running water washing with ultrapure water for 1 minute. At this time, the minimum exposure amount that can form a line and space pattern of 10 μm in width was measured. The measured value is less than 1500 J / m 2 The case is set to "A" (excellent sensitivity), and 1500J / m 2 The above case was designated as "B" (good sensitivity), and the case where no pattern was obtained was designated as "C", and the sensitivity was evaluated. The results are shown in Table 3.

[0518] <Evaluation of Flatness>

[0519] The prepared composition (positive resist) was applied on a silicon substrate having a line and space pattern with a depth of 2.0 μm and a width of 20 μm using a spin coater. Thereafter, the reaching pressure was set to 100 Pa, and the solvent was removed from the applied composition under vacuum, followed by pre-baking at 90°C for 2 minutes to form a coating having an average film thickness of 3.0 μm. Subsequently, a developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) was used for a 60-second development treatment at 25°C, followed by 1-minute running water washing with ultrapure water. The obtained coating was exposed using an exposure machine ("MPA-600FA" manufactured by Canon (Canon)) with a cumulative irradiation dose of 9,000 J / m 2 The substrate having the exposed coating film was exposed in a manner of , and the substrate was heated at 230° C. for 1 hour in a clean oven replaced with nitrogen, thereby forming an insulating film on the substrate.

[0520] The surface shape of the insulating film of the obtained substrate with insulating film was observed using a needle contact measuring machine ("AS200" manufactured by KLA Tencor), and the difference in height (ΔH) between the highest part and the lowest part of the concave-convex part of the insulating film was used as an index of flatness. The flatness was evaluated by setting the case where the ΔH was less than 500nm as "A", the case where it was 500nm or more and 800nm ​​or less as "B", and the case where it was more than 800nm ​​as "C". The results are shown in Table 3.

[0521] <Evaluation of bendability (bending resistance)>

[0522] On the polyimide film substrate, the prepared composition (positive resist) is applied using a spin coater. Thereafter, the arrival pressure is set to 100 Pa, the solvent is removed from the applied composition under vacuum, and then pre-baked at 90°C for 2 minutes to form a coating with an average film thickness of 3.0 μm. Subsequently, a developer (aqueous solution of 2.38% by mass of tetramethylammonium hydroxide) is used for 60 seconds of development at 25°C, followed by 1 minute of running water washing with ultrapure water. In a clean oven, the obtained coating is heated at 230°C for 1 hour to form a cured film on the substrate.

[0523] The obtained substrate with a cured film is cut into a size of 50 mm in length and 50 mm in width. Next, the surface of the cured film is set to the inner side, and the substrate with the cured film is bent in a manner that the cured films are in contact with each other, and kept in the state for 10 minutes. After 10 minutes, the bent substrate with the cured film is opened, and the bent portion of the surface of the cured film is observed using an optical microscope to evaluate the appearance changes. The case where the cured film has no cracks is set to "A", the case where there are cracks in a part of the cured film is set to "B", and the case where the cured film has cracks as a whole is set to "C", and the bendability (bending resistance) is evaluated. The results are shown in Table 3.

[0524] [Table 3]

[0525]

[0526] Add-1 to Add-6 in Table 3 are as follows.

[0527] "Add-1": a compound represented by the following formula (Add-1) "Add-2": a compound represented by the following formula (Add-2) "Add-3": a compound represented by the following formula (Add-3) "Add-4": a compound represented by the following formula (Add-4) "Add-5": a compound represented by the following formula (Add-5) "Add-6": a bisphenol A type epoxy resin ("EP157S65", manufactured by Mitsubishi Chemical Co., Ltd.)

[0528] [Chemistry 49]

[0529]

[0530] [Chemistry 50]

[0531]

[0532] [Chemistry 51]

[0533]

[0534] [Chemistry 52]

[0535]

[0536] [Chemistry 53]

[0537]

[0538] [Example 18] Preparation of negative resist

[0539] 100 parts by mass of polymer P-1, 5 parts by mass of an O-acyl oxime compound ("Irgacure OXE01" manufactured by BASF) as a photopolymerization initiator, 30 parts by mass of a polymerizable monomer (a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate), 5 parts by mass of an adhesion aid (γ-glycidyloxypropyltrimethoxysilane), and 0.5 parts by mass of a surfactant ("FTX-218" manufactured by NEOS) were mixed. Furthermore, a mixed solution of diethylene glycol methyl ethyl ether and cyclohexanone as a solvent was added so that the solid content concentration became 20% by mass, and then filtered using a membrane filter with a pore size of 0.2 μm to prepare a composition (negative resist).

[0540] The prepared negative resist was used to perform the same evaluations of sensitivity, flatness, and curvature as described above. As a result, good sensitivity, flatness, and curvature were also confirmed for the negative resist.

Claims

1. A composition comprising a polymer having a structural unit represented by the following formula (1): [Chemistry 1] In formula (1), A is a divalent group having an aromatic heterocyclic ring, B is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having an alkali-soluble group, X is independently -O-, -NH- or -S-. 2 . The composition according to claim 1 , wherein the aromatic heterocyclic ring in A is a nitrogen-containing aromatic ring. 3 . The composition according to claim 1 , wherein the aromatic heterocyclic ring in A is an aromatic ring having two or more nitrogen atoms. The composition according to claim 1 , wherein X is —O— or —NH—.

5. The composition according to claim 1, wherein B is a group represented by any one of the following formulas (B1) to (B10): [Chemistry 2] In formula (B1), C1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y1 and Y2 are each independently an alkali-soluble group, Z1 and Z2 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, Z1 and Z2 can each independently bond with C1 to form a ring, n1 and n3 are each independently an integer of 0 to 2, wherein, n1+n3 is an integer of 1 to 4, n2 and n4 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 3] In formula (B2), D1 is a trivalent organic group not containing an alkali-soluble group, Y3 is independently an alkali-soluble group, Z3 to Z5 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, at least one selected from Z3 and Y3 can be bonded to D1 to form a ring, n5 is an integer of 1 to 2, n6 to n8 are independently an integer of 0 to 4, * represents a bond to X, [Chemistry 4] In formula (B3), E1 is a tetravalent organic group not containing an alkali-soluble group, Y4 and Y5 are each independently an alkali-soluble group, Z6 to Z9 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, n9 and n11 are each independently an integer of 1 to 2, n10 and n12 to n14 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 5] In formula (B4), C2 and C3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y6 and Y7 are each independently an alkali-soluble group, and Z 10 and Z 11 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n15 and n16 are independently 0 or 1, wherein n15+n16 is 1 or 2, n17 and n18 are independently an integer of 0 to 3, and * represents a bond to X, [Chemistry 6] In formula (B5), D2 is a trivalent organic group containing no alkali-soluble group, and Z 12 and Z 13 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n19 and n20 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 7] In formula (B6), D3 and D4 are each independently a trivalent organic group containing no alkali-soluble group, and Y8 to Y 10 are independently alkali-soluble groups, Z 14 ~Z 17 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n21, n23 and n25 are independently an integer of 0 to 1, wherein n21+n23+n25 is an integer of 1 to 3, n22 and n24 are independently an integer of 0 to 5, n26 and n27 are independently an integer of 0 to 4, * represents a bond to X, [Chemistry 8] In formula (B7), C4 and C5 are each independently a divalent organic group containing no alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, and Y 11 ~Y 13 are independently alkali-soluble groups, Z 18 ~Z 20 are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, n28 and n32 are each independently an integer of 0 to 2, n30 is each independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, n31 is each independently an integer of 0 to 3, m is an integer of 1 to 3, * represents a bond to X, [Chemistry 9] In formula (B8), Y 14 are independently alkali-soluble groups, Z 21 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n34 is an integer of 1 to 2, n35 is an integer of 0 to 3, * represents a bond to X, [Chemistry 10] In formula (B9), Y1, Y2, Z1, Z2, n1, n3 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3 and * in formula (B1), and R 6 are each independently a hydrogen atom or an alkyl group, G1 is each independently a single bond or an oxygen atom, n is each independently an integer of 0 to 3, [Chemistry 11] In formula (B10), Y1, Y2, Z1, Z2, n1, n3, n4 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3, n4 and * in formula (B1), and R 6 are independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 Each other, R 7 Each other or adjacent R 6 and R 7 They may be bonded to form a ring, G1 is a single bond or an oxygen atom, and n is an integer of 0 to 3. The composition according to claim 1 , wherein the alkali-soluble group in B is a phenolic hydroxyl group or a carboxyl group.

7. The composition according to claim 1, further comprising a photosensitive compound. The composition according to claim 7 , wherein the photosensitive compound is a photosensitive acid generator.

9. A cured product formed using the composition according to any one of claims 1 to 8. 10 . The cured product according to claim 9 , which is an insulating film, a surface protection film or a planarizing film.

11. A display element comprising the cured product according to claim 9.

12. A polymer having a structural unit represented by the following formula (2): [Chemistry 12] In formula (2), A is a divalent group having a nitrogen-containing aromatic ring, B is a divalent group represented by any one of the following formulas (B1) to (B10), X is independently -O-, -NH- or -S-, [Chemistry 13] In formula (B1), C1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y1 and Y2 are each independently an alkali-soluble group, Z1 and Z2 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, Z1 and Z2 can each independently bond with C1 to form a ring, n1 and n3 are each independently an integer of 0 to 2, wherein, n1+n3 is an integer of 1 to 4, n2 and n4 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 14] In formula (B2), D1 is a trivalent organic group not containing an alkali-soluble group, Y3 is independently an alkali-soluble group, Z3 to Z5 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, at least one selected from Z3 and Y3 can be bonded to D1 to form a ring, n5 is an integer of 1 to 2, n6 to n8 are independently an integer of 0 to 4, * represents a bond to X, [Chemistry 15] In formula (B3), E1 is a tetravalent organic group not containing an alkali-soluble group, Y4 and Y5 are each independently an alkali-soluble group, Z6 to Z9 are each independently a monovalent organic group not containing an alkali-soluble group or a fluorine atom, n9 and n11 are each independently an integer of 1 to 2, n10 and n12 to n14 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 16] In formula (B4), C2 and C3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, Y6 and Y7 are each independently an alkali-soluble group, and Z 10 and Z 11 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n15 and n16 are independently 0 or 1, wherein n15+n16 is 1 or 2, n17 and n18 are independently an integer of 0 to 3, and * represents a bond to X, [Chemistry 17] In formula (B5), D2 is a trivalent organic group containing no alkali-soluble group, and Z 12 and Z 13 are each independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n19 and n20 are each independently an integer of 0 to 4, * represents a bond to X, [Chemistry 18] In formula (B6), D3 and D4 are each independently a trivalent organic group containing no alkali-soluble group, and Y8 to Y 10 are independently alkali-soluble groups, Z 14 ~Z 17 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n21, n23 and n25 are independently an integer of 0 to 1, wherein n21+n23+n25 is an integer of 1 to 3, n22 and n24 are independently an integer of 0 to 5, n26 and n27 are independently an integer of 0 to 4, * represents a bond to X, [Chemistry 19] In formula (B7), C4 and C5 are each independently a divalent organic group containing no alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO2-, and Y 11 ~Y 13 are independently alkali-soluble groups, Z 18 ~Z 20 are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, n28 and n32 are each independently an integer of 0 to 2, n30 is each independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, n31 is each independently an integer of 0 to 3, m is an integer of 1 to 3, * represents a bond to X, [Chemistry 20] In formula (B8), Y 14 are independently alkali-soluble groups, Z 21 are independently a monovalent organic group or a fluorine atom not containing an alkali-soluble group, n34 is an integer of 1 to 2, n35 is an integer of 0 to 3, * represents a bond to X, [Chemistry 21] In formula (B9), Y1, Y2, Z1, Z2, n1, n3 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3 and * in formula (B1), and R 6 are each independently a hydrogen atom or an alkyl group, G1 is each independently a single bond or an oxygen atom, n is each independently an integer of 0 to 3, [Chemistry 22] In formula (B10), Y1, Y2, Z1, Z2, n1, n3, n4 and * are independently the same as Y1, Y2, Z1, Z2, n1, n3, n4 and * in formula (B1), and R 6 are independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 Each other, R 7 Each other or adjacent R 6 and R 7 They may be bonded to form a ring, G1 is a single bond or an oxygen atom, and n is an integer of 0 to 3.

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