Polycyclic polyphenol resin and method for producing polycyclic polyphenol resin

Abstract

A polycyclic polyphenol resin having a repeating unit derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by formula (1A) and formula (1B), The polycyclic polyphenol resin is a polycyclic polyphenol resin in which the repeating units are linked to each other by direct bonds between aromatic rings. [Formula 1] In formula (1A), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking; Y represents a 2n-valent group having 1 to 60 carbon atoms or a single bond; when X is no crosslinking, Y represents the 2n-valent group. In formula (1B), A represents a benzene ring or a fused ring. In formulas (1A) and (1B), R 0 each independently represents an optionally substituted alkyl group having 1 to 40 carbon atoms, an optionally substituted aryl group having 6 to 40 carbon atoms, an optionally substituted alkenyl group having 2 to 40 carbon atoms, an optionally substituted alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, wherein R 0 At least one of the m's is a hydroxyl group, each m's is independently an integer of 1 to 9, each n's is an integer of 1 to 4, and each p's is independently an integer of 0 to 3.

Description

[Technical Field]

[0001] The present invention relates to a polycyclic polyphenol resin and a method for producing a polycyclic polyphenol resin. [Background technology]

[0002] Polyphenol resins having repeating units derived from hydroxy-substituted aromatic compounds, etc., are known as sealants, coating agents, resist materials, and semiconductor underlayer film-forming materials for semiconductors. For example, Patent Documents 1 and 2 propose the use of polyphenol compounds or resins having specific skeletons.

[0003] Meanwhile, known methods for producing polyphenolic resins include the addition-condensation of phenols and formalin using an acid or alkali catalyst to produce novolak resins or resol resins. However, this method of producing phenolic resins raises safety concerns because it uses formaldehyde, which has recently been identified as a potential health hazard, as a raw material for the phenolic resin. To address this issue, a method has been proposed for producing a phenolic polymer by oxidatively polymerizing phenols in a solvent such as water or an organic solvent using an enzyme with peroxidase activity, such as peroxidase, and a peroxide, such as hydrogen peroxide. Another known method is to produce polyphenylene oxide (PPO) by oxidatively polymerizing 2,6-dimethylphenol (see Non-Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2013 / 024778 [Patent Document 2] International Publication No. 2013 / 024779 [Non-patent literature]

[0005] [Non-Patent Document 1] Hideyuki Higashimura, Shiro Kobayashi, Chemistry and Industry, 53,501 (2000) Summary of the Invention [Problem to be solved by the invention]

[0006] The materials described in Patent Documents 1 and 2 still have room for improvement in terms of performance such as heat resistance and etching resistance, and there is a demand for the development of new materials that are even more excellent in these physical properties. Furthermore, polyphenol resins obtained by the method of Non-Patent Document 1 typically contain both oxyphenol units, which are formed by bonding between a carbon atom on the aromatic ring of one phenolic monomer and a phenolic hydroxyl group of the other phenolic monomer, and units having phenolic hydroxyl groups in the molecule formed by bonding between carbon atoms on the aromatic rings of phenolic monomers. Since aromatic rings are bonded to each other via oxygen atoms, such polyphenolic resins are flexible polymers, but are undesirable from the viewpoints of crosslinkability and heat resistance because the phenolic hydroxyl groups disappear.

[0007] The present invention has been made in consideration of the above problems, and aims to provide a polycyclic polyphenol resin having superior performance in terms of heat resistance, etching resistance, etc., and a method for producing a polycyclic polyphenol resin. [Means for solving the problem]

[0008] In view of the above circumstances, the present inventors have conducted extensive research and have found that the above problems can be solved by using a polycyclic polyphenol resin having a specific structure, thereby completing the present invention.

[0009] That is, the present invention includes the following aspects. [1] A polycyclic polyphenol resin having a repeating unit derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by formula (1A) and formula (1B), The polycyclic polyphenol resin is a polycyclic polyphenol resin in which the repeating units are linked to each other by direct bonds between aromatic rings. [ka] In formula (1A), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking; Y represents a 2n-valent group having 1 to 60 carbon atoms or a single bond; when X is no crosslinking, Y represents the 2n-valent group. In formula (1B), A represents a benzene ring or a fused ring. In formulas (1A) and (1B), R 0 are each independently an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, wherein R 0 At least one of the m's is a hydroxyl group, each m's is independently an integer of 1 to 9, each n's is an integer of 1 to 4, and each p's is independently an integer of 0 to 3. [2] The polycyclic polyphenol resin according to [1], wherein the aromatic hydroxy compound represented by formula (1A) is an aromatic hydroxy compound represented by formula (1). [ka] (In formula (1), X, m, n, and p are the same as those described in formula (1A), and R 1 is the same as Y in formula (1A), and R 2 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, wherein R 2 At least one of the is a hydroxyl group.) [3] The polycyclic polyphenol resin according to [2], wherein the aromatic hydroxy compound represented by the formula (1) is an aromatic hydroxy compound represented by the following formula (1-1): [ka] (In formula (1-1), Z is an oxygen atom or a sulfur atom, and R 1 , R 2 , m, p, and n have the same meanings as those explained in formula (1). [4] The polycyclic polyphenol resin according to [3], wherein the aromatic hydroxy compound represented by the formula (1-1) is an aromatic hydroxy compound represented by the following formula (1-2): [ka] (In formula (1-2), R 1 , R 2 , m, p, and n have the same meanings as those explained in formula (1). [5] The polycyclic polyphenol resin according to [4], wherein the aromatic hydroxy compound represented by the formula (1-2) is an aromatic hydroxy compound represented by the following formula (1-3): [ka] (In the above formula (1-3), R 1 is the same as that explained in the formula (1), and R 3 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, or a thiol group, and m 3 are each independently an integer of 0 to 5. [6] The polycyclic polyphenol resin according to [1], wherein the aromatic hydroxy compound represented by the formula (1A) is an aromatic hydroxy compound represented by the following formula (2): [ka] (In formula (2), R 1 is the same as Y in formula (1A), and R 5 , n and p are the same as those described in the formula (1A), and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, an alkenyl group having 2 to 34 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 34 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, and m 5 are each independently an integer of 1 to 6, and m 6 are each independently an integer from 1 to 7, where R 5 At least one of the is a hydroxyl group.) [7] The polycyclic polyphenol resin according to [6], wherein the aromatic hydroxy compound represented by the formula (2) is an aromatic hydroxy compound represented by the following formula (2-1): [ka] (In formula (2-1), R 1 , R 5 , R 6 and n are the same as those described in the formula (2), and m 5’ are each independently an integer of 1 to 4, and m 6’ are each independently an integer of 1 to 5, where R 5 At least one of the is a hydroxyl group.) [8] R 6 The polycyclic polyphenol resin according to [6] or [7], wherein at least one of the groups is a hydroxyl group. [9] The polycyclic polyphenol resin according to [7] or [8], wherein the aromatic hydroxy compound represented by the formula (2-1) is an aromatic hydroxy compound represented by the following formula (2-2): [ka] (In formula (2-2), R 1 is the same as that explained in the above formula (2), and R 7 and R 8are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, and m 7 and m 8 are each independently an integer of 0 to 7.

[10] The polycyclic polyphenol resin according to any one of [1] to [9], further having a modified portion derived from a crosslinkable compound.

[11] The polycyclic polyphenol resin according to

[10] , wherein the crosslinkable compound is an aldehyde or a ketone.

[12] The polycyclic polyphenol resin according to any one of [1] to

[11] , which has a mass average molecular weight of 400 to 100,000.

[13] 13. The polycyclic polyphenol resin according to claim 1, which has a solubility of 1% by mass or more in 1-methoxy-2-propanol and / or propylene glycol monomethyl ether acetate.

[14] 14. The film-forming composition for lithography according to claim 1, wherein A in said formula (1B) is a fused ring.

[15] R 1 But R A -R B wherein R A is a methine group, and the R B 15. The polycyclic polyphenol resin according to claim 2, wherein is an aryl group having 6 to 30 carbon atoms which may have a substituent.

[16] A composition comprising the polycyclic polyphenol resin according to any one of claims 1 to 15.

[17] 17. The composition of claim 16, further comprising a solvent.

[18] 18. The composition of claim 17, wherein the solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, ethyl lactate, and methyl hydroxyisobutyrate.

[19] 19. The composition according to claim 16, wherein the content of impurity metals is less than 500 ppb for each metal species.

[20] 20. The composition of claim 19, wherein the impurity metal comprises at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium. [twenty one] 21. The composition according to claim 19, wherein the content of the impurity metals is 1 ppb or less. [twenty two] A method for producing the polycyclic polyphenol resin according to any one of claims 1 to 15, A method for producing a polycyclic polyphenol resin, comprising a step of polymerizing one or more of the aromatic hydroxy compounds in the presence of an oxidizing agent. [twenty three] 23. The method for producing a polycyclic polyphenol resin according to claim 22, wherein the oxidizing agent is a metal salt or a metal complex containing at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polycyclic polyphenol resin having superior properties such as heat resistance and etching resistance, and a method for producing the polycyclic polyphenol resin. DETAILED DESCRIPTION OF THE INVENTION

[0011] Below, we will explain in detail the form for implementing the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0012] [Polycyclic polyphenol resin] The polycyclic polyphenol resin of this embodiment is a polycyclic polyphenol resin having repeating units derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by the following formulas (1A) and (1B), and the repeating units are linked to each other by direct bonds between aromatic rings. Because of this configuration, the polycyclic polyphenol resin of this embodiment has superior performance in terms of heat resistance, etching resistance, etc.

[0013] [ka] In formula (1A), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking; Y represents a 2n-valent group having 1 to 60 carbon atoms or a single bond; when X is no crosslinking, Y represents the 2n-valent group. In formula (1B), A represents a benzene ring or a fused ring. In formulas (1A) and (1B), R 0 are each independently an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, wherein R 0 At least one of the m's is a hydroxyl group, each m's is independently an integer of 1 to 9, and all m's are not simultaneously 0. Each n's is an integer of 1 to 4, and each p's is independently an integer of 0 to 3.

[0014] The polycyclic polyphenol resin of the present embodiment typically has the following properties (1) to (4), although not limited thereto. (1) The polycyclic polyphenol resin of this embodiment has excellent solubility in organic solvents (especially safe solvents). Therefore, for example, when the polycyclic polyphenol resin of this embodiment is used as a film-forming material for lithography, a film for lithography can be formed by a wet process such as spin coating or screen printing. (2) The polycyclic polyphenol resin of this embodiment has a relatively high carbon concentration and a relatively low oxygen concentration. Furthermore, since the polyphenol resin has phenolic hydroxyl groups in its molecule, it is useful for forming a cured product by reaction with a curing agent. However, it can also form a cured product by itself through a crosslinking reaction of the phenolic hydroxyl groups during high-temperature baking. Due to these factors, the polyphenol resin of this embodiment exhibits high heat resistance. When used as a film-forming material for lithography, film deterioration during high-temperature baking is suppressed, and a lithography film having excellent etching resistance, such as against oxygen plasma etching, can be formed. (3) As described above, the polycyclic polyphenol resin of this embodiment can exhibit high heat resistance and etching resistance, and also has excellent adhesion to resist layers and resist intermediate layer film materials. Therefore, when used as a film-forming material for lithography, a lithography film with excellent resist pattern formability can be formed. Here, "resist pattern formability" refers to the property of having no major defects in the resist pattern shape and having excellent resolution and sensitivity. (4) The polycyclic polyphenol resin of the present embodiment has a high refractive index due to its high aromatic ring density, and is suppressed from becoming discolored even when subjected to heat treatment, resulting in excellent transparency.

[0015] The polycyclic polyphenol resin of this embodiment can be preferably used as a film-forming material for lithography due to these properties, and therefore it is believed that the film-forming composition for lithography of this embodiment is provided with the desired properties described above. In particular, compared to resins crosslinked with divalent organic groups or oxygen atoms, the aromatic ring density is higher and the carbon atoms of the aromatic rings are directly bonded to each other by direct bonds, so it is believed that even though the molecular weight is relatively low, the polycyclic polyphenol resin has superior performance in terms of heat resistance, etching resistance, and the like.

[0016] The above formula (1A) and formula (1B) will be explained in detail below. In formula (1A), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. From the viewpoint of heat resistance, X is preferably an oxygen atom.

[0017] In formula (1A), Y is a 2n-valent group having 1 to 60 carbon atoms or a single bond, and when X is uncrosslinked, Y is the 2n-valent group. The 2n-valent group having 1 to 60 carbon atoms is, for example, a 2n-valent hydrocarbon group, and the hydrocarbon group may have various functional groups described below as a substituent. Furthermore, the 2n-valent hydrocarbon group indicates an alkylene group having 1 to 60 carbon atoms when n = 1, an alkanetetrayl group having 1 to 60 carbon atoms when n = 2, an alkanehexyl group having 2 to 60 carbon atoms when n = 3, and an alkaneoctyl group having 3 to 60 carbon atoms when n = 4. Examples of the 2n-valent hydrocarbon group include groups in which a 2n+1-valent hydrocarbon group is bonded to a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. Examples of the 2n+1 valent hydrocarbon group include, but are not limited to, a trivalent methine group, an ethyne group, and the like. The din-valent hydrocarbon group may have a double bond, a heteroatom, and / or an aryl group having 6 to 59 carbon atoms. Although Y may contain a group derived from a compound having a fluorene skeleton, such as fluorene or benzofluorene, the term "aryl group" used herein does not include groups derived from a compound having a fluorene skeleton, such as fluorene or benzofluorene.

[0018] In this embodiment, the 2n-valent group may contain a halogen group, a nitro group, an amino group, a hydroxyl group, an alkoxy group, a thiol group, or an aryl group having 6 to 40 carbon atoms. Furthermore, the 2n-valent group may contain an ether bond, a ketone bond, an ester bond, or a double bond.

[0019] In this embodiment, the 2n-valent group preferably contains a branched hydrocarbon group or an alicyclic hydrocarbon group rather than a linear hydrocarbon group from the viewpoint of heat resistance, and more preferably contains an alicyclic hydrocarbon group. Furthermore, in this embodiment, it is particularly preferable that the 2n-valent group contains an aryl group having 6 to 60 carbon atoms.

[0020] The linear hydrocarbon group and branched hydrocarbon group that may be contained in the 2n-valent group are not particularly limited, and examples thereof include an unsubstituted methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. The alicyclic hydrocarbon group and the aromatic group having 6 to 60 carbon atoms which may be contained in the 2n-valent group are not particularly limited, and examples thereof include an unsubstituted phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, an adamantyl group, a phenylene group, a naphthalenediyl group, a biphenyldiyl group, an anthracenediyl group, a pyrenediyl group, a cyclohexanediyl group, a cyclododecanediyl group, a dicyclopentanediyl group, a tricyclodecanediyl group, an adamantanediyl group, a benzyl group, a phenylene ... Examples thereof include a benzenetriyl group, a naphthalenetriyl group, a biphenyltriyl group, anthracenetriyl group, a pyrenetriyl group, a cyclohexanetriyl group, a cyclododecanetriyl group, a dicyclopentanetriyl group, a tricyclodecanetriyl group, an adamantanetriyl group, a benzenetetrayl group, a naphthalenetetrayl group, a biphenyltetrayl group, anthracenetetrayl group, a pyrenetetrayl group, a cyclohexanetetrayl group, a cyclododecanetetrayl group, a dicyclopentanetetrayl group, a tricyclodecanetetrayl group, and an adamantanetetrayl group.

[0021] R 0are each independently an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group, or a hydroxyl group. Here, the alkyl group may be linear, branched, or cyclic. where R 0 At least one of the groups is a hydroxyl group.

[0022] Examples of the alkyl group having 1 to 40 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. Examples of the aryl group having 6 to 40 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group. Examples of the alkenyl group having 2 to 40 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, and a pentynyl group. Examples of the alkynyl group having 2 to 40 carbon atoms include, but are not limited to, an acetylene group, an ethynyl group, and the like. Examples of the alkoxy group having 1 to 40 carbon atoms include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.

[0023] Each m is independently an integer of 1 to 9. From the viewpoint of solubility, 1 to 6 is preferred, and 1 to 4 is more preferred, and from the viewpoint of raw material availability, 1 is even more preferred.

[0024] n is an integer of 1 to 4. From the viewpoint of solubility, 1 or 2 is preferred, and from the viewpoint of raw material availability, 1 is more preferred.

[0025] Each p is independently an integer of 0 to 3. From the viewpoint of heat resistance, 1 or 2 is preferred, and 1 is more preferred from the viewpoint of raw material availability.

[0026] In this embodiment, the aromatic hydroxy compound represented by either formula (1A) or (1B) above can be used alone or in combination. In this embodiment, from the viewpoint of achieving both solvent solubility and heat resistance, it is preferable to use the aromatic hydroxy compound represented by formula (1A) above. Furthermore, from the viewpoint of achieving both solvent solubility and heat resistance, it is also preferable to use the aromatic hydroxy compound represented by formula (1B) above.

[0027] In this embodiment, the aromatic hydroxy compound represented by the above formula (1A) is preferably a compound represented by the following formula (1) from the viewpoint of ease of production. [ka] (In formula (1), X, m, n, and p are the same as those described in formula (1A), and R 1 is the same as Y in formula (1A), and R 2 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, wherein R 2 At least one of the is a hydroxyl group.)

[0028] The aromatic hydroxy compound represented by the formula (1) is preferably an aromatic hydroxy compound represented by the following formula (1-1) from the viewpoint of heat resistance. [ka] (In formula (1-1), Z is an oxygen atom or a sulfur atom, and R 1 , R 2 , m, p, and n have the same meanings as those explained in formula (1).

[0029] Furthermore, the aromatic hydroxy compound represented by the formula (1-1) is preferably an aromatic hydroxy compound represented by the following formula (1-2) from the viewpoint of raw material availability. [ka] (In formula (1-2), R 1 , R 2 , m, p, and n have the same meanings as those explained in formula (1).

[0030] Furthermore, the aromatic hydroxy compound represented by the formula (1-2) is preferably an aromatic hydroxy compound represented by the following formula (1-3) from the viewpoint of improving solubility. [ka] (In the above formula (1-3), R 1 is the same as that explained in the formula (1), and R 3 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, or a thiol group, and m 3 are each independently an integer of 0 to 5.

[0031] Moreover, the aromatic hydroxy compound represented by the formula (1A) is preferably an aromatic hydroxy compound represented by the following formula (2) from the viewpoint of dissolution stability. [ka] (In formula (2), R 1 is the same as Y in formula (1A), and R 5 , n and p are the same as those described in the formula (1A), and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, an alkenyl group having 2 to 34 carbon atoms, an alkynyl group having 2 to 34 carbon atoms, an alkoxy group having 1 to 34 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, and m 5are each independently an integer of 1 to 6, and m 6 are each independently an integer from 1 to 7, where R 5 At least one of the is a hydroxyl group.)

[0032] Furthermore, the aromatic hydroxy compound represented by the formula (2) is preferably an aromatic hydroxy compound represented by the following formula (2-1) from the viewpoint of dissolution stability. [ka] (In formula (2-1), R 1 , R 5 , R 6 and n are the same as those described in the formula (2), and m 5’ are each independently an integer of 1 to 4, and m 6’ are each independently an integer of 1 to 5, where R 5 At least one of the is a hydroxyl group.)

[0033] In the above formula (2) or formula (2-1), from the viewpoint of dissolution stability, R 6 At least one of these is preferably a hydroxyl group.

[0034] Furthermore, the aromatic hydroxy compound represented by the formula (2-1) is preferably an aromatic hydroxy compound represented by the following formula (2-2) from the viewpoint of availability of raw materials. [ka] (In formula (2-2), R 1 is the same as that explained in the above formula (2), and R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 34 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, and m 7 and m 8 are each independently an integer of 0 to 7.

[0035] In the above formula (1), formula (1-1), formula (1-2), formula (1-3), formula (2), formula (2-1) or formula (2-2), from the viewpoint of both higher heat resistance and solubility, 1 But R A -R B wherein R A is a methine group, and the R B is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. In this embodiment, examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, and a pyrenyl group. As mentioned above, groups derived from compounds having a fluorene skeleton, such as fluorene and benzofluorene, are not included in the "aryl group having 6 to 30 carbon atoms."

[0036] Specific examples of the aromatic hydroxy compounds represented by the formula (1A), (1), (1-1), (1-2), (1-3), (2), (2-1) or (2-2) are shown below, but are not limited to these.

[0037] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0038] In the above formula, R 2and X have the same meaning as explained in the above formula (1). ´ is an integer from 1 to 7. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0039] [ka]

[0040] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0041] [ka]

[0042] [ka]

[0043] In the above formula, R 2 and X have the same meaning as explained in the above formula (1). m ´ is an integer from 1 to 7, and m ´´ is an integer between 1 and 5. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0044] [ka]

[0045] In the above formula, R 2 , X and m ´ has the same meaning as explained above. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] In the above formula, R 2 and X have the same meaning as explained in the above formula (1). ´ is an integer between 1 and 7.´´ is an integer between 1 and 5. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0050] [ka]

[0051] In the above formula, R 2 and X have the same meaning as explained in the above formula (1). ´ is an integer from 1 to 7. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0052] [ka] [ka]

[0053] In the above formula, R 2 and X have the same meaning as explained in the above formula (1). ´ is an integer between 1 and 7. ´´ is an integer between 1 and 5. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0054] [ka]

[0055] In the above formula, R 2 and X have the same meaning as explained in the formula (1). ´is an integer from 1 to 7. Here, R 2 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these. [ka]

[0056] [ka]

[0057] In the above formula, R 2 and X have the same meaning as explained in the formula (1). ´ is an integer between 1 and 7. ´´ is an integer between 1 and 5. Here, R 2 At least one of the groups is a hydroxyl group.

[0058] Specific examples of the compound represented by the above formula (2) are shown below, but are not limited to these.

[0059] [ka]

[0060] [ka] [ka] [ka] [ka]

[0061] [ka] [ka] [ka] [ka]

[0062] In the aromatic hydroxy compound, R 5 and R 6 has the same meaning as that explained in the above formula (3). m 11 is an integer from 0 to 6, and m 12 is an integer between 0 and 7, and all m 11 and m 12 are never simultaneously 0. where R 5 and R 6 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0063] [ka] [ka] [ka] [ka] [ka] [ka]

[0064] [ka]

[0065] [ka]

[0066] In the aromatic hydroxy compound, R 5 and R 6 has the same meaning as that explained in the above formula (3). m 5’ are each independently an integer of 0 to 4, and m 6’ are each independently an integer of 0 to 5, and all m 5’ and m 6’ are never simultaneously 0. where R 5 and R 6 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] In the aromatic hydroxy compound, R 5 and R 6 has the same meaning as that explained in the above formula (3). m 11 is an integer from 0 to 6, and m 12 is an integer between 0 and 7, and all m 11 and m 12 are never simultaneously 0. where R 5 and R 6 At least one of the groups is a hydroxyl group. Further specific examples of the aromatic hydroxy compound according to the present embodiment are shown below, but are not limited to these.

[0071] [ka]

[0072] [ka]

[0073] In the aromatic hydroxy compound, R 5 and R 6 has the same meaning as that explained in the above formula (3). m 5‘ is an integer from 0 to 4, and m 6’ is an integer between 0 and 5, and all m 5‘ and m 6’ are never simultaneously 0. where R 5 and R 6 At least one of the groups is a hydroxyl group.

[0074] From the viewpoint of improving dissolution stability and hardening properties, all R 5 is preferably a hydroxyl group, and from the viewpoint of further improving the dissolution stability and curability, all of R 6 is preferably a hydroxyl group.

[0075] Furthermore, A in the formula (1B) is not particularly limited, and may be, for example, a benzene ring or various known fused rings such as naphthalene, anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, and ovalene. In this embodiment, it is preferable that A is various fused rings such as naphthalene, anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, and ovalene from the viewpoint of heat resistance. Furthermore, it is preferable that A is naphthalene or anthracene, since the n value and k value at a wavelength of 193 nm used in ArF exposure tend to be low and the pattern transferability tends to be excellent. In addition to the aromatic hydrocarbon rings mentioned above, A may also be a heterocycle such as pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, thiazole, or a benzo-fused product thereof. In this embodiment, the above A is preferably an aromatic hydrocarbon ring or a heterocycle, and more preferably an aromatic hydrocarbon ring.

[0076] Furthermore, A in the formula (1B) is not particularly limited, and may be, for example, a benzene ring or any of various known fused rings such as naphthalene, anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, and ovalene. In this embodiment, preferred examples of the aromatic hydroxy compound represented by the formula (1B) include aromatic hydroxy compounds represented by the following formulas (1B') and (1B''). [ka] (In formula (1B'), R 0 , m and p have the same meanings as in formula (1A). In formula (1B″), R 0 is the same as in formula (1A), and m 0 is an integer from 0 to 4, and all m 0 and never become 0 at the same time.)

[0077] Specific examples of the aromatic hydroxy compound represented by the formula (1B') are shown below, but are not limited to these.

[0078] [ka]

[0079] In the formula (B-1), n 0 is an integer of 0 to 4, and in the formula (B-2), n 0 is an integer of 0 to 6, and in the formulas (B-3) and (B-4), n 0 is an integer between 0 and 8.

[0080] Among the aromatic hydroxy compounds represented by the formulas (B-1) to (B-4), those represented by formulas (B-3) to (B-4) are preferred from the viewpoint of improving etching resistance. From the viewpoint of optical properties, those represented by formulas (B-2) to (B-3) are preferred. From the viewpoint of flatness, those represented by formulas (B-1) to (B-2) and (B-4) are preferred, and those represented by formula (B-4) are more preferred. From the viewpoint of heat resistance, it is preferred that any one carbon atom of the aromatic ring having a phenolic hydroxyl group is involved in the direct bond between the aromatic rings.

[0081] Specific examples of the aromatic hydroxy compound represented by the formula (1B'') are shown below, but are not limited to these.

[0082] [ka]

[0083] In addition to the above, from the viewpoint of further improving etching resistance, an aromatic hydroxy compound represented by the following B-5 can also be used as a specific example of formula (1B). [ka] (In formula (B-5), n 1is an integer between 0 and 8.)

[0084] In the polycyclic polyphenol resin of this embodiment, the number and ratio of each repeating unit are not particularly limited, but are preferably adjusted appropriately taking into consideration the intended use and the molecular weight value described below. The mass average molecular weight of the polycyclic polyphenol resin of the present embodiment is not particularly limited, but is preferably in the range of 400 to 100,000, more preferably 500 to 15,000, and even more preferably 3,200 to 12,000. The ratio (Mw / Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited as the required ratio varies depending on the application. However, for example, those having a more uniform molecular weight are preferably in the range of 3.0 or less, more preferably in the range of 1.05 or more and 3.0 or less, particularly preferably in the range of 1.05 or more and less than 2.0, and even more preferably in the range of 1.05 or more and less than 1.5 from the viewpoint of heat resistance.

[0085] The bonding order of the repeating units in the polycyclic polyphenol resin of this embodiment is not particularly limited. For example, the polycyclic polyphenol resin may contain two or more repeating units derived from the aromatic hydroxy compound represented by formula (1A), two or more repeating units derived from the aromatic hydroxy compound represented by formula (1B), or two or more repeating units each derived from the aromatic hydroxy compound represented by formula (1A) and the aromatic hydroxy compound represented by formula (1B).

[0086] The position at which repeating units in the polycyclic polyphenol resin of this embodiment are directly bonded to each other is not particularly limited, and when the repeating units are those represented by the general formula (1A), any one of the carbon atoms to which neither a phenolic hydroxyl group nor other substituents is bonded is involved in the direct bond between the monomers. From the viewpoint of heat resistance, it is preferred that any one carbon atom of the aromatic ring having a phenolic hydroxyl group is involved in the direct bond between the aromatic rings.

[0087] The polycyclic polyphenol resin of the present embodiment may contain a repeating unit having an ether bond formed by condensation of phenolic hydroxyl groups, or may contain a ketone structure, as long as the performance according to the application is not impaired.

[0088] The polycyclic polyphenol resin of this embodiment preferably has high solubility in a solvent, from the viewpoint of facilitating application of a wet process. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the polycyclic polyphenol resin of this embodiment preferably has a solubility in the solvent at 23°C of 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. Here, the solubility in PGME and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) × 100 (mass%)." For example, 10 g of a polycyclic polyphenol resin is considered to be soluble in 90 g of PGMEA when the solubility of the polycyclic polyphenol resin in PGMEA is "10% by mass or more," and is considered to be insoluble when the solubility is "less than 10% by mass."

[0089] [Method of producing polycyclic polyphenols] The method for producing the polycyclic polyphenol resin of this embodiment is not limited to the following, but may include, for example, a step of polymerizing one or more of the aromatic hydroxy compounds in the presence of an oxidizing agent. When carrying out such a step, the contents of K. Matsumoto, Y. Shibasaki, S. Ando and M. Ueda, Polymer, 47, 3043 (2006) can be referred to as appropriate. That is, in the oxidative polymerization of a β-naphthol-type monomer, C-C coupling at the α-position is selectively caused by an oxidative coupling reaction in which radicals that are one-electron oxidized due to the monomer are coupled, and regioselective polymerization can be carried out by using, for example, a copper / diamine-type catalyst. The oxidizing agent in this embodiment is not particularly limited as long as it causes an oxidative coupling reaction, and examples thereof include metal salts containing copper, manganese, iron, cobalt, ruthenium, lead, nickel, silver, tin, chromium, palladium, etc., peroxides such as hydrogen peroxide or perchloric acids, and organic peroxides. Among these, metal salts or metal complexes containing copper, manganese, iron, or cobalt are preferably used. Metals such as copper, manganese, iron, cobalt, ruthenium, lead, nickel, silver, tin, chromium, and palladium can also be used as oxidizing agents by being reduced in the reaction system. These are included in the metal salts. For example, the desired polycyclic polyphenol resin can be obtained by dissolving an aromatic hydroxy compound represented by general formula (1A) in an organic solvent, adding a metal salt containing copper, manganese, or cobalt, and reacting the compound with, for example, oxygen or an oxygen-containing gas to cause oxidative polymerization. According to the above-described method for producing polycyclic polyphenol resins by oxidative polymerization, molecular weight control is relatively easy, and resins with narrow molecular weight distribution can be obtained without leaving behind raw material monomers or low molecular weight components that accompany high molecular weight production, and therefore this method tends to be advantageous in terms of high heat resistance and low sublimation.

[0090] As the metal salts, halides, carbonates, acetates, nitrates or phosphates of copper, manganese, cobalt, ruthenium, chromium, palladium or the like can be used. The metal complex is not particularly limited, and known ones can be used. Specific examples thereof include, but are not limited to, copper-containing complex catalysts described in JP-B-36-18692, JP-B-40-13423, JP-A-490-490, etc., manganese-containing complex catalysts described in JP-B-40-30354, JP-B-47-5111, JP-A-56-32523, JP-A-57-44625, JP-A-58-19329, JP-A-60-83185, etc., and cobalt-containing complex catalysts described in JP-B-45-23555.

[0091] Examples of organic peroxides include, but are not limited to, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, and perbenzoic acid.

[0092] The oxidizing agents can be used alone or in combination. The amount of the oxidizing agent used is not particularly limited, but is preferably 0.002 to 10 mol, more preferably 0.003 to 3 mol, and even more preferably 0.005 to 0.3 mol, per mol of the aromatic hydroxy compound. In other words, the oxidizing agent in this embodiment can be used at a low concentration relative to the monomer.

[0093] In this embodiment, it is preferable to use a base in addition to the oxidizing agent used in the oxidative polymerization step. The base is not particularly limited and any known base can be used, and specific examples thereof include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal alkoxides, and organic bases such as primary to tertiary monoamine compounds and diamines. Each of these can be used alone or in combination.

[0094] The oxidation method is not particularly limited, and includes a method using oxygen gas or air directly, but air oxidation is preferred from the viewpoint of safety and cost. When oxidation is performed using air under atmospheric pressure, a method of introducing air into a reaction solvent by bubbling the air into the liquid is preferred from the viewpoint of increasing the rate of oxidative polymerization and increasing the molecular weight of the resin. The oxidation reaction of this embodiment can be carried out under pressure, and from the viewpoint of promoting the reaction, a pressure of 2 kg / cm can be used. 2 ~15kg / cm 2 is preferable, and from the viewpoint of safety and controllability, 3 kg / cm 2 ~10kg / cm 2 is more preferable.

[0095] In this embodiment, the oxidation reaction of the aromatic hydroxy compound can be carried out in the absence of a reaction solvent, but it is generally preferable to carry out the reaction in the presence of a solvent. Various known solvents can be used as long as they dissolve the catalyst to some extent, as long as they do not interfere with obtaining the polycyclic polyphenol resin of this embodiment. Generally, solvents such as alcohols (e.g., methanol, ethanol, propanol, butanol), ethers (e.g., dioxane, tetrahydrofuran, ethylene glycol dimethyl ether), amides or nitriles, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone), or mixtures of these with water are used. The reaction can also be carried out in a two-phase system of water-immiscible hydrocarbons (e.g., benzene, toluene, hexane) or a mixture of these with water.

[0096] The reaction conditions may be adjusted appropriately depending on the substrate concentration and the type and concentration of the oxidizing agent, but the reaction temperature can be set relatively low, preferably 5 to 150°C, and more preferably 20 to 120°C. The reaction time is preferably 30 minutes to 24 hours, and more preferably 1 to 20 hours. The stirring method during the reaction is not particularly limited, and may be shaking or stirring using a rotor or stirring blade. This step may be carried out either in a solvent or in an air stream, as long as the stirring conditions satisfy the above-mentioned conditions.

[0097] The polycyclic polyphenol resin of the present embodiment is preferably obtained as a crude product by the above-described oxidation reaction, and then further purified to remove any remaining oxidizing agent. That is, from the viewpoints of preventing deterioration of the resin over time and improving storage stability, it is preferable to avoid the presence of metal salts or metal complexes containing copper, manganese, iron, or cobalt, which are mainly used as metal oxidizing agents derived from the oxidizing agent.

[0098] The residual metal amounts derived from the oxidizing agent are preferably less than 10 ppm, more preferably less than 1 ppm, and even more preferably less than 500 ppb. A concentration of 10 ppm or more tends to prevent a decrease in the solubility of the resin in the solution due to resin deterioration, and also tends to prevent an increase in the turbidity (haze) of the solution. On the other hand, a concentration of less than 500 ppb tends to allow the solution to be used without losing its storage stability, even in solution form. Thus, in this embodiment, it is particularly preferable that the content of impurity metals is less than 500 ppb for each metal species.

[0099] The purification method is not particularly limited, but includes a step of dissolving a polycyclic polyphenol resin in a solvent to obtain a solution (S), and a step (first extraction step) of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the resin, and the solvent used in the step of obtaining the solution (S) includes an organic solvent that is not arbitrarily miscible with water. According to the purification method, it is possible to reduce the content of various metals that may be contained as impurities in the resin. More specifically, the resin can be dissolved in an organic solvent that is immiscible with water to obtain a solution (S), which can then be subjected to extraction treatment by contacting the solution (S) with an acidic aqueous solution, thereby transferring the metals contained in the solution (S) to the aqueous phase, and then separating the organic and aqueous phases to obtain a resin with a reduced metal content.

[0100] The water-immiscible solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes, specifically an organic solvent whose solubility in water at room temperature is less than 30%, more preferably less than 20%, and particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass the total amount of the resin used.

[0101] Specific examples of solvents that are arbitrarily immiscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturated solubility of polycyclic polyphenol resins and a relatively low boiling point, making it possible to reduce the load in industrial processes for distilling off the solvent or removing it by drying. These solvents can be used alone or in combination of two or more.

[0102] The acidic aqueous solution used in the above purification method is appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include, but are not limited to, mineral acid aqueous solutions prepared by dissolving mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water, and organic acid aqueous solutions prepared by dissolving organic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid in water. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, preferred are aqueous solutions of one or more mineral acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or aqueous solutions of one or more organic acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Sulfuric acid, nitric acid, and aqueous solutions of carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid are more preferred, and aqueous solutions of oxalic acid are even more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions, creating a chelating effect, which is thought to tend to more effectively remove metals. Furthermore, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of the purification method of this embodiment.

[0103] Although the pH of the acidic aqueous solution used in the purification method is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the effect on the resin. The pH range is usually about 0 to 5, and preferably about 0 to 3.

[0104] The amount of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the amount used from the viewpoint of reducing the number of extractions for metal removal and ensuring operability in consideration of the total liquid volume. From the above viewpoints, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, relative to 100% by mass of the solution (S).

[0105] In the above purification method, the acidic aqueous solution is brought into contact with the solution (S), whereby metal components can be extracted from the resin in the solution (S).

[0106] In the above purification method, the solution (S) may further contain an organic solvent that is optionally miscible with water. When the solution (S) contains an organic solvent that is optionally miscible with water, the amount of the resin charged can be increased, and separation properties are improved, tending to enable purification with high reactor efficiency. The method of adding the organic solvent that is optionally miscible with water is not particularly limited. For example, any of a method of adding the organic solvent to a solution containing the organic solvent in advance, a method of adding the organic solvent to a solution containing the organic solvent in advance, and a method of adding the organic solvent after contacting the solution containing the organic solvent with water or an acidic aqueous solution may be used. Among these, the method of adding the organic solvent to a solution containing the organic solvent in advance is preferred in terms of ease of operation and ease of control of the charged amount.

[0107] The water-miscible organic solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of the water-miscible organic solvent used is not particularly limited as long as it is within a range that allows separation of the solution phase and the aqueous phase, but is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and even more preferably 0.1 to 20 times by mass, relative to the total amount of resin used.

[0108] Specific examples of the organic solvent that is miscible with water and used in the above purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone and propylene glycol monomethyl ether are preferred, with N-methylpyrrolidone and propylene glycol monomethyl ether being more preferred. These solvents can be used alone or in combination of two or more.

[0109] The temperature during the extraction treatment is usually 20 to 90°C, preferably in the range of 30 to 80°C. The extraction operation is carried out, for example, by thoroughly mixing the solution by stirring or the like, followed by allowing it to stand. This allows the metal components contained in the solution (S) to migrate into the aqueous phase. This operation also reduces the acidity of the solution, making it possible to suppress deterioration of the resin.

[0110] The mixed solution separates into a solution phase containing the resin and the solvent and an aqueous phase upon standing, and the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation of the solution phase containing the solvent and the aqueous phase. The standing time is usually 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation multiple times.

[0111] In the above purification method, after the first extraction step, it is preferable to further include a step (second extraction step) of contacting the solution phase containing the resin with water to extract impurities in the resin. Specifically, for example, after the above extraction treatment using an acidic aqueous solution, it is preferable to further subject the solution phase containing the resin and solvent extracted and recovered from the aqueous solution to an extraction treatment with water. The above extraction treatment with water is not particularly limited, but can be carried out, for example, by thoroughly mixing the solution phase and water by stirring or the like, and then allowing the resulting mixed solution to stand. After standing, the mixed solution separates into a solution phase containing the resin and solvent and an aqueous phase, and the solution phase can be recovered by decantation or the like. In addition, in accordance with the object of this embodiment, the water used here is preferably water with a low metal content, such as ion-exchanged water. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, leaving, and separating multiple times. In addition, the conditions for the extraction treatment, such as the ratio of the two components used, temperature, and time, are not particularly limited, but may be the same as those for the contact treatment with the acidic aqueous solution.

[0112] Water that may be mixed into the solution containing the resin and solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. If necessary, a solvent can be added to the solution to adjust the resin concentration to a desired concentration.

[0113] In the method for purifying the polycyclic polyphenol resin according to this embodiment, the resin can also be purified by dissolving the resin in a solvent and passing the solution through a filter. According to the method for purifying a substance of this embodiment, the content of various metals in the resin can be effectively and significantly reduced. The amount of these metal components can be measured by the method described in the Examples below. In this embodiment, "passing through" means that the solution moves from the outside of the filter through the inside of the filter and then back to the outside of the filter, and excludes, for example, a mode in which the solution is simply brought into contact with the surface of the filter, or a mode in which the solution is brought into contact with the surface of the filter and moved outside the ion exchange resin (i.e., a mode in which the solution simply comes into contact).

[0114] [Filter purification process (liquid passing process)] In the filter-passing step of this embodiment, the filter used to remove metals from the solution containing the resin and solvent can typically be a commercially available filter for liquid filtration. While the filtration accuracy of the filter is not particularly limited, the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably less than 0.1 μm, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. The lower limit of the nominal pore size of the filter is not particularly limited, but is typically 0.005 μm. The nominal pore size here refers to the nominal pore size that indicates the separation performance of the filter, and is determined by a test method specified by the filter manufacturer, such as a bubble point test, a mercury intrusion porosimetry test, or a standard particle capture test. When a commercially available product is used, the value is the value listed in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the metal content after a single pass of the solution through the filter can be effectively reduced. In this embodiment, the filter passing step may be carried out two or more times in order to further reduce the content of each metal in the solution.

[0115] The filter may be in the form of a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, or a filter filled with a filter material such as a nonwoven fabric, cellulose, or diatomaceous earth. Among the above, the filter is preferably one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. Furthermore, it is particularly preferable to use a hollow fiber membrane filter because of its particularly high filtration accuracy and a larger filtration area compared to other forms.

[0116] Examples of the filter material include polyolefins such as polyethylene and polypropylene, polyethylene-based resins to which functional groups having ion exchange capacity have been added by graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as fluorinated polyethylene (PTFE). Among these, the filter material is preferably one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. Furthermore, polyamide is particularly preferred from the viewpoint of reducing heavy metals such as chromium. It is preferable to use a filter made of a material other than sintered metal in order to avoid metal elution from the filter material.

[0117] Examples of polyamide filters (hereinafter referred to as trademarks) include, but are not limited to, the Polyfix Nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleat P-Nylon 66 and Ultipore N66 manufactured by Nippon Pall Co., Ltd., and the LifeAsure PSN series and LifeAsure EF series manufactured by 3M Limited. Examples of polyolefin filters include, but are not limited to, Ultipleat PE Clean and Ion Clean manufactured by Nippon Pall Co., Ltd., and Protego series, Microguard Plus HC10, and Optimizer D manufactured by Nippon Entegris Co., Ltd. Examples of polyester filters include, but are not limited to, Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd. and Breeze Type PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include, but are not limited to, Ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd. Examples of fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pall Co., Ltd., and Lifesure FA series manufactured by 3M Limited. These filters may be used alone or in combination of two or more.

[0118] The filter may also contain an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution to be filtered. Examples of filters containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Entegris Co., Ltd. and Clangraft manufactured by Kurashiki Seni Kako Co., Ltd. Furthermore, examples of filters containing substances with a positive zeta potential, such as polyamide polyamine epichlorohydrin cationic resin (hereinafter referred to as "trademarks"), include, but are not limited to, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Limited, and the Life Asure EF series.

[0119] The method for isolating the resin from the resulting solution containing the resin and the solvent is not particularly limited, and can be performed by known methods such as removal under reduced pressure, separation by reprecipitation, a combination thereof, etc. If necessary, known treatments such as concentration, filtration, centrifugation, drying, etc. can be performed.

[0120] The polycyclic polyphenol resin of this embodiment may further have a modified portion derived from a crosslinkable compound. That is, the polycyclic polyphenol resin of this embodiment having the structure described above may have a modified portion obtained by reaction with a crosslinkable compound. Such (modified) polycyclic polyphenol resins also have excellent heat resistance and etching resistance, and can be used as semiconductor coating agents, resist materials, and semiconductor underlayer film forming materials.

[0121] Examples of crosslinkable compounds include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanate compounds, unsaturated hydrocarbon group-containing compounds, etc. These can be used alone or in combination as appropriate.

[0122] In this embodiment, the crosslinkable compound is preferably an aldehyde or a ketone. More specifically, it is preferably a polycyclic polyphenol resin obtained by polycondensation reaction of the polycyclic polyphenol resin of this embodiment having the above-described structure with an aldehyde or a ketone in the presence of an acid catalyst. For example, a novolac-type polycyclic polyphenol resin can be obtained by further polycondensation reaction of the polycyclic polyphenol resin of this embodiment having the above-described structure with an aldehyde or a ketone corresponding to the desired structure in the presence of an acid catalyst under normal pressure, or under increased pressure as needed.

[0123] Examples of the aldehydes include, but are not limited to, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, butylmethylbenzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, and fluoromethylbenzaldehyde. These can be used alone or in combination of two or more. Among these, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, and butylmethylbenzaldehyde are preferred from the viewpoint of providing high heat resistance.

[0124] Examples of the ketones include, but are not limited to, acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, acetylbutylmethylbenzene, acetylhydroxybenzene, acetyldihydroxybenzene, and acetylfluoromethylbenzene. These can be used alone or in combination of two or more. Among these, the use of acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, and acetylbutylmethylbenzene is preferred from the viewpoint of providing high heat resistance.

[0125] The acid catalyst used in the reaction can be appropriately selected from known catalysts and is not particularly limited. Inorganic acids and organic acids are widely known as such acid catalysts. Specific examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production, such as ease of availability and handling. The acid catalyst may be used alone or in combination of two or more. The amount of the acid catalyst used may be appropriately determined depending on the raw materials and catalyst used, as well as the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass per 100 parts by mass of the reaction raw materials.

[0126] A reaction solvent may be used during the reaction. The reaction solvent is not particularly limited as long as it allows the reaction between the aldehyde or ketone used and the polycyclic polyenol resin to proceed, and can be appropriately selected from known solvents. Examples include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and mixed solvents thereof. The solvent can be used alone or in combination of two or more. The amount of the solvent used can be appropriately determined depending on the raw materials used, the type of acid catalyst used, and the reaction conditions. The amount of the solvent used is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. The reaction temperature in the reaction can be appropriately selected depending on the reactivity of the reaction raw materials. The reaction temperature is not particularly limited, but is usually preferably in the range of 10 to 200°C. The reaction method can be appropriately selected from known methods and is not particularly limited. Examples include a method in which the polycyclic polyphenol resin of this embodiment, aldehydes or ketones, and an acid catalyst are all charged at once, or a method in which aldehydes or ketones are added dropwise in the presence of an acid catalyst. After the polycondensation reaction is completed, the resulting compound can be isolated by a conventional method and is not particularly limited. For example, to remove unreacted raw materials and acid catalysts present in the system, the temperature of the reaction vessel can be increased to 130 to 230°C, and the volatiles can be removed at about 1 to 50 mmHg, to obtain the target compound.

[0127] The polycyclic polyphenol resin of the present embodiment can be used as a composition for various applications. That is, the composition of the present embodiment contains the polycyclic polyphenol resin of the present embodiment. From the viewpoint of facilitating film formation by application of a wet process, the composition of the present embodiment preferably further contains a solvent. Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, and 1-ethoxy-2-propanol; and aromatic hydrocarbons such as toluene, xylene, and anisole. These solvents may be used alone or in combination of two or more.

[0128] Among the above solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, ethyl lactate, and methyl hydroxyisobutyrate are particularly preferred from the viewpoint of safety.

[0129] The content of the solvent is not particularly limited, but from the viewpoints of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and even more preferably 200 to 1,000 parts by mass relative to 100 parts by mass of the polycyclic polyphenol resin of this embodiment. [Example]

[0130] Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to these.

[0131] 1 The H-NMR measurement was carried out using a Bruker Advance 600II spectrometer under the following conditions: Frequency: 400MHz Solvent: d6-DMSO Internal standard: TMS Measurement temperature: 23℃

[0132] (molecular weight) Measurement was carried out by LC-MS analysis using Water's Acquity UPLC / MALDI-Synapt HDMS. (Polystyrene equivalent molecular weight) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) analysis, and the polydispersity (Mw / Mn) was also determined. Apparatus: Shodex GPC-101 (Showa Denko K.K.) Column: KF-80M x 3 Eluent: THF 1mL / min Temperature: 40℃

[0133] (Synthesis Example 1) Synthesis of R-DHN A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 16.8 g (105 mmol) of 2,6-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) and 10.1 g (20 mmol) of copper monobutyl phthalate. 30 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 110 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain 27.3 g of the target resin (R-DHN) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 3578, Mw: 4793, and Mw / Mn: 1.34. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0134] [ka]

[0135] (Synthesis Example 1-2) Synthesis of R-2,7DHN A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 16.8 g (105 mmol) of 2,7-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) and 15.2 g (30 mmol) of monobutyl copper phthalate. 40 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 110 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain 24.7 g of the target resin (R-2,7DHN) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 2832, Mw: 3476, and Mw / Mn: 1.23. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0136] [ka]

[0137] (Synthesis Example 1-3) Synthesis of R-2,3DHN The same procedure as in Synthesis Example 1-2 was repeated, except that 2,7-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) in Synthesis Example 1-2 was replaced with 2,3-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.), and 29.2 g of the target resin (R-2,3DHN) having the structure represented by the following formula was obtained. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 3124, Mw: 4433, and Mw / Mn: 1.42. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.5~9.6(2H,OH), 7.0~7.9(4H,Ph-H)

[0138] [ka]

[0139] (Synthesis Example 1-4) Synthesis of R-1,5DHN The same procedure as in Synthesis Example 1-2 was carried out, except that 2,7-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) in Synthesis Example 1-2 was changed to 1,5-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.), and 25.8 g of the target resin (R-1,5DHN) having the structure represented by the following formula was obtained. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 2988, Mw: 3773, and Mw / Mn: 1.26. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.8~9.9(2H,OH), 7.1~8.0(4H,Ph-H)

[0140] [ka]

[0141] (Synthesis Example 1-5) Synthesis of R-1,6DHN The same procedure as in Synthesis Example 1-2 was carried out, except that 2,7-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) in Synthesis Example 1-2 was changed to 1,6-dihydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.), and 23.2 g of the target resin (R-1,6DHN) having the structure represented by the following formula was obtained. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 2687, Mw: 3693, and Mw / Mn: 1.37. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.8~9.9(2H,OH), 6.8~7.9(4H,Ph-H)

[0142] [ka]

[0143] (Synthesis Example 1-6) Synthesis of R-FLBNDHN A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 47.3 g (105 mmol) of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol) (Kanto Chemical Co., Ltd. reagent), 16.8 g (105 mmol) of 2,6-dihydroxynaphthalene (Kanto Chemical Co., Ltd. reagent), and 10.1 g (20 mmol) of monobutyl copper phthalate. 120 mL of 4-butyrolactone was added as a solvent, and the reaction solution was stirred at 120 °C for 8 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 150 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 300 mL of distilled water was added to precipitate the reaction product. After cooling to room temperature, the reaction product was separated by filtration. The obtained solid was dried to obtain 51.6 g of the target resin (R-FLBNDHN) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4128, Mw: 5493, and Mw / Mn: 1.33. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.9(2H,OH), 9.1~9.3(2H,OH), 7.1~8.0(22H,Ph-H)

[0144] [ka]

[0145] That is, R-FLBNDHN was a mixture containing a homopolymer of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol), a homopolymer of 2,6-dihydroxynaphthalene, and a copolymer of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol) and 2,6-dihydroxynaphthalene.

[0146] (Synthesis Example 2) Synthesis of R-BiF A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 19.2 g (105 mmol) of 4,4-biphenol (a reagent manufactured by Kanto Chemical Co., Ltd.) and 10.1 g (20 mmol) of copper monobutyl phthalate. 80 mL of 4-butyrolactone was added as a solvent, and the reaction solution was stirred at 120 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain 21.2 g of the target resin (R-BiF) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4128, Mw: 5493, and Mw / Mn: 1.33. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.1~9.3(2H,OH), 7.1~8.2(6H,Ph-H)

[0147] [ka]

[0148] (Synthesis Example 3) Synthesis of BisN-1 A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 20.0 g (200 mmol) of 1,4-dihydroxybenzene (a reagent manufactured by Kanto Chemical Co., Ltd.), 18.2 g (100 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 mL of 1,4-dioxane. 5 mL of 95% sulfuric acid was added and the mixture was stirred at 100°C for 6 hours. The reaction solution was then neutralized with 24% aqueous sodium hydroxide solution, and 50 g of purified water was added to precipitate the reaction product. The mixture was cooled to room temperature and then filtered to separate the product. The resulting solid was dried and purified by column chromatography to obtain 20.6 g of the target compound (BisN-1) represented by the following formula: In addition, 400MHz- 1 The following peaks were observed by H-NMR, and it was confirmed that the compound had the following chemical structure: 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.4(2H,OH), 7.2~8.1(13H,Ph-H), 6.5(1H,CH) Furthermore, LC-MS analysis confirmed that the molecular weight was 366.1, which corresponds to the chemical structure below.

[0149] [ka]

[0150] (Synthesis Example 3-1) Synthesis of RBisN-1 A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 38.0 g (105 mmol) of BisN-1 and 10.1 g (20 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 100 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. The mixture was cooled to room temperature and then filtered. The resulting solid was dried to obtain 28.2 g of the target resin (RBisN-1) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 3762, Mw: 4905, and Mw / Mn: 1.30. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.6(2H,OH), 7.2~8.7(17H,Ph-H), 6.8(1H,CH)

[0151] [ka]

[0152] (Synthesis Example 4) Synthesis of BisN-2 A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 32.0 g (20 mmol) of 2,6-naphthalenediol (Sigma-Aldrich reagent), 18.2 g (100 mmol) of 4-biphenylaldehyde (Mitsubishi Gas Chemical Co.), and 200 mL of 1,4-dioxane. 10 mL of 95% sulfuric acid was added and the mixture was stirred at 100 °C for 6 hours. The reaction solution was then neutralized with 24% aqueous sodium hydroxide, and 100 g of purified water was added to precipitate the reaction product. The mixture was cooled to room temperature and then filtered. The resulting solid was dried and purified by column chromatography to obtain 25.5 g of the target compound (BisN-2) represented by the following formula: In addition, 400MHz- 1 The following peaks were observed by H-NMR, confirming that the compound had the following chemical structure: The substitution position of 2,6-dihydroxynaphthol was confirmed to be 1-position, as the signals for the 3- and 4-position protons were a doublet. 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.7(2H,OH), 7.2~8.5(19H,Ph-H), 6.6(1H,CH) Furthermore, LC-MS analysis confirmed that the molecular weight was 466.5, which corresponds to the chemical structure below.

[0153] [ka]

[0154] (Synthesis Example 4-1) Synthesis of RBisN-2 A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 50 g (105 mmol) of BisN-2 and 10.1 g (20 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 100 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. The mixture was cooled to room temperature and then filtered. The resulting solid was dried to obtain 38.2 g of the target resin (RBisN-2) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4232, Mw: 5502, and Mw / Mn: 1.30. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.7(2H,OH), 7.2~8.5(17H,Ph-H), 6.7~6.9(1H,CH)

[0155] [ka]

[0156] (Synthesis Example 4-2) Synthesis of RBisN-3 A 500 mL vessel equipped with a stirrer, a condenser and burette equipped with an internal pressure control valve, and a gas injection nozzle at the bottom for bubbling gas injection was charged with 50 g (105 mmol) of BisN-2 and 1.8 g (10 mmol) of copper acetate. 100 mL of 1-butanol was added as a solvent. Then, while stirring with a stirrer, N2 gas diluted to a 5% oxygen concentration was added at a rate of 500 mL / min with bubbling. The reaction solution was stirred at 100 °C for 6 hours while maintaining an internal pressure of 0.2 MPa. After cooling, the precipitate was collected by filtration, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the reaction product was separated by filtration. The obtained solid was dried to obtain 36.5 g of the target resin (RBisN-3) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 8795, Mw: 10444, and Mw / Mn: 1.19. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.7(2H,OH), 7.2~8.5(17H,Ph-H), 6.7~6.9(1H,CH)

[0157] [ka]

[0158] (Synthesis Example 4-3) Synthesis of RBisN-4 A 500 mL vessel equipped with a stirrer, a condenser and burette equipped with an internal pressure control valve, and a gas injection nozzle at the bottom for bubbling gas injection was charged with 50 g (105 mmol) of BisN-2 and 1.1 g (2 mmol) of monobutyl copper phthalate. 100 mL of 1-butanol was added as a solvent. While stirring with a stirrer, N2 gas diluted to a 5% oxygen concentration was added at a bubbling rate of 50 mL / min. The reaction solution was stirred at 100 °C for 6 hours while controlling the internal pressure control valve to maintain an internal pressure of 0.5 MPa. After cooling, the precipitate was collected by filtration, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the reaction product was separated by filtration. The obtained solid was dried to obtain 37.1 g of the target resin (RBisN-4) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 9354, Mw: 11298, and Mw / Mn: 1.21. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.7(2H,OH), 7.2~8.5(17H,Ph-H), 6.7~6.9(1H,CH)

[0159] [ka]

[0160] (Synthesis Example 4A) Synthesis of BisN-5 The same procedure as in Synthesis Example 4 was carried out, except that 18.2 g (100 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.) in Synthesis Example 4 was changed to 9.1 g (100 mmol) of 4-toluylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.), to obtain 23.2 g of the target compound (BisN-3) represented by the following formula. In addition, 400MHz- 1 The following peaks were observed by H-NMR, confirming that the compound had the following chemical structure: The substitution position of 2,6-dihydroxynaphthol was confirmed to be 1-position, as the signals for the 3- and 4-position protons were a doublet. 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.7(2H,OH), 7.2~8.4(14H,Ph-H), 6.6(1H,CH), 1.9(3H,C-H3) Furthermore, LC-MS analysis confirmed that the molecular weight was 404.1, which corresponds to the chemical structure below.

[0161] [ka]

[0162] (Synthesis Example 4A-1) Synthesis of RBisN-5 The procedure of Synthesis Example 4-1 was repeated except that BisN-2 in Synthesis Example 4-1 was changed to BisN-5 obtained in Synthesis Example 4A, to obtain 32.1 g of the target resin (RBisN-5) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 3452, Mw: 4802, and Mw / Mn: 1.39. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.7(2H,OH), 7.2~8.5(12H,Ph-H), 6.7~6.9(1H,CH), 1.9(3H,C-H3)

[0163] [ka]

[0164] (Synthesis Example 4B) Synthesis of BisN-6 The same procedure as in Synthesis Example 4 was carried out, except that 18.2 g (100 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.) was replaced with 18.8 g (100 mmol) of 4-cyclohexylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.), to obtain 33.5 g of the target compound (BisN-6) represented by the following formula. In addition, 400MHz- 1 The following peaks were observed by H-NMR, confirming that the compound had the following chemical structure: The substitution position of 2,6-dihydroxynaphthol was confirmed to be 1-position, as the signals for the 3- and 4-position protons were a doublet. 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.7(2H,OH), 7.2~8.4(14H,Ph-H), 6.6(1H,CH), 2.5~2.6(6H,C6-H5) Furthermore, LC-MS analysis confirmed that the molecular weight was 472.2, which corresponds to the chemical structure below.

[0165] [ka]

[0166] (Synthesis Example 4B-1) Synthesis of RBisN-6 The procedure of Synthesis Example 4-1 was repeated except that BisN-2 in Synthesis Example 4-1 was changed to BisN-6 obtained in Synthesis Example 4B, to obtain 40.4 g of the target resin (RBisN-6) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 3672, Mw: 5080, and Mw / Mn: 1.38. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.3~9.7(2H,OH), 7.2~8.5(12H,Ph-H), 6.7(1H,CH), 2.5~2.7(6H,C6-H5)

[0167] [ka]

[0168] (Synthesis Example 4C) Synthesis of BisN-7 The aromatic hydroxy compound of Synthesis Example 4C was synthesized in the same manner as in Synthesis Example 4, except that 18.2 g (100 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.) was replaced with 10 g (100 mmol) of 2-naphthaldehyde (manufactured by Kanto Chemical Co., Inc.) in Synthesis Example 4. 33.5 g of the target resin (RBisN-7) represented by the following formula was obtained in the same manner as in Synthesis Example 4-1, except that this aromatic hydroxy compound was used. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4174, Mw: 5280, and Mw / Mn: 1.26. In addition, 400MHz- 1 The following peaks were observed by H-NMR, confirming that the compound had the following chemical structure: The substitution position of 2,6-dihydroxynaphthol was confirmed to be 1-position, as the signals for the 3- and 4-position protons were a doublet. 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.6(2H,OH), 7.0~8.5(19H,Ph-H), 6.6(1H,CH), 2.5H,Ph-H), 6.7(1H,CH)

[0169] [ka]

[0170] (Synthesis Example 5) Synthesis of BiF-1 A 1 L vessel equipped with a stirrer, condenser, and buret was prepared. 150 g (800 mmol) of 4,4-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 75 g (410 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.), and 300 mL of propylene glycol monomethyl ether were charged into the vessel, and 19.5 g (105 mmol) of p-toluenesulfonic acid (a reagent manufactured by Kanto Chemical Co., Inc.) was added to prepare a reaction solution. The reaction solution was stirred at 90°C for 3 hours. The reaction solution was then neutralized with 24% aqueous sodium hydroxide solution, and 100 g of distilled water was added to precipitate the reaction product. The mixture was cooled to 5°C and then filtered. The solid obtained by filtration was dried and then purified by column chromatography to obtain 25.8 g of the target compound (BiF-1) represented by the following formula: In addition, 400MHz- 1 The following peaks were observed by H-NMR, and it was confirmed that the compound had the following chemical structure: 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.4(4H,OH), 6.8~7.8(22H,Ph-H), 6.2(1H,CH) Furthermore, LC-MS analysis confirmed that the molecular weight was 536.2, which corresponds to the chemical structure below.

[0171] [ka]

[0172] (Synthesis Example 5-1) Synthesis of RBiF-1 A 500 mL vessel equipped with a stirrer, condenser, and burette was charged with 55.0 g (105 mmol) of BiF-1 and 10.1 g (20 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 100 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and the mixture was stirred at room temperature. The mixture was then neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. The mixture was cooled to room temperature and then filtered. The resulting solid was dried to obtain 34.3 g of the target resin (RBiF-1) having the structure represented by the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4532, Mw: 5698, and Mw / Mn: 1.26. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.4~9.7(4H,OH), 6.8~8.1(20H,Ph-H), 6.3~6.5(1H,CH)

[0173] [ka]

[0174] (Synthesis Example 5-2) Synthesis of RBiF-2 A 500 mL vessel equipped with a stirrer, a condenser and burette with an internal pressure control valve, and a gas injection nozzle at the bottom for bubbling gas injection was charged with 55.0 g (105 mmol) of BiF-1 and 1.01 g (2 mmol) of monobutyl copper phthalate. 100 mL of 1-butanol was added as a solvent. Then, while stirring with a stirrer, N2 gas diluted to a 5% oxygen concentration was added at a rate of 500 mL / min with bubbling. The reaction solution was stirred at 100 °C for 6 hours. After cooling, the precipitate was collected by filtration, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the reaction product was separated by filtration. The resulting solid was dried to obtain 35.3 g of the target resin (RBiF-2) with the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 9249, Mw: 11286, and Mw / Mn: 1.26. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.4~9.7(4H,OH), 6.8~8.1(20H,Ph-H), 6.3~6.5(1H,CH)

[0175] [ka]

[0176] (Synthesis Example 5A) Synthesis of BiF-3 The same procedure as in Synthesis Example 5 was repeated, except that 75 g (410 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in Synthesis Example 5 was changed to 4-toluylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), to obtain 26.3 g of the target compound (BiF-3) represented by the following formula. In addition, 400MHz- 1 The following peaks were observed by H-NMR, and it was confirmed that the compound had the following chemical structure: 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.4(4H,OH), 6.8~7.8(18H,Ph-H), 6.2(1H,CH), 1.8(3H,C-H3) Furthermore, LC-MS analysis confirmed that the molecular weight was 474.5, which corresponds to the chemical structure below.

[0177] [ka]

[0178] (Synthesis Example 5A-1) Synthesis of RBiF-3 The same procedure as in Synthesis Example 5-1 was carried out except that BiF-1 in Synthesis Example 5-1 was changed to BiF-3 obtained in Synthesis Example 5A, and 31.2 g of the target resin (RBiF-3) having the structure represented by the following formula was obtained. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4232, Mw: 5288, and Mw / Mn: 1.25. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.4~9.7(4H,OH), 6.8~8.1(16H,Ph-H), 6.3~6.5(1H,CH), 1.8~1.9(3H,C-H3)

[0179] [ka]

[0180] (Synthesis Example 5B) Synthesis of BiF-4 32.1 g of the target compound (BiF-4) represented by the following formula was obtained in the same manner as in Synthesis Example 5, except that 75 g (410 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in Synthesis Example 5 was changed to 4-cyclohexylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.). In addition, 400MHz- 1The following peaks were observed by H-NMR, and it was confirmed that the compound had the following chemical structure: 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.4(4H,OH), 6.8~7.8(18H,Ph-H), 6.2(1H,CH), 2.4~2.6(10H,C6H10) Furthermore, LC-MS analysis confirmed that the molecular weight was 542.7, which corresponds to the chemical structure below.

[0181] [ka]

[0182] (Synthesis Example 5B-1) Synthesis of RBiF-4 The same procedure as in Synthesis Example 5-1 was carried out except that BiF-1 in Synthesis Example 5-1 was changed to BiF-4 obtained in Synthesis Example 5B, thereby obtaining 29.5 g of the target resin (RBiF-4) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4431, Mw: 5568, and Mw / Mn: 1.26. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.4~9.7(4H,OH), 6.8~8.1(16H,Ph-H), 6.3~6.5(1H,CH), 2.4~2.9(10H,C6H10)

[0183] [ka]

[0184] (Synthesis Example 5C) Synthesis of BiF-5 33.5 g of the target compound (BiF-5) represented by the following formula was obtained in the same manner as in Synthesis Example 5, except that 75 g (410 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in Synthesis Example 5 was changed to 2-naphthaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.). In addition, 400MHz- 1 The following peaks were observed by H-NMR, and it was confirmed that the compound had the following chemical structure: 1 H-NMR: (d-DMSO, internal standard TMS) δ(ppm)9.4(4H,OH), 6.8~7.8(21H,Ph-H), 6.2(1H,CH) Furthermore, LC-MS analysis confirmed that the molecular weight was 510.6, which corresponds to the chemical structure below.

[0185] [ka]

[0186] (Synthesis Example 5C-1) Synthesis of RBiF-5 The same procedure as in Synthesis Example 5-1 was carried out except that BiF-1 in Synthesis Example 5-1 was changed to BiF-5 obtained in Synthesis Example 5C, thereby obtaining 29.5 g of the target resin (RBiF-4) having the structure represented by the following formula. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4133, Mw: 5462, and Mw / Mn: 1.32. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.4~9.7(4H,OH), 6.8~8.1(19H,Ph-H), 6.3~6.5(1H,CH)

[0187] [ka]

[0188] (Synthesis Example 6) Synthesis of DB-1 (a) Preparation of dibenzochrysene sulfonic acid calcium salt A 1 L four-neck flask equipped with a mechanical stirrer was charged with 20 g (0.06 mol, HPLC purity: 99.8%) of dibenzo[g,p]chrysene and 200 g (1.94 mol) of 95% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred and reacted for 2 hours at an internal temperature of 80°C while keeping the temperature in a water bath. As a result, the contents became a uniform gray viscous liquid. While the flask containing the contents obtained above was cooled in an ice bath, 400 g of distilled water was added. During this addition, the internal temperature was maintained at 40°C or below while measuring the temperature so that the internal temperature would not exceed 40°C due to heat generation. Next, 154.4 g (2.08 mol) of powdered calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask containing the distilled water. During this addition, the internal temperature was maintained at 45°C or below while measuring the temperature so that the internal temperature would not exceed 45°C due to heat generation. This addition precipitated calcium sulfate as a white solid, and the contents became a slurry. The liquid was alkaline. The slurry obtained above was subjected to suction filtration using a stainless steel Buchner funnel and No. 2 filter paper, and the resulting filtrate (pale yellow liquid) was collected. Furthermore, the solid residue (mainly calcium sulfate) was washed with 350 g of distilled water, and the washings were also collected and concentrated under reduced pressure together with the filtrate using a rotary evaporator. As a result, 36.5 g of dibenzochrysene sulfonic acid calcium salt was obtained as a pale yellow powdery solid (yield 82.7%). Based on the results of LC / MS analysis of hydroxydibenzochrysene described below, the dibenzochrysene sulfonic acid calcium salt is believed to be a mixture of 98% 4-substituted dibenzochrysene sulfonate and the remainder 3-substituted dibenzochrysene sulfonate. (b) Preparation of hydroxydibenzochrysene 14.0 g (0.212 mol) of 85% potassium hydroxide granules (Wako Pure Chemical Industries, Ltd.) were placed in a 100 mL nickel cylindrical container and melted on a hot plate (400 °C). Subsequently, 4.0 g (0.0055 mol) of the dibenzochrysene sulfonic acid calcium salt (Mixture 8) obtained above was added. During this addition, the dibenzochrysene sulfonic acid calcium salt was added to the nickel cylindrical container over 30 minutes, and the reaction was promoted by stirring with a stainless steel spoon during addition. Furthermore, stirring was continued for 30 minutes after the addition of the dibenzochrysene sulfonic acid calcium salt was completed. As a result, a reddish-brown viscous liquid was obtained. The reddish-brown viscous liquid obtained above (the content of the nickel cylindrical container) was poured into a 200 mL stainless steel cup while still hot and cooled to solidify. 40 g of distilled water was then added to the stainless steel cup to dissolve the solid, yielding a slightly cloudy reddish-brown liquid. Next, the reddish-brown liquid was transferred to a 200 mL glass beaker, and while stirring using a magnetic stirrer, 35% hydrochloric acid (Wako Pure Chemical Industries, Ltd.) was added to obtain a content containing a brown solid. During this addition, the pH was measured with a pH meter and the addition was continued until the pH of the content reached pH 3. The brown solid was confirmed to precipitate at the time of neutralization. Subsequently, 30 g of ethyl acetate (Wako Pure Chemical Industries, Ltd.) was added to the content obtained above while stirring to dissolve the brown solid. The resulting liquid was then allowed to stand to separate into an organic phase and an aqueous phase, and the organic phase was then separated. The separated organic layer was filtered using a glass funnel and No. 2 filter paper to remove insoluble matter, and then concentrated under reduced pressure using a rotary evaporator to obtain 1.6 g of a brown powdery solid (yield 73.9%). LC / MS analysis of the brown powdery solid obtained by the above procedure revealed that the brown powdery solid was 4-substituted hydroxydibenzochrysene with a purity of 98%.

[0189] [ka]

[0190] (Synthesis Example 6-1) Synthesis of RDB-1 A 500 mL vessel equipped with a stirrer, condenser, and buret was charged with 80.0 g of DB-1 and 10.1 g (20 mmol) of copper monobutyl phthalate. 100 mL of 1-butanol was added as a solvent, and the reaction mixture was stirred at 100°C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. 5 mL of hydrochloric acid was added, stirred at room temperature, and neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 300 mL of heptane was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The resulting solid was dried to obtain 64.5 g of the target resin (RDB-1), which has a structure represented by the group shown in the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 2512, Mw: 3298, and Mw / Mn: 1.31.

[0191] [ka]

[0192] (Synthesis Example 1-A1) Synthesis of R-DHN-A1 In the synthesis of R-DHN in Synthesis Example 1, 21.5 g of the target resin (R-DHN-A1) having the structure represented by the following formula was obtained in the same manner as in Synthesis Example 1, except that 15.1 g (105 mmol) of 2-hydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) was used instead of 2,6-dihydroxynaphthalene. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 4567, Mw: 5612, and Mw / Mn: 1.23. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0193] [ka]

[0194] (Synthesis Example 1-A2) Synthesis of R-DHN-A2 In the synthesis method of R-DHN in Synthesis Example 1, 21.5 g of the target resin (R-DHN-A2) having the structure represented by the following formula was obtained in the same manner as in Synthesis Example 1, except that 15.1 g (105 mmol) of 1-hydroxynaphthalene (a reagent manufactured by Kanto Chemical Co., Ltd.) was used instead of 2,6-dihydroxynaphthalene. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 6137, Mw: 7622, ​​and Mw / Mn: 1.24. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0195] [ka]

[0196] (Synthesis Example 1-B1) Synthesis of R-DHN-B1 In the synthesis method for R-DHN in Synthesis Example 1, 20.4 g of a target resin (R-DHN-B1) having a structure represented by the following formula was obtained in the same manner as in Synthesis Example 1, except that 5.6 g (35 mmol) of 2,3-dihydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.), 5.6 g (35 mmol) of 2,6-dihydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.), and 5.6 g (35 mmol) of 1,5-dihydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.) were used instead of 2,6-dihydroxynaphthalene. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 7179, Mw: 9541, and Mw / Mn: 1.34. Furthermore, C13-NMR measurement of the resulting resin confirmed that the composition ratio of a:b:c = 1:1:1. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0197] [ka]

[0198] (Synthesis Example 1-B2) Synthesis of R-DHN-B2 In the synthesis method for R-DHN in Synthesis Example 1, 5.6 g (35 mmol) of 2,3-dihydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.), 5.6 g (35 mmol) of 2,6-dihydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.), and 5.1 g (35 mmol) of 2-hydroxynaphthalene (reagent manufactured by Kanto Chemical Co., Ltd.) were used instead of 2,6-dihydroxynaphthalene, and 18.8 g of the target resin (R-DHN-B2) having the structure represented by the following formula was obtained in the same manner as in Synthesis Example 1. The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 6912, Mw: 8533, and Mw / Mn: 1.23. Furthermore, the obtained resin was subjected to C13-NMR measurement, and it was confirmed that the composition ratio of a:b:c=1:1:1. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7~9.8(2H,OH), 7.0~7.9(4H,Ph-H)

[0199] [ka]

[0200] (Comparative Synthesis Example 1) A 100 ml vessel equipped with a stirrer, condenser, and buret was charged with 10 g (21 mmol) of BisN-2, 0.7 g (42 mmol) of paraformaldehyde, 50 mL of glacial acetic acid, and 50 mL of PGME. 8 mL of 95% sulfuric acid was added, and the reaction solution was stirred at 100 °C for 6 hours. The reaction solution was then concentrated, and 1000 mL of methanol was added to precipitate the reaction product. The precipitate was cooled to room temperature and then filtered. The resulting solid was filtered and dried to obtain 7.2 g of the target resin (NBisN-2) having the structure shown in the following formula: The polystyrene-equivalent molecular weight of the resulting resin was measured by the above-mentioned method, and the results were Mn: 778, Mw: 1793, and Mw / Mn: 2.30. The obtained resin was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the resin had the chemical structure of the following formula. δ(ppm)9.7(2H,OH), 7.2~8.5(17H,Ph-H), 6.6(1H,CH), 4.1(2H,-CH2) [ka]

[0201] [Examples 1 to 6] The resins obtained in Synthesis Examples 1 to 6-1 and Comparative Synthesis Example 1 were used to evaluate heat resistance by the evaluation method shown below. The results are shown in Table 1.

[0202] <Measurement of thermal decomposition temperature> Using an SII NanoTechnology EXSTAR6000TG / DTA device, approximately 5 mg of sample was placed in an unsealed aluminum container and heated to 700°C at a rate of 10°C / min in a nitrogen gas (30 mL / min) flow. The temperature at which a thermal loss of 5% by weight was observed was defined as the thermal decomposition temperature (Tg), and heat resistance was evaluated according to the following criteria. Rating A: Thermal decomposition temperature is 450°C or higher Rating B: Thermal decomposition temperature is 300°C or higher Rating C: Thermal decomposition temperature is less than 300°C

[0203] [Table 1]

[0204] As is clear from Table 1, it was confirmed that the resins used in Examples 1 to 6 had good heat resistance, but the resin used in Comparative Example 1 had poor heat resistance. In particular, it was confirmed that the resins used in Examples 2 to 6 exhibited significantly good heat resistance.

[0205] [Examples 7 to 12, Comparative Example 2] (Preparation of composition for forming underlayer film for lithography) Compositions for forming an underlayer film for lithography were prepared so as to have the compositions shown in Table 2. Next, these compositions for forming an underlayer film for lithography were spin-coated onto silicon substrates, and then baked in a nitrogen atmosphere at 240°C for 60 seconds and then at 400°C for 120 seconds to produce underlayer films with thicknesses of 200 to 250 nm.

[0206] Next, an etching test was carried out under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Table 2.

[0207] [Etching test] Etching equipment: Samco International RIE-10NR Output: 50W Pressure: 20Pa Time: 2 min Etching gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm)

[0208] (Evaluation of etching resistance) The etching resistance was evaluated by the following procedure. First, a novolac underlayer film was prepared under the same conditions as above, except that novolac (PSM4357 manufactured by Gun-ei Chemical Co., Ltd.) was used. The above etching test was performed on this novolac underlayer film, and the etching rate was measured.

[0209] Next, the underlayer films of Examples 7 to 12 and Comparative Example 2 were prepared under the same conditions as the novolac underlayer film, and the etching test was carried out in the same manner as above to measure the etching rate. The etching resistance was evaluated according to the following evaluation criteria, using the etching rate of the novolac underlayer film as the standard. [Evaluation criteria] A: Etching rate is less than -20% compared to the novolac underlayer film B: Etching rate is -20% to 0% compared to the underlayer film of novolac C: Etching rate is more than +0% compared to the novolac underlayer film

[0210] [Table 2]

[0211] It was found that Examples 7 to 12 exhibited superior etching rates compared to the novolac underlayer film and the resin of Comparative Example 2. On the other hand, it was found that the resin of Comparative Example 2 exhibited an etching rate inferior to that of the novolac underlayer film.

[0212] The metal content and storage stability of the solution of the polycyclic polyphenol resin (composition containing the polycyclic polyphenol resin) before and after purification were evaluated by the following methods. (Measurement of various metal contents) The metal contents in propylene glycol monomethyl ether acetate (PGMEA) solutions of various resins obtained in the following examples and comparative examples were measured using ICP-MS under the following measurement conditions. Equipment: Agilent AG8900 Temperature: 25℃ Environment: Class 100 clean room

[0213] (Storage stability evaluation) The PGMEA solutions obtained in the following Examples and Comparative Examples were kept at 23°C for 240 hours, and then the turbidity (haze) of the solutions was measured using a color difference / turbidity meter, and the storage stability of the solutions was evaluated according to the following criteria. Equipment: Color difference / turbidity meter COH400 (manufactured by Nippon Denshoku Co., Ltd.) Optical path length: 1 cm Using a quartz cell [Evaluation criteria] 0 ≦ HAZE ≦ 1.0: Good 1.0 < HAZE ≦ 2.0: Passable 2.0 < HAZE: Poor

[0214] (Example 13) Purification of R-DHN with an acid A solution (10% by mass) of R-DHN obtained in Synthesis Example 1 dissolved in PGMEA was charged at 150 g into a 1000 mL four-necked flask (bottom-draining type), and heated to 80 °C while stirring. Subsequently, 37.5 g of an oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and then left standing for 30 minutes. As a result, it separated into an oil phase and an aqueous phase, so the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was charged into the obtained oil phase, stirred for 5 minutes, left standing for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, while heating to 80 °C, the pressure inside the flask was reduced to 200 hPa or less to concentrate and distill off the residual moisture and PGMEA. Thereafter, it was diluted with EL grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of R-DHN with reduced metal content.

[0215] (Reference Example 1) Purification of R-DHN with ultrapure water The same procedure as in Example 13 was carried out except that ultrapure water was used instead of the oxalic acid aqueous solution, and a PGMEA solution of R-DHN was obtained by adjusting the concentration to 10% by mass.

[0216] For the 10% by mass PGMEA solution of R-DHN before treatment and the solutions obtained in Example 13 and Reference Example 1, the contents of various metals were measured by ICP-MS. The measurement results are shown in Table 3.

[0217] (Example 14) Purification of RBisN-2 with an acid A 1000 mL four-neck flask (open-bottom type) was charged with 140 g of a solution (10% by mass) of RBisN-2 obtained in Synthesis Example 4-1 dissolved in PGMEA and heated to 60°C with stirring. Next, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This resulted in separation into an oil phase and an aqueous phase, and the aqueous phase was removed. This operation was repeated once, and then 37.5 g of ultrapure water was added to the resulting oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, and the aqueous phase was removed. This operation was repeated three times, and then the flask was heated to 80°C while the pressure inside was reduced to 200 hPa or less, thereby concentrating and distilling off the residual water and PGMEA. The solution was then diluted with EL-grade PGMEA (a reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass, yielding a PGMEA solution of RBisN-2 with a reduced metal content.

[0218] (Reference Example 2) Purification of RBisN-2 with ultrapure water The same procedure as in Example 14 was carried out except that ultrapure water was used instead of the oxalic acid aqueous solution, and the concentration was adjusted to 10 mass % to obtain a PGMEA solution of RBisN-2.

[0219] The contents of various metals were measured by ICP-MS for the 10 mass % PGMEA solution of RBisN-2 before treatment, and for the solutions obtained in Example 14 and Reference Example 2. The measurement results are shown in Table 3.

[0220] (Example 15) Purification by filtering In a Class 1000 clean booth, a 1000 mL four-neck flask (bottom-opened) was charged with 500 g of a 10% by weight solution of the resin (R-DHN) obtained in Synthesis Example 1 dissolved in propylene glycol monomethyl ether (PGME). The air inside the flask was then removed under reduced pressure, followed by the introduction of nitrogen gas to return the pressure to atmospheric. The oxygen concentration inside the flask was adjusted to less than 1% by aeration at 100 mL / min of nitrogen gas, and the flask was then heated to 30°C with stirring. The solution was withdrawn through the bottom-opening valve and passed through a fluororesin pressure-resistant tube and through a nylon hollow fiber membrane filter (Kitz Microfilter Co., Ltd., trade name: Polyfix Nylon Series) with a nominal pore size of 0.01 μm using a diaphragm pump at a flow rate of 100 mL / min. The metal content of the resulting R-DHN solution was measured by ICP-MS. The oxygen concentration was measured using an AS ONE Corporation oxygen concentration meter "OM-25MF10" (same applies below). The measurement results are shown in Table 3.

[0221] Example 16 The liquid was passed through the filter in the same manner as in Example 15, except that a polyethylene (PE) hollow fiber membrane filter (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix) with a nominal pore size of 0.01 μm was used, and the contents of various metals in the resulting R-DHN solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0222] Example 17 The liquid was passed through the filter in the same manner as in Example 15, except that a nylon hollow fiber membrane filter with a nominal pore size of 0.04 μm (manufactured by Kitz Microfilter Co., Ltd., trade name: Polyfix) was used, and the contents of various metals in the resulting R-DHN were measured by ICP-MS. The measurement results are shown in Table 3.

[0223] Example 18 The liquid was passed through the R-DHN solution in the same manner as in Example 15, except that a Zeta Plus Filter 40QSH (manufactured by 3M Limited, with ion exchange capacity) with a nominal pore size of 0.2 μm was used, and the metal contents of the resulting R-DHN solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0224] Example 19 The R-DHN solution obtained was analyzed under the following conditions in the same manner as in Example 15, except that a Zeta Plus Filter 020GN (manufactured by 3M Limited, with ion exchange capacity, different in filtration area and filter thickness from the Zeta Plus Filter 40QSH) with a nominal pore size of 0.2 μm was used. The measurement results are shown in Table 3.

[0225] Example 20 The same procedure as in Example 15 was repeated, except that the resin (RBisN-2) obtained in Synthesis Example 4-1 was used instead of the resin (R-DHN) used in Example 15. The metal contents of the resulting RBisN-2 solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0226] Example 21 The same procedure as in Example 16 was repeated, except that the resin (RBisN-2) obtained in Synthesis Example 4-1 was used instead of the resin (R-DHN) used in Example 16. The metal contents of the resulting RBisN-2 solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0227] Example 22 The same procedure as in Example 17 was repeated, except that the resin (RBisN-2) obtained in Synthesis Example 4-1 was used instead of the compound (R-DHN) in Example 17. The metal contents of the resulting RBisN-2 solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0228] Example 23 The same procedure as in Example 18 was repeated, except that the resin (RBisN-2) obtained in Synthesis Example 4-1 was used instead of the compound (R-DHN) in Example 18. The metal contents of the resulting RBisN-2 solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0229] Example 24 The same procedure as in Example 19 was repeated, except that the resin (RBisN-2) obtained in Synthesis Example 4-1 was used instead of the compound (R-DHN) in Example 19. The metal contents of the resulting RBisN-2 solution were measured by ICP-MS. The measurement results are shown in Table 3.

[0230] (Example 25) Acid washing and filter passage combined 1 In a Class 1000 clean booth, a 300 mL four-neck flask (open-bottom) was charged with 140 g of a 10 wt% PGMEA solution of R-DHN with reduced metal content obtained in Example 13. The air inside the flask was then removed under reduced pressure, followed by the introduction of nitrogen gas to return the pressure to atmospheric. The oxygen concentration inside the flask was adjusted to less than 1% by aeration at 100 mL / min of nitrogen gas, and the flask was then heated to 30°C with stirring. The solution was withdrawn through the open-bottom valve and passed through a fluororesin pressure-resistant tube and through a diaphragm pump at a flow rate of 10 mL / min through an ion exchange filter (manufactured by Nippon Pall Corporation, product name: Ion Clean Series) with a nominal pore size of 0.01 μm. The recovered solution was then returned to the 300 mL four-neck flask, and the filter was replaced with a high-density polyethylene filter (manufactured by Nippon Entegris Co., Ltd.) with a nominal pore size of 1 nm. The resulting R-DHN solution was subjected to pumping in the same manner. The metal contents of the resulting R-DHN solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies below). The measurement results are shown in Table 3.

[0231] (Example 26) Acid washing and filter passage combined 2 In a Class 1000 clean booth, 140 g of a 10 mass % PGMEA solution of R-DHN with a reduced metal content obtained in Example 13 was placed in a 300 mL four-neck flask (open-bottom type). Subsequently, the air inside the flask was removed under reduced pressure, and nitrogen gas was introduced to return the pressure to atmospheric pressure. The oxygen concentration inside the flask was adjusted to less than 1% while aerating nitrogen gas at 100 mL per minute, and the flask was heated to 30°C with stirring. The solution was extracted from the bottom-opening valve and passed through a fluororesin pressure-resistant tube using a diaphragm pump at a flow rate of 10 mL per minute through a nylon hollow fiber membrane filter (trade name: Polyfix, manufactured by Kitz Microfilter Co., Ltd.) with a nominal pore size of 0.01 μm. The recovered solution was then returned to the 300 mL four-neck flask, and the filter was replaced with a high-density PE filter (manufactured by Nippon Entegris Co., Ltd.) with a nominal pore size of 1 nm. The solution was similarly pumped through the flask. The metal contents of the resulting R-DHN solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies below). The measurement results are shown in Table 3.

[0232] (Example 27) Acid washing and filter passage combined 3 The same procedure as in Example 25 was carried out, except that the 10% by mass PGMEA solution of R-DHN used in Example 25 was replaced with the 10% by mass PGMEA solution of RBisN-2 obtained in Example 14, and a 10% by mass PGMEA solution of RBisN-2 with reduced metal content was recovered. The metal contents of the resulting solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies below). The measurement results are shown in Table 3.

[0233] (Example 28) Acid washing and filter passage combined 4 The same procedure as in Example 26 was carried out, except that the 10% by mass PGMEA solution of R-DHN used in Example 26 was replaced with the 10% by mass PGMEA solution of RBisN-2 obtained in Example 14, and a 10% by mass PGMEA solution of RBisN-2 with reduced metal content was recovered. The metal contents of the resulting solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies below). The measurement results are shown in Table 3.

[0234] [Table 3]

[0235] As shown in Table 3, it was confirmed that the storage stability of the resin solution of this embodiment was improved by reducing the metals derived from the oxidizing agent using various purification methods. In particular, the use of an acid cleaning method and an ion exchange filter or nylon filter can effectively reduce ionic metals, and by using a high-definition, high-density polyethylene particulate removal filter in combination, a dramatic metal removal effect can be achieved.

[0236] This application is based on a Japanese patent application (Patent Application No. 2019-003493) filed on January 11, 2019, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0237] The present invention provides a novel polycyclic polyphenol resin in which aromatic hydroxy compounds having a specific skeleton are linked together without a crosslinking group, i.e., the aromatic rings are linked by a direct bond. Such polycyclic polyphenol resins have excellent heat resistance, etching resistance, thermal flow resistance, solvent solubility, etc., and are particularly excellent in heat resistance and etching resistance, and can be used as semiconductor coating agents, resist materials, and semiconductor underlayer film forming materials.

Claims

1. A polycyclic polyphenol resin having a repeating unit derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by formula (1A) and formula (1B) (excluding compounds represented by formula (M-3) below), (excluding (i) polyphenol resins represented by formulas P-1A and P-1B below, and having a weight-average molecular weight of 1900 and a dispersity of 1.4 or a weight-average molecular weight of 3600 and a dispersity of 1.5, and (ii) polyphenol resins represented by formula (α) below), The polycyclic polyphenol resin is a polycyclic polyphenol resin in which the repeating units are linked to each other by direct bonds between aromatic rings. 【Chemistry 1】 (1A) (1B) (In formula (1A), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking; Y represents a 2n-valent group having 1 to 60 carbon atoms or a single bond; when X is no crosslinking, Y is the 2n-valent group (provided that the 2n-valent group does not include a group derived from a compound having a fluorene skeleton). In formula (1B), A represents anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, or ovalene. Furthermore, in formulas (1A) and (1B), R ０ are each independently an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, wherein R ０ At least one of the above is a hydroxyl group, each m is independently an integer of 1 to 9, each n is an integer of 1 to 4, and each p is independently an integer of 0 to 3. 【Chemistry 2】 【Transformation 3】 (In formulas P-1A and P-1B, n represents the number of repeating units.) 【Chemistry 4】 wherein Z is a covalent chemical bond or a divalent linking group selected from O, C(═O), S, S(═O), S(═O) 2 , N(R), C 1-100 -hydrocarbylene, substituted C 1-100 -hydrocarbylene, —O—(C 1-20 -alkylene-O—)m1, —O—(C 5-60 -arylene-O—)m2 and C(R 3 )(R 4 ); R is selected from H, C 1-20 -alkyl, C 5-30 -aryl and C 2-20 -unsaturated aliphatic moieties; each R 1 and each R 2 is independently H, OR, C 1-30 -hydrocarbyl, substituted C 1-30 -hydrocarbyl, —C(═O)—O—R 5 , SR, S(═O)R, S(═O) 2 R, N(R 5 )(R 6 ) and N(R 7 )C(═O)R 5 ; one R 1 , one R 2 and Z together with the atoms to which they are attached can form a 5- to 6-membered ring; R 3 and R 4 are independently selected from C 1-20 -alkyl and C 5-30 -aryl; R 3 and R 4 together with the carbons to which they are attached can form a 5- or 6-membered ring which can be fused to one or more aromatic rings and is optionally substituted; R 5 and R 6 are independently C 1-20 -alkyl or C 5-30 -aryl; R 7 is H or R 6 ; R 5 and R 6 can form a 5- to 6-membered ring together with the atoms to which they are attached; each of a1 and a2 is 0 to 5; each of m1 and m2 = 1 to 100; and n = 2 to 1000.

2. The polycyclic polyphenol resin according to claim 1, wherein the aromatic hydroxy compound represented by formula (1A) is an aromatic hydroxy compound represented by formula (1). 【Transformation 5】 （１） (In formula (1), X, m, n, and p are the same as those described in formula (1A), and R １ is the same as Y in formula (1A), and R ２ are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, ２ At least one of the groups is a hydroxyl group.)

3. The polycyclic polyphenol resin according to claim 2, wherein the aromatic hydroxy compound represented by the formula (1) is an aromatic hydroxy compound represented by the following formula (1-1): 【Transformation 6】 （１－１） (In formula (1-1), Z is an oxygen atom or a sulfur atom, and R １ , R ２ , m, p, and n have the same meanings as those explained in formula (1).

4. The polycyclic polyphenol resin according to claim 3, wherein the aromatic hydroxy compound represented by the formula (1-1) is an aromatic hydroxy compound represented by the following formula (1-2): 【Transformation 7】 （１－２） (In formula (1-2), R １ , R ２ , m, p, and n have the same meanings as those explained in formula (1).

5. The polycyclic polyphenol resin according to claim 4, wherein the aromatic hydroxy compound represented by the formula (1-2) is an aromatic hydroxy compound represented by the following formula (1-3): 【Transformation 8】 （１－３） (In the above formula (1-3), R １ is the same as that explained in the formula (1), and R ３ are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, or a thiol group; ３ are each independently an integer from 0 to 5.

6. The polycyclic polyphenol resin according to claim 1, wherein the aromatic hydroxy compound represented by formula (1A) is an aromatic hydroxy compound represented by the following formula (2): 【Chemistry 9】 （２） (In formula (2), R １ is the same as Y in formula (1A), and R ５ is R in the formula (1A). ０ n and p are the same as those described in formula (1A), and R ６ are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, an alkenyl group having 2 to 34 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 34 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group; ５ are each independently an integer of 1 to 6, and m ６ are each independently an integer from 1 to 7, where R ５ At least one of the groups is a hydroxyl group.)

7. The polycyclic polyphenol resin according to claim 6, wherein the aromatic hydroxy compound represented by the formula (2) is an aromatic hydroxy compound represented by the following formula (2-1): 【Chemistry 10】 （２－１） (In formula (2-1), R １ , R ５ , R ６ and n are the same as those described in the formula (2), and m ５’ are each independently an integer of 1 to 4, and m ６’ are each independently an integer from 1 to 5, where R ５ At least one of the groups is a hydroxyl group.)

8. The R ６ The polycyclic polyphenol resin according to claim 6 or 7, wherein at least one of the above is a hydroxyl group.

9. The polycyclic polyphenol resin according to claim 7 or 8, wherein the aromatic hydroxy compound represented by the formula (2-1) is an aromatic hydroxy compound represented by the following formula (2-2): 【Chemistry 11】 （２－２） (In formula (2-2), R １ is the same as that explained in the formula (2), and R ７ and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group; ７ and m ８ are each independently an integer from 0 to 7.

10. The polycyclic polyphenol resin according to any one of claims 1 to 9, further comprising a modified portion derived from a crosslinkable compound.

11. The polycyclic polyphenol resin according to claim 10, wherein the crosslinkable compound is an aldehyde or a ketone.

12. The polycyclic polyphenol resin according to any one of claims 1 to 11, having a mass average molecular weight of 400 to 100,000.

13. The polycyclic polyphenol resin according to any one of claims 1 to 12, having a solubility of 1% by mass or more in 1-methoxy-2-propanol and / or propylene glycol monomethyl ether acetate.

14. The R １ But, R Ａ -R Ｂ wherein R Ａ is a methine group, and the R Ｂ The polycyclic polyphenol resin according to any one of claims 2, 3, 4, 5, 6, 7 and 9, wherein is an aryl group having 6 to 30 carbon atoms which may have a substituent.

15. A composition comprising the polycyclic polyphenol resin according to any one of claims 1 to 14.

16. The composition of claim 15 further comprising a solvent.

17. 17. The composition of claim 16, wherein the solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, ethyl lactate, and methyl hydroxyisobutyrate.

18. The composition according to any one of claims 15 to 17, wherein the content of impurity metals is less than 500 ppb per metal species.

19. 20. The composition of claim 18, wherein the impurity metal comprises at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium.

20. 20. The composition of claim 18 or 19, wherein the content of the impurity metals is 1 ppb or less.

21. A method for producing the polycyclic polyphenol resin according to any one of claims 1 to 14, comprising: A method for producing a polycyclic polyphenol resin, comprising the step of polymerizing one or more of the aromatic hydroxy compounds in the presence of an oxidizing agent.

22. The method for producing a polycyclic polyphenol resin according to claim 21, wherein the oxidizing agent is a metal salt or a metal complex containing at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium.

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