CN111936555A

CN111936555A - Resin, resin precursor, and resin precursor solution

Info

Publication number: CN111936555A
Application number: CN201980021572.9A
Authority: CN
Inventors: 小松伸一
Original assignee: Eneos Corp
Current assignee: Eneos Corp
Priority date: 2018-03-23
Filing date: 2019-03-13
Publication date: 2020-11-13
Also published as: KR102458537B1; JPWO2019181699A1; WO2019181699A1; TW201945435A; KR20200135430A

Abstract

A resin comprising a compound selected from the group consisting of the following general formula (1-1) [ wherein X is¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X²Represents a 4-valent organic group.]A repeating unit having an imidazopyrrolone structure represented by the formula (1-2) wherein X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X³Represents a 3-valent organic group.]At least 1 repeating unit in the group consisting of the repeating units having an imidazopyrrolone structure.

Description

Resin, resin precursor, and resin precursor solution

Technical Field

The present invention relates to a resin, a resin precursor, and a resin precursor solution.

Background

Conventionally, there has been a demand for the emergence of a resin having high light transmittance and sufficiently high heat resistance, such as glass, as a material used for substrates and the like in various fields (for example, the field of display devices). As such a resin, for example, international publication No. 2011/099518 (patent document 1) discloses a polyimide having a repeating unit represented by a specific general formula. Such polyimide has high light transmittance and sufficiently high heat resistance, and is applicable to various fields. However, in the field of such resins, the emergence of resins having light transmittance equivalent to that of the polyimide described in patent document 1 and capable of exhibiting higher heat resistance has been desired.

On the other hand, polyimidazopyrrolone (polyimidazopyrrololone) has been known as a resin having high heat resistance, and for example, in japanese patent application laid-open No. 8-290046 (patent document 2) or 5-301959 (patent document 3), polyimidazopyrrolone obtained by reacting a tetracarboxylic dianhydride component with a tetraamine component is disclosed. In patent document 2 or patent document 3, various compounds are widely disclosed as tetracarboxylic dianhydride components. However, the resins actually produced in the examples of patent document 2 or patent document 3 are only reaction products of an aromatic tetracarboxylic dianhydride component and an aromatic tetramine component (so-called wholly aromatic polyimidazopyrrolone). Further, the wholly aromatic polyimidazopyrrolone as described above is not sufficient in light transmittance, and cannot be used for glass substitution.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/099518

Patent document 2: japanese laid-open patent publication No. 8-290046

Patent document 3: japanese laid-open patent publication No. 5-301959

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a resin having sufficiently high light transmittance and higher heat resistance and having excellent mechanical strength, a resin precursor which is a precursor of the resin, and a resin precursor solution which can be suitably used for production of the resin.

Means for solving the problems

The present inventors have made intensive studies to achieve the above object, and as a result, have found that: the present invention has been completed by the fact that the resin can have sufficiently high light transmittance and higher heat resistance and can have excellent mechanical strength by containing at least 1 repeating unit selected from the group consisting of a repeating unit having a specific imidazopyrrolone structure represented by the following general formula (1-1) and a repeating unit having a specific imidazopyrrolone structure represented by the following general formula (1-2).

That is, the resin of the present invention contains at least 1 kind of repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone structure represented by the following general formula (1-1) and a repeating unit having an imidazopyrrolone structure represented by the following general formula (1-2).

[ in the formula, X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X²Represents a 4-valent organic group.]

[ in the formula, X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X³Represents a 3-valent organic group.]

Further, the resin of the present invention preferably further contains a repeating unit having an imide structure represented by the following general formula (2),

[ in the formula, X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X⁴Represents the number of carbon atomsIs an arylene group of 6 to 50.]

The resin precursor of the present invention contains at least 1 kind of repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone precursor structure represented by the following general formula (8-1) and a repeating unit having an imidazopyrrolone precursor structure represented by the following general formula (8-2).

The resin precursor of the present invention preferably further contains a repeating unit having an imide precursor structure represented by the following general formula (9).

[ in the formula, X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X⁴Represents an arylene group having 6 to 50 carbon atoms.]

In the resin of the present invention and the resin precursor of the present invention, X in each of the formulae is preferably X¹Is 1 kind selected from 4-valent organic groups represented by the following general formulas (3) to (5),

in the formula (3), m represents an integer of 0 to 2, in the formula (4), n represents an integer of 1 to 2,in the formula (5), A represents 1 selected from the group consisting of single bond and 2-valent aromatic group with 6-30 carbon atoms which can have substituent and form aromatic ring, and symbols 1-4 in the formulas (3) - (5) represent that bonding points with the symbols are respectively connected with X¹Any of the 4 bonding sites of the bond.]

Further, in the resin of the present invention and the resin precursor of the present invention, X in each of the formulae is preferably X²Is 1 kind selected from 4-valent organic groups represented by the following general formulas (6-1) to (7-1).

[ formula (7-1) wherein Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH ₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-1) to (7-1), wherein the symbols 1 to 4 represent the bonding sites having the symbols with X²Bonding ofAny of the 4 bonding points of (1).]

Further, in the resin of the present invention and the resin precursor of the present invention, X in each of the formulae is preferably X³Is 1 selected from 3-valent organic groups represented by the following general formulae (6-2) to (7-2).

[ formula (7-2) wherein Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH ₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-2) to (7-2), wherein the symbols 1 to 3 represent the bonding sites having the symbols with X³Any of the 3 bonding sites of the bond.]

The resin precursor solution of the present invention contains the resin precursor of the present invention and a solvent.

Effects of the invention

According to the present invention, a resin capable of having sufficiently high light transmittance and higher heat resistance and having excellent mechanical strength, a resin precursor as a precursor of the resin, and a resin precursor solution suitably usable for production of the resin can be provided.

Drawings

FIG. 1 is an IR spectrum of a resin constituting the film obtained in example 1.

FIG. 2 is an IR spectrum of a resin constituting the film obtained in example 13.

Detailed Description

The present invention will be described in detail below based on preferred embodiments thereof.

First, the resin of the present invention will be explained. The resin of the present invention contains at least 1 kind of repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone structure represented by the above general formula (1-1) (hereinafter, for convenience, the repeating unit having an imidazopyrrolone structure may be simply referred to as "repeating unit (a)") and a repeating unit having an imidazopyrrolone structure represented by the above general formula (1-2) (hereinafter, for convenience, the repeating unit having an imidazopyrrolone structure may be simply referred to as "repeating unit (a')").

X in the above general formula (1-1) and the above general formula (1-2)¹All are 4-valent organic groups having an alicyclic structure of 6-membered ring. The "6-membered ring" as referred to herein is not particularly limited as long as it is a ring having 6 atoms which forms a cyclic structure [ in the case of forming a polycyclic structure such as a bicyclic structure having a crosslinked structure (for example, in the case of a norbornane ring structure or a bicyclooctane ring structure), any one of the rings may be a ring having 6 atoms]. The alicyclic structure of the 6-membered ring in the 4-valent organic group is not particularly limited, and examples thereof include structures formed of aliphatic 6-membered rings represented by the following general formulae (i) to (iii). The alicyclic structure having a 6-membered ring is more preferably a 6-membered ring having a higher heat resistance, a higher resistance to tensile stress, and a higher mechanical strengthA structure formed of an aliphatic 6-membered ring (norbornene ring) represented by the above general formula (ii).

Further, X in the above general formula (1-1) and general formula (1-2) may be used¹The 4-valent organic group having a 6-membered alicyclic structure may be selected so long as it has the 6-membered alicyclic structure, and various atoms such as a hydrogen atom, an atom other than a hydrogen atom, or other substituents (including other organic groups) may be bonded to the carbon atoms forming the 6-membered alicyclic structure.

Further, X in the above general formula (1-1) and general formula (1-2) may be used¹The selected 4-valent organic group having an alicyclic structure having 6-membered rings is a repeating unit which can be more efficiently formed by using a tetracarboxylic dianhydride having an alicyclic structure having 6-membered rings as a raw material, that is, since they are repeating units which can be more efficiently formed by the reaction of tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring with tetramine and/or the reaction of tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring with triamine, therefore, a residue obtained by removing 2 anhydride groups from a tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring (4-valent organic group: further, in the compound represented by the following formula (I), with the carbonyl group in the acid anhydride group (formula: the 4 bonding points to which — C (═ O) -represents a group) are bonded to X in the above formulae.¹4 bonding points of bonding) can be cited as a preferable example.

Such tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring as described above can be represented by the following formula (I):

[ X in the formula (I) ]¹And X in the above general formula (1-1) and general formula (1-2)¹Synonymously.]. As the alicyclic structure having a 6-membered ring as described aboveExamples of the tetracarboxylic acid dianhydride of (1) include bicycloheptane tetracarboxylic acid dianhydride (BHDA), dimethanonaphthalene tetracarboxylic acid dianhydride (DNDA), bicyclooctane tetracarboxylic acid dianhydride (BODA), 3 ', 4, 4 ' -bicyclohexyl tetracarboxylic acid dianhydride (H-BPDA), and [1, 1 ' -bis (cyclohexane)]-3, 3 ', 4, 4 ' -tetracarboxylic dianhydride, [1, 1 ' -bis (cyclohexane)]-2, 3, 3 ', 4 ' -tetracarboxylic dianhydride, [1, 1 ' -bis (cyclohexane)]-2, 2 ', 3, 3 ' -tetracarboxylic dianhydride, 4 ' -methylenebis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' - (propane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' -oxybis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' -thiobis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' -sulfonylbis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' - (dimethylsilanediyl) bis (cyclohexane-1, 2-dicarboxylic anhydride), 4 ' - (tetrafluoropropane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic anhydride), Octahydro cyclopentadiene-1, 3, 4, 6-tetracarboxylic dianhydride, bicyclo [2.2.1]Heptane-2, 3, 5, 6-tetracarboxylic dianhydride, 6- (carboxymethyl) bicyclo [2.2.1]Heptane-2, 3, 5-tricarboxylic dianhydride, bicyclo [2.2.2]Octane-2, 3, 5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2]Octa-5-ene-2, 3, 7, 8-tetracarboxylic dianhydride, tricyclo [4.2.2.0^2，5]Decane-3, 4, 7, 8-tetracarboxylic dianhydride, tricyclo [4.2.2.0^2，5]Dec-7-ene-3, 4, 9, 10-tetracarboxylic acid dianhydride, 9-oxatricyclo [4.2.1.0^2，5]Nonane-3, 4, 7, 8-tetracarboxylic dianhydride, (4arH, 8acH) -decahydro-1 t, 4 t: 5c, 8 c-dimethylnaphthalene-2 c, 3c, 6c, 7 c-tetracarboxylic dianhydride, (4arH, 8acH) -decahydro-1 t, 4 t: 5c, 8 c-dimethylnaphthalene-2 t, 3t, 6c, 7 c-tetracarboxylic dianhydride and bicyclo [ 2.2.1%]Heptane-2, 3, 5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2]Octane-2, 3, 5, 6-tetracarboxylic acid, (4arH, 8acH) -decahydro-1 t, 4 t: 5c, 8 c-dimethylnaphthalene-2 c, 3c, 6c, 7 c-tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclohexanone- α ' -spiro-2" -norbornane-5, 5 ", 6, 6" -tetracarboxylic dianhydride, [2, 2 ' -bis (norbornane)]-5, 5 ', 6, 6' -tetracarboxylic dianhydride, 1, 4-phenylenebis (2-norbornane-5, 6-dicarboxylic anhydride),4, 4 '-biphenylene bis (2-norbornane-5, 6-dicarboxylic anhydride), 4' -terphenylene bis (2-norbornane-5, 6-dicarboxylic anhydride), trans isomer of cyclohexane-1, 2, 4, 5-tetracarboxylic dianhydride, cis isomer of cyclohexane-1, 2, 4, 5-tetracarboxylic dianhydride, and the like. Further, as the tetracarboxylic dianhydride having an alicyclic structure of a 6-membered ring, for example, compounds represented by the following general formulae (IA) to (IB) are also included as preferable compounds:

[ in the formula (IA), R¹、R²、R³Each independently represents 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n represents an integer of 0 to 12. In the formula (IB), A is the same as A in the formula (5), and R is⁴Each independently represents 1 selected from the group consisting of hydrogen atom and alkyl group having 1 to 10 carbon atoms, R⁵Each independently represents 1 selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.]. The tetracarboxylic dianhydrides having an alicyclic structure with a 6-membered ring can be used alone in 1 kind or in combination of a plurality of kinds.

As R in the above-mentioned general formula (IA)¹、R²、R³The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3, from the viewpoint of easier purification. In addition, R as described above may be used¹、R²、R³The alkyl group may be linear or branched. Further, from the viewpoint of ease of purification, the alkyl group is more preferably a methyl group or an ethyl group. R in the general formula (IA)¹、R²、R³From the viewpoint of obtaining higher heat resistance in the production of the resin, each is more preferably independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably both are hydrogenAn atom. In addition, from the purification of easy point of view, etc., such a formula in a plurality of R¹、R²、R³The same groups are particularly preferred. Further, n in the general formula (IA) has an upper limit of more preferably 5 (particularly preferably 3) from the viewpoint of easier purification, and has a lower limit of more preferably 1 (particularly preferably 2) from the viewpoint of stability of the raw material compound. Particularly preferably 2. Thus, n in the general formula (IA) is particularly preferably an integer of 2 to 3.

R in the above general formula (IB)⁴And R⁵Each independently represents 1 selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. May be mentioned as R⁴And R⁵The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3, from the viewpoint of obtaining higher heat resistance. In addition, R as described above may be used⁴And R⁵The alkyl group may be linear or branched. In addition, from the viewpoint of obtaining higher heat resistance, availability of raw materials, easier purification, and the like, R in the general formula (IB) is⁴And R⁵More preferably, each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably both hydrogen atoms. In addition, R in the above formula (IB)⁴And R⁵They may be the same or different, but are preferably the same from the viewpoint of ease of purification. In addition, a in the general formula (IB), which is synonymous with a in the general formula (5), represents 1 selected from the group consisting of a single bond and a 2-valent aromatic group having 6 to 30 carbon atoms which may have a substituent and form an aromatic ring. The 2-valent aromatic group which can be selected as a, and the preferable one thereof will be described later.

Examples of the compound represented by the above general formula (IA) include norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 ″ -norbornane-5, 5 ″, 6, 6 ″ -tetracarboxylic dianhydride (CpODA), norbornane-2-spiro- α -cyclohexanone- α' -spiro-2 ″ -norbornane-5, 5 ″, 6, 6 ″ -tetracarboxylic dianhydride (ChODA), and the like. The method for producing the compound represented by the above general formula (IA) is not particularly limited, and a known method (for example, the method described in international publication No. 2011/099518) can be suitably used. Examples of the compounds represented by the general formula (IB) include compounds represented by the following formulas (B-1) to (B-3). The method for producing the compound represented by the above general formula (IB) is not particularly limited, and a known method (for example, the method described in international publication No. 2015/163314 or international publication No. 2017/030019) can be suitably used.

Among such tetracarboxylic dianhydrides having an alicyclic structure with a 6-membered ring, norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 ″ -norbornane-5, 5 ″, 6, 6 ″ -tetracarboxylic dianhydride (CpODA), norbornane-2-spiro- α -cyclohexanone- α' -spiro-2 ″ -norbornane-5, 5 ″, 6, 6 ″ -tetracarboxylic dianhydride (ChODA), compound (BNBDA) represented by the formula (B-1), compound (BzDA) represented by the formula (B-2), compound (BpDA) represented by the formula (B-3), and CpODA, bda, and BzDA are preferable from the viewpoints of transparency, heat resistance, and high dimensional stability.

Further, X in the above-mentioned formula (1-1) and formula (1-2) may be used¹The selected 4-valent organic group is preferably a 4-valent organic group having an alicyclic structure of 2 or more 6-membered rings (more preferably a structure formed from a norbornene ring) from the viewpoints of transparency, heat resistance and high dimensional stability, and among these, a 4-valent organic group represented by the above general formulae (3) to (5) is more preferably selected from the viewpoints of transparency, heat resistance and high dimensional stability.

In the 4-valent organic group represented by the general formulae (3) to (5), m in the formula (3) is an integer of 0 to 2 (more preferably 1 to 2, and still more preferably 1). When the value of m exceeds the upper limit, production and purification tend to become difficult. In addition, n in the formula (4) is an integer of 1 to 2 (more preferably 1). When the value of n exceeds the upper limit, production and purification tend to become difficult.

Further, a in the general formula (5) is 1 kind selected from the group consisting of a single bond and a 2-valent aromatic group having 6 to 30 carbon atoms which may have a substituent and form an aromatic ring (further, a in the general formula (IB) is also synonymous).

The 2-valent aromatic group that can be selected as a is a 2-valent aromatic group that can have a substituent, and the number of carbon atoms that form the aromatic ring included in the aromatic group (in the case where the aromatic group has a substituent that includes carbon (such as a hydrocarbon group, the "number of carbon atoms that form an aromatic ring" referred to herein means the number of carbon atoms that do not include the substituent but only the number of carbon atoms that form the aromatic ring in the aromatic group; for example, in the case of a 2-ethyl-1, 4-phenylene group, the number of carbon atoms that form the aromatic ring is 6) is 6 to 30. Thus, the 2-valent aromatic group that can be selected as a in the formula may have a substituent and is a 2-valent group (2-valent aromatic group) having an aromatic ring having 6 to 30 carbon atoms. If the number of carbon atoms forming the above-mentioned aromatic ring exceeds the above upper limit, it tends to be difficult to sufficiently suppress coloring of the resin when the resin is produced using a resin having the repeating unit. Further, from the viewpoint of transparency and ease of purification, the number of carbon atoms of the aromatic ring forming the 2-valent aromatic group is more preferably 6 to 18, and still more preferably 6 to 12.

The 2-valent aromatic group selected as a is not particularly limited as long as the above-mentioned condition of the number of carbon atoms is satisfied, and for example, the following may be appropriately used: from benzene, naphthalene, terphenyl, anthracene, phenanthrene, triphenylene, pyrene,

Examples of the residue obtained by removing 2 hydrogen atoms from an aromatic compound such as biphenyl, terphenyl, tetraphenyl, and pentacene (the position of the removed hydrogen atom is not particularly limited as the residue, and examples thereof include 1, 4-phenylene, 2, 6-naphthylene, 2, 7-naphthylene, and 4, 4' -biphenylene9, 10-anthracenylene, etc.); and a group in which at least 1 hydrogen atom in the residue is substituted with a substituent (e.g., 2, 5-dimethyl-1, 4-phenylene, 2, 3, 5, 6-tetramethyl-1, 4-phenylene), and the like. In the above-mentioned residue, the position of the hydrogen atom to be detached is not particularly limited as described above, and for example, when the residue is a phenylene group, it may be any of the ortho-position, meta-position and para-position.

The 2-valent aromatic group that can be selected as a is preferably phenylene that may have a substituent, biphenylene that may have a substituent, naphthylene that may have a substituent, anthracenylene that may have a substituent, biphenylene that may have a substituent, and biphenylene that may have a substituent, from the viewpoint of making the resin more excellent in transparency when the resin is produced. That is, the 2-valent aromatic group selected as a is preferably a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, or a biphenylene group, each of which may have a substituent. Among such 2-valent aromatic groups, phenylene, biphenylene, and naphthylene each of which may have a substituent are more preferable, phenylene and biphenylene each of which may have a substituent are more preferable, and phenylene each of which may have a substituent is most preferable, from the viewpoint of obtaining higher effects from the above viewpoint.

Among the 2-valent aromatic groups that can be selected as a, those that can be substituted are preferred, from the viewpoint of further improving the mechanical strength of the resin during the production of the resin, and phenylene, biphenylene, naphthylene, anthracenylene, and biphenylene that can each be substituted are more preferred, phenylene, biphenylene, and naphthylene that can each be substituted are still more preferred, phenylene and biphenylene that can each be substituted are still more preferred, and phenylene that can be substituted is most preferred.

Further, among the above-mentioned 2-valent aromatic groups, from the viewpoint of obtaining higher heat resistance, a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group each of which may have a substituent are preferable, a phenylene group, a biphenylene group, a naphthylene group, and a biphenylene group each of which may have a substituent are more preferable, a phenylene group, a biphenylene group, and a naphthylene group each of which may have a substituent are further more preferable, and a phenylene group each of which may have a substituent is most preferable.

The substituent that the 2-valent aromatic group selected as a may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, and a halogen atom. Among the substituents that the 2-valent aromatic group may have, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are more preferable from the viewpoint of further improving the transparency of the resin in the production of the resin. When the number of carbon atoms of the alkyl group and the alkoxy group which are suitable as the above-mentioned substituents exceeds 10, the heat resistance of the obtained resin tends to be lowered. The alkyl group and the alkoxy group which are suitable as the above-mentioned substituent preferably have 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms from the viewpoint of obtaining higher heat resistance in the production of a resin. The alkyl group and the alkoxy group which may be selected as the above-mentioned substituents may be linear or branched, respectively.

In addition, as a in the formula (5), from the viewpoint of obtaining higher heat resistance, a single bond, a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a naphthylene group which may have a substituent, or a terphenylene group which may have a substituent is more preferable, a single bond, a phenylene group which may have a substituent, a biphenylene group which may have a substituent, or a naphthylene group which may have a substituent is further preferable, a single bond, a phenylene group which may have a substituent, or a biphenylene group which may have a substituent is particularly preferable, and a single bond or a phenylene group which may have a substituent is most preferable.

In the 4-valent organic groups represented by the above general formulae (3) to (5), the symbols 1 to 4 represent that the bonding sites with the symbols are X¹Any of the 4 bonding sites of the bond. Further, in the structure of the repeating unit, the symbols 1 to 4 are described by taking the general formula (1-1) as an example, and any one of the bonding sites with the symbols 1 to 2 among the bonding sites with the symbols becomes bonded to X in the general formula (1-1)¹With a bonding site of one of the carbonyl groups of formula (i): -C (O) -, and with the symbols 3 to 4Any one of the bonding sites becomes bonded to X in the general formula (1-1)¹The other carbonyl bond of (a).

Further, X in the above general formula (1-1)²Represents a 4-valent organic group. The 4-valent organic group is not particularly limited, and is preferably a residue obtained by removing 4 amino groups from tetraamine. Such a tetraamine may be an aromatic tetraamine or may be an alicyclic tetraamine. In addition, for the purpose of improving the storage stability and stability of the varnish, the tetraamine used herein may be-NH-NH₂One of H in (A) is silanized to become a trimethylsilyl group or a tert-butyldimethylsilyl group.

The aromatic tetraamines are not particularly limited, and known aromatic tetraamines (for example, various aromatic tetraamines such as a pyromellitic dianhydride type, diphenyl ether type, diphenyl sulfone type, diphenyl ketone type, biphenyl type, benzamide type, benzoate type, diphenyl sulfide type, Bis-A type (diphenylisopropylidene type), hexafluorobis-A type, Bis-M type (diphenylmethane type), Bis-C type (diphenylcyclohexane type), Bis-F type (diphenylfluorene type), bistribenzene type (triphenyl type), phenylenedioxy type, Bis (phenylenedioxy) type, fluorene type, spiro type, silicon type, and the like) can be suitably used.

Examples of the aromatic tetraamines include 3, 3 ', 4, 4' -tetraaminodiphenyl ether (TAB-E), 3 ', 4, 4' -tetraaminodiphenyl sulfone (TAB-S), 3 ', 4, 4' -tetraaminodiphenyl ketone (TAB-K), 3 ', 4, 4' -Tetraaminobiphenyl (TABP), 1, 2, 4, 5-Tetraaminobenzene (TAB), 3 ', 4, 4' -tetraaminodiphenylmethane, 3 ', 4, 4' -tetraaminodiphenylcyclohexane, 3 ', 4, 4' -tetraaminodiphenylfluorene, 3 ', 4, 4' -tetraaminodiphenylsulfide, 2-isopropylidenebis (3, 4-diaminobenzene), 2-bis (3, 4-diaminophenyl) propane, 2-hexafluoroisopropylidene bis (3, 4-diaminobenzene), 2-bis (3, 4-diaminophenyl) hexafluoropropane, 3 ', 4, 4' -tetraaminodiphenyl ester, 3 ', 4, 4' -tetraaminodiphenylamide, 3 ', 4, 4' -tetraaminoterphenyl, 9-fluorenylidene bis (3, 4-diaminobenzene), 9-bis (3, 4-diaminophenyl) fluorene, 9-fluorenylidene bis (3, 4-diaminobenzene), 1, 2-bis (3, 4-diaminophenoxy) benzene, 1, 3-bis (3, 4-diaminophenoxy) benzene, 1, 4-bis (3, 4-diaminophenoxy) benzene, 4, 4' -bis (3, 4-diaminophenoxy) biphenyl, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] propane, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] sulfone, 2-bis [3- (3, 4-diaminophenoxy) phenyl ] sulfone, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] methane, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] ketone, 2-bis [4- (3, 4-diaminophenoxy) phenyl ] ether and the like.

Examples of the alicyclic tetraamine include hydride compounds of the above-mentioned various aromatic tetraamines (for example, 3 ', 4, 4' -tetraaminodicyclohexyl ether, 3 ', 4, 4' -tetraaminodicyclohexylsulfone, 3 ', 4, 4' -tetraaminodicyclohexyl ketone, 3 ', 4, 4' -tetraaminodicyclohexyl, 1, 2, 4, 5-tetraaminocyclohexane, and the like), which are preferable.

Among these tetraamines, aromatic tetraamines are preferable from the viewpoint of heat resistance, and TAB-E, TAB-S, TAB-K, TABP, TAB, 2-isopropylidenebis (3, 4-diaminobenzene), 2-hexafluoroisopropylidenebis (3, 4-diaminobenzene) are more preferable, and TAB-E, TAB-S, TAB-K, TABP, and TAB are particularly preferable.

Further, X in the above formula (1-1) may be²The selected 4-valent organic group is preferably a 4-valent group represented by the above general formulae (6-1) to (7-1) from the viewpoint of mechanical strength. Here, Z in the formula (7-1)¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄-O-isPhenylenedioxy group, -O-C of₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) -a group represented by and-N (C)₆H₅) -1 of the group consisting of the groups represented. Z as above¹Among them, from the viewpoint of satisfying both heat resistance and mechanical strength, an ether group and a single bond represented by — O — are preferable, and from the viewpoint of satisfying both transparency and mechanical strength, a carbonyl group and — S (O) represented by — C (O) -are preferable₂-a sulfonyl group represented. In addition, the bonding points with symbols 1 to 4 in the formulae (6-1) to (7-1) are respectively bonded to X²Any of the 4 bonding sites of the bond. Further, the 4-valent group represented by the above general formulae (6-1) to (7-1) can be introduced into X as a residue obtained by removing 4 amino groups from the tetraamine by using an appropriately selected one (for example, TAB-E, TAB-S, TAB-K, TABP, TAB or the like) from the tetraamine at the time of production of the repeating unit²The position of (a).

The repeating unit (a) represented by the general formula (1-1) can be efficiently introduced into the resin by, for example, reacting (polymerizing) the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with the tetraamine. Therefore, the resin containing the repeating unit (a) represented by the general formula (1-1) is preferably a polymer of a first monomer containing the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and a second monomer containing the tetraamine.

Further, X in the above general formula (1-2)³Represents a 3-valent organic group. The 3-valent organic group is not particularly limited, and is preferably a residue obtained by removing 3 amino groups from triamine. Such as described aboveThe triamine may be an aromatic triamine or may also be an alicyclic triamine. In addition, the triamines used herein may also be substituted with-NH-in order to improve the storage stability and stability of the varnish₂One of H in (A) is silanized to become a trimethylsilyl group or a tert-butyldimethylsilyl group.

The aromatic triamine is not particularly limited, and known aromatic triamines (for example, benzenetriamine type, diphenyl ether type, diphenyl sulfone type, diphenyl ketone type, biphenyl type, benzamide type, benzoate type, diphenyl sulfide type, Bis-a type (diphenylisopropylidene type), hexafluorobis-a type, Bis-M type (diphenylmethane type), Bis-C type (diphenylcyclohexane type), Bis-F type (diphenylfluorene type), bistriene type (triphenyl type), phenylenedioxy type, Bis (phenylenedioxy) type, fluorene type, spiro type, silicon type and the like are suitably used).

Examples of the aromatic triamine include 3, 4, 4 '-triaminodiphenyl ether (TrAB-E), 3, 4, 4' -triaminodiphenyl sulfone (TrAB-S), 3, 4, 4 '-triaminodiphenyl ketone (TrAB-K), 3, 4, 4' -triaminobiphenyl (TrABP), 1, 2, 4-triaminobenzene (TrAB), 3, 4, 4 '-triaminodiphenylmethane, 3, 4, 4' -triaminodiphenylcyclohexane, 3, 4, 4 '-triaminodiphenylfluorene, 3, 4, 4' -triaminodiphenylsulfide, 3, 4, 4 '-triaminodiphenylether, 3, 4, 4' -triaminodiphenylamide, and 3, 4, 4 ″ -triaminoterphenyl.

Examples of the alicyclic triamine include hydrogenated products of the above-mentioned various aromatic triamines (for example, 3, 4, 4 '-triaminodicyclohexyl ether, 3, 4, 4' -triaminodicyclohexylsulfone, 3, 4, 4 '-triaminodicyclohexyl ketone, 3, 4, 4' -triaminobicyclohexyl, 1, 2, 4-triaminocyclohexane, and the like), which are preferable.

Among these triamines, aromatic triamines are preferable from the viewpoint of heat resistance, and TrAB-E, TrAB-S, TrAB-K, TrABP and TrAB are more preferable, and TrAB-E, TrAB-S, TrAB-K is particularly preferable.

Further, X in the above formula (1-2) may be mentioned³Selected organic radicals having a valence of 3, fromFrom the viewpoint of mechanical strength, the group having a valence of 3 represented by the above general formulae (6-2) to (7-2) is preferable. Here, Z in the formula (7-2)¹Is selected from the group consisting of a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) -a group represented by and-N (C)₆H₅) -1 of the group consisting of the groups represented. Z as above¹Among them, from the viewpoint of satisfying both heat resistance and mechanical strength, an ether group and a single bond represented by — O — are preferable, and from the viewpoint of satisfying both transparency and mechanical strength, a carbonyl group and — S (O) represented by — C (O) -are preferable₂-a sulfonyl group represented. In the formulae (6-2) to (7-2), the bonding points with symbols 1 to 3 are each bonded to X³Any of the 3 bonding sites of the bond. The 3-valent group represented by the above general formulae (6-2) to (7-2) can be introduced into X as a residue obtained by removing 3 amino groups from the triamine by using an appropriately selected one (e.g., TrAB-E, TrAB-S, TrAB-K, TrABP, TrAB, etc.) from the triamine during the production of the repeating unit³The position of (a).

The repeating unit (a') represented by the general formula (1-2) can be efficiently introduced into the resin by, for example, reacting (polymerizing) the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring with the triamine. Therefore, the resin containing the repeating unit (a') represented by the general formula (1-2) is preferably a polymer of a first monomer containing the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and a second monomer containing the triamine.

The resin of the present invention preferably further contains a repeating unit having an imide structure represented by the above general formula (2) (hereinafter, this repeating unit having an imide structure may be simply referred to as "repeating unit (B)" for convenience).

Further, the present inventors presume that: when the resin of the present invention is a resin containing at least 1 repeating unit selected from the group consisting of the repeating units (A) and (A ') and the repeating unit (B), a cyclic moiety containing 2 nitrogen atoms (particularly preferably a moiety of an imidazole structure: further, when X is X), contained in the structure of at least 1 repeating unit selected from the group consisting of the repeating units (A) and (A') at the time of production thereof²、X³When each of the repeating units is aromatic, the structural moiety thereof may be an imidazole structure) functions as a self-catalyst in the production of the repeating unit (B) (when thermally imidized), and the reaction for forming the repeating unit (B) having an imide structure can be further promoted, and a copolymer containing the repeating unit (B) (a resin of the present invention containing at least 1 repeating unit selected from the group consisting of the repeating units (a) and (a'): reactant) has a higher molecular weight, and therefore, compared with the case of producing a resin composed only of the repeating unit (B), the strength, heat resistance and other properties of the resin containing the repeating unit (B) can be further improved, and a film more robust to tensile stress in particular can be obtained. In the resin (copolymer) containing the repeating units (a) and/or (a ') and the repeating unit (B), since the reaction for forming the repeating unit (B) can be promoted by the structure of the repeating unit (a) and/or (a') formed during the production of the copolymer, even if the total amount (content) of the repeating units (a) and (a ') is small, the resin (copolymer) can be produced in a more preferable manner than when the resin (copolymer) contains only the repeating unit (a) and/or (a') and the repeating unit (B)The resin composed of the repeating unit (B) can also produce a resin having higher characteristics.

X in the above-mentioned general formula (2)¹The 4-valent organic group which is an alicyclic structure having a 6-membered ring is a group represented by formula (1-1)¹Synonyms (and their preferences are the same).

X in the general formula (2)⁴Is an arylene group having 6 to 50 carbon atoms. The number of carbon atoms of the arylene group is preferably 6 to 40, more preferably 6 to 30, and further preferably 12 to 20. When the number of carbon atoms is less than the lower limit, the heat resistance of the resin tends to be lowered during the production of the resin, and when the number of carbon atoms exceeds the upper limit, the transparency of the resin tends to be lowered during the production of the resin.

X in the above general formula (2)⁴From the viewpoint of obtaining higher heat resistance and mechanical strength, at least one of the groups represented by the following general formulae (a) to (d) is preferable:

[ in the formula (c), R¹¹Represents 1 selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, an ethyl group, a hydroxyl group and a trifluoromethyl group, and in the formula (d), Q represents a group selected from the group consisting of a 9, 9-fluorenylidene group; formula (II): -O-, -S-, -CO-, -CONH-, -NHCO-, -SO₂-、-SO-、-C(CF₃)₂-、-O-C₆H₄-O-、-C(CH₃)₂-、-CH₂-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-O-C₆H₄-C(CF₃)₂-C₆H₄-O-、-O-C₆H₄-SO₂-C₆H₄-O-、-O-C₆H₄-CO-C₆H₄-O-、-C(CH₃)₂-C₆H₄-C(CH₃)₂-、-O-C₆H₄-C₆H₄-O-、-CONH-C₆H₄-NHCO-、-NHCO-C₆H₄-CONH-、-C₆H₄-and-O-C₆H₄-O-、-O-C₆H₄-O-C₆H₄A group represented by-O-, -COO-, -OCO-, -NH-CO-NH-, -N (Ph) -, -P (═ O) (Ph) -; 1, 1-cyclohexylidene; 1, 1-cyclopentylidene; and 1 kind of group composed of the following general formula (e):

(in the formula (e), R^aEach independently represents 1 of alkyl, phenyl and tolyl with 1-10 carbon atoms, and y represents an integer of 1-100. )]。

R in the above general formula (c)¹¹From the viewpoint of heat resistance, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable. Further, as R in the general formula (c)¹¹From the viewpoint of the linear expansion coefficient, a methyl group, a hydroxyl group, or a trifluoromethyl group is more preferable.

In the group represented by the general formula (e), R may be selected as Q in the general formula (d)^aEach independently represents 1 of an alkyl group having 1 to 10 carbon atoms, a phenyl group and a tolyl group. When the number of carbon atoms of the alkyl group exceeds the upper limit, the heat resistance and transparency of the resin tend to be lowered in the production of the resin. R as defined above^aPreferably, methyl, ethyl, propyl, isopropyl, phenyl, and tolyl are used, more preferably methyl and ethyl, and still more preferably methyl. In the general formula (e), y represents an integer of 1 to 100, preferably 3 to 50, and more preferably 5 to 25. When y is less than the lower limit, the mechanical strength tends to be lowered, and when y exceeds the upper limit, the heat resistance and transparency of the resin tend to be lowered in the production of the resin.

In addition, Q in the general formula (d) is preferably Q from the viewpoint of obtaining a cured product having heat resistance, transparency and mechanical strength in a more balanced manner at a sufficient levelIs 9, 9-fluorenylidene, formula: -CONH-, -NHCO-, -O-C₆H₄-O-、-O-、-C(CH₃)₂-、-C₆H₄-、-O-C₆H₄-SO₂-C₆H₄-O-、-O-C₆H₄-CO-C₆H₄-O-、-CH₂-、-O-C₆H₄-C₆H₄-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-SO₂A group represented by-SO-, -OCO-or-COO-, or a 1, 1-cyclohexylidene group; particularly preferred is 9, 9-fluorenylidene, or a compound of the formula: -CONH-, -NHCO-, -CH₂-、-O-C₆H₄-O-、-O-C₆H₄-C₆H₄-O-、-SO₂-, -OCO-, -COO-or-O-, most preferably 9, 9-fluorenylidene, or a group of the formula: -CONH-, -SO₂-、-OCO-、-COO-、-CH₂-or-O-. Further, Q in the general formula (d) is preferably a group represented by the general formula (e) from the viewpoint of adhesiveness or laser peelability, and is preferably a group represented by the formula: -OCO-, -COO-, -CONH-, -NHCO-.

In addition, from the viewpoint of obtaining a resin having heat resistance, transparency and mechanical strength in a more balanced manner at a sufficient level, X as described above⁴Preferably selected from the group consisting of 4, 4 ' -Diaminobenzanilide (DABAN), 4 ' -diaminodiphenyl ether (DDE), 2 ' -bis (trifluoromethyl) benzidine (TFMB), 9 ' -bis (4-aminophenyl) Fluorene (FDA), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, p-diaminobenzene (PPD), p-diaminotoluene, p-diaminoxylene, p-diaminotrimethylbenzene, p-diaminotetramethylbenzene, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl (also known as m-tolidine), 3 ' -dimethyl-4, 4 ' -diaminobiphenyl (alias: o-tolidine), 3 ' -dimethoxy-4, 4 ' -diaminobiphenyl (alias: dianisidine), 4 ' -diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4 ' -bis (4-aminogroup)The aromatic diamine may be at least 1 aromatic diamine selected from the group consisting of benzamide) -3, 3 ' -dihydroxybiphenyl (BABB), 3 ' -diaminodiphenyl sulfone (3, 3 ' -DDS), and 4, 4 ' -diaminodiphenyl sulfone (4, 4 ' -DDS), from which 2-valent groups (arylene groups) having 2 amino groups have been removed, more preferably at least 1 aromatic diamine selected from the group consisting of 4, 4 ' -Diaminobenzanilide (DABAN), 4 ' -diaminodiphenyl ether (DDE), 2 ' -bis (trifluoromethyl) benzidine (TFMB), 9 ' -bis (4-aminophenyl) Fluorene (FDA), m-tolidine (m-Tol), 4 ' -diamino-3, 3 ' -Dihydroxybiphenyl (DAHB), p-diaminobenzene (PPD), and 4-aminophenyl-4-aminobenzoic acid (baba) The 2-valent group (arylene group) obtained by removing 2 amino groups from an aromatic diamine is more preferably a 2-valent group (arylene group) obtained by removing 2 amino groups from at least 1 aromatic diamine selected from the group consisting of 4, 4 ' -Diaminobenzanilide (DABAN), 4 ' -diaminodiphenyl ether (DDE), and 2, 2 ' -bis (trifluoromethyl) benzidine (TFMB).

The repeating unit (B) represented by the above general formula (2) can be efficiently introduced into the resin by, for example, reacting (polymerizing) the tetracarboxylic dianhydride having the 6-membered ring alicyclic structure with a diamine. The tetracarboxylic dianhydrides having an alicyclic structure of 6-membered ring as described above are the same as those described above.

The diamine that can be used for introducing the repeating unit (B) represented by the general formula (2) into the resin is not particularly limited, and may be an aliphatic diamine or an aromatic diamine. As such a diamine, an aromatic diamine is preferable from the viewpoint of heat resistance and the simplicity of a polymerization method. The aromatic diamine is more preferably an aromatic diamine represented by the following general formula (iv). In addition, the diamines used herein may also be-NH-in order to improve the storage stability and stability of the varnish₂One of H in (A) is silanized to become a trimethylsilyl group or a tert-butyldimethylsilyl group.

H₂N-X⁴-NH₂ (iv)

[ formula (iv) wherein X⁴Represents an arylene group having 6 to 50 carbon atoms.]。

The above formula: h₂N-X⁴-NH₂The aromatic diamine is not particularly limited, and those known in the art and those commercially available can be suitably used. Examples of the aromatic diamine include 4, 4 '-diaminodiphenylmethane, 3' -diaminodiphenylmethane, 4 '-diaminodiphenylethane, 3' -diaminodiphenylethane, 4 '-diaminobiphenyl, 3' -diaminobiphenyl, 4 '-diaminodiphenylether, 3' -diaminodiphenylether, 3, 4 '-diaminodiphenylether, 2-bis (4-aminophenoxyphenyl) propane, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] benzene, bis [4, 4' -aminophenoxy ] phenyl ] benzene, and the like]Sulfone, bis [4- (3-aminophenoxy) phenyl]Sulfone, bis [4- (4-aminophenoxy) phenyl]Ketones, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene, 9-bis (3-chloro-4-aminophenyl) fluorene, 9-bis (3-bromo-4-aminophenyl) fluorene, 1-bis (4-aminophenyl) cyclohexane, 1-bis (4-aminophenyl) cyclopentane, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 4 '-diaminobiphenyl, 4' -diamino-2, 2 ' -dimethylbiphenyl, 4 ' -diamino-3, 3 ' -dimethylbiphenyl, 3, 3 ' -diaminobiphenyl, 2 ' -diaminobiphenyl, 3, 4 ' -diaminobiphenyl, 2, 6-diaminonaphthalene, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 4 ' - [1, 3-phenylenebis (1-methyl-ethylidene)]Bis-anilines, 4' - [1, 4-phenylenebis (1-methyl-ethylidene)]Dianiline, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -diaminobenzanilide, 3, 4 '-diaminobenzanilide, 9' -bis (4-aminophenyl) fluorene, o-toluene sulfone, p-toluylene, o-toluylene, 2, 3, 5, 6-tetramethyl-1, 4-phenylenediamine,3, 3 ', 5, 5 ' -tetramethylbenzidine, 1, 5-bis (4-aminophenoxy) pentane, 2-bis (4-aminophenoxyphenyl) hexafluoropropane, 2 ' -bis (trifluoromethyl) benzidine, 4-aminophenyl-4-aminobenzoic acid, 4 ' -bis (4-aminobenzamide) -3, 3 ' -dihydroxybiphenyl, and the like. The aromatic diamine may be used alone in 1 kind or in combination of 2 or more kinds.

When 2 or more aromatic diamines are used in combination, it is preferable to use a compound selected from 4, 4 '-Diaminobenzanilide (DABAN), 4' -diaminodiphenyl ether (DDE), 2 '-bis (trifluoromethyl) benzidine (TFMB), 9' -bis (4-aminophenyl) Fluorene (FDA), p-diaminobenzene (PPD), 2 '-dimethyl-4, 4' -diaminobiphenyl (also known as m-tolidine), 4 '-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4' -bis (4-aminobenzamide) -3, 3 '-dihydroxybiphenyl (BABB), 3' -diaminodiphenyl sulfone (3, 3 ' -DDS) and 4, 4 ' -diaminodiphenyl sulfone (4, 4 ' -DDS), and more preferably at least 2 selected from 4, 4 ' -Diaminobenzanilide (DABAN), 4 ' -diaminodiphenyl ether (DDE), 2 ' -bis (trifluoromethyl) benzidine (TFMB), 9 ' -bis (4-aminophenyl) Fluorene (FDA), p-diaminobenzene (PPD), 4-aminophenyl-4-aminobenzoic acid (BAAB), 3 ' -diaminodiphenyl sulfone (3, 3 ' -DDS) and 4, 4 ' -diaminodiphenyl sulfone (4, 4 ' -DDS) are used. When 2 or more aromatic diamines are used in combination, the aromatic diamines more preferably contain at least 1 selected from the group consisting of a combination of 4, 4 '-Diaminobenzanilide (DABAN) and 4, 4' -diaminodiphenyl ether (DDE), a combination of 4, 4 '-Diaminobenzanilide (DABAN) and 2, 2' -bis (trifluoromethyl) benzidine (TFMB), a combination of 4, 4 '-Diaminobenzanilide (DABAN) and p-diaminobenzene (PPD), a combination of 3, 3' -diaminodiphenyl sulfone (3, 3 '-DDS) and 4, 4' -diaminodiphenyl sulfone (4, 4 '-DDS), a combination of 4-aminophenyl-4-aminobenzoic acid (BAAB) and 2, 2' -bis (trifluoromethyl) benzidine (TFMB), and a combination of 4-aminophenyl-4-aminobenzoic acid (BAAB) and p-diaminobenzene (PPD) And (4) combining.

As described above, the repeating unit (B) can be introduced into the resin more efficiently by reacting (polymerizing) the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with the diamine. Therefore, the resin of the present invention containing the repeating unit (B) is preferably a polymer of a first monomer containing the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring (other tetracarboxylic dianhydrides and the like may be contained together with the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring) and a second monomer (amine component) containing tetramine and/or triamine and diamine.

In the resin of the present invention, the total amount (content) of the repeating unit (a) and the repeating unit (a') is not particularly limited, and is preferably 3 to 100 mol%, more preferably 5 to 50 mol%, based on the molar ratio of all the repeating units contained in the resin. When the molar ratio is less than the lower limit, the obtained resin may not necessarily be sufficiently endowed with the properties derived from the repeating units (a) and/or (a'). Further, a so-called ladder-like structure can be formed by at least 1 kind of repeating unit selected from the group consisting of the repeating unit (a) and the repeating unit (a'), and a resin containing the repeating unit can impart higher heat resistance based on the structure.

The resin of the present invention preferably further contains the repeating unit (B) as described above. As described above, the resin of the present invention is preferably a copolymer containing at least 1 kind of repeating unit selected from the group consisting of the repeating units (a) and (a') and the repeating unit (B). In the case of containing the repeating unit (B) in this way, the total amount (total amount) of the repeating unit (a), the repeating unit (a'), and the repeating unit (B) is preferably 20 to 100 mol% (more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, further preferably 50 to 100 mol%, and particularly preferably 60 to 100 mol%) with respect to all the repeating units. The lower limit of the numerical range is more preferably 70 mol%, still more preferably 80 mol%, and most preferably 90 mol% of the total amount (total amount) of the repeating unit (a), the repeating unit (a'), and the repeating unit (B). When the total amount (total amount) of the repeating units is less than the lower limit, high heat resistance tends not to be imparted.

When the resin of the present invention is a copolymer containing at least 1 kind of repeating unit selected from the group consisting of the repeating units (a) and (a ') and the repeating unit (B), the content of the repeating unit (B) is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, and particularly preferably 10 to 90 mol% based on the total amount (total amount) of the repeating unit (a), the repeating unit (a'), and the repeating unit (B). When the content (molar ratio) of the repeating unit (B) relative to the total amount of the repeating unit (a), the repeating unit (a'), and the repeating unit (B) is less than the lower limit, it tends to be difficult to obtain higher properties in terms of transparency and dimensional stability, while when it exceeds the upper limit, it tends to be difficult to obtain higher properties in terms of high heat resistance and mechanical properties.

The resin of the present invention as described above is not particularly limited as long as it contains at least 1 kind of repeating unit selected from the group consisting of the repeating units (a) and (a '), and may be, for example, a resin containing the repeating unit (a) and the repeating unit (a '), or a resin containing the repeating unit (a) and the repeating unit (a ') and the repeating unit (B). Further, the resin of the present invention may contain a repeating unit other than the repeating unit (a), the repeating unit (a'), and the repeating unit (B). Examples of the other repeating units include repeating units formed by the reaction of a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with at least 1 selected from the group consisting of diamines, triamines and tetraamines; a repeating unit formed by a reaction of the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring with a polyfunctional alcohol, a polyfunctional phenol, a polyfunctional thiol, or a polyfunctional thiophenol, and the like. The other tetracarboxylic dianhydrides include, but are not particularly limited to, pyromellitic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 3 ', 4, 4' -biphenylsulfonetetracarboxylic dianhydride, and 1, 4, 5, 8Naphthalene tetracarboxylic dianhydride, 2, 3, 6, 7-naphthalene tetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 3 ', 4, 4 ' -dimethyldiphenylsilane tetracarboxylic dianhydride, 3 ', 4, 4 ' -tetraphenylsilane tetracarboxylic dianhydride, 1, 2, 3, 4-furantetracarboxylic dianhydride, 4, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3 ', 4, 4 ' -perfluoroisopropylidene dibenzoic dianhydride, 4, 4 ' - (2, 2-hexafluoroisopropylidene) dibenzoic dianhydride, 3, aromatic tetracarboxylic acid dianhydrides such as 3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 2, 3, 3 ', 4' -biphenyltetracarboxylic acid dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4, 4 '-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4, 4' -diphenylmethane dianhydride; butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, cyclooctane tetracarboxylic dianhydride, cyclononane tetracarboxylic dianhydride, cyclodecane tetracarboxylic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 3- (carboxymethyl) -1, 2, 4-cyclopentanetricarboxylic acid 1, 4: 2, 3-dianhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 4- (2, 5-dioxotetrahydrofuryl-3-yl) -1, 2, 3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, tricyclo [6.4.0.0 ]^2，7]Dodecane-1, 8: aliphatic or alicyclic tetracarboxylic dianhydrides such as 2, 7-tetracarboxylic dianhydride, trans-isomer of cyclopentane-1, 2, 3, 4-tetracarboxylic dianhydride, cis-isomer of cyclopentane-1, 2, 3, 4-tetracarboxylic dianhydride, trans-isomer of cyclobutane-1, 2, 3, 4-tetracarboxylic dianhydride, and cis-isomer of cyclobutane-1, 2, 3, 4-tetracarboxylic dianhydride.

The polyfunctional alcohol, the polyfunctional phenol, the polyfunctional thiol, and the polyfunctional thiophenol are not particularly limited, and examples thereof include aliphatic diols, alicyclic diols, diphenols, bisphenols, aliphatic dithiols, alicyclic dithiols, and dithiols.

Further, at least 1 kind of repeating unit selected from the group consisting of the repeating unit (a) and the repeating unit (a') may be formed by reacting the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with the amine component, and may be formed by reacting at least 1 kind of diester dicarboxylic acid and diester dicarboxylic acid dichloride, which are derivatives (modified products) of the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring, with at least 1 kind of amine component selected from the group consisting of the triamine and the tetramine. Further, at least 1 kind of repeating unit selected from the group consisting of the repeating unit (a) and the repeating unit (a') may be formed by reacting the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with an equivalent of at least 1 kind of amine component selected from the group consisting of the derivative of triamine and the derivative of tetramine.

Regarding the diester dicarboxylic acid and the diester dicarboxylic acid dichloride which are derivatives (modified products) of the tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring, for example, when the diester dicarboxylic acid is prepared as the derivative, a method of obtaining the corresponding diester dicarboxylic acid by reacting the tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring with an arbitrary alcohol can be used, and when the diester dicarboxylic acid dichloride is prepared as the derivative, a method of obtaining the diester dicarboxylic acid dichloride by reacting the tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring with an arbitrary alcohol and then reacting the diester dicarboxylic acid with a chlorinating agent (thionyl chloride, oxalyl chloride, etc.) can be used.

Further, examples of the triamine derivative and the tetramine derivative include silanized tetramine and/or silanized triamine obtained by reacting at least 1 compound selected from the group consisting of the triamine and the tetramine with a silanizing agent. For example, the triamine may contain-NH-of the triamine₂Compounds in which one of the radicals H is silanized to form a trimethylsilyl or tert-butyldimethylsilyl groupAnd the like. Examples of the silylated tetraamines include tetrasilyl derivatives such as TAB-E, TAB-S, TAB-K, TABP and TAB, and examples of the silylated triamines include trimethylsilyl derivatives such as TrAB-E, TrAB-S, TrAB-K, TrABP and TrAB. Examples of the silylation agent include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, hexamethyldisilazane, and trimethylsilyl chloride. The method for producing such a silylated amine is also not particularly limited, and a known method can be suitably employed. Further, commercially available silanized amines can be suitably used.

The repeating unit (B) may be formed by reacting a diester dicarboxylic acid or a diester dicarboxylic acid dichloride, which is a derivative (modified product) of the tetracarboxylic dianhydride having an alicyclic structure having 6-membered rings, with at least 1 amine component selected from the diamines, in addition to the reaction between the tetracarboxylic dianhydride having an alicyclic structure having 6-membered rings and the diamine. Further, the repeating unit (B) may be formed by reacting the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with the diamine derivative.

The diamine derivative includes a silylated diamine obtained by reacting the diamine with a silylating agent, and examples thereof include a diamine represented by the formula: h₂N-X⁴-NH₂The aromatic diamine represented by (a) is reacted with a silylating agent to obtain a silylated diamine. Examples of the silylated diamine include disilyl derivatives such as DDE, TFMB, FDA, PPD, and m-tolidine. Examples of the silylation agent include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, hexamethyldisilazane, and trimethylsilyl chloride. The method for producing such a silylated diamine is also not particularly limited, and a known method can be suitably employed. Further, commercially available products of such silylated diamines can be suitably used.

The resin of the present invention preferably has a glass transition temperature (Tg) of 300 ℃ or higher, more preferably 300 to 550 ℃, and still more preferably 350 to 500 ℃. When the glass transition temperature (Tg) is lower than the lower limit, it tends to be difficult to achieve a high level of heat resistance, while when it exceeds the upper limit, it tends to be difficult to produce a resin having the above characteristics. The glass transition temperature (Tg) can be measured in a tensile mode using a thermomechanical analyzer (trade name "TMA 8311" manufactured by Rigaku). That is, a resin film having a size of 20mm in the vertical direction and 5mm in the horizontal direction (the thickness of the film is not particularly limited since it does not affect the measured value, but is preferably 5 to 100 μm) can be formed as a measurement sample, and the measurement is performed under a nitrogen atmosphere under the conditions of a stretching mode (49mN) and a temperature rise rate of 5 ℃/min, and the curve before and after the inflection point of the TMA curve due to the glass transition is extrapolated.

In addition, as the resin, 5% weight reduction temperature is preferably 450 ℃ or more, more preferably 460 to 550 ℃, and even more preferably 470 to 530 ℃. When the above-mentioned 5% weight reduction temperature is lower than the lower limit, it tends to be difficult to achieve sufficient heat resistance, while when it exceeds the upper limit, it tends to be difficult to produce a resin having the above-mentioned properties. The above-mentioned 5% weight loss temperature can be determined by gradually heating the sample from room temperature (e.g., 30 ℃) while flowing nitrogen gas under a nitrogen atmosphere and measuring the temperature at which the weight of the sample used is reduced by 5%.

Further, the softening temperature of the resin is preferably 300 ℃ or higher, more preferably 350 to 550 ℃, and still more preferably 400 to 500 ℃. When the softening temperature is lower than the lower limit, it tends to be difficult to achieve sufficient heat resistance, while when it exceeds the upper limit, it tends to be difficult to produce a resin having the above-described properties. The softening temperature can be measured by a penetration mode using a thermomechanical analyzer (trade name "TMA 8311" manufactured by Rigaku). In the measurement, the size of the sample (vertical, horizontal, thickness, etc.) does not affect the measured value, and therefore, the size of the sample may be appropriately adjusted to a size that can be mounted on a jig of a thermomechanical analyzer (product name "TMA 8311" manufactured by Rigaku).

The elongation at break of the resin is preferably 3% or more, more preferably 5% or more, and particularly preferably 7% or more. When the elongation at break point is less than the lower limit, toughness tends to be low and mechanical properties tend to be brittle. The tensile strength of the resin of the present invention is preferably 50MPa or more, more preferably 70MPa or more, and particularly preferably 100MPa or more. When the tensile strength is less than the lower limit, a film having higher toughness cannot be obtained. The upper limit of the tensile strength of the resin is not particularly limited, but is preferably 1000MPa or less. When the tensile strength is above the upper limit, the processing tends to be difficult. The values of tensile strength and elongation at break as described above can be determined by tests in accordance with JIS K7162 (published in 1994), and can be determined as follows, for example. That is, first, in addition to setting the thickness to 10 μm, a test piece was prepared in accordance with the standard of model a22 (reduced-size test piece) described in JIS K7139 (published in 2009), the measurement sample was arranged so that the width between the jigs was 57mm and the width of the clamped portion was 10mm (the full width of the end portion of the test piece) using an electromechanical universal material testing machine (for example, model "5943" made by INSTRON), and then a tensile test in which the measurement sample was pulled was performed under the conditions of a load cell of 1.0kN and a test speed of 5 mm/min, and the values of the tensile strength (stress at break [ unit: MPa ]) and the elongation at break (unit:%) thus obtained were used.

The coefficient of linear expansion (CTE) of the resin is preferably-50 to 100ppm/K, more preferably 0 to 50 ppm/K. When the linear expansion coefficient exceeds the upper limit, peeling tends to occur easily due to the thermal history when the composite is formed by combining the metal or inorganic substance having a linear expansion coefficient in the range of 5 to 20 ppm/K. When the linear expansion coefficient is less than the lower limit, peeling tends to occur easily due to the thermal history even when the composite is formed by combining with a metal or an inorganic material. As a method for measuring the linear expansion coefficient of the resin, the following method is used. That is, first, a film made of the resin and having a size of 20mm in the longitudinal direction and 5mm in the transverse direction (the thickness of the film is not particularly limited since it does not affect the measured value, but is preferably 5 to 100 μm) is formed as a measurement sample, a change in the longitudinal direction length of the sample at 50 to 200 ℃ is measured using a thermomechanical analyzer (trade name "TMA 8311" manufactured by Rigaku) as a measurement device under a nitrogen atmosphere in a stretching mode (49mN), and under a nitrogen atmosphere, conditions of the stretching mode (49mN) and a temperature rise rate of 5 ℃/min are employed to obtain an average value of the length change per 1 ℃ in a temperature range of 50 to 200 ℃, and the obtained value is used.

The resin is preferably a resin having sufficiently high transparency when formed into a film, and more preferably a resin having a total light transmittance of 80% or more (more preferably 83% or more, particularly preferably 85% or more). Such a total light transmittance can be easily achieved by appropriately selecting the type of the organic group of the repeating unit in the resin, the content thereof, and the like. Further, from the viewpoint of obtaining higher colorless transparency, the resin is more preferably a resin having a haze (haze) of 5 to 0 (more preferably 4 to 0, particularly preferably 3 to 0). When the haze value exceeds the upper limit, it tends to be difficult to achieve a higher level of colorless transparency. Further, from the viewpoint of obtaining higher colorless transparency, the resin having a Yellowness (YI) of 10 to 0 (more preferably 8 to 0, and particularly preferably 6 to 0) is more preferable. When the above-mentioned yellowness index exceeds the above upper limit, it tends to be difficult to achieve a higher level of colorless transparency. The total light transmittance, haze (turbidity) and Yellowness (YI) described above can be measured using a measurement device of the trade name "haze meter NDH-5000" manufactured by Nippon Denshoku industries Co., Ltd or the trade name "spectrocolorimeter SD 6000" manufactured by Nippon Denshoku industries Co., Ltd (the total light transmittance and haze are measured using the trade name "haze meter NDH-5000" manufactured by Nippon Denshoku industries Co., Ltd, and the yellowness is measured using the trade name "spectrocolorimeter SD 6000" manufactured by Nippon Denshoku industries Ltd.), using a film made of the above resin and having a thickness of 10 μm as a measurement sample, and the values thus measured are used. The vertical and horizontal sizes of the measurement sample may be changed as long as they are dimensions (5cm square or more) of a measurement site that can be placed in the measurement device. The total light transmittance is determined by measurement according to JIS K7361-1 (published 1997), the haze (turbidity) is determined by measurement according to JIS K7136 (published 2000), and the Yellowness (YI) is determined by measurement according to ASTM E313-05 (published 2005).

The resin may further contain various additives used according to the purpose of the resin, or components (e.g., catalysts) used in the production of the resin, other resins, and the like, as long as the effects of the present invention are not impaired, and examples thereof include an imidization accelerating catalyst, a chemical imidizing agent, an antioxidant (e.g., phenol-based, phosphite-based, and thioether-based resins), an ultraviolet absorber, a hindered amine-based light stabilizer, a nucleating agent, a resin additive (e.g., a filler made of an inorganic compound such as nano silica, talc, glass fibers, and alumina fibers), a coupling agent (e.g., a silane coupling agent), a processability improver, a lubricant, a dye, a pigment, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, and an undercoating agent. When other resins are contained (at the time of addition), other resins such as cellulose nanofibers, nylon, polycarbonate, polyester, polyamide, polyketone, polyetherketone, polysulfone, polyethersulfone, PMMA, polyethylene, polypropylene, polystyrene, teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, and Triacetylcellulose (TAC) can be used.

Next, the resin precursor of the present invention will be described. The resin precursor of the present invention contains at least 1 kind of repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone precursor structure represented by the above general formula (8-1) (hereinafter, this repeating unit having an imidazopyrrolone precursor structure may be referred to simply as "repeating unit (C)" for convenience) and a repeating unit having an imidazopyrrolone precursor structure represented by the above general formula (8-2) (hereinafter, this repeating unit having an imidazopyrrolone precursor structure may be referred to simply as "repeating unit (C')" for convenience).

X in the above-mentioned general formula (8-1) and general formula (8-2)¹4-valent organic groups each having an alicyclic structure with 6-membered rings, and X in the above general formulae (1-1) and (1-2)¹Synonyms (and their preferences are the same). Further, X in the above general formula (8-1)²Represents a 4-valent organic group, and X in the above general formula (1-1)²Synonyms (and their preferences are the same). Further, X in the above general formula (8-2)³Represents a 3-valent organic group, and X in the above general formula (1-2)³Synonyms (and their preferences are the same).

The at least 1 repeating unit selected from the group consisting of the repeating unit represented by the general formula (8-1) and the repeating unit represented by the general formula (8-2) can be formed, for example, by the reaction between the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and tetramine and/or the reaction between the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and triamine. Furthermore, the repeating unit represented by the desired general formula (8-1) and/or general formula (8-2) can be introduced into the resin by appropriately selecting the monomer component in accordance with the design of the object.

The resin precursor of the present invention preferably further contains a repeating unit having an imide precursor structure represented by the above general formula (9) (hereinafter, this repeating unit having an imide precursor structure may be simply referred to as "repeating unit (D)" for convenience).

X in the above-mentioned general formula (9)¹A 4-valent organic group which is an alicyclic structure having a 6-membered ring, and X in the above general formulae (1-1) and (1-2)¹Synonyms (and their preferences are the same). In addition, X in the above general formula (9)⁴Is an arylene group having 6 to 50 carbon atoms and X in the general formula (2)⁴Synonyms (and their preferences are the same).

The repeating unit represented by the above general formula (9) can be obtained, for example, by reacting the tetracarboxylic dianhydride having the above 6-membered ring alicyclic structure with the aromatic diamine represented by the above general formula (iv). Further, the repeating unit represented by the desired general formula (9) can be introduced into the resin by appropriately selecting the monomer component in accordance with the design of the object.

In the resin precursor of the present invention, the total amount (content) of the repeating unit (C) and the repeating unit (C') is not particularly limited, and is preferably 3 to 100 mol%, more preferably 5 to 50 mol%, based on the molar ratio, of all the repeating units contained in the resin. When the molar ratio is less than the lower limit, the resin obtained by using the resin precursor does not necessarily have sufficient properties derived from the repeating unit (a) and/or the repeating unit (a').

The resin precursor of the present invention preferably further contains the repeating unit (D). As described above, the resin precursor of the present invention is preferably a copolymer containing at least 1 kind of repeating unit selected from the group consisting of the repeating unit (C) and the repeating unit (C') and the repeating unit (D). In the case of containing the repeating unit (D) in this way, the total amount (total amount) of the repeating unit (C), the repeating unit (C') and the repeating unit (D) is preferably 20 to 100 mol% (more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, further preferably 50 to 100 mol%, particularly preferably 60 to 100 mol%) with respect to all the repeating units. The lower limit of the numerical range is more preferably 70 mol%, still more preferably 80 mol%, and most preferably 90 mol% with respect to the total amount (total amount) of the repeating unit (C), the repeating unit (C'), and the repeating unit (D). When the total amount (total amount) of the repeating units is less than the lower limit, the resin obtained by using the resin precursor does not necessarily have sufficient properties of at least 1 repeating unit selected from the group consisting of the repeating unit (a) and the repeating unit (a') and the repeating unit (B).

When the resin precursor of the present invention is a copolymer containing at least 1 kind of repeating unit selected from the group consisting of the repeating unit (C) and the repeating unit (C ') and the repeating unit (D), the content of the repeating unit (D) is preferably 1 to 99 mol%, more preferably 25 to 95 mol%, and particularly preferably 50 to 90 mol% based on the total amount (total amount) of the repeating unit (C), the repeating unit (C'), and the repeating unit (D). When the content (molar ratio) of the repeating unit (D) relative to the total amount of the repeating unit (C), the repeating unit (C ') and the repeating unit (D) is less than the lower limit, the resin obtained by using the resin precursor tends not to be sufficiently endowed with the properties derived from the repeating unit (B), while when the content exceeds the upper limit, the resin obtained by using the resin precursor tends not to be sufficiently endowed with the properties derived from the repeating unit (a) and/or the repeating unit (a').

The resin precursor of the present invention as described above is not particularly limited as long as it contains at least 1 kind of repeating unit selected from the group consisting of the repeating units (C) and (C '), and for example, the resin precursor may contain the repeating unit (C) and the repeating unit (C '), or may contain the repeating unit (C) and/or the repeating unit (C ') and the repeating unit (D). The resin precursor of the present invention may further contain a repeating unit other than the repeating unit (C), the repeating unit (C'), and the repeating unit (D). As such other repeating units, there can be used: a repeating unit formed by reacting a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with at least 1 selected from the group consisting of diamines, triamines and tetramines; a repeating unit formed by the reaction of at least 1 kind selected from the group consisting of diester dicarboxylic acids and diester dicarboxylic acid dichlorides, which are derivatives (modified products) of the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring, with at least 1 kind selected from the group consisting of diamines, triamines, and tetramines; a repeating unit capable of being formed by a reaction of the tetracarboxylic dianhydride having an alicyclic structure of 6-membered ring with a polyfunctional alcohol, a polyfunctional phenol, a polyfunctional thiol, or a polyfunctional thiophenol; a repeating unit capable of being formed by the reaction of the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and at least 1 selected from the group consisting of the triamine derivative and the tetramine derivative; and so on.

The resin precursor may contain various additives, components (e.g., catalysts) used in the production of the resin, other resins, etc., depending on the use of the finally formed resin, and may contain, for example, an imidization accelerating catalyst, a chemical imidizing agent, an antioxidant (phenol-based, phosphite-based, thioether-based, etc.), an ultraviolet absorber, a hindered amine-based light stabilizer, a nucleating agent, a resin additive (a filler made of an inorganic compound such as nano silica, talc, glass fiber, alumina fiber, etc.), a coupling agent (a silane coupling agent, etc.), a processability improver, a lubricant, a dye, a pigment, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (a flow assistant), a release agent, a primer, etc., within a range not to impair the effects of the present invention. When other resins are contained (at the time of addition), other resins such as cellulose nanofibers, nylon, polycarbonate, polyester, polyamide, polyketone, polyetherketone, polysulfone, polyethersulfone, PMMA, polyethylene, polypropylene, polystyrene, teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, and Triacetylcellulose (TAC) can be used.

Hereinafter, a method that can be suitably used as a method for producing the resin and the resin precursor of the present invention as described above will be described. Since the resin precursor of the present invention can be obtained as a reaction intermediate in the production of the resin of the present invention, a method that can be suitably used as a method for producing the resin precursor of the present invention will be described below together with a method for suitably using the method for producing the resin precursor of the present invention.

The method that can be suitably used for producing the resin of the present invention is not particularly limited, and for example, a production method (I) of a resin comprising the following steps can be suitably used:

a step (a) in which a resin precursor (the resin precursor of the present invention) containing at least 1 kind of repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone precursor structure represented by the general formula (8-1) and a repeating unit having an imidazopyrrolone precursor structure represented by the general formula (8-2) is obtained by reacting a first monomer containing the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with a second monomer containing at least 1 kind of the tetramine and the triamine in the presence of an organic solvent; and

and (B) a step (B) of heating the resin precursor to obtain a resin (the resin of the present invention) containing at least 1 repeating unit selected from the group consisting of the repeating unit having an imidazopyrrolone structure represented by the general formula (1-1) and the repeating unit having an imidazopyrrolone structure represented by the general formula (1-2).

Hereinafter, the method (I) for producing a resin, which is a method suitably used for producing a resin of the present invention, will be described as being divided into the step (a) and the step (B).

< Process (A) >

The step (a) is a step of obtaining a resin precursor (preferably, the resin precursor of the present invention) by reacting a first monomer containing the tetracarboxylic dianhydride having the 6-membered ring and the at least 1 second monomer containing the tetramine and the triamine, in the presence of an organic solvent.

The first monomer used in the above-mentioned step may be any one as long as it is a tetracarboxylic dianhydride containing the 6-membered ring alicyclic structure, and a derivative of the 6-membered ring alicyclic structure tetracarboxylic dianhydride, another tetracarboxylic dianhydride other than the 6-membered ring alicyclic structure tetracarboxylic dianhydride, and the like can be suitably used in accordance with the intended structures of the resin precursor and the resin of the present invention. For example, when a repeating unit other than the repeating unit (C) and the repeating unit (C') is introduced into the resin precursor of the present invention, the resin precursor may contain, for example, the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and a derivative thereof (for example, diester dicarboxylic acid and diester dicarboxylic acid dichloride which are modified products of the tetracarboxylic dianhydride), or may contain another tetracarboxylic dianhydride other than the above. In addition, for example, when a diester dicarboxylic acid or a diester dicarboxylic acid dichloride is used as the derivative of the tetracarboxylic dianhydride having the alicyclic structure having a 6-membered ring and a diamine is reacted with the tetracarboxylic dianhydride, other repeating units derived from the diester group in the derivative and the group represented by — COOH in the general formula (9) in which H is substituted with a methyl group, an ethyl group, or the like may be introduced. When the varnish contains other repeating units in which H in the group represented by-COOH in the general formula (9) is substituted with a methyl group, an ethyl group or the like, the varnish can be improved in storage stability and stability.

The second monomer used in the above-mentioned step may be any monomer containing 1 of the tetraamines and the triamines, and may suitably contain tetraamines other than the tetraamines and the triamines, diamines, and triamines, depending on the intended structures of the resin precursor and the resin of the present invention. For example, when the resin precursor of the present invention contains a repeating unit represented by the above general formula (8-1) and/or a repeating unit represented by the above general formula (8-2) and further contains a repeating unit having an imide precursor structure represented by the above general formula (9) (when the resin precursor of the present invention finally obtained contains a repeating unit represented by the above general formula (8-1) and/or a repeating unit represented by the above general formula (8-2) and further contains a repeating unit having an imide precursor structure represented by the above general formula (9)), the aromatic diamine represented by the above general formula (iv) may be further contained. Further, as the tetraamine and the other tetraamines, diamines, and other triamines other than the above-mentioned triamines, for example, a silylated diamine obtained by silylating an aromatic diamine represented by the general formula (iv) can be used, and in this case, a repeating unit in which H of a group represented by — COOH in the general formula (9) is substituted with a silyl group can be formed. This also improves the storage stability of the varnish.

As the organic solvent used in the above-mentioned step, a known solvent that can be used at the time of polymerization can be suitably used, and among them, an organic solvent that can dissolve both the first monomer and the second monomer is preferable. Examples of such organic solvents include: aprotic polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, γ -valerolactone, γ -caprolactone, -valerolactone, -caprolactone, α -methyl- γ -butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, tetramethylurea (tetramethylurea), 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, and pyridine; phenol solvents such as m-cresol, p-cresol, xylenol, phenol, and halogenated phenol; ether solvents such as tetrahydrofuran, dioxane, cellosolve, and ethylene glycol dimethyl ether (glyme); aromatic solvents such as benzene, toluene and xylene; nitrile solvents such as acetonitrile and benzonitrile; acetate solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and propylene glycol methyl acetate; ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, and acetone.

In addition, from the viewpoints of solubility, film-forming properties, productivity, industrial availability, presence or absence of existing facilities, price, and the like, the organic solvents are preferably N-methyl-2-pyrrolidone, N-dimethylacetamide, γ -butyrolactone, propylene carbonate, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone; more preferably N-methyl-2-pyrrolidone, N-dimethylacetamide, gamma-butyrolactone, tetramethylurea; n, N-dimethylacetamide and gamma-butyrolactone are particularly preferable. Further, the organic solvent can be used alone in 1 kind, or in combination of 2 or more kinds.

In the step (a), as a method for reacting the first monomer with the second monomer, a method capable of performing a polymerization reaction of the first monomer with the second monomer can be suitably used, and is not particularly limited, and for example, the following method is preferably employed: the first monomer and the second monomer are added to the organic solvent at a reaction temperature in an inert atmosphere such as nitrogen, helium, or argon to carry out a reaction. In this way, the reaction in an inert atmosphere tends to allow the finally obtained resin to sufficiently exhibit the characteristics derived from the repeating units.

The pressure conditions for reacting the first monomer and the second monomer as described above are not particularly limited, and may be appropriately set within a range in which the first monomer and the second monomer can be reacted, and from the viewpoint of not requiring pressure control and being a simpler process, it is more preferable to react the first monomer and the second monomer under atmospheric pressure.

The temperature condition for reacting the first monomer with the second monomer is not particularly limited as long as it is appropriately set on the basis of the monomer that can be used to form the moiety (repeating unit) having the imidazopyrrolone precursor structure represented by the general formula (8-1) and/or the moiety (repeating unit) having the imidazopyrrolone precursor structure represented by the general formula (8-2) by reacting these monomers, but is preferably set to-20 to 100 ℃ (more preferably 5 to 80 ℃). The reaction time for reacting the first monomer and the second monomer is preferably set to about 1 to 72 hours (more preferably 3 to 48 hours). When the reaction temperature or the reaction time is lower than the lower limit, the molecular weight of the resin precursor tends not to be sufficiently increased. When the reaction temperature or the reaction time exceeds the upper limit, the resin precursor may be depolymerized by the monomer species to lower the molecular weight, or may be insolubilized (gelled or precipitated) by crosslinking, and therefore the reaction temperature and the reaction time are preferably set within the above ranges.

The content of each component in the first monomer and the second monomer may be appropriately set according to the target design (for example, the type of the repeating unit of the target resin). In the reaction of the first monomer and the second monomer, a catalyst (for example, trimethylamine, triethylamine, tributylamine, imidazole, methylimidazole, dimethylimidazole, tetrahexylamine, 1, 8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, α -picoline, and the like as a basic compound), triphenyl phosphite, triphenyl phosphate, triphenylphosphine oxide, imidazole-based amino acids, and the like as a phosphorus-based compound, may be appropriately used as necessary. The total amount (total amount) of the first monomer and the second monomer is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, based on the total amount (mass of the organic solvent, the mixed solution of the first monomer and the second monomer) of the organic solvent, the first monomer and the second monomer. When the total amount (total amount) of the first monomer and the second monomer is less than the lower limit, the reaction rate tends to be low and the resin precursor having a sufficient polymerization degree cannot be obtained, while when it exceeds the upper limit, the following tendency is exhibited: the monomer is not completely dissolved, and the reaction rate is locally increased, so that a crosslinking reaction or the like proceeds, and a uniform resin precursor cannot be obtained.

The resin precursor of the present invention can be obtained by the above-mentioned step (a). In the step (a), since the resin precursor of the present invention is prepared in an organic solvent by carrying out a reaction in the organic solvent, a reaction solution obtained after the reaction is a reaction solution (solution) containing the organic solvent and the resin precursor of the present invention. The resin of the present invention can be produced more efficiently by using the reaction solution thus obtained as it is in the step (B).

< Process (B) >

The step (B) is a step of heating the resin precursor to obtain a resin (the resin of the present invention) containing at least 1 kind of repeating unit selected from the group consisting of the repeating unit having an imidazopyrrolone structure represented by the general formula (1-1) and the repeating unit having an imidazopyrrolone structure represented by the general formula (1-2).

Further, both the repeating unit having an imidazopyrrolone precursor structure represented by the above general formula (8-1) and the repeating unit having an imidazopyrrolone precursor structure represented by the above general formula (8-2) can be subjected to intramolecular condensation through the above-mentioned heating step, thereby cyclizing the structure of the repeating units. Therefore, the repeating unit having an imidazopyrrolone structure represented by the general formula (1-1) and/or the repeating unit having an imidazopyrrolone structure represented by the general formula (1-2) can be formed more efficiently by heating the resin precursor. Further, the repeating unit having an imide precursor structure represented by the above general formula (9) may be subjected to intramolecular condensation through the above-mentioned heating step, whereby the structure of the repeating unit may be cyclized to be imidized, and the repeating unit having an imide structure represented by the above general formula (2) may be formed. Therefore, for example, even when the resin precursor is a resin precursor containing a repeating unit having an imidazopyrrolone precursor structure represented by the general formula (8-1) and/or a repeating unit having an imidazopyrrolone precursor structure represented by the general formula (8-2) and a repeating unit having an imide precursor structure represented by the general formula (9), the resin containing a repeating unit having an imidazopyrrolone structure represented by the general formula (1-1) and/or a repeating unit having an imidazopyrrolone structure represented by the general formula (1-2) and a repeating unit having an imide structure represented by the general formula (2) can be efficiently produced by simultaneously performing intramolecular condensation reactions of the respective repeating units in the resin precursor by heating. In addition, when the heat treatment is performed as described above, since the molecular chain of the resin precursor molecules can be repolymerized and the resin precursor molecules can be subjected to intramolecular condensation, the molecular weight can be further increased.

The conditions for carrying out the above-mentioned heat treatment are not particularly limited, but the heating temperature is preferably 50 to 550 ℃ (more preferably 75 to 500 ℃, and still more preferably 100 to 450 ℃), and the heating time is preferably 0.1 to 50 hours ((more preferably 0.5 to 10). when the above-mentioned heating temperature and heating time are lower than the above-mentioned lower limit, water, alcohol, silanol, or the like generated by intramolecular condensation in each repeating unit in the resin precursor cannot be distilled off efficiently, the reaction is inhibited, the molecular weight of the obtained resin is difficult to increase, and when the above-mentioned upper limit is exceeded, thermal decomposition or coloration tends to occur easily CsF), a toluene azeotropic method, a chemical imidization method, a partial chemical imidization method, and the like.

The atmosphere conditions during the above-mentioned heat treatment are not particularly limited, and from the viewpoint of preventing oxidation of the terminal amino group by oxygen, main chain cleavage, coloration, or deterioration, it is preferable to set the atmosphere to an inert gas atmosphere such as nitrogen or vacuum.

The pressure conditions in the heat treatment are not particularly limited, but are preferably 0.1hPa to 10MPa, and more preferably 10hPa to 1 MPa. When the pressure is lower than the lower limit, generation of bubbles and voids due to an increase in the drying rate, an increase in the surface roughness of the film surface, an increase in the haze value, and the like tend to be easily caused, while when the pressure exceeds the upper limit, the cyclization reaction and the post-polymerization (post-polymerization reaction) between the oligomers due to an increase in the water concentration tend to be suppressed.

In the step (B), the reaction liquid obtained in the step (a) (the reaction liquid obtained by reacting the first monomer and the second monomer in the presence of the organic solvent (the solution containing the organic solvent and the resin precursor of the present invention)) may be subjected to a treatment of removing the organic solvent by evaporation (solvent removal treatment), the solvent may be removed from the reaction liquid, and then the heating treatment may be performed to form a resin in a desired form. For example, in the case of forming a film-like resin, the reaction solution obtained in the step (a) may be directly applied to a substrate (for example, a glass plate) and the organic solvent may be evaporated and removed, followed by the heating treatment. The temperature condition in the process of evaporating and removing the organic solvent (solvent removal process) is preferably 0 to 180 ℃, and more preferably 30 to 150 ℃. When the temperature condition in the solvent removal treatment is lower than the lower limit, it tends to be difficult to sufficiently evaporate and remove the solvent, while when the temperature condition exceeds the upper limit, the following tendency is exhibited: depolymerization of the resin precursor or boiling of the solvent occurs, forming bubbles and voids in the final product (resin).

As described above, the resin of the present invention can be efficiently produced by the steps (a) and (B). As described above, the method that can be suitably used for producing the resin of the present invention is described by exemplifying the above-described method (I) for producing the resin, but the method for producing the resin of the present invention is not limited to the above-described method (I) for producing the resin, and any method can be suitably used as long as it can obtain a resin (the above-described resin of the present invention) containing at least 1 selected from the group consisting of the repeating unit having an imidazopyrrolone structure represented by the above-described general formula (1-1) and the repeating unit having an imidazopyrrolone structure represented by the above-described general formula (1-2).

The resin and the resin precursor of the present invention are described above, and the resin precursor solution of the present invention is described below.

The resin precursor solution of the present invention contains the above-mentioned resin precursor of the present invention and a solvent.

As the organic solvent used for the resin precursor solution (varnish), the same organic solvents as those described in the above-mentioned method (I) for producing a resin can be suitably used. Therefore, the resin precursor solution of the present invention can be prepared by using the reaction solution obtained after the reaction in the step (a) as it is as a resin precursor solution.

The content of the pre-resin precursor in the resin precursor solution is not particularly limited, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. When the content is less than the lower limit, it tends to be difficult to produce a film-like resin using the resin precursor solution, and when the content exceeds the upper limit, it tends to be as follows: a decrease in coatability, a decrease in leveling effect, an irregularity on the surface of a coating film after coating, an occurrence of wrinkles on the surface of a coating film after coating, and the like due to a high viscosity, a decrease in fluidity, and the like are liable to occur, and the processability is lowered, and it is difficult to produce resins of various forms (for example, film-like resins) using the resin precursor solution. The resin precursor solution can be suitably used for producing the resin of the present invention, and can be suitably used for producing resins of various shapes. For example, a resin precursor solution such as that described above may be applied to various substrates, imidized, and cured to easily produce a resin in a thin film shape.

Further, various additives (deterioration inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, modifiers, antistatic agents, flame retardants, plasticizers, nucleating agents, stabilizers, adhesion improvers, lubricants, mold release agents, dyes, foaming agents, antifoaming agents, surface modifiers, hard coating agents, leveling agents, surfactants, fillers (glass fibers, fillers, talc, mica, silica, etc.)) that can be used for the preparation of the resin may be appropriately added to the resin precursor solution. In the case of using such an additive, the content of the additive in the resin precursor solution is not particularly limited, but is preferably set to about 0.0001 to 80 mass% (more preferably about 0.1 to 50 mass%). In addition, other resins (for example, cellulose nanofibers, nylon, polycarbonate, polyester, polyamide, polyketone, polyetherketone, polysulfone, polyethersulfone, PMMA, polyethylene, polypropylene, polystyrene, teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, triacetyl cellulose (TAC), and the like) may be added to the resin precursor solution as appropriate depending on the use of the finally obtained resin. The amount of the other resin added to the resin precursor solution is not particularly limited, but is preferably set to about 0.1 to 50 mass% (more preferably 1 to 30 mass%). The resin precursor solution of the present invention as described above can be suitably used as a resin varnish for obtaining the resin of the present invention.

Examples

The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis example 1: Synthesis of CpODA)

A tetracarboxylic dianhydride represented by the following formula (A-1) (norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride, wherein the tetracarboxylic dianhydride represented by the following general formula (A-1) is hereinafter referred to as" CpODA "), was synthesized by the method described in Synthesis example 1, example 1 and example 2 of International publication No. 2011/099518.

< abbreviations for monomers, etc. >

The tetracarboxylic dianhydride, the aromatic tetramine, the aromatic triamine, and the aromatic diamine used in the following examples and the like are abbreviated as follows. In the examples, the following abbreviations may be used.

(1) Tetracarboxylic dianhydride (first monomer)

CpODA: tetracarboxylic dianhydride represented by the formula (A-1) (Synthesis example 1)

CBDA: 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride

CPDA: 1, 2, 3, 4-cyclopentanetetracarboxylic dianhydride

H-BPDA: 3, 3 ', 4, 4' -dicyclohexyltetracarboxylic dianhydride

BODA: bicyclo [2.2.2] octane-2, 3, 5, 6-tetracarboxylic acid dianhydride

(2) Aromatic tetramine, aromatic triamine and aromatic diamine (second monomer)

TAB-E: 3, 3 ', 4, 4' -tetraaminodiphenyl ether

TAB-S: 3, 3 ', 4, 4' -tetraaminodiphenyl sulfone

TAB-K: 3, 3 ', 4, 4' -tetraaminodiphenyl ketone

TrAB-E: 3, 4, 4' -triaminodiphenyl ether

DABAN: 4, 4' -diaminobenzanilides

PPD (p): p-diaminobenzene

The monomers mentioned above, CBDA, CPDA, H-BPDA, BODA, TAB-E, TAB-S, TAB-K, TrAB-E, DABAN and PPD, are commercially available (CBDA: Tokyo Chemical Co., Ltd., CPDA: Tokyo Chemical Co., Ltd., H-BPDA: LCY Chemical Corp. Ltd., BODA: LCY Chemical Corp. Ltd., TAB-E: Gongshan refining Industrial Co., Ltd., TAB-S: Gongshan refining Industrial Co., Ltd., TAB-K: Gongshan refining Industrial Co., Ltd., TrAB-E: Tokyo Chemical Co., Ltd., DABAN: Japanese pure Chemical Co., Ltd., PPD: Paramine "from Daxin Industrial Co., Ltd.).

(example 1)

< Process for producing resin precursor >

First, a 30ml three-necked flask was heated with an air heating gun and sufficiently dried. Then, the atmosphere gas in the three-necked flask which was sufficiently dried was replaced with nitrogen, and the atmosphere in the three-necked flask was changed to a nitrogen atmosphere. Next, 0.2303g (1.00mmol) of TAB-E as a second monomer was added to the three-necked flask, and 5.53g of Tetramethylurea (TMU) as a solvent was further added thereto and stirred to dissolve the TAB-E in the TMU to obtain a solution. Next, 0.3844g (1.00mmol) of CpODA as a first monomer was added to the three-necked flask containing the solution under a nitrogen atmosphere to obtain a liquid mixture for polymerization. The concentration of the first monomer and the second monomer in the mixed solution for polymerization (hereinafter, this concentration is simply referred to as "polymerization concentration") is 10% by mass. Then, the mixture solution for polymerization was stirred at room temperature (25 ℃) for 5 hours under a nitrogen atmosphere to react CpODA with TAB-E to form a resin precursor (polyimidazopyrrolone precursor), thereby obtaining a reaction solution containing the resin precursor. Further, it is known from the kind of the monomer used that the obtained resin precursor contains a repeating unit having an imidazopyrrolone precursor structure represented by the following formula (101).

< Process for producing resin >

A large glass slide (trade name "S9213" manufactured by Sonlang Nitz industries, Ltd., longitudinal length of 76mm, lateral length of 52mm, and thickness of 1.3mm) was prepared as a glass substrate, and the reaction solution (polyimidazopyrrolone precursor solution) obtained as described above was spin-coated on the surface of the glass substrate so that the thickness of the coating film after heat curing became 10 μm, thereby forming a coating film on the glass substrate. Then, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ℃ and left standing for 2 hours, and the solvent was evaporated and removed from the coating film (solvent removal treatment).

After the solvent removal treatment as described above was performed, the glass substrate on which the coating film was formed was put into an inert atmosphere oven (inert oven) through which nitrogen was flowed at a flow rate of 3L/min, and was allowed to stand in the inert atmosphere oven under a nitrogen atmosphere at a temperature of 25 ℃ for 0.5 hour, then heated at a temperature of 80 ℃ for 0.5 hour, and further heated at a temperature of 380 ℃ (final heating temperature: firing temperature) for 1 hour, thereby curing the coating film, and a film (resin film) made of resin (polyimidazopyrrolone) was formed on the glass substrate, thereby obtaining a resin film laminated glass in which a resin film was coated on the glass substrate.

Then, the resin film laminated glass obtained in this manner was immersed in hot water at 90 ℃ to peel the resin film from the glass substrate, thereby obtaining a resin film (a film having a size of 76mm in the vertical direction, 52mm in the horizontal direction, and a thickness of 10 μm).

In order to identify the molecular structure of the compound forming the resin thin film obtained as described above, an IR spectrum was measured using an IR measuring instrument (trade name: FT/IR-4100, manufactured by Nippon spectral Co., Ltd.). The IR spectrum obtained as a result of the above measurement is shown in fig. 1. From the results shown in FIG. 1, it can also be seen that: among the compounds constituting the thin film formed in this example, 1701.8cm in the IR spectrum^-1A peak of characteristic absorption originating from the imide ring was observed and was found at 1625.3cm^-1A peak in the characteristic absorption from the imidazole ring was observed. From the molecular structure identified based on the above-mentioned measurement results, it was confirmed that: the resulting film was indeed a film made of polyimidazopyrrolone. Further, from the types of monomers obtained, it is known that: heating the resin precursor to first perform an intramolecular dehydration condensation reaction of the repeating unit having an imidazopyrrolone precursor structure represented by the above formula (101) to form a repeating unit having an imidazopyrrolone intermediate structure represented by the following formula (102); then, the intramolecular dehydration condensation reaction of the repeating unit is further performed to form a repeating unit having an imidazopyrrolone structure represented by the following formula (103). Thus, it was found from the kind of the monomer used and the results of the IR measurement that a resin containing a repeating unit having an imidazopyrrolone structure was obtained in this example.

(example 2)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.2303 g: 0.50mmol) and DABAN (0.1136 g: 0.50mmol) was used as the second monomer, and the polymerization concentration was adjusted to 15% by mass instead of using TAB-E alone as the second monomer and changing the amount of TMU used to 3.47g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

(example 3)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.0345 g: 0.15mmol) and DABAN (0.1932 g: 0.85mmol) was used as the second monomer in place of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 15% by mass by changing the amount of TMU used to 3.47g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

(example 4)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.023 g: 0.10mmol) and DABAN (0.2045 g: 0.90mmol) was used as the second monomer instead of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 15% by mass by changing the amount of TMU used to 3.47g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

(example 5)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.0115 g: 0.05mmol) and DABAN (0.2159 g: 0.95mmol) was used as the second monomer in place of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 15% by mass by changing the amount of TMU used to 3.47g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

(example 6)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-S (0.0278 g: 0.10mmol) and DABAN (0.2045 g: 0.90mmol) was used as the second monomer instead of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.47g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TAB-S and repeating units having an imide structure formed by the reaction of CpODA with DABAN.

(example 7)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-S (0.0139 g: 0.05mmol) and DABAN (0.2159 g: 0.95mmol) was used as the second monomer in place of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.46g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TAB-S and repeating units having an imide structure formed by the reaction of CpODA with DABAN.

(example 8)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-K (0.0363 g: 0.15mmol) and DABAN (0.1932 g: 0.85mmol) was used as the second monomer in place of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.46g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TAB-K and repeating units having an imide structure formed by the reaction of CpODA with DABAN.

(example 9)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-K (0.0242 g: 0.10mmol) and DABAN (0.2045 g: 0.90mmol) was used as the second monomer instead of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.45g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TAB-K and repeating units having an imide structure formed by the reaction of CpODA with DABAN.

(example 10)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-K (0.0121 g: 0.05mmol) and DABAN (0.2159 g: 0.95mmol) was used as the second monomer in place of using TAB-E alone as the second monomer, and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.45g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TAB-K and repeating units having an imide structure formed by the reaction of CpODA with DABAN.

(example 11)

A resin precursor and a resin were produced in the same manner as in example 1 except that H-BPDA (0.3063 g: 1.00mmol) was used as the first monomer in place of using CpODA as the first monomer, and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.15g, to obtain a resin film. Further, the results of the IR measurement are: the resin obtained contained repeating units having an imidazopyrrolone structure formed by the reaction of H-BPDA with TAB-E.

(example 12)

Except that bicyclo octanoic acid dianhydride was used: a resin precursor and a resin were produced in the same manner as in example 1 except that BODA (0.2502 g: 1.00mmol) was used as the first monomer in place of using CpODA as the first monomer and the polymerization concentration was adjusted to 15% by mass by changing the amount of TMU used to 2.61g, to obtain a resin film. Further, the results of the IR measurement are: the resin obtained contains a repeating unit having an imidazopyrrolone structure formed by the reaction of BODA with TAB-E.

(example 13)

A resin precursor and a resin were produced in the same manner as in example 1 except that TrAB-E (0.2153 g: 1.00mmol) alone was used as the second monomer in place of TAB-E, the polymerization concentration was adjusted to 10 mass% by changing the amount of TMU used to 5.40g, and the final heating temperature (firing temperature) during heating in an inert atmosphere oven was changed to 370 ℃. The IR measurement results of the obtained resin film are shown in fig. 2. At 1701.5cm^-1A peak of characteristic absorption originating from the imide ring was observed and was found at 1626.1cm^-1A peak in the characteristic absorption from the imidazole ring was observed. From the molecular structure identified based on the above measurement results, it is known that: the resulting resin contains repeating units having an imidazopyrrolone structure formed by the reaction of CpODA with TrAB-E.

(example 14)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.0461 g: 0.20mmol) and PPD (0.0865 g: 0.80mmol) was used as the second monomer in place of using TAB-E alone as the second monomer and the polymerization concentration was adjusted to 5.5% by mass by changing the amount of TMU used to 8.88g, to obtain a resin film. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with PPD.

(example 15)

A resin precursor and a resin were produced in the same manner as in example 14 except that the final heating temperature (firing temperature) in the inert atmosphere oven was changed to 400 ℃. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with PPD.

(example 16)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.0461 g: 0.20mmol) and PPD (0.0865 g: 0.80mmol) was used as the second monomer, the polymerization concentration was adjusted to 10 mass% instead of using TAB-E alone as the second monomer, the used amount of TMU was changed to 4.65g, and the final heating temperature (firing temperature) during heating in an inert atmosphere oven was changed to 400 ℃. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with PPD.

(example 17)

A resin precursor and a resin were produced in the same manner as in example 16 except that the final heating temperature (firing temperature) in the inert atmosphere oven was changed to 420 ℃. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103) above and a repeating unit having an imide structure formed by the reaction of CpODA with PPD.

(example 18)

A resin precursor and a resin were produced in the same manner as in example 1 except that a mixture of TAB-E (0.0230 g: 0.100mmol), PPD (0.0730 g: 0.675mmol) and DABAN (0.0511 g: 0.225mmol) was used as the second monomer, the polymerization concentration was adjusted to 10% by mass instead of using TAB-E alone as the second monomer and the amount of TMU used was changed to 4.784g, and the final heating temperature (firing temperature) during heating in an inert atmosphere oven was changed to 400 ℃. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103), a repeating unit having an imide structure formed by the reaction of CpODA with PPD, and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

(example 19)

A resin precursor and a resin were produced in the same manner as in example 18 except that the final heating temperature (firing temperature) in the inert atmosphere oven was changed to 420 ℃. Further, the results of the IR measurement are: the resulting resin contains a repeating unit having an imidazopyrrolone structure represented by formula (103), a repeating unit having an imide structure formed by the reaction of CpODA with PPD, and a repeating unit having an imide structure formed by the reaction of CpODA with DABAN.

Comparative example 1

Preparation of a resin precursor and a resin were attempted in the same manner as in example 1 except that CBDA (0.1961 g: 1.00mmol) was used as the first monomer in place of using CpODA as the first monomer, a mixture of TAB-E (0.0230 g: 0.10mmol) and DABAN (0.2045 g: 0.90mmol) was used as the second monomer in place of using TAB-E alone as the second monomer, and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 1.69 g. However, gelation occurred during the preparation of the resin precursor, and film formation was not possible from the beginning.

Comparative example 2

A resin precursor and a resin were prepared in the same manner as in example 1 except that CPDA (0.2101 g: 1.00mmol) was used as the first monomer in place of using CpODA as the first monomer, a mixture of TAB-E (0.0230 g: 0.10mmol) and DABAN (0.2045 g: 0.90mmol) was used as the second monomer in place of using TAB-E alone as the second monomer, and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 1.75 g. However, the obtained resin was brittle and cracked, and a product having a thin film shape could not be obtained.

Comparative example 3

A resin precursor and a resin were produced in the same manner as in example 1 except that DABAN (0.2273 g: 1.00mmol) was used as the second monomer in place of TAB-E, and the polymerization concentration was adjusted to 20% by mass by changing the amount of TMU used to 2.45g, to obtain a resin film.

[ evaluation of the Properties of the resins (resin films) obtained in examples 1 to 19 and comparative example 3 ]

The properties of the resins (resin films) obtained in examples 1 to 19 and comparative example 3 were evaluated as follows, and the results are shown in table 1 (in comparative examples 1 and 2, since a film-like resin (resin film) could not be obtained from the beginning, no sample could be prepared, and the following measurements could not be performed). Table 1 also shows the types of monomers used in examples 1 to 19 and comparative examples 1 to 3.

< measurement of Total light transmittance >

The total light transmittance (unit:%) of the resin constituting the resin film obtained in each example and the like was measured as follows. That is, the total light transmittance (unit:%) of each resin film was determined by using each resin film (thickness: 10 μm) as a measurement sample as it is and using a measurement device under the trade name "haze meter NDH-5000" manufactured by Nippon Denshoku industries Co., Ltd., according to JIS K7361-1 (published 1997). The results obtained are shown in table 1.

< measurement of glass transition temperature (Tg) >

The value (unit:. degree. C.) of the glass transition temperature (Tg) of the resin constituting the resin film obtained in each example and the like was measured as follows. That is, a sample having a size of 20mm in the longitudinal direction and 5mm in the transverse direction cut out from each resin film (thickness: 10 μm) was used (the thickness of the sample was directly used as the thickness of the film obtained in the examples), and a thermomechanical analyzer (trade name "TMA 8311" manufactured by Rigaku) was used as the measuring device, and the measurement was performed under a nitrogen atmosphere under a stretching mode (49mN) at a temperature rise rate of 5 ℃/min to obtain a TMA curve, and the value (unit:. degree. C.) of the glass transition temperature (Tg) of the resin constituting the film obtained in each example was obtained by extrapolating the curve before and after the inflection point of the TMA curve due to the glass transition. The results obtained are shown in table 1.

< measurement of tensile Strength and elongation at Break >

The tensile strength (unit: MPa) and elongation at break (unit:%) of the resin films obtained in examples and the like were measured as follows. That is, first, a model name "super dumpbell cutter (model: SDMK-1000-D, according to a22 standard of JIS K7139 (published in 2009)) manufactured by dumpbell was attached to an SD type sample cutter of control lever type (model SDL-200 manufactured by dumpbell, ltd.), and the respective resin films were cut so that the size of each resin film became the full length: 75mm, distance between ear parts: 57mm, length of parallel portion: 30mm, radius of shoulder: 30mm, width of end: 10mm, width of central parallel portion: 5mm, thickness: 10 μm, dumbbell-shaped test pieces (test pieces in accordance with JIS K7139 model A22 (reduced-size test pieces) except that the thickness was set to 10 μm) were prepared as measurement samples, respectively. Next, the measurement sample was arranged so that the width between the grips became 57mm and the width of the grip portion became 10mm (the entire width of the end portion) using an electromechanical universal material testing machine (model number "5943" manufactured by INSTRON), and then a load cell: 1.0kN, test speed: tensile test in which the above-mentioned measurement sample was stretched was conducted under the condition of 5 mm/min, and values of tensile strength and elongation at break were obtained. The above-mentioned test is a test according to JIS K7162 (published in 1994). When the distance between the tab portions of the sample (width between the jigs: 57mm) was L0 and the distance between the tab portions of the sample until breakage (width between the jigs at the time of breakage: 57mm + α) was L, the value (%) of the elongation at break was determined by the following equation. The results obtained are shown in table 1.

[ elongation at Break (%)]＝{(L-L₀)/L₀}×100

< measurement of coefficient of Linear expansion (CTE) >

The CTE (unit: ppm/K) of the resin constituting the resin thin film obtained in each example and the like was determined as follows. That is, first, the longitudinal direction is formed by each resin film: 20mm, transverse: a film (thickness: 10 μm) having a size of 5mm was used for measurement. Then, the obtained film for measurement was vacuum-dried (120 ℃ C., 1 hour) and then heat-treated at 200 ℃ C. for 1 hour under a nitrogen atmosphere to prepare a measurement sample (dried film). Then, using the obtained measurement sample (dried film), the length change of the sample at 50 to 200 ℃ was measured under a nitrogen atmosphere in a tensile mode (49mN) under a condition that the temperature rise rate was 5 ℃/min by using a thermomechanical analyzer (trade name "TMA 8311" manufactured by Rigaku), and the average value of the length change per 1 ℃ in a temperature range of 100 to 200 ℃ was obtained. The results obtained are shown in table 1.

TABLE 1

From the results shown in table 1, it can be seen that: films (examples 1 to 19) made of the resin of the present invention all had a total light transmittance of 80% or more, and were confirmed to have sufficient transparency; further, the Tg was 389.8 ℃ C. (about 390 ℃ C.) or higher, and it was confirmed that the polyimide exhibited higher heat resistance as compared with the polyimide obtained in comparative example 3. In particular, the resin constituting the film obtained in example 1 was found to have an extremely high heat resistance, as seen from its Tg of 448 ℃.

Furthermore, the films (examples 1 to 19) made of the resin of the present invention all had a breaking strength of 50MPa or more. On the other hand, when an alicyclic tetracarboxylic dianhydride such as CBDA or CPDA having a cyclic structure other than a 6-membered ring (a cyclic structure having a 4-or 5-membered ring) was used (comparative examples 1 and 2), a film could not be obtained from the beginning, and for example, even if the film formation step was performed in comparative example 2, the obtained resin was brittle and cracked, and the film shape could not be maintained. From the above results, it is clear that: according to the films (examples 1 to 19) made of the resin of the present invention, a sufficiently high strength can be obtained. In addition, it is known that: the film made of polyimide obtained in comparative example 3 had a breaking strength of 31MPa and exhibited sufficient mechanical strength as a self-supporting film when compared with the film made of polyimide obtained in comparative example 3, but the films made of the resin of the present invention (examples 1 to 19) all had a breaking strength of 50MPa or more and exhibited higher mechanical strength.

From the above results, it is understood that according to the present invention (examples 1 to 19), the transparency and heat resistance of the obtained resin can be sufficiently improved, and the mechanical strength based on the breaking strength can be sufficiently improved. Further, it can be seen that: the films (examples 1 to 19) made of the resin of the present invention each had a CTE of 50ppm/K or less, had a low CTE, and were sufficiently high in processability.

Industrial applicability of the invention

As described above, according to the present invention, it is possible to provide a resin capable of having sufficiently high light transmittance and higher heat resistance and having excellent mechanical strength, a resin precursor which is a precursor of the resin, and a resin precursor solution which can be suitably used for production of the resin.

Therefore, as described above, the resin of the present invention has not only sufficiently high transparency (light transmittance), but also higher heat resistance, and can be suitably used as a transparent material having very high heat resistance, and the like, and is therefore particularly useful as a protective coating agent for producing, for example, a film for a flexible wiring substrate, a heat-resistant insulating tape, an electric wire enamel, a semiconductor, a liquid crystal alignment film, a transparent conductive film for an organic EL, a flexible substrate film, a flexible transparent conductive film, a transparent conductive film for an organic thin film type solar cell, a transparent conductive film for a dye-sensitized solar cell, a flexible gas barrier film, a film for a touch panel, a TFT substrate film (LTPS, suitable for polycrystalline silicon), a TFT substrate film for a flat panel detector, a seamless resin tape for a copier (so-called transfer tape), a transparent electrode substrate (a transparent electrode substrate for an organic EL, a transparent electrode substrate for a copier, a transparent electrode substrate, Transparent electrode substrates for solar cells, transparent electrode substrates for electronic paper, and the like), interlayer insulating films, sensor substrates, substrates for image sensors, reflective plates for Light Emitting Diodes (LEDs) (reflective plates for LED lighting: LED reflector), LED reflector lighting cover, cover ray film, high-ductility composite substrate, semiconductor-suitable resist, lithium ion battery, organic memory substrate, organic transistor substrate, organic semiconductor substrate, color filter substrate, medical heat-resistant tray, medical gamma ray-resistant resin petri dish, medical transparent high-heat-resistant pipette, transparent high-heat-resistant lens, vehicle sensor lens, cell phone face authentication lens, solder reflow lens, infrared camera lens, optical filter, ambient light sensor, all-solid-state battery adhesive, all-solid-state battery gel material, and the like. In addition to the above-mentioned applications, the resin of the present invention can be suitably used for, for example, automobile parts, aerospace parts, bearing parts, sealing materials, support parts, gears, valve parts, and the like by forming the resin into a powder or various molded bodies.

Claims

1. A resin comprising at least 1 repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone structure represented by the following general formula (1-1) and a repeating unit having an imidazopyrrolone structure represented by the following general formula (1-2),

in the formula (1-1), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X²Represents a 4-valent organic group, and a salt thereof,

in the formula (1-2), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X³Represents a 3-valent organic group.

2. The resin according to claim 1, further comprising a repeating unit having an imide structure represented by the following general formula (2),

in the formula (2), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X⁴Represents an arylene group having 6 to 50 carbon atoms.

3. The resin of claim 1 or 2, wherein X in the formula¹Is 1 kind selected from 4-valent organic groups represented by the following general formulas (3) to (5),

in the formula (3), m represents an integer of 0 to 2, in the formula (4), n represents an integer of 1 to 2, in the formula (5), A represents 1 selected from the group consisting of a single bond and a 2-valent aromatic group having 6 to 30 carbon atoms which may have a substituent and form an aromatic ring, and symbols 1 to 4 in the formulae (3) to (5) represent that bonding points with the symbols are respectively associated with X¹Any of the 4 bonding sites of the bond.

4. A resin according to any one of claims 1 to 3 wherein X in the formula²Is 1 kind selected from 4-valent organic groups represented by the following general formulas (6-1) to (7-1),

in the formula (7-1), Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene group represented bySulfide group represented by S-, amide group represented by NHCO-, ester type represented by COO-, and C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-1) to (7-1), wherein the symbols 1 to 4 represent the bonding sites having the symbols with X²Any of the 4 bonding sites of the bond.

5. A resin according to any one of claims 1 to 4 wherein X in the formula³Is 1 kind selected from 3-valent organic groups represented by the following general formulas (6-2) to (7-2),

in the formula (7-2), Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, -O--C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-2) to (7-2), wherein the symbols 1 to 3 represent the bonding sites having the symbols with X³Any of the 3 bonding sites of the bond.

6. A resin precursor containing at least 1 repeating unit selected from the group consisting of a repeating unit having an imidazopyrrolone precursor structure represented by the following general formula (8-1) and a repeating unit having an imidazopyrrolone precursor structure represented by the following general formula (8-2),

in the formula (8-1), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X²Represents a 4-valent organic group, and a salt thereof,

in the formula (8-2), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X³Represents a 3-valent organic group.

7. The resin precursor according to claim 6, further comprising a repeating unit having an imide precursor structure represented by the following general formula (9),

in the formula (9), X¹A 4-valent organic group having an alicyclic structure of 6-membered ring, X⁴Represents an arylene group having 6 to 50 carbon atoms.

8. The resin precursor according to claim 6 or 7, wherein X in the formula¹Is 1 kind selected from 4-valent organic groups represented by the following general formulas (3) to (5),

9. A resin precursor according to any one of claims 6 to 8 wherein X in the formula²Is 1 kind selected from 4-valent organic groups represented by the following general formulas (6-1) to (7-1),

in the formula (7-1), Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene, -CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-1) to (7-1), wherein the symbols 1 to 4 represent the bonding sites having the symbols with X²Any of the 4 bonding sites of the bond.

10. A resin precursor according to any one of claims 6 to 9 wherein X in the formula³Is 1 kind selected from 3-valent organic groups represented by the following general formulas (6-2) to (7-2),

in the formula (7-2), Z¹Represents a group selected from a single bond, 9-fluorenylidene group, formula: -an ether group represented by-O, -a carbonyl group represented by-C (═ O) -, -a sulfoxide group represented by-S (═ O) -, -S (═ O)₂-sulfonyl group represented by, -CH₂Methylene group represented by-C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂-hexafluoroisopropylidene represented by the formula, -thioether group represented by the formula S-, amide group represented by NHCO-, ester type represented by COO-, and-C₆H₄A phenylene group represented by the formula, -O-C₆H₄Phenylenedioxy group represented by-O-, or-O-C₆H₄-C₆H₄Biphenylenedioxy group represented by-O-or-O-C₆H₄-Z²-C₆H₄-O- [ Z in formula²Represents an ether group represented by-O-, a carbonyl group represented by-C (═ O) -, -S (═ O)₂-sulfonyl group represented by, -C (CH)₃)₂Isopropylidene group represented by, -C (CF)₃)₂Hexafluoroisopropylidene group represented by the formula-and-CH₂1 species of the group consisting of methylene groups represented by]Bis (phenylenedioxy) group, -P (═ O) (C) represented by₆H₅) A group represented by-and-N (C)₆H₅) 1 of the groups represented by the formulae (6-2) to (7-2), wherein the symbols 1 to 3 represent the bonding sites having the symbols with X³Any of the 3 bonding sites of the bond.

11. A resin precursor solution comprising the resin precursor according to any one of claims 6 to 10 and a solvent.