TW201945435A - Resin, resin precursor and resin precursor solution - Google Patents

Abstract

This resin comprises at least one repeating unit selected from the group consisting of: a repeating unit having an imidazopyrrolone structure represented by general formula (1-1), where X1 represents a tetravalent organic group having an alicyclic structure of a 6-membered ring, and X2 represents a tetravalent organic group; and an imidazopyrrolone structure represented by general formula (1-2), where X1 represents a tetravalent organic group having an alicyclic structure of a 6-membered ring, and X3 represents a trivalent organic group.

Description

Resin, resin precursor and resin precursor solution

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

From the past, there has been a demand for resins with high light transmission properties such as glass and sufficiently high heat resistance, as materials for substrates 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 described in a specific general formula. Such a polyimide is one having high light transmittance and sufficiently high heat resistance, and can be applied to various fields. However, in the field of such resins, there is a demand for the appearance of a resin that can exhibit a higher degree of heat resistance while having the same light transmittance as the polyimide described in Patent Document 1.

On the other hand, as a resin having high heat resistance, polyimidazopyrrolone has been conventionally known, for example, Japanese Patent Application Laid-Open No. 8-290046 (Patent Document 2) or Japanese Patent Application Laid-Open No. 5-301959 ( Patent Document 3) discloses a polyimidazopyrrolidone obtained by reacting a tetracarboxylic dianhydride component with a tetraamine component. In addition, in Patent Document 2 or Patent Document 3, various compounds are widely disclosed as tetracarboxylic dianhydride components. However, the resins actually manufactured in the examples of Patent Document 2 or Patent Document 3 are only reactants of the aromatic tetracarboxylic dianhydride component and the aromatic tetraamine component (so-called fully aromatic). Group polyimidazopyrrolidone). In addition, such a wholly aromatic polyimidazopyrrolidone is insufficient from the viewpoint of light transmittance and cannot be used for glass replacement applications.

[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2011/099518
[Patent Document 2] Japanese Patent Laid-Open No. 8-290046
[Patent Document 3] Japanese Unexamined Patent Publication No. 5-301959

[Problems to be Solved by the Invention]

The present invention has been made in view of the problems associated with the aforementioned prior art, and an object thereof is to provide a resin having a sufficient degree of light transmittance, a higher degree of heat resistance, and excellent mechanical strength, and a precursor of the resin. Resin precursors, and resin precursor solutions that can be suitably used in the manufacture of the resin.

[Means to solve the problem]

As a result of repeated intensive studies in order to achieve the foregoing object, the inventors of the present invention have found that by including a repeating unit selected from a specific imidazopyrrolidone structure represented by the following general formula (1-1), and having the following general formula At least one repeating unit of the group formed by the repeating unit of the specific imidazopyrrolidone structure represented by (1-2) can make the resin have a high degree of light transmittance and a higher degree of heat resistance, and can become Those who have excellent mechanical strength have completed the present invention.

That is, the resin of the present invention contains a resin selected from the group consisting of the following general formula (1-1):

[Wherein X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ² represents a tetravalent organic group]
Represents a repeating unit of an imidazopyrrolidone structure, and has the following general formula (1-2):

[Wherein X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ³ represents a trivalent organic group]
Represents at least one repeating unit of a group consisting of repeating units of an imidazopyrrolidone structure.

The resin of the present invention preferably further contains the following general formula (2):

[Wherein X ¹ represents a tetravalent organic group having an alicyclic structure having 6 member rings, and X ⁴ represents an aryl group having 6 to 50 carbon atoms]
Represents a repeating unit of hydrazone structure.

The resin precursor of the present invention contains a resin selected from the group consisting of the following general formula (8-1):

[Wherein X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ² represents a tetravalent organic group]
Represents a repeating unit of the imidazopyrrolidone precursor structure, and has the following general formula (8-2):

[Wherein X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ³ represents a trivalent organic group]
Represents at least one repeating unit of a group formed by repeating units of the imidazopyrrolidone precursor structure.

The resin precursor of the present invention described above preferably further contains the following general formula (9):

[Wherein X ¹ represents a tetravalent organic group having an alicyclic structure having 6 member rings, and X ⁴ represents an aryl group having 6 to 50 carbon atoms]
A repeating unit representing the structure of a pyrimide precursor.

In addition, in the resin of the present invention and the resin precursor of the present invention, each of X ¹ in the above formula is preferably represented by the following general formulae (3) to (5):

[In formula (3), m represents an integer of 0 to 2, in formula (4), n represents an integer of 1 to 2, and in formula (5), A represents a group selected from a single bond; and may have a substituent and form an aromatic group. The ring carbon number is one of a group formed by a divalent aromatic group having 6 to 30 carbon atoms. The symbols * 1 to * 4 in the formulas (3) to (5) indicate that the bonding sites with the symbols are respectively Bonded to any of the four bonding sites of X ¹ ]
It shows one kind selected from the tetravalent organic group.

Further, in the resin of the present invention and the resin precursor of the present invention, each of X ² in the above formula is preferably represented by the following general formulae (6-1) to (7-1):

[In formula (7-1), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C (CF ₃ ) ₂ -and a group of methylene groups represented by -CH _2- ] One type of group consisting of a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-, the formula ( 6-1) The symbols * 1 ~ * 4 in (7-1) indicate that the bonding part with the symbol is any of the 4 bonding parts respectively bonded to X ² ]
It shows one kind selected from the tetravalent organic group.

Further, in the resin of the present invention and the resin precursor of the present invention, each of X ³ in the above formula is preferably represented by the following general formulae (6-2) to (7-2):

[In formula (7-2), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C (CF ₃ ) ₂ -and a group of methylene groups represented by -CH _2- ] One type of group consisting of a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-, the formula ( 6-2) The symbols * 1 to * 3 in (7-2) indicate that the bond site with this symbol is any of the three bond sites that are respectively bonded to X ³ ]
One of the trivalent organic groups.

The resin precursor solution of the present invention includes the resin precursor and the solvent of the present invention.

[Effect of the invention]

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

Hereinafter, the present invention will be described in detail based on its suitable embodiments.

First, the resin of the present invention will be described. The resin of the present invention contains a repeating unit selected from the imidazopyrrolidone structure represented by the general formula (1-1) (hereinafter, the repeating unit having the imidazopyrrolidone structure is referred to as a case, and is simply referred to as a convenience Is a "repeating unit (A)"), and a repeating unit having an imidazopyrrolidone structure represented by the above-mentioned general formula (1-2) (hereinafter, the repeating unit having an imidazopyrrolidone structure is convenient for convenience) A group of at least one type of repeating unit (referred to only as "repeat unit (A ')").

X ¹ in the general formula (1-1) and the general formula (1-2) is a tetravalent organic group having an alicyclic structure having a 6-membered ring. The "6-membered ring" referred to herein is not particularly limited as long as it is a ring having a cyclic structure with six atoms [moreover, when a polycyclic structure such as a bicyclic structure including a crosslinked structure is formed ( For example, a norbornane ring structure or a bicyclic octane ring structure, etc.), as long as any one of the rings is a ring with 6 atoms]. The six-membered alicyclic structure in such a tetravalent organic group is not particularly limited, and examples thereof include the following general formulae (i) to (iii):

The structure shown by the aliphatic 6-membered ring. From the viewpoint of obtaining a higher degree of heat resistance and a higher degree of resistance to tensile stress and a higher degree of mechanical strength, the 6-membered alicyclic structure is more preferably based on the above-mentioned general A structure composed of an aliphatic 6-membered ring (norbornene ring) represented by formula (ii).

In addition, a tetravalent organic group having a 6-membered alicyclic structure which can be selected as X ¹ in the general formula (1-1) and the general formula (1-2), as long as it has the aforementioned 6-membered ring lipid The ring structure is sufficient, and carbon atoms forming the alicyclic structure of the aforementioned 6-membered ring may be bonded to various atoms such as hydrogen atoms, atoms other than hydrogen atoms, or other substituents (including other organic groups).

In addition, a tetravalent organic group having a 6-membered alicyclic structure which can be selected as X ¹ in the general formula (1-1) and the general formula (1-2), since the repeating units (A) and The aforementioned repeating units (A ') are those which can be formed more efficiently by using a tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring as a raw material, that is, these can be obtained by having a 6-membered ring A reaction of a tetracarboxylic dianhydride of a cyclic alicyclic structure with a tetramine, and / or a reaction of a tetracarboxylic dianhydride having an alicyclic structure of a 6-membered ring with a triamine, so that it can be formed more efficiently. Residues from which two acid anhydride groups are removed from a tetracarboxylic dianhydride having an alicyclic structure of 6 members (a tetravalent organic group: In addition, in a compound represented by the following formula (I), an acid anhydride group is bonded The four bonding sites of the carbonyl group (formula: -C (= O) -represented group) are the four bonding sites bonded to X ¹ in each of the above formulas as suitable.

Such a tetracarboxylic dianhydride having a 6-membered alicyclic structure can be represented by the following formula (I):

[X ¹ in formula (I) is synonymous with X ^{1 in} general formula (1-1) and general formula (1-2)]
Means. Examples of such a tetracarboxylic dianhydride having a 6-membered alicyclic structure include bicycloheptane tetracarboxylic dianhydride (BHDA), dimethanonaphthalenetetracarboxylic dianhydride (DNDA) , Bicyclooctane tetracarboxylic dianhydride (BODA), 3,3 ', 4,4'-Bicyclohexyltetracarboxylic dianhydride (H-BPDA), [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, 4,4'-methylenebis (cyclohexane-1,2-dicarboxylic anhydride), 4 , 4 '-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic anhydride), 4,4'-oxybis (cyclohexane-1,2-dicarboxylic anhydride) , 4,4'-thiobis (cyclohexane-1,2-dicarboxylic anhydride), 4,4'-sulfofluorenylbis (cyclohexane-1,2-dicarboxylic anhydride), 4,4 ' -(Dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic anhydride), 4,4 '-(tetrafluoropropane-2,2-diyl) bis (cyclohexane-1,2 -Dicarboxylic anhydride), octahydrocyclopentadiene-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] oct-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 dianhydride, 9-oxatricyclo [4.2.1.0 ^2,5 ] Nonane-3,4,7,8-tetracarboxylic dianhydride, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dibridgemethylenenaphthalene-2c, 3c, 6c, 7c-tetra Carboxylic dianhydride, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dibridged methylene naphthalene-2t, 3t, 6c, 7c-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane Alkane-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dibridged methylene naphthalene-2c, 3c, 6c, 7c-tetracarboxylic dianhydride, norbane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbidine -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-dextrin Phenylbis (2-norbornane-5,6-dicarboxylic anhydride), 4,4'-dynephenylbis (2-norbornane-5,6-dicarboxylic anhydride), 4,4 '' -Extended triphenylbis (2-norbornane-5,6-dicarboxylic anhydride), cyclohexane-1,2,4,5-tetracarboxylic dianhydride trans isomer, cyclohexane -1,2 Cis isomers of 4,5-tetracarboxylic dianhydride. In addition, such a tetracarboxylic dianhydride having an alicyclic structure with 6 member rings may include, for example, the following general formulae (IA) to (IB):

[In the formula (IA), R ¹ , R ² , and R ³ each independently represent one 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 0 to 12 Integer. In the formula (IB), A is synonymous with A in the formula (5), and R ⁴ independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. R ^{The 5} series independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms]
Compounds shown as appropriate. Such a tetracarboxylic dianhydride having a 6-membered alicyclic structure may be used singly or in combination.

The carbon number of the alkyl group that can be selected as R ¹ , R ² , and R ³ in the general formula (IA) is preferably 1 to 6, more preferably 1 to 5, from the viewpoint of easier purification. More preferably, it is 1-4, and especially preferable is 1-3. The alkyl group which can be selected as such R ¹ , R ² , and R ³ may be linear or branched. Furthermore, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification. In addition, R ¹ , R ² , and R ³ in the general formula (IA) are more preferably each independently a hydrogen atom, a methyl group, an ethyl group, and an n-propyl group from the viewpoint of obtaining a higher degree of heat resistance when manufacturing a resin. Or isopropyl; still more preferably a hydrogen atom or a methyl group; particularly preferred are hydrogen atoms. The plurality of R ¹ , R ² , and R ^{3 in} such a formula are particularly preferably the same from the viewpoint of ease of purification and the like. Further, regarding n in the aforementioned general formula (IA), from the viewpoint of easier purification, the upper limit value is more preferably 5 (particularly 3), and from the viewpoint of stability of the raw material compound, the lower limit value is more preferable. Good is 1 (extra good is 2). Particularly good is 2. As such, n in the general formula (IA) is particularly preferably an integer of 2 to 3.

R ⁴ and R ⁵ in the general formula (IB) are each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. The carbon number of the alkyl group which can be selected as such R ⁴ and R ⁵ has the viewpoint of obtaining higher heat resistance, and is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4, Particularly good is 1 to 3. The alkyl group which can be selected as such R ⁴ and R ⁵ may be linear or branched. In addition, R ⁴ and R ⁵ in the general formula (IB) are more preferably independently a hydrogen atom, a methyl group, and an ethyl group from the viewpoints of obtaining higher heat resistance, easier availability of raw materials, and easier purification. , N-propyl, isopropyl; still more preferably a hydrogen atom, a methyl group; particularly preferred are hydrogen atoms. In addition, R ⁴ and R ⁵ in the formula (IB) may be the same as or different from each other, and are preferably the same from the viewpoint of ease of purification and the like. In addition, A in the general formula (IB) is synonymous with A in the general formula (5), and represents a divalent group selected from a single bond; and a carbon atom having 6 to 30 carbon atoms that may have a substituent and form an aromatic ring. One group of aromatic groups. The divalent aromatic group which can be selected as such A, or a suitable one thereof, will be described later.

Examples of the compound represented by the 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 general formula (IA) is not particularly limited, and a known method (for example, the method described in International Publication No. 2011/099518) can be appropriately adopted. Examples of the compound represented by the general formula (IB) include the following formulae (B-1) to (B-3):

Represented compounds. The method for producing the compound represented by the general formula (IB) is not particularly limited, and a known method (for example, the method described in International Publication No. 2015/163314, International Publication No. 2017/030019, etc.) can be appropriately adopted.

As a tetracarboxylic dianhydride having such a 6-membered alicyclic structure, in terms of transparency, heat resistance, and high dimensional stability, norbornane-2-spiro-α-cyclopentanone-α 'is particularly preferred. -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), the compound (BNBDA) represented by the above formula (B-1), the above formula (B-2 The compound (BzDA) represented by) and the compound (BpDA) represented by the above formula (B-3) are preferred; more preferred are CpODA, BNBDA, and BzDA.

In addition, the tetravalent organic group that can be selected as X ¹ in the formulae (1-1) and (1-2) has a transparency, heat resistance, and high dimensional stability, preferably 2 Among the above-mentioned 6-membered alicyclic structures (preferably a structure composed of a norbornene ring), in terms of transparency, heat resistance, and high dimensional stability, the above general formula (3) The 4-valent organic group represented by ~ (5) is more preferable.

Regarding such a tetravalent 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 even more preferably 1). When such a value of m exceeds the aforementioned upper limit, production and purification tend to be difficult. In addition, n in the formula (4) is an integer of 1 to 2 (more preferably 1). When such a value of n exceeds the above-mentioned upper limit, production and purification tend to become difficult.

In addition, A in the general formula (5) is one selected from the group consisting of a single bond and a divalent aromatic group having 6 to 30 carbon atoms that may have a substituent and form an aromatic ring (re) (A is also synonymous with the general formula (IB)).

The divalent aromatic group which can be selected as such A is a divalent aromatic group which may have a substituent, and forms the number of carbon atoms of the aromatic ring included in the aromatic group (also referred to herein as "formation The number of carbons of the aromatic ring ", when the aromatic group has a carbon-containing substituent (hydrocarbon group, etc.), the number of carbons in the substituent is not included, and only the number of carbons of the aromatic ring in the aromatic group. For example, 2 In the case of -ethyl-1,4-phenylene, the number of carbon atoms forming an aromatic ring is 6) is 6-30. As described above, the divalent aromatic group that can be selected as A in the formula is a divalent group (divalent aromatic group) which may have a substituent and has an aromatic ring having 6 to 30 carbon atoms. When the number of carbons forming such an aromatic ring exceeds the above-mentioned upper limit, when the resin is prepared using a resin having the repeating unit, it tends to be difficult to sufficiently suppress the coloration of the resin. From the viewpoint of transparency and ease of purification, the number of carbon atoms of the aromatic ring forming the divalent aromatic group is more preferably 6 to 18, and still more preferably 6 to 12.

The divalent aromatic group that can be selected as such A is not limited as long as it satisfies the above-mentioned carbon number condition. For example, benzene, naphthalene, bitriphenyl, anthracene, phenanthrene, and triphenylene can be appropriately used. , Hydrazone, pyrene, biphenyl, bitriphenyl, biquaterphenyl, bipentabenzene and other aromatic compounds leaving two hydrogen atom residues (moreover, such residues, the position of the hydrogen atom to be removed It is not particularly limited, and examples thereof include 1,4-phenylene, 2,6-naphthyl, 2,7-naphthyl, 4,4'-biphenyl, 9,10-anthryl, and the like ); And at least one hydrogen atom in the residue is substituted with a substituent (for example, 2,5-dimethyl-1,4-phenylene, 2,3,5,6-tetramethyl-1 , 4-phenylene) and the like. Moreover, in such a residue, as described above, there is no particular restriction on the position of the hydrogen atom to be detached. For example, when the residue is a phenyl group, it may be any position of an ortho, meta, or para position. .

The divalent aromatic group that can be selected as such A is from the viewpoint that the transparency of the resin becomes more excellent when formulating a resin. The phenyl group which may have a substituent and the extension which may have a substituent are preferred. A phenyl group, a naphthyl group which may have a substituent, an anthracene group which may have a substituent, and a triphenylene which may have a substituent. That is, the divalent aromatic group which can be selected as such A is preferably a phenylene group, a phenylene group, a phenylene group, a phenylene group, or a phenylene group which may have a substituent. Moreover, among such divalent aromatic groups, since a higher effect is obtained from the above point of view, it is particularly preferred to use a phenylene group, a phenylene group, and a naphthyl group which may each have a substituent. The phenylene group and the phenylene group of the substituent are more preferable; the phenylene group which may have a substituent is most preferable.

Among the divalent aromatic groups that can be selected as such A, from the viewpoint that the mechanical strength of the resin is more excellent during the production of the resin, in particular, phenylene, phenylene, Phenyl, anthracenyl and phenyltriphenyl are preferred; phenyl, phenyl, and naphthyl, respectively, which may have a substituent are more preferred; phenyl, Diphenylene is even more preferred; most preferred is a diphenylene which may have a substituent.

Furthermore, among such divalent aromatic groups, a viewpoint of obtaining higher heat resistance is obtained, and in particular, phenylene, phenylene, naphthyl, anthracene, and phenylene, which may have substituents, are respectively Triphenyl is preferred; phenyl, phenylene, naphthyl, and phenyltriphenyl, respectively, which may have a substituent are more preferred; phenyl, phenylene, The p-naphthyl group is more preferred; the p-phenylene group which may have a substituent is most preferred.

Moreover, the substituent which the divalent aromatic group which can be selected as such A is not specifically limited, For example, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned. Among the substituents that such a divalent aromatic group may have, from the viewpoint that the transparency of the resin is better when the resin is produced, especially an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Better. When the number of carbon atoms of the alkyl group and the alkoxy group suitable as such a substituent exceeds 10, the heat resistance of the obtained resin tends to decrease. In addition, the carbon number of the alkyl group and the alkoxy group which are suitable as such a substituent is preferably from 1 to 6, more preferably from 1 to 5, and even more preferably from the viewpoint of obtaining a higher degree of heat resistance when manufacturing a resin. 1 ~ 4, especially good 1 ~ 3. The alkyl group and alkoxy group which can be selected as such a substituent may be linear or branched, respectively.

In addition, A in such formula (5) has a viewpoint of obtaining higher heat resistance, and is more preferably a single bond, a phenylene group which may have a substituent, a phenylene group which may have a substituent, or a substituent. A naphthyl group which may be a substituent or a diphenyl group which may have a substituent; and more preferably a single bond, a phenyl group which may have a substituent, a biphenyl group which may have a substituent or a naphthylene which may have a substituent Particularly preferred is a single bond, a phenylene group which may have a substituent or a phenylene group which may have a substituent; most preferred is a single bond or a phenylene group which may have a substituent.

Among the tetravalent organic groups represented by the above general formulae (3) to (5), the symbols * 1 to * 4 indicate that the bonding sites with the symbols are any of the four bonding sites respectively bonded to X ¹ By. In addition, when the general formula (1-1) is taken as an example for explanation, in the structure of the repeating unit, the symbols * 1 ~ * 4 are attached to the symbols with the symbols * 1 ~ * 2. The bonding site of any of the bonding sites is a bonding site bonded to one of the carbonyl groups (formula: -C (= O)-) bonded to X ¹ in the general formula (1-1). And the bond site of any of the bond sites marked with * 3 ~ * 4 is a bond with the carbonyl bond of the other bonded by X ¹ in the general formula (1-1) Parts.

X ² in the general formula (1-1) represents a tetravalent organic group. Such a tetravalent organic group is not particularly limited, and a residue obtained by removing four amine groups from tetraamine is preferred. Such a tetraamine may be an aromatic tetraamine or an alicyclic tetraamine. Further, as used herein, the tetraamine, in order to enhance stability or storage stability of paint, -NH ₂ may be a silicon to be in the alkylation of H, alkyl, or become trimethyl silicon t- butyldimethyl silicon group .

Such an aromatic tetramine is not particularly limited, and known aromatic tetraamines (for example, phenyltetraamine type, diphenyl ether type, diphenylfluorene type, diphenyl ketone type, biphenyl type, benzene, etc.) can be appropriately used. Formamidine type, benzoate type, diphenyl sulfide type, Bis-A type (diphenylisopropylidene type), hexafluoro Bis-A type, Bis-M type (diphenylmethane type) ), Bis-C type (diphenylcyclohexane type), Bis-F type (diphenylfluorene type), bitriphenyl type (triphenyl type), diphenylene dioxy type, bis (diphenylene) Aromatic tetramines such as dioxo), hydrazone, spiral, silicon, etc.).

Examples of such an aromatic tetramine include 3,3 ', 4,4'-tetraaminodiphenyl ether (TAB-E), 3,3', 4,4'-tetraaminodiphenylsulfonium (TAB-S), 3,3 ', 4,4'-tetraaminodiphenyl ketone (TAB-K), 3,3', 4,4'-tetraaminobiphenyl (TABP), 1, 2,4,5-tetraaminobenzene (TAB), 3,3 ', 4,4'-tetraaminodiphenylmethane, 3,3', 4,4'-tetraaminodiphenylcyclohexyl Alkanes, 3,3 ', 4,4'-tetraaminodiphenylphosphonium, 3,3', 4,4'-tetraaminodiphenylsulfide, 2,2-isopropylidenebis (3 , 4-diaminobenzene), 2,2-bis (3,4-diaminophenyl) propane, 2,2-hexafluoroisopropylidenebis (3,4-diaminobenzene), 2 2,2-bis (3,4-diaminophenyl) hexafluoropropane, 3,3 ', 4,4'-tetraaminodiphenyl ester, 3,3', 4,4'-tetraaminodiphenyl Phenylamidoamine, 3,3 '', 4,4 ''-tetraaminobitriphenyl, 9,9-amidinobis (3,4-diaminophenyl), 9,9-bis (3 , 4-diaminophenyl) fluorene, 9,9-fluorenylenebis (3,4-diaminophenyl), 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-diamine Phenylphenoxy) biphenyl, 2,2-bis [4- (3,4-diaminophenoxy) phenyl] propane 2,2-bis [4- (3,4-diaminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3,4-diaminophenoxy) phenyl] Hydrazone, 2,2-bis [3- (3,4-diaminophenoxy) phenyl] fluorene, 2,2-bis [4- (3,4-diaminophenoxy) phenyl] Methane, 2,2-bis [4- (3,4-diaminophenoxy) phenyl] one, 2,2-bis [4- (3,4-diaminophenoxy) phenyl] Ether, etc.

Examples of the alicyclic tetraamine include the hydrides of various aromatic tetraamines described above (for example, 3,3 ', 4,4'-tetraaminodicyclohexyl ether, 3,3', 4,4 ' -Tetraaminodicyclohexylfluorene, 3,3 ', 4,4'-tetraaminodicyclohexyl ketone, 3,3', 4,4'-tetraaminodicyclohexane, 1,2,4 , 5-tetraaminocyclohexane, etc.) as suitable.

From the viewpoint of heat resistance, such a tetraamine is particularly preferably an aromatic tetramine; more preferably TAB-E, TAB-S, TAB-K, TABP, TAB, 2,2-isopropylidenebis ( 3,4-diaminobenzene), 2,2-hexafluoroisopropylidenebis (3,4-diaminobenzene); particularly preferred are TAB-E, TAB-S, TAB-K, TABP, TAB .

In addition, the tetravalent organic group which can be selected as X ² in the formula (1-1) is preferably 4 represented by the general formulae (6-1) to (7-1) from the viewpoint of mechanical strength. Price base. Here, Z ¹ in formula (7-1) represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H _4- Phenylene, represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ , -OC ₆ H ₄ -Z ² -C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, and a sulfonyl group represented by -S (= O) _{2- 1} type of group consisting of isopropylidene represented by -C (CH ₃ ) _2- , hexafluoroisopropylidene represented by -C (CF ₃ ) ₂ -and methylene represented by -CH _2- One of the groups consisting of a bis (phenylene dioxy) group represented by], a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-. Such Z ¹ has a viewpoint of considering both heat resistance and mechanical strength, especially an ether group and a single bond represented by -O-, and a viewpoint of considering both transparency and mechanical strength, especially -C (= O) A carbonyl group represented by-and a sulfofluorenyl group represented by -S (= O) ₂ -are preferred. In addition, the bonding sites with symbols * 1 to * 4 in the formulas (6-1) to (7-1) are each bonded to any of the four bonding sites of X ² . In addition, the tetravalent group represented by the general formulae (6-1) to (7-1) is selected from those tetraamines (for example, TAB-E, TAB-S, TAB-K, TABP) , TAB, etc.), used in the manufacture of repeating units, can be used as the residue after removing 4 amine groups from the tetraamine, and introduced at the position of X ² .

The repeating unit (A) represented by the general formula (1-1) can be reacted (polymerized) with the tetraamine dianhydride having an alicyclic structure having a 6-membered ring, and the tetraamine, for example. More efficient introduction into the resin. Therefore, the resin containing the repeating unit (A) represented by the general formula (1-1) is preferably the first monomer containing the aforementioned tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring, and the aforementioned tetraamine Polymer of the second monomer.

X ³ in the general formula (1-2) represents a trivalent organic group. Such a trivalent organic group is not particularly limited, and a residue obtained by removing three amine groups from a triamine is preferred. Such a triamine may be an aromatic triamine or an alicyclic triamine. Further, as used herein, the triamine, in order to enhance stability or storage stability of paint, -NH ₂ may be a silicon to be in the alkylation of H, alkyl silicon becomes trimethyl-butyldimethyl or t- Silane base.

Such an aromatic triamine is not particularly limited, and a known aromatic triamine (for example, a phenyltriamine type, a diphenyl ether type, a diphenylfluorene type, a diphenyl ketone type, a biphenyl type, a benzene type, etc.) can be appropriately used. Formamidine type, benzoate type, diphenyl sulfide type, Bis-A type (diphenylisopropylidene type), hexafluoro Bis-A type, Bis-M type (diphenylmethane type) ), Bis-C type (diphenylcyclohexane type), Bis-F type (diphenylfluorene type), bitriphenyl type (triphenyl type), diphenylene dioxy type, bis (diphenylene) Aromatic triamines such as dioxo), hydrazone, helical, silicon, etc.).

Examples of such an aromatic triamine include 3,4,4'-triaminodiphenyl ether (TrAB-E), 3,4,4'-triaminodiphenylphosphonium (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'-triaminodiphenylphosphonium, 3,4 , 4'-triaminodiphenylsulfide, 3,4,4'-triaminodiphenyl ester, 3,4,4'-triaminodiphenylphosphonium amine, 3,4,4 '' -Triaminobitriphenyl and the like.

Examples of the alicyclic triamine include hydrides of various aromatic triamines described above (for example, 3,4,4'-triaminodicyclohexyl ether, 3,4,4'-triaminodicyclohexyl Hydrazone, 3,4,4'-triaminodicyclohexyl ketone, 3,4,4'-triaminodicyclohexane, 1,2,4-triaminocyclohexane, etc.) as suitable .

From the viewpoint of heat resistance, such triamines are particularly preferably aromatic triamines; more preferred are TrAB-E, TrAB-S, TrAB-K, TrABP, and TrAB; and particularly preferred are TrAB-E, TrAB-S. , TrAB-K.

The trivalent organic group that can be selected as X ³ in the formula (1-2) is preferably 3 represented by the general formulae (6-2) to (7-2) from the viewpoint of mechanical strength. Price base. Here, Z ¹ in formula (7-2) is selected from the group consisting of a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H _4- Phenylene, represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ , -OC ₆ H ₄ -Z ² -C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, and a sulfonyl group represented by -S (= O) _{2- 1} type of group consisting of isopropylidene represented by -C (CH ₃ ) _2- , hexafluoroisopropylidene represented by -C (CF ₃ ) ₂ -and methylene represented by -CH _2- One of the groups consisting of a bis (phenylene dioxy) group represented by], a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-. Such Z ¹ has the viewpoint of considering both heat resistance and mechanical strength. Among them, an ether group represented by -O- and a single bond are preferred. From the viewpoint of considering both transparency and mechanical strength, -C (= A carbonyl group represented by O)-and a sulfonyl group represented by -S (= O) _2- . In addition, the bonding sites with symbols * 1 to * 3 in formulas (6-2) to (7-2) are each bonded to any of the three bonding sites of X ³ . In addition, the trivalent group represented by such general formulae (6-2) to (7-2) is appropriately selected from the above triamines (for example, TrAB-E, TrAB-S, TrAB-K, TrABP). , TrAB, etc.), used in the manufacture of repeating units, can be introduced at the position of X ³ as a residue after removing three amine groups from the triamine.

Further, the repeating unit (A ') represented by the general formula (1-2) can be reacted (polymerized) with the triamine by reacting the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring, for example. More efficient introduction into the resin. Therefore, the resin containing the repeating unit (A ′) represented by the general formula (1-2) is preferably a first monomer containing the aforementioned tetracarboxylic dianhydride having an alicyclic structure having 6 member rings, and a resin containing the aforementioned three Polymer of amine second monomer.

In addition, the resin of the present invention preferably further contains a repeating unit having a fluorene imine structure represented by the general formula (2) (hereinafter, the repeating unit having a fluorene imine structure is referred to simply as a case in which it is referred to for convenience). "Repeat Unit (B)").

Furthermore, the present inventors and others have speculated that when the resin of the present invention is a resin containing at least one repeating unit selected from the group consisting of repeating units (A) and (A '), and repeating unit (B), At the time of its manufacture, a cyclic structural part containing two nitrogen atoms in a structure of at least one repeating unit selected from the group consisting of repeating units (A) and (A ') (imidazole is particularly preferred) Structural part of the structure: In addition, when X ² and X ³ are respectively aromatic, their structural parts may each be an imidazole structure), which can be used as a self-catalyst when manufacturing the repeating unit (B) (during the thermal amidation). The effect is to further promote the reaction to form a repeating unit (B) having a fluorene imine structure, and the copolymer containing the repeating unit (B) (containing a group selected from the group consisting of repeating units (A) and (A ')) The resin of the present invention having at least one repeating unit (reactant) has a larger molecular weight, so that the repeating unit (B) can be contained in comparison with a case where a resin composed of only the repeating unit (B) is produced. The resin has higher properties such as strength and heat resistance. In particular, a stronger film can be obtained for tensile stress. In this way, in the resin (copolymer) containing the repeating unit (A) and / or (A ') and the repeating unit (B), the repeating unit (A) and / Or (A ') structure to promote the reaction of forming repeating units (B), so even if the total amount (content) of repeating units (A) and (A') is a trace amount, compared with only repeating units (B) The resin formed can also be used to produce resins with higher characteristics.

X ¹ in the general formula (2) is a tetravalent organic group having a 6-membered alicyclic structure, and is synonymous with X ¹ in the general formula (1-1) (the same applies to those as appropriate).

X ⁴ in the general formula (2) is an arylene group having 6 to 50 carbon atoms. The carbon number of such an arylene is preferably 6 to 40, more preferably 6 to 30, and even more preferably 12 to 20. When such a carbon number does not reach the aforementioned lower limit, the heat resistance of the resin tends to decrease when the resin is formulated. On the other hand, when it exceeds the aforementioned upper limit, the resin's transparency tends to decrease when the resin is formulated.

In addition, X ⁴ in the general formula (2) has the viewpoint of obtaining higher heat resistance and mechanical strength, and is preferably the following general formulas (a) to (d):

[In formula (c), R ¹¹ represents one 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. In the formula (d), Q It is selected from the group consisting of 9,9-fluorenylene; formula: -O-, -S-, -CO-, -CONH-, -NHCO-, -SO _2- , -SO-, -C (CF ₃ ) _2- , -OC ₆ H ₄ -O-, -C (CH ₃ ) _2- , -CH _2- , -OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -C (CF ₃ ) ₂ -C ₆ H ₄ -O-,
-OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -C (CH ₃ ) ₂ -C ₆ H ₄ -C (CH _{3 ) 2 -, - OC 6 H} 4 -C 6 H 4 -O -, - CONH-C 6 H 4 -NHCO -, - NHCO-C 6 H 4 -CONH -, - C 6 H 4 - and, -OC ₆ H ₄ -O-, -OC ₆ H ₄ -OC ₆ H ₄ -O-, -COO-, -OCO-, -NH-CO-NH-, -N (Ph)-, -P (= O) A group represented by (Ph)-; 1,1-cyclohexylene; 1,1-cyclopentylene; and the following general formula (e):

(In the formula (e), R ^a independently represents any one of an alkyl group, a phenyl group, and a tolyl group having 1 to 10 carbon atoms, and y represents an integer from 1 to 100)
1 type of group formed by the base of representation]
At least one of the bases.

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

Among the groups represented by the general formula (e) that can be selected as Q in the general formula (d), R ^a is independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a tolyl group. Any one kind. When the carbon number of such an alkyl group exceeds the aforementioned upper limit, the heat resistance or transparency of the resin tends to decrease when the resin is formulated. Such R ^{a is} preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a tolyl group; more preferably a methyl group, an ethyl group; and even more preferably a methyl group. In addition, y in the general formula (e) represents an integer of 1 to 100, more preferably 3 to 50, and still more preferably 5 to 25. When y does not reach the lower limit, the mechanical strength tends to decrease. On the other hand, when y exceeds the upper limit, when the resin is formulated, the heat resistance or transparency of the resin tends to decrease.

From the viewpoint that a hardened product having heat resistance, transparency, and mechanical strength can be obtained in a well-balanced manner at a sufficient level, Q in the general formula (d) is preferably a 9,9-fluorenyl group, a formula : -CONH-, -NHCO-, -OC ₆ H ₄ -O-, -O-, -C (CH ₃ ) _2- , -C ₆ H _4- , -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -CH _2- , -OC ₆ H ₄ -C ₆ H ₄ -O-,
-OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -O-, -SO _2- , -SO-, -OCO-, or a base represented by -COO-, or 1,1-cyclohexyl Hexyl; particularly preferred is 9,9-arylene, or
-CONH-, -NHCO-, -CH _2- , -OC ₆ H ₄ -O-, -OC ₆ H ₄ -C ₆ H ₄ -O-, -SO _2- , -OCO-, -COO-, or A base represented by -O-; the most preferred is 9,9-arylene, or a formula represented by -CONH-, -SO _2- , -OCO-, -COO-, -CH _2- , or -O-. Furthermore, from the viewpoint of adhesiveness or laser peelability, Q in the general formula (d) is preferably a base represented by the general formula (e), and from the viewpoint of linear expansion coefficient and heat resistance, Formula: a base represented by -OCO-, -COO-, -CONH-, -NHCO-.

From the viewpoint that a resin having heat resistance, transparency, and mechanical strength can be obtained in a well-balanced manner at a sufficient level, such X ^{4 is} preferably selected from 4,4′-diaminobenzidine aniline ( DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 9,9'-bis (4-aminophenyl) ) (FDA), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, p-diamine Phenylbenzene (PPD), p-diaminotoluene, p-diaminoxylene, p-diaminotrimethylbenzene, p-diaminotetramethylbenzene, 2,2'-dimethyl-4,4 ' -Diaminobiphenyl (alias: m-benzidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (alias: o-benzidine), 3,3'- Dimethoxy-4,4'-diaminobiphenyl (alias: bifenisidine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4-amine Benzoic acid (BAAB), 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl (BABB), 3,3'-diaminodiphenylphosphonium (3 , 3'-DDS) and 4,4'-diaminodiphenylphosphonium (4,4'-DDS) in a group consisting of at least one aromatic diamine with two divalent groups removed from two amine groups (Strandyl); better Selected from the group consisting of 4,4'-diaminobenzidine aniline (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB ), 9,9'-bis (4-aminophenyl) pyrene (FDA), m-toluidine (m-Tol), 4,4'-diamino-3,3'-dihydroxybiphenyl (DAHB), p-diaminobenzene (PPD), and 4-aminophenyl-4-aminobenzoic acid (BAAB) in a group of at least one aromatic diamine to remove two of two amine groups Valent group (arylene); and more preferably selected from 4,4'-diaminobenzidine aniline (DABAN), 4,4'-diaminodiphenyl ether (DDE), and 2,2 '-Bis (trifluoromethyl) benzidine (TFMB) is a group consisting of at least one type of aromatic diamine in which two divalent groups (arylene) of two amine groups are removed.

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

The diamine which can be used to introduce the repeating unit (B) represented by the general formula (2) into a resin is not particularly limited, and may be an aliphatic diamine or an aromatic diamine. Such a diamine is preferably an aromatic diamine from the viewpoints of heat resistance and simplicity of the polymerization method. Such an aromatic diamine is more preferably the following general formula (iv):

[In formula (iv), X⁴ Represents an arylene group having 6 to 50 carbon atoms]
An aromatic diamine. In addition, the diamine used here may be -NH in order to improve the storage stability or stability of the paint.₂ One of H is silylated to become trimethylsilyl or t-butyldimethylsilyl.

Such a formula: The aromatic diamine represented by H ₂ NX ⁴ -NH ₂ is not particularly limited, and a known one may be appropriately used or a commercially available one may be appropriately used. Examples of such an aromatic diamine include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3- Aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy) phenyl] one, 2,2'-bis (trifluoromethyl) -4,4'-diamine Biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis ( 3-fluoro-4-aminophenyl) fluorene, 9,9-bis (3-chloro-4-aminophenyl) fluorene, 9,9-bis (3-bromo-4-aminophenyl) fluorene , 1,1-bis (4-aminophenyl) cyclohexane, 1,1-bis (4-aminophenyl) cyclopentane, p-diaminobenzene, m-diaminobenzene, o -Diaminobenzene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3 ' -Dimethylbiphenyl, 3,3'-diaminobiphenyl 2,2'-diaminobiphenyl, 3,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 4 , 4 '-[1,3-phenylenebis (1-methyl-ethylene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methyl-ethylene) )] Bisaniline, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( 4-aminophenoxy) biphenyl, 4,4'-diaminobenzidineaniline, 3,4'-diaminobenzidineaniline, 9,9'-bis (4-aminophenylphenyl) ) 茀, o-benzidine hydrazone, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3 ', 5,5'-tetramethylbenzidine, 1,5- Bis (4-aminophenoxy) pentane, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, 4- Aminophenyl-4-aminobenzoic acid, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl and the like. Moreover, such an aromatic diamine can be used individually by 1 type or in combination of 2 or more types.

When two or more kinds of aromatic diamines are used in combination, it is preferable to use 4,4'-diaminobenzidine aniline (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 9,9'-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD), 2,2 '-Dimethyl-4,4'-diaminobiphenyl (alias: m-bistoluidine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4 -Aminobenzoic acid (BAAB), 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl (BABB), 3,3'-diaminodiphenyl At least two selected from osmium (3,3'-DDS) and 4,4'-diaminodiphenyl hydrazone (4,4'-DDS); preferably, 4,4'-diamino Benzamidine aniline (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 9,9'-bis (4 -Aminophenyl) fluorene (FDA), p-diaminobenzene (PPD), 4-aminophenyl-4-aminobenzoic acid (BAAB), 3,3'-diaminodiphenylfluorene (3,3'-DDS) and 4,4'-diaminodiphenylphosphonium (4,4'-DDS). When two or more kinds of aromatic diamines are used in combination, a combination of 4,4'-diaminobenzidine aniline (DABAN) and 4,4'-diaminodiphenyl ether (DDE) is more preferable. Combination, 4,4'-diaminobenzidine aniline (DABAN) and 2,2'-bis (trifluoromethyl) benzidine (TFMB), 4,4'-diaminobenzidine aniline (DABAN) in combination with p-diaminobenzene (PPD), 3,3'-diaminodiphenylphosphonium (3,3'-DDS) and 4,4'-diaminodiphenylphosphonium ( 4,4'-DDS), 4-aminophenyl-4-aminobenzoic acid (BAAB) and 2,2'-bis (trifluoromethyl) benzidine (TFMB), and 4- At least one combination selected from the group consisting of aminophenyl-4-aminobenzoic acid (BAAB) and p-diaminobenzene (PPD).

In addition, 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 having a 6-membered ring with the diamine, for example. in. Therefore, the resin of the present invention containing the above-mentioned repeating unit (B) is preferably the first monomer containing the aforementioned tetracarboxylic dianhydride having an alicyclic structure having 6-membered rings. A tetracarboxylic dianhydride having an alicyclic structure, together with other tetracarboxylic dianhydrides, etc.), and a polymer containing tetraamine and / or triamine, and a second monomer (amine component) of the diamine.

In addition, 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 relative to all repeating units contained in the resin. The ear ratio is a reference, preferably 3 to 100 mole%, and more preferably 5 to 50 mole%. When such a molar ratio does not reach the aforementioned lower limit, there is a tendency that the properties derived from the repeating unit (A) and / or (A ') cannot be sufficiently imparted to the obtained resin. Furthermore, if at least one repeating unit selected from the group consisting of the repeating unit (A) and the repeating unit (A ') is formed, a so-called ladder structure can be formed. Based on the structure, the The resin imparts a higher degree of heat resistance.

As described above, the resin of the present invention preferably further contains the above-mentioned repeating unit (B). As described above, the resin of the present invention is preferably a copolymer containing at least one repeating unit selected from the group consisting of the repeating units (A) and (A ') and the repeating unit (B). When the repeating unit (B) is contained in this way, the total amount (total amount) of the repeating unit (A), the repeating unit (A '), and the repeating unit (B) is preferably relative to all repeating units. 20 to 100 mole% (more preferably 30 to 100 mole%, still more preferably 40 to 100 mole%, yet more preferably 50 to 100 mole%, particularly preferably 60 to 100 mole%) . In addition, regarding the total amount (total) of the repeating unit (A), the repeating unit (A '), and the repeating unit (B), the lower limit of the numerical value range is more preferably 70 mol%, and more It is preferably 80 mol%, and most preferably 90 mol%. When the total amount (total amount) of such repeating units does not reach the aforementioned lower limit, there is a tendency that a high degree of heat resistance cannot be imparted.

When the resin of the present invention contains at least one type of repeating unit selected from the group consisting of the repeating units (A) and (A ′) and a copolymer with the repeating unit (B), the repeating unit (B The content of) is preferably 1 to 99 mol%, more preferably the total amount (total) of the aforementioned repeating unit (A), the aforementioned repeating unit (A '), and the aforementioned repeating unit (B). 5 ~ 95 mole%, especially good is 10 ~ 90 mole%. Relative to the 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) does not reach the aforementioned lower limit, transparency is achieved. From the viewpoint of dimensional stability, it is difficult to obtain higher characteristics. On the other hand, when the upper limit is exceeded, it is difficult to obtain higher characteristics from the viewpoint of high heat resistance and mechanical characteristics.

The resin of the present invention is not particularly limited as long as it contains at least one type of repeating unit selected from the group consisting of the repeating units (A) and (A ′). Those containing the repeating unit (A) and the repeating unit (A ') may also include the repeating unit (A) and the repeating unit (A') and the repeating unit (B). Furthermore, the resin of the present invention may contain other repeating units other than the repeating unit (A), the repeating unit (A ′), and the repeating unit (B). Such other repeating units can be formed, for example, from a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring, and selected from the group consisting of diamine, triamine, and tetraamine A repeating unit formed by the reaction of at least one species of a group; a tetracarboxylic dianhydride having a 6-membered alicyclic structure, and a polyfunctional alcohol, polyfunctional phenol, polyfunctional thiol, and polyfunctional thiophenol And the like. Such other tetracarboxylic dianhydrides are not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-biphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4'-oxydi Phthalic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy) diphenylphosphonium dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro Isopropylidene diphthalic dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 3,3', 4,4'-biphenyltetra Carboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) Phthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4, Aromatic tetracarboxylic dianhydrides such as 4'-diphenylmethane dianhydride; butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, cyclooctane tetracarboxylic dianhydride, cyclononane tetracarboxylic dianhydride, cyclodecane tetracarboxylic dianhydride, meso-butane Alkane-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-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexyl Ene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, tricyclic [6.4.0.0 ^2,7 ] Dodecane-1,8: 2,7-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride trans isomer, The cis isomer of cyclopentane-1,2,3,4-tetracarboxylic dianhydride, the trans isomer of cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane Aliphatic or alicyclic tetracarboxylic dianhydride, such as the cis isomer of alkane-1,2,3,4-tetracarboxylic dianhydride.

The polyfunctional alcohol, the polyfunctional phenol, the polyfunctional thiol, and the polyfunctional thiophenol are not particularly limited. For example, aliphatic diols, alicyclic diols, diphenols, bisphenols, and fatty acids can be used. Group dithiols, alicyclic dithiols, dithiophenols, dithiophenols and the like.

In addition, at least one repeating unit selected from the group consisting of the repeating unit (A) and the repeating unit (A ′) is used in the aforementioned tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring and In addition to the formation of the reaction of the amine component, for example, a diester dicarboxylic acid of a derivative (modified) of a tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring and a dichloride of a diester dicarboxylic acid may be used. At least one of the compounds is formed by reacting the modified product with at least one amine component selected from the triamine and the tetraamine. Furthermore, at least one type of repeating unit selected from the group consisting of the aforementioned repeating unit (A) and the aforementioned repeating unit (A ') may also make the aforementioned tetracarboxylic dianhydride having an alicyclic structure of 6 members ring, It is formed by reacting with an equivalent of at least one amine component selected from the derivative of the triamine and the derivative of the tetraamine.

Regarding the diester dicarboxylic acid and the diester dicarboxylic acid dichloride derivative (modified product) of the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring, for example, a diester dicarboxylic acid is prepared as the aforementioned In the case of a derivative, a method of obtaining a corresponding diester dicarboxylic acid by reacting the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring with an arbitrary alcohol, and the like can be used to prepare the diester dicarboxylic acid. When a carboxylic acid dichloride is used as the derivative, a tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring may be reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid. A method in which an acid is reacted with a chlorinated reagent (such as thionyl chloride, chloracetin, etc.) to obtain a diester dicarboxylic acid dichloride, and the like.

Furthermore, examples of the derivative of the triamine and the derivative of the tetraamine include a silylated compound obtained by reacting at least one compound selected from the group consisting of the triamine and the tetraamine with a silylating agent. Tetraamine and / or silane triamine. For example, one of the -NH ₂ groups in the aforementioned triamine is silylated to form a trimethylsilyl group or a t-butyldimethylsilyl group. Examples of such silylated tetraamines include, for example, tetrasilyl derivatives such as TAB-E, TAB-S, TAB-K, TABP, and TAB, and such silylated triamines, such as Trisilyl derivatives such as TrAB-E, TrAB-S, TrAB-K, TrABP, and TrAB are listed. Examples of such silylating agents include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, and hexamethyldisilazane , Trimethylsilyl chloride, etc. The method for producing such a silylated amine is also not particularly limited, and a known method can be appropriately adopted. Moreover, such a silylated amine can also use a commercial item suitably.

In addition, the repeating unit (B) may be formed by reacting a tetracarboxylic dianhydride having a 6-membered ring alicyclic structure with the diamine, for example, a 6-membered alicyclic ring may be used. A diester dicarboxylic acid of a derivative (modified product) of a tetracarboxylic dianhydride structure and a diester dicarboxylic acid dichloride, and the modified product is reacted with at least one amine component selected from the aforementioned diamines. form. Further, the repeating unit (B) may be formed by reacting a tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and a derivative of the diamine.

Examples of the derivative of the diamine include a silylated diamine obtained by reacting the diamine with a silylating agent. Examples of the derivative include an aromatic diamine represented by the formula: H ₂ NX ⁴ -NH ₂ and silane. Diamine obtained by the reaction of a chemical agent. Examples of such a silylated diamine include disilyl derivatives such as DDE, TFMB, FDA, PPD, and m-benzylamine. Examples of such silylating agents include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, and hexamethyldisilazane , Trimethylsilyl chloride, etc. The method for producing such a silylated diamine is also not particularly limited, and a known method can be appropriately adopted. Moreover, such a silylated diamine can also use a commercial item suitably.

The resin of the present invention is preferably a glass transition temperature (Tg) of 300 ° C or higher, more preferably 300 ° C to 550 ° C, and still more preferably 350 to 500 ° C. When such a glass transition temperature (Tg) does not reach the aforementioned lower limit, it is difficult to achieve a high level of heat resistance. On the other hand, when the aforementioned upper limit is exceeded, it is difficult to produce a resin having such characteristics. In addition, such a glass transition temperature (Tg) can be measured by a tensile mode using a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku). That is, a thin film of resin with a length of 20 mm and a width of 5 mm (the thickness of the film has no effect on the measured value and is not particularly limited, and preferably 5 to 100 μm) is used as a measurement sample under a nitrogen environment. The measurement was performed under the conditions of a tensile mode (49 mN) and a heating rate of 5 ° C / min, and was obtained by extrapolating the inflection points of the TMA curve caused by glass transition and the curves before and after.

In addition, such a resin is preferably a 5% weight reduction temperature of 450 ° C or more, more preferably 460 to 550 ° C, and still more preferably 470 to 530 ° C. When such a 5% weight reduction temperature does not reach the aforementioned lower limit, it tends to be difficult to achieve sufficient heat resistance. On the other hand, when the aforementioned upper limit is exceeded, it is difficult to produce a resin having such characteristics. In addition, such a 5% weight reduction temperature can be obtained by slowly heating from room temperature (for example, 30 ° C) while flowing nitrogen under a nitrogen environment, and measuring the temperature at which the weight of the sample used is reduced by 5%.

Further, such a resin is preferably a softening temperature of 300 ° C or higher, more preferably 350 to 550 ° C, and still more preferably 400 to 500 ° C. When such a softening temperature does not reach the aforementioned lower limit, it is difficult to achieve sufficient heat resistance. On the other hand, when it exceeds the aforementioned upper limit, it is difficult to produce a resin having such characteristics. In addition, such a softening temperature can be measured by a penetration mode by using a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku). In addition, during the measurement, the size of the sample (vertical, horizontal, thickness, etc.) has no effect on the measured value. Therefore, as long as the size of the sample is appropriately adjusted so that it can be mounted on the thermomechanical analysis device (trade name manufactured by Rigaku, " TMA8311 ″).

Such a resin preferably has an elongation at break point of 3% or more, more preferably 5% or more, and particularly preferably 7% or more. When the elongation at such a break point does not reach the aforementioned lower limit, there is a tendency that the toughness is low and the mechanical properties are weak. The tensile strength of the resin of the present invention is preferably 50 MPa or more, more preferably 70 MPa or more, and particularly preferably 100 MPa or more. When such a tensile strength does not reach the aforementioned lower limit, a film having higher toughness cannot be obtained. The upper limit of the tensile strength of such a resin is not particularly limited, but is preferably 1000 MPa or less. When such a tensile strength becomes a value exceeding the said upper limit, there exists a tendency for processing to become difficult. The values of such tensile strength and elongation at break can be obtained by a test in accordance with JIS K7162 (issued in 1994). For example, values obtained as described below can be used. That is, first, a test piece conforming to the specifications of model A22 (reduced-size test piece) described in JIS K7139 (issued in 2009), except for a thickness of 10 μm, is prepared using an electromechanical universal material testing machine (for example, manufactured by INSTRON). Model "5943"), the aforementioned measurement sample is arranged with a width of 57 mm between the clamps and a width of 10 mm (the full width of the end of the test piece), and then a dynamometer: 1.0 kN and a test speed : The tensile test for stretching the aforementioned measurement sample is performed at a condition of 5 mm / min. The obtained tensile strength (stress at break [unit: MPa]) and the value of the elongation at break (unit:%) can be used. value.

The linear expansion coefficient (CTE) of such a resin is preferably -50 to 100 ppm / K, and more preferably 0 to 50 ppm / K. When such a linear expansion coefficient exceeds the above-mentioned upper limit, when it is combined with a metal or an inorganic substance having a linear expansion coefficient in the range of 5 to 20 ppm / K and composited, there is a tendency that peeling tends to occur due to a thermal history. In addition, when the linear expansion coefficient does not reach the lower limit, when it is combined with a metal or an inorganic substance to form a composite, the peeling tends to occur easily due to a thermal history. The method for measuring the linear expansion coefficient of such a resin is the method described below. That is, first, a thin film of 20 mm in length and 5 mm in width made of the aforementioned resin is formed (the thickness of the film does not affect the measured value, so there is no particular limitation, preferably 5 to 100 μm) as a measurement sample. A thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku) was used as a measuring device. In a nitrogen environment, a tensile mode (49mN) was used. In a nitrogen environment, a tensile mode (49mN) was used. A heating rate was 5 ° C / The condition of minutes is to measure the change in length in the longitudinal direction of the aforementioned sample at 50 ° C to 200 ° C, and to use the average value obtained by calculating the change in length per 1 ° C in the temperature range of 50 ° C to 200 ° C. value.

Further, such a resin is preferably one having sufficiently high transparency when forming a film, and more preferably one 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 or the content of the repeating unit in the resin. In addition, such a resin has the viewpoint of obtaining a higher degree of colorless transparency, and is more preferably a haze (turbidity) of 5 to 0 (more preferably, 4 to 0, particularly preferably 3 to 0). When the value of such a haze exceeds the aforementioned upper limit, it tends to be difficult to achieve a higher level of colorless transparency. Further, with such a resin, the viewpoint of obtaining a higher degree of colorless transparency, and more preferably a yellowness (YI) of 10 to 0 (more preferably 8 to 0, particularly preferably 6 to 0). When such a yellowness exceeds the above-mentioned upper limit, it tends to be difficult to achieve a higher level of colorless transparency. In addition, for such a total light transmittance, haze (turbidity), and yellowness (YI), a brand name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. or Nippon Denshoku Industries Co., Ltd. can be used. Co., Ltd.'s product name "Spectrophotometer SD6000" is used as a measuring device. (The product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. is used to measure the total light transmittance and haze. The trade name "Spectrophotometer SD6000" manufactured by Industrial Co., Ltd. measures yellowness), and a 10 µm-thick film made of the aforementioned resin is used as a measurement sample, and the measured value is used. In addition, the vertical and horizontal sizes of the measurement sample need only be a size (5 cm square or more) that can be placed on the measurement site of the measurement device, and the vertical and horizontal sizes can be appropriately changed. In addition, such a total light transmittance is obtained by measuring in accordance with JIS K7361-1 (issued in 1997), and a haze (turbidity) is measured by performing in accordance with JIS K7136 (issued in 2000) The yellowness (YI) was determined by measuring in accordance with ASTM E313-05 (published in 2005).

In addition, such a resin may contain various additives used according to the purpose of the resin, components (such as catalysts, etc.) used in the production of the resin, other resins, etc., as long as the effect of the present invention is not impaired. For example, it may contain a fluorene imidation accelerator, a chemical fluoridation agent, an antioxidant (phenol, phosphite, thioether, etc.), an ultraviolet absorber, a hindered amine light stabilizer, a nucleating agent, and a resin. Additives (fillers made of inorganic compounds such as nanometer silicon dioxide, talc, glass fibers, alumina fibers, etc.), coupling agents (silane coupling agents, etc.), processability improvers, lubricating materials, dyes, pigments, flame retardants Materials, defoamers, leveling agents, rheology control agents (flow aids), release agents, primers, etc. When other resins are added (when added), for example, cellulose nanofiber, nylon, polycarbonate, polyester, polyamide, polyketone, polyetherketone, polyfluorene, polyetherfluorene, PMMA can be used. , Polyethylene, polypropylene, polystyrene, Teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, triacetin cellulose (TAC) and other resins.

Next, the resin precursor of the present invention will be described. The resin precursor of the present invention is a repeating unit containing an imidazopyrrolidone precursor structure selected from the group consisting of the imidazopyrrolidone precursor represented by the above general formula (8-1) For convenience, it is simply referred to as "repeating unit (C)"), and a repeating unit having the structure of the imidazopyrrolidone precursor represented by the above general formula (8-2) The repeating unit of the precursor structure is simply referred to as a "repeat unit (C ')") for the convenience of at least one repeating unit.

X ¹ in the general formula (8-1) and the general formula (8-2) is a tetravalent organic group having an alicyclic structure having 6 member rings, and is the same as the general formula (1-1) and ( X ^{1 in} 1-2) is synonymous (the same applies to those who are suitable). In addition, X ² in the general formula (8-1) represents a tetravalent organic group, and is synonymous with X ² in the general formula (1-1) (the same applies to those as appropriate). Further, X ³ in the above-mentioned general formula (8-2) represents a trivalent organic group, and is synonymous with X ³ in the above-mentioned general formula (1-2) (which is also the same as applicable).

Such at least one repeating unit selected from the group consisting of a repeating unit represented by the general formula (8-1) and a repeating unit represented by the general formula (8-2), for example, the above-mentioned lipid having a 6-membered ring can be used. The reaction of a tetracarboxylic dianhydride having a ring structure with a tetramine and / or a reaction of a tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring and a triamine are formed. In addition, the monomer component can be appropriately selected by the design according to the target, and a desired repeating unit represented by the general formula (8-1) and / or the general formula (8-2) can be introduced into the resin.

Further, the resin precursor of the present invention preferably further contains a repeating unit having a fluorene imine precursor structure represented by the general formula (9) (hereinafter, the repeating unit having a fluorene imine precursor structure may be hereinafter described, as appropriate, For convenience, it is simply referred to as "repeat unit (D)").

X ¹ in the general formula (9) is a tetravalent organic group having an alicyclic structure having 6 member rings, and is synonymous with X ¹ in the general formulae (1-1) and (1-2) (which is suitable The same). In addition, X ⁴ in the general formula (9) is an arylene group having 6 to 50 carbon atoms, and is synonymous with X ⁴ in the general formula (2) (the same applies to those that are suitable).

Such a repeating unit represented by the general formula (9) can be obtained, for example, by reacting a tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring with an aromatic diamine represented by the general formula (iv). Furthermore, the monomer component can be appropriately selected by the design according to the target, and the desired repeating unit represented by the general formula (9) can be introduced into the resin.

Moreover, 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 relative to all the repeating units contained in the resin, Based on the mole ratio, it is preferably 3 to 100 mole%, and more preferably 5 to 50 mole%. When such a molar ratio does not reach the aforementioned lower limit, there is a tendency that the characteristics obtained from the repeating unit (A) and / or the repeating unit (A ') cannot be sufficiently imparted to the resin obtained by using the resin precursor. .

The resin precursor of the present invention preferably further contains the repeating unit (D). As described above, the resin precursor of the present invention preferably contains at least one repeating unit selected from the group consisting of the repeating unit (C) and the repeating unit (C '), and is copolymerized with the repeating unit (D). Thing. When the repeating unit (D) is contained in this way, the total amount (total) of the repeating unit (C), the repeating unit (C '), and the repeating unit (D) is preferably more than all repeating units. 20 to 100 mole% (more preferably 30 to 100 mole%, still more preferably 40 to 100 mole%, yet more preferably 50 to 100 mole%, particularly preferably 60 to 100 mole%) . Regarding the total amount (total) of the repeating unit (C), the repeating unit (C '), and the repeating unit (D), the lower limit of the numerical value range is more preferably 70 mol%, and more preferably It is 80 mol%, preferably 90 mol%. When the total amount (total amount) of such repeating units does not reach the aforementioned lower limit, the resin obtained by using the resin precursor may not be able to adequately provide a unit selected from repeating units (A) and repeating units (A '). At least one repeating unit of the formed group, and the tendency of the characteristics of the repeating unit (B).

When the resin precursor of the present invention is a copolymer containing at least one 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 moles relative to the total amount (total) of the repeating unit (C), the repeating unit (C '), and the repeating unit (D). %, More preferably 25 to 95 mole%, and particularly good 50 to 90 mole%. With respect to the 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) does not reach the aforementioned lower limit, there is a right The resin obtained by using the resin precursor does not necessarily tend to sufficiently impart characteristics derived from the repeating unit (B). On the other hand, when the above-mentioned upper limit is exceeded, the resin obtained by using the resin precursor may not be obtained. The characteristic derived from the repeating unit (A) and / or the repeating unit (A ') can be sufficiently imparted.

The resin precursor of the present invention is not particularly limited as long as it contains at least one repeating unit selected from the group consisting of the repeating units (C) and (C '). For example, it may contain The repeating unit (C) and the repeating unit (C ') may include the repeating unit (C) and / or the repeating unit (C') and the repeating unit (D). Further, the resin precursor of the present invention may contain the repeating unit (C), the repeating unit (C '), and other repeating units other than the repeating unit (D). Such other repeating units may use a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring, and a group selected from the group consisting of diamine, triamine, and tetraamine. A repeating unit formed by the reaction of at least one of the above; a diester dicarboxylic acid selected from a derivative (modified) of a tetracarboxylic dianhydride derived from the aforementioned alicyclic structure having a 6-membered ring, and a diester dicarboxylic acid A repeating unit formed by the reaction of at least one species of a group consisting of carboxylic acid dichloride and at least one species selected from the group consisting of diamine, triamine, and tetraamine; Tetracarboxylic dianhydride of alicyclic structure, a repeating unit formed by the reaction of a polyfunctional alcohol, polyfunctional phenol, polyfunctional thiol, polyfunctional thiophenol; The carboxylic dianhydride is a repeating unit formed by a reaction with at least one selected from the group consisting of a derivative of the triamine and a derivative of the tetraamine.

Moreover, such a resin precursor may contain various additives or components (such as catalysts, etc.) used in the production of the resin, as long as the effect of the present invention is not impaired, depending on the purpose of the resin to be finally formed. And other resins, for example, may contain fluorinated imidization catalysts, chemical fluorinated imidization agents, antioxidants (phenol-based, phosphite-based, thioether-based, etc.), ultraviolet absorbers, and hindered amine-based light stabilizers. , Nuclear agents, resin additives (fillers composed of inorganic compounds such as nanometer silicon dioxide, talc, glass fibers, alumina fibers, etc.), coupling agents (silane coupling agents, etc.), processability improvers, lubricants, dyes , Pigments, flame retardant materials, defoamers, levelers, rheology control agents (flow aids), release agents, primers, etc. When other resins are added (when added), for example, cellulose nanofiber, nylon, polycarbonate, polyester, polyamide, polyketone, polyetherketone, polyfluorene, polyetherfluorene, PMMA can be used. , Polyethylene, polypropylene, polystyrene, Teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, triacetin cellulose (TAC) and other resins.

Hereinafter, a method that can be suitably used as a method for producing such a resin and a resin precursor of the present invention will be described. In addition, the resin precursor of the present invention can be obtained as a reaction intermediate when the resin of the present invention is produced. Therefore, the method suitable for the production of the resin of the present invention will be described below together with a description of its suitability. The method is used as a method for manufacturing the resin precursor of the present invention.

The method for producing the resin of the present invention can be suitably used without any particular limitation. For example, it can be suitably used in the presence of an organic solvent by making the tetracarboxylic dianhydride containing the aforementioned alicyclic structure having 6 member rings The first monomer is reacted with a second monomer containing at least one of the aforementioned tetraamine and the aforementioned triamine to obtain a compound containing an imidazopyrrolidone precursor structure selected from the group consisting of the imidazopyrrolidone represented by the general formula (8-1). Steps of a resin precursor (the resin precursor of the present invention described above) of at least one repeating unit of the repeating unit and the repeating unit having the imidazopyrrolidone precursor structure represented by the general formula (8-2) ( A), and by heating the aforementioned resin precursor, obtaining a repeating unit selected from the group consisting of an imidazopyrrolidone structure represented by the general formula (1-1) and an imidazo group represented by the general formula (1-2) Step (B) of a resin (the resin of the present invention described above) of at least one repeating unit of a group of repeating units of a pyrrolidone structure
(I). Hereinafter, the resin manufacturing method (I) that can be suitably used for the method for manufacturing the resin of the present invention will be described by dividing into steps (A) and (B).

<Step (A)>
In step (A), in the presence of an organic solvent, the first monomer containing a tetracarboxylic dianhydride having the alicyclic structure having a 6-membered ring and at least 1 of the tetraamine and the triamine are contained. This second monomer reacts to obtain a resin precursor (preferably the resin precursor of the present invention described above).

The above-mentioned first monomer used in such a step may contain the aforementioned tetracarboxylic dianhydride having an alicyclic structure having 6 members. The target resin precursor of the present invention and the structure of the resin may be used appropriately. A derivative of the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring, or a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having an alicyclic structure with a 6-membered ring. For example, when introducing a repeating unit other than the repeating unit (C) and the repeating unit (C ') into the resin precursor of the present invention, for example, the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring may be contained, And its derivatives (for example, diester dicarboxylic acid and diester dicarboxylic acid dichloride modified by the tetracarboxylic dianhydride), and may also contain other tetracarboxylic dianhydrides. In addition, for example, when a diester dicarboxylic acid and a diester dicarboxylic acid dichloride are used as the derivative of the tetracarboxylic dianhydride having an alicyclic structure having a 6-membered ring, when reacting with a diamine, it is derived from this The diester group in the derivative may be introduced into another repeating unit in which H of the group represented by -COOH in the general formula (9) is substituted with a methyl group or an ethyl group. When other repeating units in a form in which H in the group represented by -COOH in the general formula (9) is substituted with a methyl group or an ethyl group, the storage stability or stability of the paint can be improved.

The second monomer used in such a step may contain any one of the aforementioned tetraamine and the aforementioned triamine, and may appropriately contain the aforementioned tetraamine according to the target resin precursor and the structure of the resin of the present invention. And other tetraamines, diamines, and other triamines other than the aforementioned triamines. For example, the resin precursor of the present invention contains a repeating unit represented by the general formula (8-1) and / or a repeating unit represented by the general formula (8-2), and further contains a compound having the general formula (9) When the repeating unit of the sulfonium imine precursor structure is represented (the resin precursor of the present invention finally obtained, the repeating unit represented by the general formula (8-1) and / or the general formula (8-2) When the repeating unit further includes a repeating unit having a fluorene imine precursor structure represented by the general formula (9), the aromatic diamine represented by the general formula (iv) may be further contained. In addition, for the tetraamine and other tetraamines, diamines, and other triamines other than the triamine, for example, a silylated diamine obtained by silanizing an aromatic diamine represented by the general formula (iv) can be used. In this case, A repeating unit in which H in the group represented by -COOH in the general formula (9) is substituted with a silane group can be formed. This can also improve the storage or stability of the paint.

As the organic solvent used in such a step, a known solvent that can be used during polymerization can be appropriately used, and among them, an organic solvent that can dissolve both the first monomer and the second monomer is preferable. Examples of such an organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfine, and γ -Butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, butyl carbonate Aprotic systems, propylene carbonate, triethylene glycol, tetramethylurea (tetramethylurea), 1,3-dimethyl-2-imidazolidone, hexamethylphosphonium triamine, pyridine, etc. Polar solvents; phenol-based solvents such as m-cresol, p-cresol, xylenol, phenol, and halogenated phenols; ether solvents such as tetrahydrofuran, dioxane, cyperidine, and glycol ethers; benzene , Toluene, xylene and other aromatic solvents; acetonitrile, benzonitrile and other nitrile solvents; ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol methyl acetate and other acetate solvents; Ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, and acetone.

In addition, such an organic solvent is preferably N-methyl-2-pyrrolidone, N, N from the viewpoints of solubility, film-forming property, productivity, industrial availability, existence of existing equipment, and price. -Dimethylacetamide, γ-butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone; more preferably N-methyl-2-pyrrolidine Ketones, N, N-dimethylacetamide, γ-butyrolactone, tetramethylurea; particularly preferred are N, N-dimethylacetamide, γ-butyrolactone. In addition, such an organic solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

In addition, in the step (A), the method for reacting the first monomer with the second monomer can be appropriately used, and the method for polymerizing the first monomer and the second monomer can be appropriately used. The method is preferably performed by adding the first monomer and the second monomer to the organic solvent at a reaction temperature under an inert environment such as nitrogen, helium, and argon. As described above, due to the reaction under an inert environment, there is a tendency that the resin finally obtained can fully exhibit the characteristics derived from the repeating unit.

In this way, the pressure conditions when the first monomer and the second monomer are reacted are not particularly limited, as long as they are appropriately set in a range in which the first monomer and the second monomer can react, pressure control is not required, and For a simpler step, it is more preferable that the first monomer and the second monomer are reacted at atmospheric pressure.

In addition, the temperature conditions for reacting the first monomer with the second monomer are such that an imidazopyrrolidone precursor having the general formula (8-1) can be formed by reacting these monomers. The structure part (repeating unit) of the structure and / or the structure part (repeating unit) having the structure of the imidazopyrrolidone precursor represented by the above general formula (8-2), the temperature is appropriately set according to the monomer used The conditions are sufficient, and there is no particular limitation, and it is preferably -20 to 100 ° C (more preferably 5 to 80 ° C). The reaction time when the first monomer is reacted with the second monomer is preferably about 1 to 72 hours (more preferably 3 to 48 hours). When such a reaction temperature or reaction time does not reach the aforementioned lower limit, there is a tendency that the molecular weight of the resin precursor is not sufficiently increased. Furthermore, when the reaction temperature or reaction time exceeds the aforementioned upper limit, the molecular weight of the resin precursor may be reduced due to the depolymerization of the resin precursor due to the type of monomer, or the resin precursor may not be dissolved (gelated) due to crosslinking. Or precipitation), the reaction temperature or reaction time is preferably within the above range.

In addition, the content of each component in the first monomer and the second monomer may be appropriately set according to the design of the target (for example, the type of the repeating unit of the target resin, etc.). Moreover, in such a reaction between the first monomer and the second monomer, a catalyst (for example, trimethylamine, triethylamine, tributylamine, imidazole, methylimidazole, dimethyl) Imidazole, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, α-methylpyridine, etc.) or phosphorus-based compounds triphenyl phosphite, Triphenyl phosphate, triphenylphosphine, triphenylphosphine oxide, etc., or imidazole amino acids and the like. The total amount (total amount) of the first monomer and the second monomer is relative to the total amount of the organic solvent, the first monomer, and the second monomer (the total amount of the organic solvent, the first monomer, and the second monomer). The mass of the mixed liquid) is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. When the total amount (total amount) of the first monomer and the second monomer does not reach the aforementioned lower limit, the reaction rate tends to decrease and a resin precursor having a sufficient degree of polymerization cannot be obtained. At the above upper limit, there is a tendency that the monomer is not completely dissolved and the reaction rate is locally increased, and as a result, a crosslinking reaction or the like proceeds, and a uniform resin precursor is not obtained.

By such a step (A), the above-mentioned resin precursor of the present invention can be obtained. In addition, in such a step (A), the reaction is performed in an organic solvent, and the resin precursor of the present invention is prepared in an organic solvent. Therefore, the reaction solution obtained after the reaction contains the organic solvent and the above-mentioned present invention. Resin precursor (solution). By directly using the reaction solution thus obtained in step (B), the resin of the present invention described above can be produced more efficiently.

<Step (B)>
Step (B) is to obtain the imidazole containing the repeating unit selected from the imidazopyrrolidone structure represented by the general formula (1-1) and the imidazole represented by the general formula (1-2) by heating the resin precursor. A step of at least one type of repeating unit resin (the resin of the present invention described above) in a group formed by repeating units having a pyrrolidone structure.

Furthermore, the repeating unit having the structure of the imidazopyrrolidone precursor represented by the general formula (8-1) and the repeating unit having the structure of the imidazopyrrolidone precursor represented by the general formula (8-2) may be borrowed. The intramolecular condensation is performed by such a heating step, and the structure of the repeating unit is cyclized. Therefore, by heating the resin precursor, a repeating unit having an imidazopyrrolidone structure represented by the general formula (1-1) and / or an imidazo group having the general formula (1-2) can be formed more efficiently. A repeating unit of the pyrrolidone structure. In addition, the repeating unit having a fluorene imine precursor structure represented by the aforementioned general formula (9) can also undergo intramolecular condensation by such a heating step, thereby cyclizing the structure of the repeating unit and fluorinating the fluorene. A repeating unit having a fluorene imine structure represented by the aforementioned general formula (2) can be formed. Therefore, for example, even if the foregoing resin precursor is a repeating unit having an imidazopyrrolidone precursor structure represented by the aforementioned general formula (8-1) and / or having an imidazopyrrolidone represented by the general formula (8-2) When the repeating unit of the precursor structure and the resin precursor having the repeating unit of the fluorene imine precursor structure represented by the aforementioned general formula (9) are used, the repeating units in the resin precursor may be simultaneously performed by heating. Intramolecular condensation reaction can efficiently produce a repeating unit containing an imidazopyrrolidone structure represented by the general formula (1-1) and / or a repeat having an imidazopyrrolidone structure represented by the general formula (1-2) The unit is a resin having a repeating unit of a fluorene imine structure represented by the general formula (2). In addition, when the heat treatment is performed in this manner, the resin precursor molecules can be re-polymerized with molecular chains while undergoing intra-molecular condensation, so that the molecular weight can be further increased.

The conditions for performing such a heating treatment are not particularly limited, and the heating temperature is preferably 50 to 550 ° C (more preferably 75 to 500 ° C, and more preferably 100 to 450 ° C), and the heating time is preferably: 0.1 to 50 hours ((more preferably 0.5 to 10). When such heating temperature and heating time do not reach the aforementioned lower limit, it is impossible to efficiently distill off the intramolecular condensation in each repeating unit of the resin precursor The generated water, alcohol, or silanol tends to hinder the progress of the reaction, making it difficult to increase the molecular weight of the obtained resin. On the other hand, when the above upper limit is exceeded, there is a tendency that thermal decomposition or coloring tends to occur. When heating, it is also possible to appropriately use a condensing agent (such as acetic anhydride, propionic anhydride, or carbodiimide, etc.), a catalyst (p-TsOH, CsF), or a toluene azeotropic method as required. , Chemical fluorene imidization, partial chemical fluorination and so on.

In addition, the environmental conditions during such heat treatment are not particularly limited. From the viewpoint of preventing oxidation, terminal chain cutting, coloring, or deterioration of terminal amine groups caused by oxygen, an inert gas environment such as nitrogen or a vacuum is preferred. .

In addition, the pressure condition during such heat treatment is not particularly limited, but is preferably 0.1 hPa to 10 MPa, and more preferably 10 hPa to 1 MPa. When such a pressure does not reach the aforementioned lower limit, it tends to cause an increase in the drying speed to cause bubbles or voids, an increase in the surface roughness of the film surface, and an increase in the Haze value. On the other hand, when it exceeds the aforementioned upper limit, The tendency of cyclization reaction or post-polymerization (post-polymerization reaction) of oligomers to each other due to an increase in water concentration is suppressed.

In addition, in such a step (B), the reaction liquid obtained in the step (A) (which is obtained by reacting the first monomer and the second monomer in the presence of the organic solvent) may be directly used. The reaction liquid (a solution containing the organic solvent and the resin precursor of the present invention described above)) is subjected to evaporation treatment to remove the organic solvent (solvent removal treatment), and after the solvent is removed from the reaction solution, the heating is performed by It is processed to form a resin in a desired form. For example, when forming a film-like resin, as long as the reaction solution obtained in the above step (A) is directly coated on a substrate (such as a glass plate, etc.), a process of evaporating and removing the organic solvent is sequentially performed, and the heating is performed. Deal with it. The temperature conditions in the process (solvent removal process) for evaporating and removing such an organic solvent are preferably 0 to 180 ° C, and more preferably 30 to 150 ° C. When the temperature condition in such a solvent removal process does not reach the aforementioned lower limit, it tends to be difficult to evaporate and remove the solvent sufficiently. On the other hand, when the aforementioned upper limit is exceeded, the resin precursor is depolymerized or the solvent is boiled. The tendency to form bubbles or 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). In the above, the method for producing the resin of the present invention that has been suitably used has been described by exemplifying the above-mentioned resin production method (I), but the method for producing the resin of the present invention is not limited to the above-mentioned resin production method (I ), As long as a repeating unit selected from the group consisting of an imidazopyrrolidone structure represented by the general formula (1-1) and the unit having an imidazopyrrolidone structure represented by the general formula (1-2) can be obtained. A method of at least one kind of resin (the resin of the present invention described above) may be appropriately adopted.

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

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

As the organic solvent used for such a resin precursor solution (painting), it is possible to suitably use the same organic solvent as that described in the resin production method (I). Therefore, the resin precursor solution of the present invention can be prepared by directly using the reaction solution obtained after performing the above-mentioned step (A) as a resin precursor solution.

The content of the previous resin precursor in such a resin precursor solution is not particularly limited, but is preferably 1 to 80% by mass, and more preferably 5 to 50% by mass. When the content is less than the aforementioned lower limit, it is difficult to produce a film-like resin using the resin precursor solution. On the other hand, when the content exceeds the aforementioned upper limit, coating may be easily caused by high viscosity or reduced fluidity. Degradation of properties, reduction of leveling effect, unevenness of the coating film surface after coating, wrinkle generation on the coating film surface after coating, etc., processability is reduced, and it is difficult to use the resin precursor solution to produce resins in various forms ( Such as thin film resin). Furthermore, such a resin precursor solution can be suitably used for the production of the resin of the present invention described above, and can be suitably used for the production of various shapes of resins. For example, such a resin precursor solution can be coated on various substrates, and then cured by imidization, thereby easily producing a film-shaped resin.

Furthermore, such a resin precursor solution may be appropriately added and utilized by various additives (preventive agents for degradation, antioxidants, light stabilizers, ultraviolet absorbers, modifiers, antistatic agents, flame retardants) that can be used for resin preparation. Agents, plasticizers, nucleating agents, stabilizers, adhesion improvers, lubricants, release agents, dyes, foaming agents, defoamers, surface modifiers, hard coating agents, leveling agents, surfactants , Fillers (glass fiber, filler, talc, mica, silica, etc.). 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 about 0.0001 to 80% by mass (more preferably 0.1 to 50% by mass). In addition, such a resin precursor solution may be appropriately added with other resins (for example, cellulose nanofiber, nylon, polycarbonate, polyester, polyamide, polyketone, polyether, etc.) depending on the purpose of the resin finally obtained. Ketone, polyfluorene, polyetherfluorene, PMMA, polyethylene, polypropylene, polystyrene, Teflon (registered trademark), PPO, PPS, COC, COP, polyacetal, triethyl cellulose (TAC), etc. ) To use. The addition amount of other resins in the resin precursor solution is not particularly limited, but is preferably about 0.1 to 50% by mass (more preferably 1 to 30% by mass). Furthermore, such a resin precursor solution of the present invention can be suitably used as a resin varnish for obtaining the resin of the present invention.

[Example]

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis Example 1: Synthesis of CpODA)
According to the method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, the following formula (A-1) was synthesized:

Tetracarboxylic dianhydride (norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid Dianhydride: The tetracarboxylic dianhydride represented by the general formula (A-1) is hereinafter referred to as "CpODA").

＜ Abbreviation for monomers etc. ＞
Regarding the tetracarboxylic dianhydride, aromatic tetraamine, aromatic triamine, and aromatic diamine used in the following examples and the like, abbreviations and the like are described below. In addition, the description in an Example uses the following abbreviations etc. as needed.

(1) Tetracarboxylic dianhydride (first monomer)
CpODA: tetracarboxylic dianhydride represented by the above formula (A-1) (Synthesis Example 1)
CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride
CPDA: 1,2,3,4-cyclopentane tetracarboxylic dianhydride
H-BPDA: 3,3 ', 4,4'-Bicyclohexyltetracarboxylic dianhydride
BODA: Bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic 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'-tetraaminodiphenylphosphonium
TAB-K: 3,3 ', 4,4'-tetraaminodiphenyl ketone
TrAB-E: 3,4,4'-triaminodiphenyl ether
DABAN: 4,4'-diaminobenzidine aniline
PPD: p-diaminobenzene. Furthermore, for these monomers, CBDA, CPDA, H-BPDA, BODA, TAB-E, TAB-S, TAB-K, TrAB-E, DABAN, and PPD are all used. Commercial products (CBDA: manufactured by Tokyo Chemical Industry, CPDA: manufactured by Tokyo Chemical Industry, H-BPDA: manufactured by LCY Chemical Corp., BODA: manufactured by LCY Chemical Corp., TAB-E: manufactured by Wakayama Seika Chemical Industry Co., Ltd., TAB-S : Made by Wakayama Seika Chemical Industry Co., Ltd., TAB-K: Made by Wakayama Seika Chemical Industry Co., Ltd., TrAB-E: Made by Tokyo Kasei Co., Ltd., DABAN: Made by Japan Pure Chemical Co., Ltd., PPD: Dah Sing Chemical Industry Co., Ltd. "Paramine").

(Example 1)
＜ Resin precursor preparation steps ＞
First, a 30 ml three-necked flask was heated with a hot air blower and dried sufficiently. Next, the atmosphere gas in the three-necked flask which was sufficiently dried was replaced with nitrogen, so that the inside of the three-necked flask became a nitrogen environment. Next, 0.2303 g (1.00 mmol) of TAB-E as a second monomer was added to the three-necked flask, and then 5.53 g of tetramethylurea (TMU) as a solvent was added and stirred, so that the TMU was used in the TMU. TAB-E was dissolved to obtain a solution. Next, in a three-necked flask containing the dissolving solution, 0.3844 g (1.00 mmol) of CpODA as the first monomer was added under a nitrogen atmosphere to obtain a mixed solution for polymerization. The concentration of the first monomer and the second monomer in the polymerization mixture (such concentration is hereinafter simply referred to as "polymerization concentration") is 10% by mass. After that, the polymerization mixture was stirred under a nitrogen atmosphere at room temperature (25 ° C) for 5 hours, and CpODA and TAB-E were reacted to form a resin precursor (polyimidazopyrrolidone precursor) to obtain a resin-containing precursor.物 的 反应 液。 The reaction solution. In addition, the obtained resin precursor can be known from the type of the monomer used, and it contains the following formula (101):

Represents the repeating unit of the imidazopyrrolidone precursor structure.

＜ Resin preparation procedure ＞
A large glass slide (trade name "S9213" manufactured by Songlang Glass Industry Co., Ltd., vertical: 76 mm, horizontal 52 mm, and thickness 1.3 mm) was prepared as a glass substrate, and the reaction solution (polyimidazopyrrole) obtained as described above was prepared. A ketone precursor solution) is spin-coated on the surface of the glass substrate so that the thickness of the coating film after heating and curing becomes 10 μm, and a coating film is formed on the glass substrate. Thereafter, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ° C. and left for 2 hours, and the solvent was removed from the coating film by evaporation (solvent removal treatment).

After performing such a solvent removal treatment, the glass substrate on which the aforementioned coating film has been formed is placed in an oxygen-free oven (nitrogen oven) with nitrogen flowing at a flow rate of 3 L / min. In a nitrogen-free oven at 25 ° C in a nitrogen environment. After being left for 0.5 hours under temperature conditions, heating was performed at a temperature condition of 80 ° C for 0.5 hour, and further heating was performed at a temperature condition of 380 ° C (final heating temperature: firing temperature) for 1 hour to harden the coating film on the glass substrate. A film (resin film) made of a resin (polyimidazopyrrolidone) is formed, and a resin film laminated glass on which the resin film is coated on the glass substrate is obtained.

Next, the resin film laminated glass obtained in this way was immersed in hot water at 90 ° C., and the resin film was peeled from the glass substrate to obtain a resin film (a film having a length of 76 mm, a width of 52 mm, and a thickness of 10 μm).

In order to identify the molecular structure of the compound forming the resin film obtained in this way, the IR spectrum was measured using an IR measuring machine (manufactured by JASCO Corporation, trade name: FT / IR-4100). The IR spectrum obtained as a result of such a measurement is shown in FIG. 1. It is also apparent from the results shown in FIG. 1 that among the compounds constituting the thin film formed in this example, a peak derived from the characteristic absorption of the fluorene imine ring was observed at 1701.8 cm ^-1 in the IR spectrum, and was at 1625.3 cm ^-1 observed a peak derived from the characteristic absorption of the imidazole ring. From the molecular structure identified based on such measurement results, it was confirmed that the obtained film was indeed a film composed of polyimidazopyrrolidone. Furthermore, it is known from the obtained monomer types that by heating the resin precursor, first, an intramolecular dehydration condensation reaction having a repeating unit of the imidazopyrrolidone precursor structure represented by the above formula (101) is performed to form Has the following formula (102):

The repeating unit of the imidazopyrrolidone intermediate structure represented, and then the intramolecular dehydration condensation reaction of the repeating unit is further performed to form the following formula (103):

Represents a repeating unit of the imidazopyrrolidone structure. In this way, from the type of monomer used or the result of IR measurement, it can be seen that a resin containing a repeating unit having an imidazopyrrolidone structure was obtained in this example.

(Example 2)
In addition to using a mixture of TAB-E (0.2303g: 0.50mmol) and DABAN (0.1136g: 0.50mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 3.47 g, except that the polymerization concentration was adjusted to 15% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure represented by the above formula (103) and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and DABAN.

(Example 3)
In addition to using a mixture of TAB-E (0.0345g: 0.15mmol) and DABAN (0.1932g: 0.85mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 3.47 g, except that the polymerization concentration was adjusted to 15% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure represented by the above formula (103) and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and DABAN.

(Example 4)
In addition to using a mixture of TAB-E (0.023g: 0.10mmol) and DABAN (0.2045g: 0.90mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 3.47 g, except that the polymerization concentration was adjusted to 15% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure represented by the above formula (103) and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and DABAN.

(Example 5)
In addition to using a mixture of TAB-E (0.0115 g: 0.05 mmol) and DABAN (0.2159 g: 0.95 mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 3.47 g, except that the polymerization concentration was adjusted to 15% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure represented by the above formula (103) and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and DABAN.

(Example 6)
In addition to using a mixture of TAB-S (0.0278g: 0.10mmol) and DABAN (0.2045g: 0.90mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 2.47 g, except that the polymerization concentration was adjusted to 20% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TAB-S, and a fluorene imine formed by the reaction of CpODA and DABAN. Structural repeating unit.

(Example 7)
In addition to using a mixture of TAB-S (0.0139g: 0.05mmol) and DABAN (0.2159g: 0.95mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 2.46 g, except that the polymerization concentration was adjusted to 20% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TAB-S, and a fluorene imine formed by the reaction of CpODA and DABAN. Structural repeating unit.

(Example 8)
In addition to using a mixture of TAB-K (0.0363g: 0.15mmol) and DABAN (0.1932g: 0.85mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 2.46 g, except that the polymerization concentration was adjusted to 20% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TAB-K, and a fluorene imine formed by the reaction of CpODA and DABAN. Structural repeating unit.

(Example 9)
In addition to using a mixture of TAB-K (0.0242g: 0.10mmol) and DABAN (0.2045g: 0.90mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 2.45 g, except that the polymerization concentration was adjusted to 20% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TAB-K, and a fluorene imine formed by the reaction of CpODA and DABAN. Structural repeating unit.

(Example 10)
In addition to using a mixture of TAB-K (0.0121g: 0.05mmol) and DABAN (0.2159g: 0.95mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 2.45 g, except that the polymerization concentration was adjusted to 20% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TAB-K, and a fluorene imine formed by the reaction of CpODA and DABAN. Structural repeating unit.

(Example 11)
Except using H-BPDA (0.3063g: 1.00mmol) as the first monomer instead of using CpODA as the first monomer, and changing the amount of TMU used to 2.15g, and adjusting the aforementioned polymerization concentration to 20% by mass, A resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure formed by a reaction between H-BPDA and TAB-E.

(Example 12)
In addition to using bicyclooctanoic dianhydride: BODA (0.2502g: 1.00mmol) as the first monomer instead of using CpODA as the first monomer, and changing the amount of TMU used to be 2.61g, the aforementioned polymerization concentration was adjusted to 15% by mass Other than that, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contained a repeating unit having an imidazopyrrolidone structure formed by a reaction between BODA and TAB-E.

(Example 13)
Instead of using TrAB-E (0.2153g: 1.00mmol) as the second monomer instead of using TAB-E as the second monomer, and changing the amount of TMU used to 5.40g, the aforementioned polymerization concentration was adjusted to 10% by mass In addition, the resin precursor and the resin were produced in the same manner as in Example 1 except that the final heating temperature (firing temperature) was changed to 370 ° C during heating in an oxygen-free oven to obtain a resin film. The results of IR measurement of the obtained resin film are shown in FIG. 2. At 1701.5cm ^-1 characteristic peaks was observed from the absorption ring (PEI), and the characteristic peaks was observed from the absorption of the imidazole ring in 1626.1cm ^-1. From the molecular structure identified based on the measurement results, the obtained resin contains a repeating unit having an imidazopyrrolidone structure formed by the reaction of CpODA and TrAB-E.

(Example 14)
In addition to using a mixture of TAB-E (0.0461g: 0.20mmol) and PPD (0.0865g: 0.80mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 8.88 g, except that the polymerization concentration was adjusted to 5.5% by mass, a resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and 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) was changed to 400 ° C during heating in an oxygen-free oven, and a resin film was obtained. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and PPD.

(Example 16)
In addition to using a mixture of TAB-E (0.0461g: 0.20mmol) and PPD (0.0865g: 0.80mmol) as the second monomer instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 4.65 g, the resin precursor and resin were produced in the same manner as in Example 1 except that the polymerization concentration was adjusted to 10% by mass, and the final heating temperature (firing temperature) was changed to 400 ° C during heating in an oxygen-free oven, A resin film was obtained. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and 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) was changed to 420 ° C during heating in an oxygen-free oven, and a resin film was obtained. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), and a repeating unit having a fluorene imine structure formed by a reaction between CpODA and PPD.

(Example 18)
Instead of using TAB-E (0.0230 g: 0.100 mmol), PPD (0.0730 g: 0.675 mmol) and DABAN (0.0511 g: 0.225 mmol) as the second monomer instead of using TAB-E as the second monomer alone, The amount of TMU used was changed to 4.784 g, the aforementioned polymerization concentration was adjusted to 10% by mass, and the final heating temperature (firing temperature) was changed to other than 400 ° C. during heating in an oxygen-free oven, which is the same as in Example 1. A resin precursor and a resin were produced in the same manner to obtain a resin film. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), a repeating unit having a fluorene imine structure formed by a reaction between CpODA and PPD, and A repeating unit with a fluorene imine structure formed by the reaction of CpODA and 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) was changed to 420 ° C during heating in an oxygen-free oven, and a resin film was obtained. Furthermore, as a result of IR measurement, the obtained resin contains a repeating unit having an imidazopyrrolidone structure represented by the above formula (103), a repeating unit having a fluorene imine structure formed by a reaction between CpODA and PPD, A repeating unit with a fluorene imine structure formed by the reaction of CpODA and DABAN.

(Comparative example 1)
Instead of using CBDA (0.1961 g: 1.00 mmol) as the first monomer instead of using CpODA as the first monomer, a mixture of TAB-E (0.0230 g: 0.10 mmol) and DABAN (0.2045 g: 0.90 mmol) was used as the second monomer. Instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 1.69 g, and adjusting the above-mentioned polymerization concentration to 20% by mass, an attempt was made to prepare a resin precursor and the same as in Example 1. Resin. However, gelation occurred during the preparation of the resin precursor, and it was impossible to form a film from the beginning.

(Comparative example 2)
Instead of using CPDA (0.2101 g: 1.00 mmol) as the first monomer instead of using CpODA as the first monomer, a mixture of TAB-E (0.0230 g: 0.10 mmol) and DABAN (0.2045 g: 0.90 mmol) was used as the second monomer. Instead of using TAB-E as the second monomer alone, and changing the amount of TMU used to 1.75 g, and adjusting the aforementioned polymerization concentration to 20% by mass, a resin precursor and resin were prepared in the same manner as in Example 1. . However, the obtained resin was brittle and cracked, and a film shape could not be obtained.

(Comparative example 3)
Except that DABAN (0.2273 g: 1.00 mmol) was used as the second monomer instead of using TAB-E as the second monomer, and the amount of TMU used was changed to 2.45 g, and the aforementioned polymerization concentration was adjusted to 20% by mass. A resin precursor and a resin were produced in the same manner as in Example 1 to obtain a resin film.

[Characteristic evaluation of the resin (resin film) 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 addition, for Comparative Examples 1 and 2, film-like resins could not be obtained originally ( Resin film), so the sample cannot be prepared, and the following measurement cannot be performed). In addition, 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 was measured as follows. That is, each resin film (thickness: 10 μm) was directly used as a measurement sample, and a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measurement device, and the measurement was performed in accordance with JIS K7361- 1 (issued in 1997) to obtain the total light transmittance (unit:%) of each resin film. The results obtained are shown in Table 1.

<Measurement of glass transition temperature (Tg)>
The value (unit: ° 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 length of 20 mm and a width of 5 mm cut from each resin film (thickness: 10 μm) is used (the thickness of the sample is directly used as the thickness of the film obtained in the example), and thermomechanical analysis is used As a measuring device, a device (trade name "TMA8311" manufactured by Rigaku) was used in a nitrogen environment under a tensile mode (49 mN) and a temperature rise rate of 5 ° C / min to obtain a TMA curve. The inflection point of the TMA curve was extrapolated from the curve before and after it to obtain the value (unit: ° C) of the glass transition temperature (Tg) of the resin constituting the film obtained in each example. 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 each example were measured as follows. That is, first, each resin film is attached to an SD-type joystick-type sample cutter (a cutter (model SDL-200) manufactured by DUMBELL Co., Ltd.), and a brand name "Super Dumbell Cut" manufactured by DUMBELL Co., Ltd. is installed. Device (model: SDMK-1000-D, in accordance with JIS K7139 (A22 specification issued in 2009)), with the size of each resin film, the total length is 75mm, the distance between the ear parts: 57mm, the length of the parallel part: 30mm 2. Radius of the shoulder: 30mm, width of the end: 10mm, width of the central parallel portion: 5mm, thickness: 10μm. Cut out the dumbbell-shaped test pieces (except for the thickness of 10μm according to JIS K7139 model) A22 (scale test piece) specifications), as a measurement sample. Next, using an electro-mechanical universal material testing machine (model "5943" manufactured by INSTRON), the measurement samples were arranged so that the width between the clamps became 57 mm, and the width of the clamping portion was 10 mm (the full width of the end portion). Then, a tensile test was performed under the conditions of a dynamometer: 1.0 kN and a test speed: 5 mm / minute to stretch the measurement sample, and the values of tensile strength and elongation at break were obtained. Such a test is a test based on JIS K7162 (issued in 1994). In addition, the distance between the ear pieces of the sample (= the width between the clamps: 57mm) is L0, and the distance between the ear pieces of the sample (the width between the clamps at the time of fracture: 57mm + α) is L When using the following formula:

The value of elongation at break (%) is calculated. The results obtained are shown in Table 1.

<Measurement of linear expansion coefficient (CTE)>
The CTE (unit: ppm / K) of the resin which comprises the resin film obtained by each Example etc. was calculated | required as follows. That is, first, a measurement film (thickness: 10 μm) having a size of 20 mm in length and 5 mm in width was formed from each resin film. Next, the obtained measurement film was vacuum-dried (120 ° C, 1 hour), and then heat-treated at 200 ° C for 1 hour in a nitrogen environment to prepare a measurement sample (dry film). Next, using the obtained measurement sample (dry film), a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku) was used as a measurement device under a nitrogen environment, a tensile mode (49 mN), and a temperature increase rate of 5 ° C / On the condition of minutes, the change in length of the aforementioned sample at 50 ° C to 200 ° C was measured, and the average value of the change in length per 1 ° C in the temperature range of 100 ° C to 200 ° C was determined. The results obtained are shown in Table 1.

It is clear from the results shown in Table 1 that the films made of the resin of the present invention (Examples 1 to 19) all had a total light transmittance of 80% or more, and it was confirmed that they had sufficient transparency, and the Tg was 389.8 ° C (about 390) ° C) or more, it was confirmed that the polyimide obtained in Comparative Example 3 exhibited a higher degree of heat resistance. In particular, the resin constituting the film obtained in Example 1 had a Tg of 448 ° C, and was found to be a resin having extremely high heat resistance.

Furthermore, the films (Examples 1 to 19) made of the resin of the present invention all had a breaking strength of 50 MPa or more. In contrast, when using an alicyclic tetracarboxylic dianhydride having a cyclic structure other than a 6-membered ring (a 4-membered ring or a 5-membered ring structure) such as CBDA or CPDA (Comparative Examples 1 and 2), A film cannot be obtained from the beginning. For example, even if the film-forming step was performed in Comparative Example 2, the obtained resin was brittle and cracked, and the film shape could not be maintained. From these results, it is understood that according to the film (Examples 1 to 19) made of the resin of the present invention, a sufficiently high strength can be obtained. In addition, when compared with the film made of polyfluorene imine obtained in Comparative Example 3, it was found that the film made of polyfluorene imine obtained in Comparative Example 3 had a breaking strength of 31 MPa, and showed sufficient as a self-supporting film system. Mechanical strength, but the films made of the resin of the present invention (Examples 1 to 19) all had a breaking strength of 50 MPa or more, showing higher mechanical strength.

From these results, it is understood that according to the present invention (Examples 1 to 19), the transparency or heat resistance of the obtained resin can be made sufficiently high, and at the same time, the mechanical strength based on the breaking strength can be made sufficiently high. In addition, it can be seen that the films (Examples 1 to 19) made of the resin of the present invention all have a CTE value of 50 ppm / K or less, have a low CTE, and have a sufficiently high processability.

[Industrial availability]

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

Therefore, as described above, the resin of the present invention is not only sufficiently high in transparency (light transmittance), but also has higher heat resistance, and can be suitably used as a transparent material having very high heat resistance. Therefore, it is particularly useful. It is used for manufacturing films for flexible wiring boards, heat-resistant insulating tapes, wire enamels, protective coatings for semiconductors, liquid crystal alignment films, transparent conductive films for organic EL, flexible substrate films, and flexible transparent conductive Films, transparent conductive films for organic thin film solar cells, transparent conductive films for dye-sensitized solar cells, flexible gas barrier films, films for touch panels, TFT substrate films (LTPS, suitable for polycrystalline silicon) , TFT substrate film for flat panel sensor, seamless resin tape for copier (so-called transfer belt), transparent electrode substrate (transparent electrode substrate for organic EL, transparent electrode substrate for solar cell, transparent electrode substrate for electronic paper, etc.), Interlayer insulation film, sensor substrate, image sensor substrate, light-emitting diode (LED) reflector (LED reflector: LED reflector), LED Cover for lighting, cover for LED reflector lighting, adhesive film, highly ductile composite substrate, semiconductor suitable resist, lithium ion battery, organic memory substrate, organic transistor substrate, organic semiconductor substrate , Color filter substrate, medical heat-resistant bracket, medical gamma-resistant resin petri dish, medical transparent high heat-resistant pipette, transparent high heat-resistant lens, lens for car sensor, mobile device face certification Lenses, solder reflow compatible lenses, lenses for infrared cameras, optical filters, ambient light sensors, adhesives for all-solid-state batteries, gel materials for all-solid-state batteries, and other materials. In addition, the resin of the present invention can be suitably applied to, for example, automotive parts, aerospace parts, bearing parts, and the like by changing its shape to a powder or various shaped bodies in addition to the uses described above. Sealing materials, Palin parts, gear and valve parts, etc.

[Fig. 1] IR spectrum chart of a resin constituting the film obtained in Example 1. [Fig.

[Fig. 2] IR spectrum chart of resin constituting the film obtained in Example 13. [Fig.

Claims (11)

A resin containing a resin selected from the group consisting of the following general formula (1-1): [Wherein X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ² represents a tetravalent organic group] A repeating unit of an imidazopyrrolidone structure represented by, and having the following general formula (1-2 ): [In the formula, X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ³ represents a trivalent organic group.] At least one type of repeating unit of a group consisting of repeating units of an imidazopyrrolidone structure. The resin as claimed in claim 1, which further contains the following general formula (2): [In the formula, X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ⁴ represents an arylene group having 6 to 50 carbon atoms.] A repeating unit of a perylene imine structure. For example, the resin of claim 1 or 2, wherein X ¹ in the above formula is represented by the following general formulae (3) to (5): [In formula (3), m represents an integer of 0 to 2, in formula (4), n represents an integer of 1 to 2, and in formula (5), A represents a group selected from a single bond; and may have a substituent and form an aromatic group. The ring carbon number is one of a group formed by a divalent aromatic group having 6 to 30 carbon atoms. The symbols * 1 to * 4 in the formulas (3) to (5) indicate that the bonding sites with the symbols are respectively ^One of the four bonding sites bonded to X ¹ ] is one selected from tetravalent organic groups. The resin according to any one of claims 1 to 3, wherein X ² in the above formula is represented by the following general formulae (6-1) to (7-1): [In formula (7-1), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C (CF ₃ ) ₂ -and a group of methylene groups represented by -CH _2- ] One type of group consisting of a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-, the formula ( 6-1) The symbols * 1 ~ * 4 in (7-1) indicate that the bond part with the symbol is any of the 4 bond parts respectively bonded to X ² ]] Organic selection Choose one. The resin according to any one of claims 1 to 4, wherein X ³ in the above formula is represented by the following general formulae (6-2) to (7-2): [In formula (7-2), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C (CF ₃ ) ₂ -and a group of methylene groups represented by -CH _2- ] One of the groups formed by a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-; 6-2) ~ (7-2) The symbols * 1 ~ * 3 indicate that the bond part with the symbol is any one of the three bond parts respectively bonded to X ³ ] Organic selection Choose one. A resin precursor containing a resin selected from the group consisting of the following general formula (8-1): [In the formula, X ¹ represents a tetravalent organic group having an alicyclic structure having 6 members, and X ² represents a tetravalent organic group] The repeating unit of the imidazopyrrolidone precursor structure represented by the formula, and having the following general formula (8 -2): [Wherein, X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ³ represents a trivalent organic group] at least one type of repeat formed by a repeating unit of the imidazopyrrolidone precursor structure represented by unit. The resin precursor as claimed in claim 6, further comprising the following general formula (9): [In the formula, X ¹ represents a tetravalent organic group having a 6-membered alicyclic structure, and X ⁴ represents an arylene group having 6 to 50 carbon atoms.] Represents a repeating unit of a pyrimide precursor structure. For example, the resin precursor of claim 6 or 7, wherein X ¹ in the above formula is represented by the following general formulae (3) to (5): [In formula (3), m represents an integer of 0 to 2, in formula (4), n represents an integer of 1 to 2, and in formula (5), A represents a group selected from a single bond; and may have a substituent and form an aromatic group. The ring carbon number is one of a group formed by a divalent aromatic group having 6 to 30 carbon atoms. The symbols * 1 to * 4 in the formulas (3) to (5) indicate that the bonding sites with the symbols are respectively ^One of the four bonding sites bonded to X ¹ ] is one selected from tetravalent organic groups. The resin precursor according to any one of claims 6 to 8, wherein X ² in the above formula is represented by the following general formulae (6-1) to (7-1): [In formula (7-1), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C ₂ -a group of methylene groups represented by -CH _2- ] One type of group consisting of a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-, formula (6 -1) ~ (7-1) The symbols * 1 ~ * 4 indicate that the bonding part with the symbol is any of the 4 bonding parts that are respectively bonded to X ² ]] 4-valent organic Base selection 1 kind. The resin precursor according to any one of claims 6 to 9, wherein X ³ in the above formula is represented by the following general formulae (6-2) to (7-2): [In formula (7-2), Z ¹ represents a group selected from a single bond, 9,9-fluorenylene, an ether group represented by -O-, a carbonyl group represented by -C (= O)-, -S (= O)-represented by fluorenylene, -S (= O) ₂ -represented by sulfofluorenyl, -CH ₂ -represented by methylene, -C (CH ₃ ) ₂ -represented by isopropylidene, -C (CF ₃ ) ₂ -Hexafluoroisopropylidene, -S-thioether group, -NHCO-amidino group, -COO-ester type, -C ₆ H ₄ -extension Phenyl, phenylenedioxy represented by -OC ₆ H ₄ -O-, phenylenedioxy represented by -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -Z ^2- C ₆ H ₄ -O- [wherein Z ² represents an ether group represented by -O-, a carbonyl group represented by -C (= O)-, a sulfonyl group represented by -S (= O) _2- , C (CH ₃ ) ₂ -an isopropylidene group represented by -C (CF ₃ ) ₂ -a hexafluoroisopropylidene group represented by -C (CF ₃ ) ₂ -and a group of methylene groups represented by -CH _2- ] One type of group consisting of a bis (phenylene dioxy) group, a group represented by -P (= O) (C ₆ H ₅ )-, and a group represented by -N (C ₆ H ₅ )-, the formula ( 6-2) ~ (7-2) The symbols * 1 ~ * 3 indicate that the bond part with the symbol is any one of the three bond parts respectively bonded to X ³ ] Organic selection Choose one. A resin precursor solution containing the resin precursor and the solvent according to any one of claims 6 to 10.