JP2018044180A - Polyimide resin composition and polyimide varnish - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin composition that can be cured into a product having sufficient translucency as a glass substitute and also having sufficiently high levels of heat resistance and mechanical strength.SOLUTION: A polyimide resin composition contains a polyimide containing a specific repeating unit, and at least one compound selected from the group consisting of an imidazole compound, a phosphorous compound, and an amine compound.SELECTED DRAWING: None

Description

  The present invention relates to a polyimide resin composition and a polyimide varnish.

In the field of display devices such as displays using organic electroluminescence elements and liquid crystal displays, materials such as glass that have high light transmission and sufficiently high heat resistance have emerged as materials used for substrates and the like. It has been sought. In recent years, polyimide has attracted attention as a material used for glass substitute applications and the like, and various tetracarboxylic dianhydrides have been studied as monomers for producing such polyimide. For example, in JP-A No. 2001-2670 (Patent Document 1) and JP-A No. 2002-255955 (Patent Document 2), 1,2-bis (4′-oxa-3 ′, 5′-dioxotri) Cyclo [5.2.1.0 ^2,6 ] decan-8′-yloxy) ethane is disclosed. However, even when a polyimide is produced using such tetracarboxylic dianhydrides described in Patent Documents 1 and 2, the heat resistance and mechanical strength of the polyimide (mechanical strength based on the elongation at break). ) Could not be advanced enough.

JP 2001-2670 A JP 2002-255955 A

  The present invention has been made in view of the above-described problems of the prior art, has sufficient light transmittance that can be used for glass replacement, and has sufficiently high heat resistance and sufficiently excellent mechanical strength. It aims at providing the polyimide resin composition which can be used as the hardened | cured material which has this, and the polyimide varnish which can be utilized suitably for manufacture of the hardened | cured material of such a polyimide.

  As a result of intensive studies to achieve the above object, the present inventors have represented a polyimide resin composition by a repeating unit (A) represented by the following general formula (1) and a general formula (2) below. A polyimide containing at least one repeating unit selected from the group consisting of a repeating unit (B) and a repeating unit (C) represented by the following general formula (3); an imidazole compound, phosphorus And at least one compound selected from the group consisting of amine compounds, and can be used for glass replacement when the polyimide resin composition is cured. The inventors have found that it is possible to have sufficient light transmission, sufficiently high heat resistance and sufficiently excellent mechanical strength, and have completed the present invention.

  That is, the polyimide resin composition of the present invention has the following general formula (1):

[In the formula (1), R ¹ , R ² and R ³ each independently represents 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 is 0 to 12 R ⁴ represents an arylene group having 6 to 50 carbon atoms. ]
A repeating unit (A) represented by the following general formula (2):

[In Formula (2), A may have a substituent and is 1 type selected from the group which consists of a bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30. R ⁴ represents an arylene group having 6 to 50 carbon atoms, and a plurality of R ⁵ each independently represents one type selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. ]
And a repeating unit (B) represented by the following general formula (3):

[In Formula (3), R ⁴ represents an arylene group having 6 to 50 carbon atoms, and a plurality of R ⁶ are independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ⁶ bonded to the same carbon atom may be combined to form a methylidene group, and R ⁷ and R ⁸ are each independently a hydrogen atom and 1 type selected from the group which consists of a C1-C10 alkyl group is shown. ]
A polyimide containing at least one repeating unit selected from the group consisting of repeating units (C) represented by:
At least one compound selected from the group consisting of an imidazole compound, a phosphorus compound, and an amine compound;
It is characterized by including.

  Such a polyimide resin composition of the present invention is a cured product having sufficient light transmittance that can be used for glass substitute applications, and having sufficiently high heat resistance and sufficiently excellent mechanical strength. Is possible. The polyimide resin composition of the present invention may further contain a solvent, and the polyimide resin composition in a form further containing such a solvent forms polyimides (compositions) of various shapes such as a film. The polyimide varnish (resin solution) can be suitably used.

  Moreover, the polyimide varnish of this invention consists of the polyimide resin composition of the said invention of the form which further contains a solvent, It is characterized by the above-mentioned. Such a polyimide varnish of the present invention is a cured product of a polyimide resin composition having sufficient light transmittance that can be used for glass substitute applications, and having sufficiently high heat resistance and sufficiently excellent mechanical strength. It can be suitably used for manufacturing.

  According to the present invention, the polyimide resin composition has sufficient light transmittance that can be used for glass substitute applications, and can be a cured product having sufficiently high heat resistance and sufficiently excellent mechanical strength. It is possible to provide a polyimide varnish that can be suitably used for manufacturing a cured product of such a product and such a polyimide.

2 is a ¹ H NMR graph of a compound finally obtained in Synthesis Example 2 (tetracarboxylic dianhydride: second product). 6 is a ¹³ C NMR graph of a compound finally obtained in Synthesis Example 2 (tetracarboxylic dianhydride: second product). 2 is a two-dimensional NMR (DEPT135) of a compound (tetracarboxylic dianhydride: second product) finally obtained in Synthesis Example 2. 2 is a two-dimensional NMR (DQF COSY) of a compound (tetracarboxylic dianhydride: second product) finally obtained in Synthesis Example 2. 2 is a graph of two-dimensional NMR (HMQC) of a compound finally obtained in Synthesis Example 2 (tetracarboxylic dianhydride: second product). 2 is a graph of two-dimensional NMR (HMBC) of a compound finally obtained in Synthesis Example 2 (tetracarboxylic dianhydride: second product). 3 is a graph of two-dimensional NMR (NOESY) of a compound finally obtained in Synthesis Example 2 (tetracarboxylic dianhydride: second product).

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Polyimide resin composition]
The polyimide resin composition of the present invention is
From the repeating unit (A) represented by the general formula (1), the repeating unit (B) represented by the general formula (2), and the repeating unit (C) represented by the general formula (3). A polyimide containing at least one repeating unit selected from the group consisting of the following (for convenience, sometimes referred to as “first component”);
At least one compound selected from the group consisting of an imidazole compound, a phosphorus compound, and an amine compound (hereinafter sometimes referred to as “second component” for convenience),
It is characterized by including. Hereinafter, each component will be described separately.

<Polyimide (first component)>
The polyimide (first component) according to the present invention comprises at least one repeating unit selected from the group consisting of the repeating unit (A), the repeating unit (B), and the repeating unit (C). It contains. Hereinafter, each repeating unit will be described separately.

<Repeating unit (A)>
The repeating unit (A) that the polyimide according to the present invention may contain is a repeating unit represented by the above general formula (1) (in the general formula (1), R ¹ , R ² , and R ³ are each independent. 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, n represents an integer of 0 to 12, and R ⁴ represents an arylene group having 6 to 50 carbon atoms. ).

The alkyl group that can be selected as R ¹ , R ² , or R ^{3 in the} general formula (1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, the glass transition temperature is lowered and a sufficiently high heat resistance cannot be achieved. Moreover, as carbon number of the alkyl group which can be selected as such R < ¹ >, R < ² >, R < ³ >, it is preferable that it is 1-6 from a viewpoint that refinement | purification becomes easier, and it is 1-5. Is more preferable, it is still more preferable that it is 1-4, and it is especially preferable that it is 1-3. Further, such an alkyl group that can be selected as R ¹ , R ² , or R ³ may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.

As R < ¹ >, R < ² >, R < ³ > in the said General formula (1), when manufacturing a polyimide, from a viewpoint that higher heat resistance is acquired, it is each independently a hydrogen atom or C1-C10. In particular, from the viewpoint of easy availability of raw materials and easier purification, each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. It is more preferably a group, and particularly preferably a hydrogen atom or a methyl group. Moreover, it is especially preferable that several R < ¹ >, R < ² >, R < ³ > in such a formula is the same from viewpoints, such as the ease of refinement | purification.

The arylene group that can be selected as R ⁴ in the general formula (1) has 6 to 50 carbon atoms, and the aryl group preferably has 6 to 40 carbon atoms, More preferably, it is 6-30, and it is still more preferable that it is 12-20. When the number of carbon atoms is less than the lower limit, the heat resistance of the resulting polyimide tends to be reduced. On the other hand, when the carbon number exceeds the upper limit, the solubility of the obtained polyimide in a solvent tends to be lowered.

As R ⁴ in the general formulas (4) and (5), the following general formulas (a) to (d) are used from the viewpoint of heat resistance and mechanical strength:

[In the formula (c), R ¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a hydroxyl group, and a trifluoromethyl group, and in the formula (d), Q is , 9,9-fluorenylidene group; formula: -O -, - S -, - CO -, - CONH -, - SO 2 -, - C (CF 3) 2 -, - C (CH 3) 2 -, - _{CH 2 -, - O-C} 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - O-C 6 H 4 -C (CF 3) 2 -C 6 H 4 -O-, _{-O-C 6 H 4 -SO 2} -C 6 H 4 -O -, - C (CH 3) 2 -C 6 H 4 -C (CH 3) 2 -, - O-C 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 is represented by _{-O-C 6} H 4 -O- A group; and the following general formula (e):

(In the formula (e), each R ^a independently represents any one of an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a tolyl group, and y represents an integer of 1 to 18.)
1 group selected from the group consisting of: ]
It is preferable that it is at least 1 sort (s) of group represented by these.

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, from the viewpoint of heat resistance. Furthermore, R ¹¹ in the general formula (c) is more preferably a methyl group, a hydroxyl group, or a trifluoromethyl group from the viewpoint of the linear expansion coefficient.

In the group represented by the general formula (e) that can be selected as Q in the general formula (d), each R ^a is independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a tolyl group. Any one of these. When the carbon number of such an alkyl group exceeds the upper limit, the heat resistance and transparency of the polyimide film tend to be reduced. Such ^Ra 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 or an ethyl group, and even more preferably a methyl group. Moreover, y in the said general formula (e) shows the integer of 1-15, it is more preferable that it is 3-12, and it is still more preferable that it is 5-10. If y is less than the lower limit, the mechanical strength tends to decrease. On the other hand, if y exceeds the upper limit, the heat resistance and transparency of the polyimide film tend to decrease.

Moreover, as Q in the general formula (d), 9, 9- from the viewpoint that it is possible to obtain a cured product having a sufficient balance of heat resistance, transparency, and mechanical strength. Fluorenylidene group, or formula: —CONH—, —O—C ₆ H ₄ —O—, —O—, —C (CH ₃ ) ₂ —, —O—C ₆ H ₄ —SO ₂ —C ₆ H _{4 -O -, - CH 2 -,} - O-C 6 H 4 -C 6 H 4 -O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - SO ₂ -, - OCO-, or, preferably a group represented by -COO-, 9,9-fluorenylidene group, or the _{formula: -CONH -, - CH 2 -} , - O-C 6 H 4 -O- _{, -O-C 6 H 4 -C} 6 H 4 -O -, - SO 2 -, - OCO -, - COO-, or -O- group represented by is particularly A 9,9-fluorenylidene group or a group represented by the formula: —CONH—, —SO ₂ —, —OCO—, —COO—, —CH ₂ — or —O— is most preferable. Furthermore, Q in the general formula (d) is preferably a group represented by the general formula (e) from the viewpoints of adhesiveness and laser peelability, and has a linear expansion coefficient and heat resistance. Is preferably a group represented by the formula: -OCO-, -COO-, -CONH-.

Further, when two or more types of R ⁴ are used in combination, from the viewpoint that it becomes possible to obtain a cured product having a sufficient balance between heat resistance, transparency and mechanical strength, as a combination thereof. It is preferable that 2 or more types selected from the groups represented by the general formulas (a) to (d) are included. In the case of using a combination of ^{R 4} 2 or more, the combination of ^{R 4,} the general formula (a) (c), the general formula (c) (d), the general formula (a) ( It is more preferable that d) or the above general formulas (d) and (d) are included.

Moreover, as such R ⁴ , 4,4′-diaminobenzanilide can be obtained from the viewpoint that a cured product having a sufficient balance of heat resistance, transparency and mechanical strength can be obtained. (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 (also known as m-tolidine), 4,4′-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl (BABB), 3,3′-diaminodiphenylsulfo (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'-DDS) at least one aromatic diamine selected from the group consisting of two divalent amino groups And (4) -diaminobenzanilide (DABAN), 4,4′-diaminodiphenyl ether (DDE), 2,2′-bis (trifluoromethyl) benzidine (TFMB), At least one aromatic diamine selected from the group consisting of 9'-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD) and 4-aminophenyl-4-aminobenzoic acid (BAAB) More preferably, it is a divalent group (arylene group) obtained by removing two amino groups from 4,4′-diaminobenzanilide (DABAN), 4 Divalent form in which two amino groups are removed from at least one aromatic diamine selected from the group consisting of 4′-diaminodiphenyl ether (DDE) and 2,2′-bis (trifluoromethyl) benzidine (TFMB) And more preferably an arylene group.

  Moreover, n in the said General formula (1) shows the integer of 0-12. When such a value of n exceeds the upper limit, purification becomes difficult. Further, the upper limit value of the numerical value range of n in the general formula (1) is more preferably 5 and particularly preferably 3 from the viewpoint of easier purification. Further, the lower limit of the numerical range of n in the general formula (1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material compound. Thus, as n in General formula (1), it is especially preferable that it is an integer of 2-3.

  The repeating unit (A) represented by the general formula (1) has the following general formula (101):

Wherein ^{(101), R 1, R} 2, R 3, n is the formula ^{(1) R 1, R 2} , R 3, n and are as defined in (also Formula those its preferred ( It is synonymous with R ¹ , R ² , R ³ , and n in ¹ ). ]
The starting compound (A) represented in the _formula: H ^{2 N-R} 4 -NH aromatic diamine represented by ₂ ^{[R 4} in the formula has the same meaning as ^{R 4} in the general formula (1) (The preferred ones are also synonymous.) ] And can be formed. That is, the repeating unit (A) represented by the general formula (1) can be contained in the polyimide by reacting the raw material compound (A) with the aromatic diamine.

  In addition, the method for producing the tetracarboxylic dianhydride represented by the general formula (101) is not particularly limited, and a known method can be appropriately employed. You may employ | adopt the method as described in 2011/099517, the method as described in international publication 2011/099518, etc.

Moreover, the method for producing the aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ is not particularly limited, and a known method can be appropriately employed. Moreover, as such aromatic diamine, what is necessary is just to satisfy | fill the conditions of said formula, a well-known thing can be utilized suitably, and a commercially available thing may be used suitably. Examples of such aromatic diamines include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 3,3′-diaminodiphenylethane, and 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] sulfone, bis [4- (3-aminophenoxy) phenyl Sulfone, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, 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-ethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisaniline, 2,2′-dimethyl-4,4′-diaminobipheny 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4 -Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 9,9'-bis (4-aminophenyl) Fluorene, o-tolidine sulfone, 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-aminophen Le 4-aminobenzoic acid, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl, and the like. Such aromatic diamines may be used singly or in combination of two or more.

  When two or more aromatic diamines are used in combination, 4,4′-diaminobenzanilide (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 (also known as m-) Trisine), 4,4′-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl ( BABB), 3,3′-diaminodiphenylsulfone (3,3′-DDS) and 4,4′-diaminodiphenylsulfone (4 4′-DDS) is preferably used, and 4,4′-diaminobenzanilide (DABAN), 4,4′-diaminodiphenyl ether (DDE), and 2,2′-bis are preferably used. (Trifluoromethyl) benzidine (TFMB), 9,9′-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD), 4-aminophenyl-4-aminobenzoic acid (BAAB), 3 , 3′-diaminodiphenylsulfone (3,3′-DDS) and 4,4′-diaminodiphenylsulfone (4,4′-DDS) are preferably used. When two or more aromatic diamines are used in combination, 4,4′-diaminobenzanilide (DABAN) and 4,4′-diaminodiphenyl ether (DDE) are combined, and 4,4′-diaminobenzanilide (DABAN). ) And 2,2′-bis (trifluoromethyl) benzidine (TFMB), 4,4′-diaminobenzanilide (DABAN) and p-diaminobenzene (PPD), 3,3′-diaminodiphenylsulfone (3,3′-DDS) and 4,4′-diaminodiphenylsulfone (4,4′-DDS), 4-aminophenyl-4-aminobenzoic acid (BAAB) and 2,2′-bis (tri Combination of fluoromethyl) benzidine (TFMB) and 4-aminophenyl-4-amino Ikikosan more preferably contains at least one combination selected from the combinations of (BAAB) and p- diaminobenzene (PPD).

<Repeating unit (B)>
The repeating unit (B) that the polyimide according to the present invention may contain is a repeating unit represented by the general formula (2) (in the general formula (2), A may have a substituent). And one selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms that form an aromatic ring, R ⁴ represents an arylene group having 6 to 50 carbon atoms, Several R < ⁵ > shows 1 type selected from the group which consists of a hydrogen atom and a C1-C10 alkyl group each independently.

  As described above, A in the general formula (2) is a divalent aromatic group which may have a substituent, and is a carbon that forms an aromatic ring contained in the aromatic group. (“The number of carbons forming the aromatic ring” herein means that when the aromatic group has a substituent containing carbon (such as a hydrocarbon group), the carbon in the substituent is In the case of a 2-ethyl-1,4-phenylene group, the number of carbons forming the aromatic ring is 6. ) Is 6-30. Thus, A in the general formula (1) is a divalent group (divalent aromatic group) which may have a substituent and has an aromatic ring having 6 to 30 carbon atoms. is there. When the number of carbons forming such an aromatic ring exceeds the upper limit, it tends to be difficult to sufficiently suppress coloring of the polyimide containing the repeating unit. Moreover, from the viewpoint of transparency and ease of purification, the number of carbons forming the aromatic ring of the divalent aromatic group is more preferably 6-18, and further preferably 6-12. preferable.

  Such a divalent aromatic group is not particularly limited as long as it satisfies the above condition of the number of carbons. For example, benzene, naphthalene, terphenyl, anthracene, phenanthrene, triphenylene, pyrene, Residues from which two hydrogen atoms are eliminated from an aromatic compound such as chrysene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, etc. Although not particularly limited, for example, 1,4-phenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 4,4′-biphenylene group, 9,10-anthracenylene group and the like can be mentioned. Groups in which at least one hydrogen atom in the residue is substituted with a substituent (for example, 2,5-dimethyl-1,4-phenylene group, 2,3,5, - can be appropriately used tetramethyl-1,4-phenylene group). In such a residue, as described above, the position of the leaving hydrogen atom is not particularly limited. For example, when the residue is a phenylene group, any of the ortho, meta, and para positions is used. It may be the position.

  As such a divalent aromatic group, the phenylene group which may have a substituent from the viewpoint that the solubility of the polyimide in the solvent becomes better and higher processability is obtained, A biphenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, and a terphenylene group which may have a substituent are preferable. . That is, such a divalent aromatic group is preferably a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, or a terphenylene group, each of which may have a substituent. Further, among such divalent aromatic groups, a higher effect can be obtained from the above viewpoint, and thus a phenylene group, a biphenylene group, and a naphthylene group, each of which may have a substituent, are more preferable. A phenylene group and a biphenylene group which may have a substituent are more preferable, and a phenylene group which may have a substituent is most preferable.

  In A in general formula (2), the substituent that the divalent aromatic group may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, and a halogen atom. . Among the substituents that such a divalent aromatic group may have, from the viewpoint that when a polyimide is produced, the solubility of the polyimide in the solvent becomes better and higher workability can be obtained. And an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are more preferable. When the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent exceeds 10, when used as a polyimide monomer, the heat resistance of the resulting polyimide tends to decrease. In addition, the number of carbon atoms of an alkyl group and an alkoxy group suitable as such a substituent is preferably 1 to 6 from the viewpoint of obtaining higher heat resistance when a polyimide is produced. 5 is more preferable, 1 to 4 is further preferable, and 1 to 3 is particularly preferable. Moreover, the alkyl group and alkoxy group which can be selected as such a substituent may be linear or branched, respectively.

  Further, among these divalent aromatic groups, when a polyimide is produced, the solubility of the polyimide in the solvent becomes better, and from the viewpoint that a higher degree of workability can be obtained, the substituents are each A phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and a terphenylene group, each of which may have a substituent, a phenylene group, a biphenylene group, or a naphthylene group. More preferred are a phenylene group and a biphenylene group, each of which may have a substituent, and most preferred is a phenylene group which may have a substituent.

  Furthermore, among such divalent aromatic groups, from the viewpoint of obtaining higher heat resistance, a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, which may each have a substituent, It is preferably a terphenylene group, each of which may have a substituent, more preferably a phenylene group, a biphenylene group, a naphthylene group or a terphenylene group, each of which may have a substituent, A phenylene group, a biphenylene group, and a naphthylene group are more preferable, and a phenylene group that may have a substituent is most preferable.

  In A in the general formula (2), the substituent that the divalent aromatic group may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, and a halogen atom. Among such substituents that the divalent aromatic group may have, the solubility of the polyimide in the solvent becomes more excellent, and from the viewpoint of obtaining higher workability, the number of carbon atoms is 1 to 1. More preferred are 10 alkyl groups and alkoxy groups having 1 to 10 carbon atoms. When the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent exceeds 10, the heat resistance of the polyimide tends to decrease. In addition, the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent is preferably 1 to 6 and more preferably 1 to 5 from the viewpoint that higher heat resistance can be obtained. 1 to 4 is more preferable, and 1 to 3 is particularly preferable. In addition, each of the alkyl group and alkoxy group that can be selected as such a substituent may be linear or branched.

The alkyl group which may be selected as R ⁵ in the general formula (2) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, sufficiently high heat resistance cannot be achieved. Moreover, as carbon number of the alkyl group which can be selected as such R < ⁵ >, it is preferable that it is 1-6 from a viewpoint that refinement | purification becomes easier, It is more preferable that it is 1-5, 4 is more preferable, and 1 to 3 is particularly preferable. Such an alkyl group that can be selected as R ⁵ may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.

R ⁵ in the general formula (2) is a viewpoint that, when a polyimide is produced, higher heat resistance is obtained, raw materials are easily obtained, purification is easier, and the like. Therefore, each independently is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, a plurality of R ⁵ in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.

Further, in the repeating unit represented by the general formula (2), R ⁴ in the formula (2) is the same as the R ⁴ in the general formula (1), even those that suitable The same as R ⁴ in the general formula (1).

  The repeating unit (B) represented by the general formula (2) has the following general formula (201):

[In the formula (201), A has the same meaning as A in the general formula (2) (the preferred one is also the same as A in the general formula (2)), and a plurality of R ⁵ are each the same meaning as in formula (2) R ⁵ in (what its preferred also the same meaning as R ⁵ in the general formula (2).). ]
It can be formed from the raw material compound (B) represented by the above and the aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ . That is, the repeating unit (B) represented by the general formula (2) includes the raw material compound (B) and the aromatic diamine (the aromatic diamine represented by the above general formula (102)) and It can be made to contain in a polyimide by making it react.

A method for producing such a raw material compound (B) is not particularly limited, and a known method can be appropriately employed. For example, a method described in International Publication No. 2015/163314 is employed. May be. The aromatic diamine represented by the formula: H ₂ N—R ⁴ —NH ₂ is the same as described above.

<Repeating unit (C)>
The repeating unit (C) that the polyimide according to the present invention may contain is a repeating unit represented by the above general formula (3) (in the general formula (3), R ⁴ is an arylene group having 6 to 50 carbon atoms). A plurality of R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or bonded to the same carbon atom; Two R ⁶ groups together may form a methylidene group, and R ⁷ and R ⁸ are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. It is shown.)

The alkyl group that can be selected as R ⁶ in the general formula (3) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, sufficiently high heat resistance cannot be achieved. As the number of carbon atoms in the alkyl group such may be selected as R ^6, from the viewpoint of purification becomes easier, is preferably 1-6, more preferably 1-5, 1 4 is more preferable, and 1 to 3 is particularly preferable. Such an alkyl group that can be selected as R ⁶ may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.

Moreover, the general formula (3) a plurality of R ⁶ in the two R ⁶ are attached to the same carbon atom may form them together methylidene group (= CH ₂₎ It may be. That is, two R ⁶ bonded to the same carbon atom in the general formula (3) are combined to form the carbon atom (of the carbon atoms forming the norbornane ring structure, R ⁶ is bonded to two May be bonded as a methylidene group (methylene group) by a double bond.

As the plurality of R ⁶ in the general formula (3), when a polyimide is produced, higher heat resistance is obtained, the acquisition (preparation) of raw materials is easier, and purification is easier. From the viewpoints of being, etc., each independently is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a hydrogen atom or a methyl group. In addition, the plurality of R ⁶ in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.

In the general formula (3), R ⁷ and R ⁸ are each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. When the carbon number of such an alkyl group that can be selected as R ⁷ and R ⁸ exceeds 10, the heat resistance of the polyimide decreases. Moreover, as an alkyl group which can be selected as such R < ⁷ > and R < ⁸ >, from a viewpoint that higher heat resistance is obtained, it is preferable that it is 1-6, and it is more preferable that it is 1-5, It is more preferable that it is 1-4, and it is especially preferable that it is 1-3. Further, such an alkyl group that can be selected as R ⁷ and R ⁸ may be linear or branched.

In addition, R ⁷ and R ⁸ in the general formula (3) are such that a high degree of heat resistance is obtained when the polyimide is produced, the raw material is easily obtained, the purification is easier, and the like. From these viewpoints, it is more preferably each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, R ⁷ and R ⁸ in the formula (3) may be the same or different from each other, but they are the same from the viewpoint of ease of purification and the like. It is preferable that

Moreover, it is especially preferable that all of the plurality of R ⁶ , R ⁷ and R ⁸ in the general formula (3) are hydrogen atoms. Thus, in the repeating unit represented by the general formula (3), when all of the substituents represented by R ⁶ , R ⁷ and R ⁸ are hydrogen atoms, the yield of the compound is improved. However, higher heat resistance tends to be obtained.

Further, in the general formula (3), a repeating unit represented by formula, R ⁴ in the formula (3) is the same as the R ⁴ in the general formula (1), even those that suitable The same as R ⁴ in the general formula (1).

  The repeating unit (C1) represented by the general formula (3) has the following general formula (301):

[In the formula (301), a plurality of R ⁶ have the same meaning as R ⁶ in the general formula (3) (the preferred one is also synonymous with R ⁶ in the general formula (3)). R ^{7, R 8} are the same meanings as ^R 7, ^{R 8} in the general formula (3) (also those its preferred meaning as ^R 7, ^{R 8} in the general formula (3).). ]
It can be formed from the raw material compound (C) represented by the above and the aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ . That is, the repeating unit (C) represented by the general formula (3) can be contained in the polyimide by reacting the raw material compound (C) with the aromatic diamine.

A method for producing such a raw material compound (C) is not particularly limited, and a known method can be appropriately employed. For example, a method described in International Publication No. 2017/030019 is employed. May be. The aromatic diamine represented by the formula: H ₂ N—R ⁴ —NH ₂ is the same as described above.

As described above, the repeating units (A) to (C) are described separately. As described above, the polyimide according to the present invention includes the repeating unit (A), the repeating unit (B), and the repeating unit ( Any material containing at least one repeating unit selected from the group consisting of C) may be used. Thus, the polyimide contains, for example, one type selected from the group consisting of the repeating unit (A), the repeating unit (B), and the repeating unit (C). Or one containing two or more types of repeating units selected from the group consisting of the repeating unit (A), the repeating unit (B), and the repeating unit (C) (for example, When the repeating unit (A) and the repeating unit (B) are included in combination, when the repeating unit (B) and the repeating unit (C) are included in combination, the repeating unit (A) and the repeating unit are included. If (B) and comprising in combination with the repeating unit (C), when the repeating units of different types of R ⁴ a (a) comprises two or more repeats of different types of R ⁴ In the case where two or more kinds of the position (B) are contained, a combination of two or more kinds of the above (B) may be used.) In the polyimide according to the present invention, the repeating unit (A) and the repeating unit may be used. The total amount (total content) of the unit (B) and the repeating unit (C) is 20 to 100 mol% (more preferably 30 to 100 mol%, more preferably 40 to 100 mol%) with respect to all the repeating units. More preferably, it is 50 to 100 mol%, particularly preferably 60 to 100 mol%). Further, regarding the total amount (total amount) of the repeating unit (A), the repeating unit (B) and the repeating unit (C), the lower limit of the numerical range is more preferably 70 mol%, and 80 mol%. More preferably, it is most preferable that it is 90 mol%. When the total amount (total amount) of the repeating unit (A), the repeating unit (B), and the repeating unit (C) is less than the lower limit, the heat resistance based on the glass transition temperature (Tg) is higher. It tends to be difficult to achieve a standard level.

Moreover, in such a polyimide, the other repeating unit may be included in the range which does not impair the effect of this invention. Such other repeating units are not particularly limited, and examples thereof include known repeating units that can be used as polyimide repeating units. As such other repeating units, for example, other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C) are used, and these are represented by the above formula: H ₂ N—R ⁴ —NH _2. It is good also as a repeating unit formed by making it react with the aromatic diamine represented by these.

  Such other tetracarboxylic dianhydrides are not particularly limited. For example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5 Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2- Dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2′-binorbornane-5,5 ′, 6 , 6′-tetracarboxylic acid-5,5 ′, 6,6′-dianhydride or the like, or cycloaliphatic tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-bi Enylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4- Furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 4, 4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride And aromatic tetracarboxylic dianhydrides such as

As such other repeating units, from the viewpoint that it becomes possible to obtain a cured product having a sufficient balance of properties such as heat resistance, transparency, mechanical strength and solvent solubility, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, and 4,4 ′-(2,2-hexafluoroisopropylidene ) at least one tetracarboxylic dianhydride selected from the group consisting of diphthalic dianhydride, the formula: this is reacted with an aromatic diamine represented by H _{2 N-R} ⁴ -NH 2 Is preferably a repeating unit formed of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride It is more a repeating unit formed by reacting at least one tetracarboxylic dianhydride selected from the above and an aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH _2. preferable.

  Moreover, as a number average molecular weight (Mn) of such a polyimide, it is preferable that it is 1,000-1,000,000 in polystyrene conversion, and it is more preferable that it is 10,000-500,000. If the number average molecular weight is less than the lower limit, it is difficult not only to achieve sufficient heat resistance, but also does not sufficiently precipitate from an organic solvent during production, and it tends to be difficult to obtain polyimide efficiently, When the upper limit is exceeded, the viscosity increases, and it takes a long time to dissolve or requires a large amount of solvent, which tends to make processing difficult.

  Moreover, as a weight average molecular weight (Mw) of such a polyimide, it is preferable that it is 1,000-5,000,000 in polystyrene conversion. Moreover, as a lower limit of the numerical range of such a weight average molecular weight (Mw), it is more preferable that it is 5,000, It is further more preferable that it is 10,000, It is especially preferable that it is 20,000. Moreover, as an upper limit of the numerical range of a weight average molecular weight (Mw), it is more preferable that it is 5,000,000, It is further more preferable that it is 500,000, It is especially preferable that it is 100,000. When the weight average molecular weight is less than the lower limit, it is difficult to achieve sufficient heat resistance, and it does not sufficiently precipitate from an organic solvent during production, and it tends to be difficult to obtain polyimide efficiently, When the upper limit is exceeded, the viscosity increases, so that it takes a long time to dissolve or a large amount of solvent is required, which tends to make processing difficult.

  Furthermore, the molecular weight distribution (Mw / Mn) of such a polyimide is preferably 1.1 to 5.0, and more preferably 1.5 to 3.0. If the molecular weight distribution is less than the lower limit, it tends to be difficult to produce, while if it exceeds the upper limit, it tends to be difficult to obtain a uniform film. In addition, the molecular weight (Mw or Mn) and molecular weight distribution (Mw / Mn) of such polyimide are measured by a gel permeation chromatography (GPC) measuring device (Degasser: DG-2080-54 manufactured by JASCO, Liquid pump: JASCO PU-2080, interface: JASCO LC-NetII / ADC, column: Shodex GPC column KF-806M (× 2), column oven: JASCO 860-CO, RI detector : It can be obtained by converting the data measured using JA-20 RI-2031, column temperature 40 ° C., chloroform solvent (flow rate 1 mL / min.) In polystyrene. If measurement is difficult, use it for the production of the polyimide. Based on the viscosity of the polyamic acid, by analogy the molecular weight and the like, it may be used to screen a polyimide according to the use or the like.

Moreover, not particularly limited as a method for producing such a polyimide, the raw material compound (A) ~ (C), the formula: aromatic diamine represented by H _{2 N-R} ⁴ -NH 2 The method which can be made into polyimide by making it react can be employ | adopted suitably. Such reaction conditions may be set as appropriate according to the type of raw material compound and aromatic diamine used. A specific method for producing such polyimide will be described together with a method for producing a composition described later.

<Compound (second component)>
The compound (second component) according to the present invention is at least one compound selected from the group consisting of imidazole compounds, phosphorus compounds, and amine compounds.

  Such an imidazole compound is not particularly limited, and is imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 2-undecylimidazole, 2- Heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, benzimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- (2-methylimidazolylethyl) -1,3 5-Triazi 2,4-diamino-6- (2-undecylimidazolylethyl) -1,3,5-triazine, 2,4-diamino-6- (2-ethyl-4-methylimidazolylethyl) -1,3 Examples include 5-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like.

  Among such imidazole compounds, imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, and 2-undecylimidazole are used from the viewpoint of heat resistance and mechanical strength of the cured product. 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2-methylimidazole are more preferable, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2- Phenylimidazole is more preferable, and 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole are particularly preferable.

  The phosphorus compound is not particularly limited as long as it is an organic compound containing phosphorus. For example, phenyl phosphoric acid, trimethyl phosphate, dimethyl phosphite, diethyl phosphite, trimethyl phosphite, Phosphoric acid compounds such as phosphoric acid, tributyl phosphate, triphenyl phosphate, and triphenyl phosphite: triphenylphosphine, triparatolylphosphine, tritertiarybutylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, 1,4- Tertiary phosphorus compounds such as bisdiphenylphosphinobutane; benzyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, normal butyltriphenylphosphonium chloride, normal butyltriphenylphosphonium dicyanamide Enacetyltriphenylphosphonium chloride, hexyltriphenylphosphonium bromide, octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, benzyltriphenylphosphonium bromide 2-methylbenzyltriphenylphosphonium bromide, methyl Quaternary phosphorus salts such as triphenylphosphonium iodide, phenacetyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; triphenylphosphine oxide, diphenylphosphinylhydroquinone, triphenylphosphine triphenylborane, etc. But It is below.

  Examples of such phosphorus compounds include triphenylphosphine, tripalatolylphosphine, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, and phenylphosphorus from the viewpoint of heat resistance and mechanical strength of the cured product. More preferred are acid, trimethyl phosphate, dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triphenylphosphine, tripalatolylphosphine, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, More preferred is phenylphosphoric acid.

  Furthermore, the amine compound is preferably a tertiary amine compound or a quaternary amine salt from the viewpoint of ease of production of the polyimide resin composition. Examples of such amine compounds include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine, triethylamine, tributylamine, trioctylamine, N, N-dimethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] none-5-ene (DBN), tris ( Tertiary amine compounds such as dimethylaminomethyl) phenol, San-Apro U-CAT 18X; DBU organic acid salts (eg, DBU octylate, DBU p-toluenesulfonate, DBU formate, DBU Orthophthalate), DBU pheno Quaternary amine salts such as resin salt, DBN phenol resin salt, U-CAT 5002, manufactured by San Apro, tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium hydrochloride, tetraethylammonium hydrochloride, tetramethylammonium tetraphenylborate; Etc.

  Among these amine compounds, triethylamine, tributylamine, trioctylamine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) from the viewpoint of heat resistance and mechanical strength of the cured product. 1,5-diazabicyclo [4.3.0] none-5-ene (DBN), DBU organic acid salt is preferable, triethylamine, DBU, DBN, DBU phenol salt, DBU octylate is more preferable, Triethylamine, DBU phenol salt, and DBU octylate are particularly preferred.

  Among these compounds (second component), phosphorus compounds are particularly preferable and triphenylphosphine is most preferable because flame retardancy can be imparted to the polyimide resin composition. In addition, as such a compound (second component), one kind may be used alone, or two or more kinds may be used in combination.

<Composition of composition>
The polyimide resin composition of the present invention comprises the first component polyimide and the second component compound.

  In such a polyimide resin composition, the content of the polyimide (first component) and the content of the compound (second component) are not particularly limited, but the content of the second component relative to 100 parts by mass of the first component is The amount is preferably 0.1 to 25 parts by mass, and more preferably 0.5 to 15 parts by mass. If the content of such a compound (second component) is less than the lower limit, the mechanical strength of the cured product tends to decrease, and if it exceeds the upper limit, the heat resistance of the cured product tends to decrease.

  Such a polyimide resin composition may be in the form of a cured product from which the solvent has been removed, or may be in the form of a varnish containing a solvent. Thus, the polyimide resin composition in a form further containing a solvent can be suitably used for a polyimide varnish for forming a cured product of various forms of polyimide. Thus, when the polyimide resin composition of the present invention contains a solvent (when it is a polyimide resin composition in a form further containing a solvent), examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, γ-modified prolactone, δ-valerolactone, γ-modified prolactone, ε-modified prolactone, α-methyl Aprotic polar solvents such as γ-butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; m-cresol , P-cresol, xylenol, phenol, halogen Phenol solvents such as fluorinated phenols; ether solvents such as tetrahydrofuran, dioxane, cellosolve and glyme; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as cyclopentanone and cyclohexanone; acetonitrile and benzonitrile Nitrile solvents such as ethyl acetate, butyl acetate, isobutyl acetate, acetic acid ester solvents such as propylene glycol methyl acetate, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and other ketone solvents It is done. Examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ from the viewpoints of solubility, film formability, productivity, industrial availability, presence / absence of existing equipment, and price. -Butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferred, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, tetramethylurea are more preferred, N, N-dimethylacetamide and γ-butyrolactone are particularly preferred. In addition, you may utilize such an organic solvent individually by 1 type or in combination of 2 or more types.

  Moreover, in the polyimide resin composition in a form further containing such a solvent, the content of the solvent is not particularly limited, but is preferably 50 to 99% by mass, more preferably 50 to 90% by mass, More preferably, it is 60-90 mass%, and it is especially preferable that it is 70-90 mass%. If the content of such a solvent is less than the lower limit, it is difficult to make the polyimide resin composition sufficiently dissolved in the solvent, and it tends to be difficult to obtain a uniform varnish. When the upper limit is exceeded, the mechanical strength of the cured product tends to decrease.

  Such a polyimide resin composition may contain other components in addition to the polyimide (first component), the compound (second component), and the solvent. Such other components are not particularly limited. For example, antioxidants (phenolic, phosphite, thioether, etc.), ultraviolet absorbers, hindered amine light stabilizers, nucleating agents, resin additives (fillers) , Talc, glass fiber, etc.), flame retardants, processability improvers and lubricants. Moreover, it does not restrict | limit especially as these other components (antioxidant etc.), A well-known thing can be utilized suitably and a commercially available thing may be utilized.

  The polyimide resin composition of the present invention can be used as a polyimide resin composition in the form of a cured product (a cured product of a polyimide resin composition; a polyimide resin composition in a form not containing a solvent). The polyimide resin composition in the form of such a cured product preferably has a glass transition temperature (Tg) of 340 ° C. or higher, more preferably 350 to 550 ° C., and still more preferably 400 to 550 ° C. If such a glass transition temperature (Tg) is less than the lower limit, it tends to be difficult to achieve a high level of heat resistance as required in the present application. It tends to be difficult to produce a polyimide having the above. Such a glass transition temperature (Tg) can be measured by a tensile mode using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku). That is, a polyimide resin composition (cured product) film having a size of 20 mm in length and 5 mm in width (the thickness of the film is not particularly limited because it does not affect the measured value, but is 5 to 100 μm. The measurement sample is formed under a nitrogen atmosphere, using a tensile mode (49 mN) and a heating rate of 5 ° C./min. The inflection point of the TMA curve resulting from the glass transition On the other hand, it can obtain | require by extrapolating the curve before and behind that.

  Moreover, as a polyimide resin composition of the form of such hardened | cured material, that whose 5% weight reduction temperature is 400 degreeC or more is preferable, and the thing of 450-550 degreeC is more preferable. If such a 5% weight loss temperature is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, whereas if it exceeds the upper limit, it is difficult to produce a polyimide resin composition having such characteristics. It tends to be. Note that such 5% weight loss temperature is raised from room temperature (for example, 25 ° C.) to 40 ° C. while flowing nitrogen gas in a nitrogen gas atmosphere, and then gradually heated to 40 ° C. as a measurement start temperature. It can be determined by measuring the temperature at which the weight of the sample used is reduced by 5%.

  Furthermore, as a polyimide resin composition in the form of such a cured product, those having a softening temperature of 300 ° C. or higher are preferable, and those having a softening temperature of 350 to 550 ° C. are more preferable. If such a softening temperature is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide resin composition having such characteristics. is there. Such a softening temperature can be measured in a penetration mode using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku). In measurement, the sample size (vertical, horizontal, thickness, etc.) does not affect the measured value, so it can be attached to the jig of the thermomechanical analyzer to be used (trade name “TMA8311” manufactured by Rigaku). The sample size may be appropriately adjusted to a suitable size.

  Moreover, as a polyimide resin composition of the form of such hardened | cured material, a thermal decomposition temperature (Td) is preferably 450 degreeC or more, and a 480-600 degreeC thing is more preferable. If such a thermal decomposition temperature (Td) is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it is difficult to produce a polyimide having such characteristics. There is a tendency. In addition, such a thermal decomposition temperature (Td) was measured using a TG / DTA220 thermogravimetric analyzer (manufactured by SII Nanotechnology Co., Ltd.) in a nitrogen atmosphere under a heating rate of 10 ° C./min. It can be determined by measuring the temperature at the intersection of the tangent lines drawn on the decomposition curve before and after thermal decomposition under the conditions of

  The polyimide resin composition in the form of such a cured product preferably has an elongation at break of 5% or more, more preferably 10% or more, and particularly preferably 20% or more. If the elongation at break is less than the lower limit, the toughness tends to be low and mechanically brittle. Such elongation at break can be measured according to the method described in “JIS K7161” of Japanese Industrial Standard.

  Moreover, it is preferable that the linear expansion coefficient (CTE) of the polyimide resin composition of the form of such hardened | cured material is 0-100 ppm / K, and it is more preferable that it is 10-70 ppm / K. When such a linear expansion coefficient exceeds the upper limit, peeling tends to occur due to thermal history when combined with a metal or inorganic material having a linear expansion coefficient range of 5 to 20 ppm / K. Moreover, when the linear expansion coefficient is less than the lower limit, the solubility and the film characteristics tend to be lowered.

  As a method for measuring the linear expansion coefficient of the polyimide resin composition in the form of such a cured product, the following method is employed. That is, first, a film having a length of 20 mm and a width of 5 mm made of a polyimide resin composition in the form of the cured product (thickness of the film is not particularly limited because it does not affect the measured value, 5-100 μm) is preferably used as a measurement sample, and a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) is used as a measurement device, under a nitrogen atmosphere, in a tensile mode (49 mN), Adopting a temperature increase rate of 5 ° C./min, the temperature was raised from room temperature to 200 ° C. (first temperature increase), allowed to cool to 30 ° C. or less, and then raised from that temperature to 400 ° C. (second time) And the change in the length of the sample in the longitudinal direction at the time of the temperature rise is measured. Next, using the TMA curve obtained by the measurement at the time of the second temperature increase (measurement when the temperature is raised from the temperature at the time of standing to 400 ° C.), 1 in the temperature range of 100 ° C. to 200 ° C. The average value of the change in length per degree C is obtained, and the obtained value is measured as the linear expansion coefficient of polyimide. Thus, as a linear expansion coefficient of the polyimide resin composition (cured product) of the present invention, an average value of changes in length per 1 ° C. in a temperature range of 100 ° C. to 200 ° C. is obtained based on the TMA curve. The value obtained by this is adopted.

  In addition, such a polyimide resin composition preferably has a sufficiently high transparency when a film is formed, and has a total light transmittance of 80% or more (more preferably 85% or more, particularly preferably). 87% or more) is more preferable. Such total light transmittance can be easily achieved by appropriately selecting the type of polyimide or the like.

  Moreover, as a polyimide resin composition of the form of such hardened | cured material, a haze (turbidity) is 5-0 (more preferably 4-0, especially preferably 3) from a viewpoint of obtaining more highly colorless transparency. It is more preferable that it is ˜0). If the haze value exceeds the upper limit, it tends to be difficult to achieve a higher level of colorless transparency.

  Furthermore, the polyimide resin composition in the form of such a cured product has a yellowness (YI) of 5 to 0 (more preferably 4 to 0, particularly preferably 3) from the viewpoint of obtaining a higher degree of colorless transparency. It is more preferable that it is ˜0). When such yellowness exceeds the upper limit, it tends to be difficult to achieve a higher level of colorless transparency.

  Such total light transmittance, haze (turbidity) and yellowness (YI) are measured by a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. or manufactured by Nippon Denshoku Industries Co., Ltd. The total light transmittance and haze were measured with a product name “Spectral Color Meter SD6000” (trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd.). Measure the yellowness with the product name “spectral colorimeter SD6000”.), Adopt the value measured using a film of 5-100 μm thick made of a polyimide resin composition in the form of a cured product as a sample for measurement. Can do. In addition, the vertical and horizontal sizes of the measurement sample may be any size that can be arranged at the measurement site of the measurement apparatus, and the vertical and horizontal sizes may be appropriately changed. In addition, such total light transmittance is calculated | required by measuring based on JISK7361-1 (issued in 1997), and a haze (turbidity) performs the measurement based on JISK7136 (issued in 2000). The yellowness (YI) is obtained by performing measurement in accordance with ASTM E313-05 (issued in 2005).

  In the polyimide resin composition in the form of such a cured product, the absolute value of retardation (Rth) in the thickness direction measured at a wavelength of 590 nm is preferably 150 nm or less in terms of thickness of 10 μm, preferably 100 nm or less. More preferably, it is more preferably 50 nm or less, and particularly preferably 25 nm or less. That is, the retardation (Rth) value is preferably −150 nm to 150 nm (more preferably −100 nm to 100 nm, still more preferably −50 to 50 nm, particularly preferably −25 to 25 nm). When the absolute value of retardation (Rth) in the thickness direction exceeds the upper limit, when used in a display device, the contrast tends to decrease and the viewing angle tends to decrease. In addition, when the absolute value of the retardation (Rth) falls within the above range, when used in a display device, the effect of suppressing the decrease in contrast and the effect of improving the viewing angle tend to be more advanced. Thus, when used in a display device, the absolute value of the retardation (Rth) in the thickness direction is from the viewpoint that the reduction in contrast can be suppressed to a higher degree and the viewing angle can be further improved. A lower value is preferred.

  Such “absolute value of thickness direction retardation (Rth)” is a refractive index (589 nm) of a film made of a polyimide resin composition in the form of a cured product, using a trade name “AxoScan” manufactured by AXOMETRICS as a measuring device. The thickness of the film made of the polyimide resin composition was measured using light having a wavelength of 590 nm under the conditions of temperature: 25 ° C. and humidity: 40%. A value (converted value) obtained by measuring the retardation in the direction and converting it into a retardation value per 10 μm of the film thickness based on the measured value of retardation in the thickness direction (measured value by automatic measurement (automatic calculation) of the measuring device). ) And calculating the absolute value from the converted value. Thus, the “absolute value of retardation (Rth) in the thickness direction” can be obtained by calculating the absolute value (| converted value |) of the converted value. The size of the film of the measurement sample is not particularly limited as long as it is larger than the photometry part (diameter: about 1 cm) of the stage of the measuring instrument. However, the length is 76 mm, the width is 52 mm, and the thickness is 5 to 20 μm. It is preferable.

  In addition, the value of the “refractive index of the film (589 nm)” used for the measurement of retardation (Rth) in the thickness direction is the same type of polyimide resin composition as the polyimide resin composition forming the film to be measured for retardation. After forming an unstretched film made of the above, use the unstretched film as a measurement sample (in the case where the film to be measured is an unstretched film, use the film as it is as a measurement sample. In-plane direction of the measurement sample using a refractive index measurement device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.) as a measurement device, using a light source of 589 nm and a temperature condition of 23 ° C. It can be obtained by measuring the refractive index for light of 589 nm (in a direction perpendicular to the thickness direction). Since the measurement sample is unstretched, the refractive index in the in-plane direction of the film is constant in any direction within the plane, and the intrinsic refractive index of the polyimide resin composition is measured by measuring the refractive index. (Because the measurement sample is not stretched, Nx is the refractive index in the in-plane retardation axis direction, and Ny is the refractive index in the in-plane direction perpendicular to the delay axis direction. Become). Thus, the intrinsic refractive index (589 nm) of the polyimide resin composition is measured using an unstretched film, and the obtained measurement value is used for the measurement of retardation (Rth) in the thickness direction described above. Here, the size of the film of the measurement sample is not particularly limited as long as it is a size that can be used in the refractive index measurement device, and may be 1 cm square (1 cm in length and width) and 5 to 20 μm in thickness.

  In addition, when such a polyimide resin composition is in the form of a cured product, for example, a film for a flexible wiring board, a heat-resistant insulating tape, a wire enamel, a semiconductor protective coating agent, a liquid crystal alignment film, a transparent for organic EL Conductive film, flexible substrate film, flexible transparent conductive film, transparent conductive film for organic thin-film solar cells, transparent conductive film for dye-sensitized solar cells, flexible gas barrier film, touch panel film, flat panel detector TFT Substrate film, seamless polyimide belt for copying machines (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 ( ED) reflector (LED illumination reflector: LED reflector), LED illumination cover, LED reflector illumination cover, coverlay film, high ductility composite substrate, semiconductor resist, lithium ion battery, organic memory It is particularly useful as a material for producing a substrate for an organic transistor, a substrate for an organic transistor, a substrate for an organic semiconductor, a color filter base material and the like. In addition, when such a polyimide resin composition is in the form of a cured product, in addition to the above-described uses, the shape thereof is powdered or various molded bodies, for example, It can also be used as appropriate for automotive parts, aerospace parts, bearing parts, seal materials, bearing parts, gear wheels, valve parts, and the like.

  Further, when such a polyimide resin composition further includes a solvent, it can be suitably used as a varnish (polymid varnish) used when forming into various films and various parts as described above. Can do. Hereinafter, the method which can be suitably employ | adopted as a method for manufacturing such a polyimide resin composition of this invention is demonstrated.

<About the method for manufacturing a composition>
The method for producing such a polyimide resin composition of the present invention is not particularly limited, and it is possible to produce a polyimide resin composition containing the polyimide (first component) and the compound (second component). For example, at least one compound (second component) selected from the group consisting of the imidazole compound, the phosphorus compound, and the amine compound, a polymerization solvent, A tetracarboxylic dianhydride containing at least one selected from the group consisting of the raw material compound (A), the raw material compound (B) and the raw material compound (C) (if necessary, And may further contain other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C)); and the above formula: H ₂ N—R ⁴ —NH ₂ [wherein R ⁴ is the above general formula Formula (1) And at least one aromatic diamine is selected from the compounds represented by R ⁴ as synonymous] in; by reacting the repeating units (A), the repeating unit (B), and A polyimide resin composition containing a polyimide (the first component) containing at least one repeating unit selected from the group consisting of the repeating units (C); and the compound (the second component) The method (I) for obtaining can be suitably employed. In addition, the raw material compounds (A) to (C) used in the method (I), the aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ , and used as necessary. Other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C) are the same as those described in the polyimide resin composition of the present invention (the preferred ones are also the same). Is).

  In such a method (I), in the presence of the compound (the second component) and a polymerization solvent, the tetracarboxylic dianhydride (if necessary, other than the raw material compounds (A) to (C) The specific conditions for reacting the aromatic diamine with other tetracarboxylic dianhydride may be not particularly limited. In addition, as such a method (I), for example, in the presence of the compound (second component) and a polymerization solvent, the tetracarboxylic dianhydride (if necessary, the raw material compounds (A) to ( (It may further contain other tetracarboxylic dianhydrides other than C)) and the above aromatic diamine, and the following general formula (4):

Wherein ^{(4), R 1, R} 2, R 3, R 4, n have the same meanings as ^{R 1, R 2, R 3} , R 4, n in the general formula (1) (the preferred Those are also synonymous with R ¹ , R ² , R ³ and n in the general formula (1). ]
A repeating unit (A ′) represented by the following general formula (5):

Wherein ^(5), R 4, ^{R 5} and A ^{R 4} in the same definition as ^R 4, ^{R 5} and A in the general formula (2) (Formula others its preferred (2) , R ⁵ and A. ]
And a repeating unit (B ′) represented by the following general formula (6):

^{[R 4,} R 6, ^{R 7} and ^{R 8} in the formula (6) is the same as the ^{R 4,} R 6, ^{R 7} and ^{R 8} in the general formula (3) (as its preferred Are also synonymous with R ⁴ , R ⁶ , R ⁷ and R ^{8 in the} general formula (3). ]
A step of obtaining a polyamic acid composition containing a polyamic acid containing at least one repeating unit selected from the group consisting of repeating units (C ′) represented by the formula (2) and the compound (second component). (I),
The polyamic acid in the polyamic acid composition is imidized and at least one selected from the group consisting of the repeating unit (A), the repeating unit (B), and the repeating unit (C). Step (II) of obtaining a polyimide resin composition containing a polyimide containing the repeating unit (the first component); and the compound (the second component);
The method (I-1) including Hereinafter, such steps (I) and (II) will be described.

First, step (I) will be described. In the step (I), the polycarboxylic acid and the compound (the second component) are reacted with the tetracarboxylic dianhydride and the aromatic diamine in the presence of a polymerization solvent. And a polyamic acid composition containing the component). The raw material compounds (A) to (C) used in the method (I-1), the aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ , and used as necessary. Other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C) are the same as those described in the polyimide resin composition of the present invention (the preferred ones are also the same). Is). The “tetracarboxylic dianhydride” used in such step (I) only needs to contain at least one selected from the group consisting of the raw material compounds (A) to (C). Accordingly, other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C) may be included. The repeating unit (A ′) can be formed from the reaction between the raw material compound (A) and the aromatic diamine, and the repeating unit (B ′) can be formed from the raw material compound (B) and the aromatic diamine. The repeating unit (C ′) can be formed from the reaction between the raw material compound (C) and the aromatic diamine.

  As a polymerization solvent used in such a method, a known solvent that can be used at the time of polymerization can be used as appropriate, and among them, a solvent that can dissolve both the tetracarboxylic dianhydride and the aromatic diamine. Preferably there is. Further, as such a polymerization solvent, the solvent described in the above-mentioned “polyimide resin composition further including a solvent” can be appropriately used. Examples of such solvents include the aprotic polar solvents described above; the phenol solvents described above; the ether solvents described above; and the aromatic solvents described above. Such organic solvents may be used singly or in combination of two or more.

In such a method, the amount of the tetracarboxylic dianhydride used (the total amount of the raw material compounds (A) to (C) and the other tetracarboxylic dianhydride) and the aromatic diamine are used. The ratio to the amount (the total amount of the compounds represented by the formula: H ₂ N—R ⁴ —NH ₂ ) is not particularly limited, but the tetra used for the reaction with respect to 1 equivalent of the amino group of the aromatic diamine. The amount of all acid anhydride groups in the carboxylic dianhydride is preferably 0.5 to 2 equivalents, more preferably 0.8 to 1.2 equivalents. When the preferred use ratio of such tetracarboxylic dianhydride and the above aromatic diamine is less than the lower limit, the polymerization reaction does not proceed efficiently, and a high molecular weight polyamic acid tends to be obtained, whereas, the upper limit. If it exceeds 1, it tends to be impossible to obtain a high molecular weight polyamic acid as described above.

Furthermore, the amount of the polymerization solvent used is the amount of tetracarboxylic dianhydride used in the reaction (the total amount of the raw material compounds (A) to (C) used in the reaction and the other tetracarboxylic dianhydrides. ) And the amount of the aromatic diamine (the total amount of the compound represented by the formula: H ₂ N—R ⁴ —NH ₂ ) (the total amount of the reactant [substrate]) with respect to the total amount of the reaction solution The amount is preferably 1 to 80% by mass (more preferably 5 to 50% by mass). If the amount of the polymerization solvent used is less than the lower limit, it tends to be impossible to obtain a polyamic acid efficiently. On the other hand, if the upper limit is exceeded, stirring becomes difficult due to high viscosity, and a high molecular weight product cannot be obtained. There is a tendency.

  In such step (I), in the presence of at least one compound (second component) selected from the group consisting of an imidazole compound, a phosphorus compound, and an amine compound, The tetracarboxylic dianhydride is reacted with the aromatic diamine. In such a reaction, the compound (second component) acts as a catalyst for promoting the polymerization reaction, and it is possible to improve the molecular weight of the polyamic acid formed by the reaction. It is possible to improve the molecular weight. Therefore, the cured product of the composition containing such a polyimide (first component) and the compound (second component) has sufficient light transmittance that can be used for glass replacement, and has sufficiently high heat resistance. It becomes possible to have sufficiently good mechanical strength.

Moreover, the usage-amount of the at least 1 sort (s) (compound 2nd component) selected from the group which consists of an imidazole type compound, a phosphorus type compound, and an amine type compound is the quantity of the said tetracarboxylic dianhydride ( The raw material compounds (A) to (C) used in the reaction and the total amount of the other tetracarboxylic dianhydrides) and the amount of the aromatic diamine (formula: H ₂ N—R ⁴ —NH ₂₎ The ratio of the compound of the second component to the total amount of the compound (the total amount of the compound) and the amount of the compound (the second component) (the total amount of the imidazole compound, the phosphorus compound, and the amine compound) Is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. When the content of such a compound (second component) is less than the lower limit, it is difficult to improve the molecular weight of the polyamic acid, and as a result, the heat resistance and mechanical strength of the cured product tend to decrease. On the other hand, when the upper limit is exceeded, a side reaction proceeds, a uniform polyamic acid cannot be obtained, and various physical properties of the cured product tend to decrease.

  The tetracarboxylic dianhydride (at least one selected from the group consisting of the raw material compounds (A) to (C) and the other tetracarboxylic dianhydride added as necessary) And the reaction temperature at the time of making it react with the said aromatic diamine should just adjust suitably to the temperature which can make these compounds react, Although it does not restrict | limit, It is preferable to set it as 15-100 degreeC. In addition, as a method of reacting the tetracarboxylic dianhydride and the aromatic diamine, a method capable of performing a polymerization reaction of the tetracarboxylic dianhydride and the aromatic diamine can be appropriately used, and is particularly limited. For example, after adding the compound (second component) to the polymerization solvent in an inert atmosphere such as nitrogen, helium, argon, etc. at atmospheric pressure, the tetracarboxylic acid is added to the polymerization solvent at the reaction temperature. You may employ | adopt the method of adding acid dianhydride and the said aromatic diamine, and making it react for 10 to 48 hours after that. If the reaction temperature or reaction time is less than the lower limit, it tends to be difficult to cause sufficient reaction. On the other hand, if the upper limit is exceeded, the probability of mixing a substance (such as oxygen) that degrades the polymer increases and the molecular weight increases. It tends to decrease.

Thus, selected from the group consisting of the raw material compound (A), the raw material compound (B), and the raw material compound (C) in the presence of the compound (second component) and the polymerization solvent. A tetracarboxylic dianhydride containing at least one selected from the above (may further contain other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C) if necessary), and the above formula : An aromatic diamine represented by H ₂ N—R ⁴ —NH ₂ (at least one selected from the group consisting of compounds represented by the above formula: H ₂ N—R ⁴ —NH ₂ ) A polyamic acid containing at least one repeating unit selected from the group consisting of the repeating unit (A ′), the repeating unit (B ′), and the repeating unit (C ′) by reacting. And the compound (second component) Can be obtained.

  Next, process (II) is demonstrated. In step (II), the polyamic acid in the polyamic acid composition is imidized and selected from the group consisting of the repeating unit (A), the repeating unit (B), and the repeating unit (C). It is the process of obtaining the polyimide resin composition containing the polyimide (said 1st component) containing the said at least 1 sort (s) of repeating unit; and the said compound (said 2nd component).

  The method for imidizing the polyamic acid in such a polyamic acid composition is not particularly limited as long as it is a method capable of imidizing polyamic acid, and a known method can be appropriately employed. , A method of imidizing the polyamic acid in the polyamic acid composition using an imidizing agent such as a so-called condensing agent, and a temperature condition of 60 to 450 ° C. (more preferably 80 to 400 ° C.) for the polyamic acid composition. It is preferable to employ a method of imidizing the polyamic acid in the polyamic acid composition by performing a heating process at step A.

  In such imidization, when adopting a method of imidizing the polyamic acid using an imidizing agent such as a so-called condensing agent, it is preferable to imidize the polyamic acid in a solvent in the presence of the condensing agent. . As such a solvent, those similar to the polymerization solvent used in the above step (I) can be suitably used. Thus, when adopting a method of imidizing using an imidizing agent such as a so-called condensing agent, the polyamic acid is chemically imided using an imidizing agent such as a condensing agent in the polymerization solvent (organic solvent). It is preferable to adopt the step of obtaining the polyimide by making it. In addition, in the case of imidizing by employing chemical imidization using an imidizing agent such as a condensing agent, the imidization step described in the step (II) is used as the dehydrating condensing agent (carboxylic acid anhydride). Or a carbodiimide, an acid azide, an active esterifying agent, etc.), and the polyamic acid may be dehydrated and closed to imidize.

  In such a method (I-1), the polyamic acid composition also contains the second component compound in the chemical imidation, and the second component serves as an imidization catalyst. Therefore, it is not always necessary to heat at a high temperature during imidation, and it is possible to obtain a polyimide by imidization under a low temperature condition (more preferably, a temperature condition of about 100 ° C. or less).

  When employing such chemical imidization to imidize, in the presence of the compound (second component) and the polymerization solvent (organic solvent) in step (I), the tetracarboxylic dianhydride and the above After obtaining a reaction liquid (reaction liquid containing the second component and the polyamic acid) obtained by reacting with an aromatic diamine, the reaction liquid is used as it is and subjected to chemical imidization using a condensing agent. It is preferable.

  In addition, the condensing agent used in the case of employing chemical imidization in such step (II) may be any one that can be used when the polyamic acid is condensed to form a polyimide. Carboxylic anhydrides such as acetic acid, propionic anhydride and trifluoroacetic anhydride, carbodiimides such as N, N'-dicyclohexylcarbodiimide (DCC), acid azides such as diphenylphosphoric acid azide (DPPA), and active esterification such as castro reagents And dehydrating condensing agents such as 2-chloro-4,6-dimethoxytriazine (CDMT). Among such condensing agents, acetic anhydride, propionic anhydride, and trifluoroacetic anhydride are preferable, acetic anhydride and propionic anhydride are more preferable, and acetic anhydride is still more preferable from the viewpoint of reactivity, availability, and practicality. Such condensing agents may be used alone or in combination of two or more.

  Moreover, when chemically imidizing using such a condensing agent (imidizing agent), the polyamic acid composition obtained after implementing step (I) is used from the viewpoint of more efficiently producing polyimide. A reaction liquid (the polyamide) obtained by reacting the tetracarboxylic dianhydride and the aromatic diamine in the presence of the compound (second component) and the polymerization solvent (organic solvent) without isolation. It is more preferable to employ a method in which an acid and a reaction solution containing the compound (second component) are used as they are, and a condensing agent (imidizing agent) is added to the reaction solution to imidize.

  Moreover, the temperature conditions in particular in such chemical imidation are not restrict | limited, The temperature conditions generally utilized in the case of chemical imidation can be employ | adopted suitably. As temperature conditions in such chemical imidation, it is preferably 0 ° C to 120 ° C, more preferably 10 ° C to 100 ° C, and further preferably 20 ° C to 80 ° C. If such a temperature exceeds the upper limit, an undesirable side reaction tends to proceed and polyimide cannot be obtained. On the other hand, if the temperature is lower than the lower limit, the reaction rate of chemical imidation decreases or the reaction itself does not proceed. Tend not to be obtained.

  The reaction time for such chemical imidation is preferably 0.1 to 48 hours. If the reaction temperature or time is less than the lower limit, it is difficult to sufficiently imidize, and it tends to be difficult to precipitate polyimide in an organic solvent. On the other hand, if the upper limit is exceeded, the polymer is deteriorated. There is a tendency that the mixing probability of the substance (oxygen, etc.) to be increased increases and the molecular weight decreases.

  The amount of the condensing agent (imidizing agent) used is not particularly limited, but is preferably 0.05 to 4.0 mol with respect to 1 mol of the repeating unit in the polyamic acid. More preferably, it is 2 mol. If the amount of such a condensing agent (imidizing agent) is less than the lower limit, the reaction rate of chemical imidization tends to decrease, or the reaction itself does not proceed sufficiently and polyimide cannot be obtained sufficiently, When the upper limit is exceeded, an undesirable side reaction proceeds, and thus polyimide cannot be obtained efficiently.

  In addition, as atmospheric conditions for performing such chemical imidization, from the viewpoint of preventing coloring due to oxygen in the air and molecular weight reduction due to water vapor in the air, an inert gas atmosphere such as nitrogen gas or under vacuum It is preferable that Moreover, it does not restrict | limit especially as pressure conditions at the time of performing such chemical imidation, However, It is preferable that it is 0.01 hPa-1 MPa, and it is more preferable that it is 0.1 hPa-0.3 MPa. If such pressure is less than the lower limit, the solvent, the condensing agent, and the reaction accelerator are gasified, the stoichiometry is lost, the reaction is adversely affected, and the reaction tends to be difficult to proceed sufficiently. On the other hand, when the upper limit is exceeded, an undesirable side reaction proceeds, or the solubility of the polyamic acid tends to decrease and precipitate.

  In the imidization in the step (II), as described above, the polyamic acid composition is subjected to a treatment of heating the polyamic acid composition at a temperature of 60 to 450 ° C. (more preferably 80 to 400 ° C.). A method of imidizing the polyamic acid in the composition can also be employed. In the case of adopting a method for imidizing the polyamic acid in the polyamic acid composition by performing such a heat treatment, the reaction tends to be delayed if the heating temperature is less than the lower limit, while the upper limit is used. If it exceeds 1, it tends to be colored or a decrease in molecular weight due to thermal decomposition. Moreover, it is preferable that reaction time (heating time) in the case of employ | adopting the method imidized by performing the said heat processing shall be 0.5 to 5 hours. If the reaction time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if the upper limit is exceeded, coloring tends to occur and molecular weight is decreased due to thermal decomposition.

  Further, in the case where the polyamic acid in the polyamic acid composition is imidized by performing the heat treatment, the polyamic acid composition contains the compound (second component) and is heated. Since the compound (second component) sometimes allows imidization while promoting repolymerization of the molecular chain of the polyamic acid, it is possible to further improve the molecular weight of the resulting polyimide, and thereby the cured product In this case, the heat resistance and mechanical strength can be sufficiently improved.

  Further, when a method including such steps (I) and (II) is used, and when a method of imidizing by applying the heat treatment during imidization is employed, the step (I ) And the reaction solution obtained by reacting the tetracarboxylic dianhydride and the aromatic diamine in the presence of the compound (second component) and the polymerization solvent (such as the organic solvent). (The reaction solution containing the polyamic acid) is used as it is, the solvent is removed from the reaction solution by evaporation (solvent removal treatment), the solvent is removed from the reaction solution, and then the heat treatment is performed. By adopting a method for imidizing the polyamic acid in the polyamic acid composition, the resulting polyimide resin composition may be a cured polyimide resin composition. By taking out the polyamic acid composition in the form of a film or the like by the process of evaporating and removing the solvent, a heat treatment is performed to obtain a polyimide resin composition (cured product) in a desired form. Is possible.

  The temperature condition in the treatment for removing the solvent by evaporation (solvent removal treatment) is preferably 0 to 180 ° C, more preferably 30 to 150 ° C. If the temperature condition in such a solvent removal treatment is less than the lower limit, it tends to be difficult to remove the solvent sufficiently by evaporation, whereas if the upper limit is exceeded, the solvent will boil and the film contains bubbles and voids. Tend to be. In the method including the steps (I) and (II), when producing a film-like polyimide resin composition, the reaction solution obtained in the step (I) is directly applied onto a substrate (for example, a glass plate). Then, a treatment for evaporating and removing the solvent and a heat treatment may be performed, and a film-like polyimide resin composition can be produced by a simple method. In addition, it does not restrict | limit especially as a coating method of such a reaction liquid, A well-known method (casting method etc.) can be employ | adopted suitably.

Further, when the step (II) is performed by employing the method of imidizing by performing the heat treatment, the step (I) and the step (II) may be performed simultaneously as a series of steps. Thus, as a method of simultaneously performing the step (I) and the step (II) as a series of steps, for example, the raw material compound (A) represented by the general formula (101), the general formula (201) A tetracarboxylic dianhydride containing at least one selected from the group consisting of a raw material compound (B) represented by the above and a raw material compound (C) represented by the above general formula (301) (necessary And may further contain other tetracarboxylic dianhydrides other than the raw material compounds (A) to (C)), and an aromatic represented by the above formula: H ₂ N—R ⁴ —NH ₂ By performing a heating treatment from the stage of reacting with diamine, the formation of polyamic acid (intermediate) and the subsequent formation of polyimide (imidation) are allowed to proceed almost simultaneously, so that steps (I) and (II) The method of applying It can be.

  Further, even when the step (I) and the step (II) are simultaneously performed by performing the heating treatment from the step of reacting the tetracarboxylic dianhydride and the aromatic diamine, the compound In order to react the tetracarboxylic dianhydride and the aromatic diamine in the presence of the (second component) and the polymerization solvent, the formation of the polyamic acid in the step (I) and the step (II) are performed by heating. When imidization of polyamic acid is caused continuously, when preparing polyimide in a solvent, the reaction rate of polyamic acid formation and imidization becomes very fast, and the molecular weight becomes larger (more stretched) Become). In addition, when the step (I) and the step (II) are simultaneously performed by heating in this manner, the reaction between the tetracarboxylic dianhydride and the aromatic diamine proceeds and the reaction is generated by the reaction. It is also possible to evaporate and remove the water, so that the reaction can proceed efficiently without using a so-called condensing agent (dehydrating condensing agent).

  In the case where a polyimide is formed by heating and reacting the tetracarboxylic dianhydride and the aromatic diamine in the presence of the compound (second component) and the polymerization solvent (steps by heating ( I) and step (II) are performed simultaneously), and the temperature condition during the heating is preferably 100 to 250 ° C, more preferably 120 to 250 ° C, and more preferably 150 to 220 ° C. More preferably. If such a temperature condition is less than the lower limit, the reaction temperature is below the boiling point of water, so that water does not evaporate, the reaction progress is inhibited by water, and the molecular weight of the polyimide contained in the composition is reduced. On the other hand, if the upper limit is exceeded, side reactions such as thermal decomposition of the solvent occur, and the polyimide obtained after heating, the organic solvent, and the compound (second component) In the mixed liquid (varnish), the amount of impurities increases, and when a cured product such as a film is formed using this, the physical properties of the polyimide resin composition in the form of the resulting cured product tend to decrease. is there.

  As described above, the method (I-1) including the step (I) and the step (II) that can be suitably employed as a method for producing the polyimide resin composition of the present invention has been described. The method for producing the polyimide resin composition is not limited to the method described above. For example, depending on the type of the tetracarboxylic dianhydride, the aromatic diamine, etc., even when the reaction is performed under the condition where the compound (second component) does not exist (without using the compound (second component)) ), When a sufficiently high molecular weight polyamic acid is obtained, for example, instead of using the compound (second component) instead of the step (I), in the presence of the polymerization solvent, After reacting the tetracarboxylic dianhydride and the aromatic diamine to form a polyamic acid to obtain a reaction solution containing the polyamic acid, the compound (second component) is added to obtain a polyamic acid composition. You may manufacture the polyimide resin composition by giving the process (I ') to obtain, and implementing the process similar to the above-mentioned process (II) after that. In the case where the step (I) and the step (II) are simultaneously performed, for example, under the condition where the compound (second component) does not exist depending on the kind of the tetracarboxylic dianhydride or the aromatic diamine. Even when the reaction is performed (without using the compound (second component)), when a sufficiently high molecular weight polyimide is obtained, for example, the above-described steps are performed except that the compound (second component) is not used. A method similar to the method of simultaneously performing (I) and step (II) is adopted to form a polyimide, and after obtaining a reaction solution containing polyimide, the compound (second component) is added to the reaction solution. Thus, a polyimide resin composition may be manufactured. In addition, in a polyimide resin composition obtained by adopting such a method (a method of producing a polyimide resin composition by adding the compound (second component) after obtaining a reaction solution containing polyimide), this is also used. In the process of obtaining a cured product by use (for example, in the process of applying such a polyimide resin composition to a substrate to obtain a cured product in the form of a film, etc.), it has already been formed by the second component in the composition. Since it becomes possible to promote repolymerization of the molecular chain of the polyimide, it is possible to further improve the molecular weight of the polyimide in the composition, and to obtain a cured product (polyimide resin composition in the form of a cured product) obtained It is possible to make it sufficiently excellent in heat resistance and mechanical strength. Thus, the polyimide (first component); and at least one compound (second component) selected from the group consisting of the imidazole compound, the phosphorus compound, and the amine compound; In the case where the polyimide resin composition containing is used in the form of a cured product, the molecular weight of the polyimide is improved by the second component at any stage until the cured product is formed. It is possible to make the cured product (polyimide resin composition in the form of a cured product) sufficiently excellent in heat resistance and mechanical strength.

[Polyimide varnish]
The polyimide varnish of the present invention is characterized by comprising the polyimide resin composition of the present invention in a form further containing a solvent. Thus, the said polyimide varnish consists of the above-mentioned "polyimide resin composition of the form which further contains a solvent." In other words, the polyimide varnish of the present invention includes the repeating unit (A) represented by the general formula (1), the repeating unit (B) represented by the general formula (2), and the general formula (3). The polyimide (the first component) containing at least one repeating unit selected from the group consisting of repeating units (C) represented by: an imidazole compound, a phosphorus compound, and an amine compound A polyimide resin composition (a polyimide resin composition in a form containing a solvent) containing at least one compound selected from the group consisting of: the second component; and the solvent. .

  In addition, the polyimide varnish of the present invention is a polymerization solvent used in the production of the polyimide resin composition obtained by carrying out a method that can be suitably employed as a method for producing the polyimide resin composition described above. When it is soluble in (organic solvent), it can be prepared by using the reaction solution obtained after the reaction as it is as a polyimide varnish.

  The polyimide varnish of the present invention is a reaction solution obtained by reacting the tetracarboxylic dianhydride with the aromatic diamine by carrying out the step (I) (containing the polyamic acid of the present invention). Using the reaction solution) as it is, imidizing the reaction solution by adding an imidizing agent, and preparing polyimide in a polymerization solvent (organic solvent), the polyimide (first component) and the compound (first You may manufacture by obtaining the solution containing 2 components) and the said organic solvent.

  Moreover, as a solvent used for the polyimide varnish of this invention, the thing similar to the solvent demonstrated in the above-mentioned "polyimide resin composition of the form which further contains a solvent" can be utilized suitably. In addition, as an organic solvent used for the polyimide varnish of the present invention, for example, from the viewpoint of transpiration and removability of the solvent when the polyimide varnish is used as a coating liquid, a halogen solvent having a boiling point of 200 ° C. or less (for example, , Dichloromethane (boiling point 40 ° C), trichloromethane (boiling point 62 ° C), carbon tetrachloride (boiling point 77 ° C), dichloroethane (boiling point 84 ° C), trichloroethylene (boiling point 87 ° C), tetrachloroethylene (boiling point 121 ° C), tetrachloroethane (boiling point) 147 ° C.), chlorobenzene (boiling point 131 ° C.), o-dichlorobenzene (boiling point 180 ° C.), etc.) may be used.

  Moreover, as a solvent in such a polyimide varnish, N-methyl-2-pyrrolidone, N, N- from the viewpoint of solubility, film-forming property, productivity, industrial availability, presence / absence of existing facilities, and price. Dimethylacetamide, γ-butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferred, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, tetramethylurea Are more preferable, and N, N-dimethylacetamide and γ-butyrolactone are particularly preferable. In addition, you may utilize such a solvent individually by 1 type or in combination of 2 or more types.

  Moreover, such a polyimide varnish can also be suitably used as a coating liquid or the like for producing various processed products. For example, in the case of forming a film, the polyimide varnish of the present invention is used as a coating liquid, and this is applied onto a substrate to obtain a coating film, and then the polyimide resin is removed by removing the solvent. You may form the film which consists of a hardened | cured material of a composition. Such a coating method is not particularly limited, and a known method (spin coating method, bar coating method, dip coating method, etc.) can be appropriately used.

  In such a polyimide varnish, the content (dissolution amount) of the polyimide (first component) is not particularly limited, but is preferably 1 to 50% by mass, and more preferably 10 to 30% by mass. . When the content is less than the lower limit, the film thickness after film formation tends to be thin when used for film formation and the like. On the other hand, when the content exceeds the upper limit, a part tends to be insoluble in the solvent. .

  In such a polyimide varnish, the content (dissolution amount) of the compound (second component) is not particularly limited, but is preferably 0.001 to 13% by mass, and preferably 0.005 to 5% by mass. It is more preferable that If the content is less than the lower limit, a self-supporting film tends to be hardly obtained. On the other hand, if the content exceeds the upper limit, the heat resistance of the cured product tends to decrease.

  Moreover, in such a polyimide varnish, it is preferable that content of the said compound (2nd component) with respect to 100 mass parts of said polyimides (1st component) is 0.1-25 mass parts, 0.5-15 More preferably, it is part by mass. If the content of the second component is less than the lower limit, the mechanical strength tends to decrease when the cured product is used. On the other hand, if the content exceeds the upper limit, the heat resistance of the cured product tends to decrease. In addition, as described above, the content of the solvent in such a polyimide varnish is preferably 50 to 99% by mass, more preferably 50 to 90% by mass, and 60 to 90% by mass. Is more preferable, and it is especially preferable that it is 70-90 mass%.

  Furthermore, such polyimide varnishes include antioxidants (phenolic, phosphite-based, thioether-based, etc.), ultraviolet absorbers, hindered amine light stabilizers, nucleating agents, resin additives (depending on the purpose of use). Fillers, talc, glass fibers, etc.), flame retardants, processability improvers and lubricants may be further added. In addition, as these other components, it does not restrict | limit, A well-known thing can be utilized suitably, and a commercially available thing may be utilized.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example.

(Synthesis Example 1: Synthesis of tetracarboxylic dianhydride A)
In accordance with the method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, as tetracarboxylic dianhydride A, the following general formula (I):

(Norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride: CpODA) Was synthesized.

(Synthesis Example 2: Synthesis of tetracarboxylic dianhydride B)
As tetracarboxylic dianhydride B, a compound (BzDA) represented by the following general formula (II-2) was synthesized as follows. That is, first, 5-norbornene-2,3-dicarboxylic acid anhydride (750 g, 4.57 mol), methanol (3.75 L) and concentrated hydrochloric acid (37.5 mL) were introduced into a 10 L reaction vessel, A mixture was obtained. Next, the mixed solution was stirred for 4 hours under reflux conditions to obtain a reaction solution. Then, methanol was depressurizingly distilled from the reaction liquid using the rotary evaporator, and the liquid substance was obtained. Next, the liquid was dissolved in ethyl acetate (3.8 L) and transferred to a separatory funnel. Next, the liquid was washed twice with a saturated aqueous sodium hydrogen carbonate solution (1.5 L) and further washed once with water (1.5 L) to obtain an organic layer. Thereafter, ethyl acetate was distilled off from the organic layer under reduced pressure using a rotary evaporator to obtain dimethyl 5-norbornene-2,3-dicarboxylate (918 g, yield: 95.6%).

  Next, under an argon atmosphere, palladium acetate (0.801 g, 3.66 mmol), triorthotolylphosphine (1.09 g, 3.66 mmol) and N, N-dimethylformamide (4.05 L) were added to a 20 L reaction vessel. The mixture was introduced inside, heated at a heating temperature of 50 ° C., and stirred for 30 minutes. Next, the nadic acid dimethyl ester (750 g, 3.57 mol), 1,4-dibromobenzene (421 g, 1.78 mol), triethylamine (722 g, 7.33 mol), formic acid (328 g, 7.33 mol) and N, N-dimethylformamide (4.5 L) were further added to obtain a mixture. Next, the mixture was stirred for 8 hours while heating at a heating temperature of 80 ° C. to obtain a reaction solution. In the reaction solution thus obtained, black palladium (Pd (0)) powder (palladium black) derived from the palladium catalyst was precipitated.

  Next, the reaction solution was dissolved in toluene (18 L), and the resulting solution was transferred to a separatory funnel. The solution was then washed once with water (7.1 L), twice with 5% hydrochloric acid (3.6 L), twice with saturated aqueous sodium bicarbonate (3.6 L), and further with water (3.6 L). After washing twice, the palladium black powder was removed from the solution by filtration to obtain a filtrate. Next, while heating the filtrate at 60 ° C., the filtrate was concentrated under reduced pressure until no liquid such as toluene was distilled off to obtain a yellow oily product.

Next, toluene (69 g) was added to the obtained yellow oily product to obtain a mixed liquid whose mass was adjusted to 1005 g, and the mixed liquid was heated and stirred to 60 ° C., and then reached 60 ° C. As soon as cyclohexane (7.1 L) was added to the mixture, a white solid precipitated. After confirming the precipitation of the white solid, the heating temperature condition of the mixed solution is changed to 50 ° C., and the mixed solution is stirred at 30 ° C. for 30 minutes, and then the temperature of the mixed solution reaches room temperature. The mixture was allowed to cool to obtain a mixed solution in which a white solid was precipitated. Then, the white solid which precipitated in this liquid mixture was filtered by filtering this liquid mixture. Thereafter, a Buchner funnel (Nucce) was used for the obtained white solid, and cyclohexane (1.4 L) was used as a cleaning liquid, and the white solid was stirred and washed with cyclohexane on the Buchner funnel. The washed white solid was then dried under vacuum conditions at 80 ° C. for 5 hours to obtain a first product (441 g). In order to confirm the absolute structure of the obtained first product (compound), one-dimensional NMR ( ¹ H and ¹³ C) and two-dimensional NMR (DEPT135, DQF COSY, HMQC, HMBC, NOESY) were measured. As a result, the first product (compound) is represented by the following general formula (II-1):

A tetraester compound having a structure in which the benzene ring represented by the formula has an exo conformation with respect to both norbornane rings and an endo conformation with respect to the norbornane ring to which each methyl ester group is bonded. I found out. The yield was 50%.

  Next, a part (436 g, 0.875 mol) of the tetraester compound (the first product) together with 10 L of acetic acid (6.3 kg) and trifluoromethanesulfonic acid (6.56 g, 0.044 mol). It added to the reaction container with a reflux tube. Next, the atmosphere gas in the reaction vessel was replaced with argon, and then the solution was heated under an atmosphere of argon at atmospheric pressure with a heating temperature of 116 ° C. In such heating, acetic acid is added to the solution in the reaction vessel while distilling off the vapor generated from the solution using a Dean-Stark tube so that the amount of the solution in the reaction vessel becomes constant. The process to perform was given. Then, heating was stopped when 7 hours had elapsed from the start of the evaporation of the vapor generated from the solution. The amount of the liquid component (main component is acetic acid) distilled off after 7 hours from the start of the vapor distillation was 3.5 kg.

Next, a white solid (powder) was obtained by performing vacuum filtration on the solution thus obtained in the reaction vessel. The obtained white solid was subjected to a washing step of washing with acetic acid (1.4 L) once and further with ethyl acetate (1.4 L) five times. Thereafter, the obtained white solid was dried under a vacuum condition at a temperature of 80 ° C. for 5 hours to obtain a second product (297 g). In order to confirm the absolute structure of the obtained second product (compound), one-dimensional NMR ( ¹ H and ¹³ C) and two-dimensional NMR (DEPT135, DQF COSY, HMQC, HMBC, NOESY) were measured. It was. As a result of such measurement, the ¹ H NMR graph of the second product is shown in FIG. 1, the ¹³ C NMR graph is shown in FIG. 2, the two-dimensional NMR (DEPT135) graph is shown in FIG. The two-dimensional NMR (DQF COSY) graph is shown in FIG. 4, the two-dimensional NMR (HMQC) graph is shown in FIG. 5, the two-dimensional NMR (HMBC) graph is shown in FIG. 6, and the two-dimensional NMR (NOESY) graph is shown. A graph is shown in FIG. As a result of such measurement, the obtained second product has the following general formula (II-2):

And a compound having a structure in which the benzene ring has an exo conformation with respect to both norbornane rings and an endo conformation with respect to the norbornane ring to which each acid anhydride group is bonded ( BzDA). The yield was 84%.

(Synthesis Example 3: Synthesis of tetracarboxylic dianhydride C)
As tetracarboxylic dianhydride C, in accordance with the method described in Examples 1-2 of WO 2017/030019, the following general formula (III):

(BNBDA) was synthesized. Such tetracarboxylic dianhydride C was produced as follows.

<About abbreviations of monomers, etc.>
Abbreviations and the like are described below for the tetracarboxylic dianhydrides, aromatic diamines, and additives (imidazole compounds, phosphorus compounds, or amine compounds) used in each example. In the description in the examples, the following abbreviations are used in some cases.

(1) Tetracarboxylic dianhydride CpODA: compound represented by the above general formula (I) obtained in Synthesis Example 1 BzDA: represented by the above General Formula (II-2) obtained in Synthesis Example 2 Compound BNBDA: Compound represented by general formula (III) obtained in Synthesis Example 3 s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (manufactured by JFE Chemical Co., Ltd.)
HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) Aromatic diamine DDE: 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
TFMB: 2,2′-bis (trifluoromethyl) benzidine (manufactured by Seika Industry Co., Ltd.)
DABAN: 4,4′-diaminobenzanilide (manufactured by Nippon Pure Chemicals Co., Ltd.)
PPD: 1,4-paraphenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
FDA: 9,9′-bis (4-aminophenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.)
4,4′-DDS: 4,4′-diaminodiphenyl sulfone (manufactured by Seika Corporation)
3,3′-DDS: 3,3′-diaminodiphenyl sulfone (manufactured by Seika Corporation)
DDM: 4,4′-diphenyldiaminomethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
BAAB: 4-aminophenyl-4-aminobenzoic acid (manufactured by Nippon Pure Chemicals Co., Ltd.)
BABB: 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl.

(3) Additive (imidazole compound, phosphorus compound, or amine compound)
<Imidazole compounds>
Imidazole derivative (A): 1,2-dimethylimidazole (trade name “12DMZ”: manufactured by Shikoku Chemicals)
Imidazole derivative (B): 2-ethyl-4-methylimidazole (trade name “2E4MZ”: manufactured by Shikoku Chemicals).

<Amine compound>
Tertiary amine compound (A): Triethylamine (manufactured by Sigma-Aldrich)
Tertiary amine compound (B): DBU (trade name “DBU”: manufactured by San Apro)
Tertiary amine compound (C): DBN (trade name “DBN”: manufactured by San Apro)
Quaternary amine salt (A): phenol salt of DBU (trade name “U-cat SA1”: manufactured by San Apro)
Quaternary amine salt (B): DBU octylate (trade name “U-Cat SA102”: manufactured by San Apro).

<Phosphorus compounds>
Phosphoric acid compound (A): Phenyl phosphoric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tertiary phosphorus compound (A): Triphenylphosphine (trade name “TPP”: manufactured by Hokuko Chemical Industries)
Tertiary phosphorus compound (B): Triparatolylphosphine (trade name “TPTP”: manufactured by Hokuko Chemical Industries)
Quaternary phosphorus salt (A): Tetraphenylphosphonium tetraphenylborate (trade name “TPP-K”: manufactured by Hokuko Chemical Industries)
Quaternary phosphorus salt (B): Tetraphenylphosphonium bromide (trade name “TPP-PB”: manufactured by Hokuko Chemical Industries)
Quaternary phosphorus salt (C): benzyltriphenylphosphonium bromide (trade name “U-cat 5003”: manufactured by San Apro).

Example 1
Under a nitrogen atmosphere, 4.06 g (10.0 mmol) of DDE as an aromatic diamine is introduced into a 200 mL reaction vessel, and 2.00 g (10.0 mmol) of BzDA is introduced as a tetracarboxylic dianhydride. As a result, DDE (aromatic diamine) and BzDA (tetracarboxylic dianhydride) were introduced into the screw tube.

  Next, 7.08 g of dimethylacetamide (N, N-dimethylacetamide) and 7.07 g of γ-butyrolactone as organic solvents are introduced into the reaction vessel, and the tertiary amine compound (A) is added as an additive. By introducing 0.050 g (0.50 mmol), DDE (aromatic diamine), BzDA (tetracarboxylic dianhydride), the tertiary amine compound (A) (additive: triethylamine), N, A mixed solution containing a mixed solvent (organic solvent) of N-dimethylacetamide and γ-butyrolactone was obtained.

  Next, the atmosphere in the reaction vessel containing the mixed solution was changed to a nitrogen atmosphere and stirred while heating for 3 hours under a nitrogen atmosphere at a temperature of 180 ° C. (hereinafter, the time for heating and stirring in such a heating and stirring step) Is referred to as “reaction time”). In such a heating and stirring step, a small amount of nitrogen was flowed to extract the organic solvent and by-product water, and the reaction was allowed to proceed. Thus, a viscous uniform light yellow reaction solution (polyimide solution) was obtained in the reaction vessel. The reaction solution (polyimide solution) thus obtained remained in a state where triethylamine as the additive was contained. Thus, the obtained reaction liquid is a varnish composition (polyimide varnish: liquid polyimide resin containing a solvent) containing polyimide having a repeating unit derived from the reaction of BzDA and DDE, triethylamine, and the organic solvent. Composition).

  Next, the varnish composition comprising the reaction solution is applied to a glass substrate having a length of 210 mm and a width of 148 mm (A5 size) using a bar coater to form a coating film of the varnish composition on a glass plate. did. Then, the glass plate on which the coating film was formed was put into an oven, and after standing in a nitrogen atmosphere at a temperature condition of 60 ° C. for 4 hours, the temperature was raised from 60 ° C. to 250 ° C., A polyimide having a coating film cured by standing at 250 ° C. for 1 hour and coated on a glass plate with a thin film (polyimide resin composition film) comprising a polyimide resin composition containing polyimide and triethylamine. Coated glass was obtained. Next, the film of the polyimide resin composition was peeled from the polyimide-coated glass thus obtained to recover the film, and a colorless transparent film (polyimide film) made of the polyimide resin composition was obtained. . The film thickness thus obtained was 40 μm.

(Examples 2 to 13)
Example 1 except that 0.050 g (0.50 mmol) of the tertiary amine compound (A) was used as an additive instead of using the types of additives shown in Table 1 below in the amounts shown in Table 1 below. In the same manner as described above, a varnish composition was produced, and then a colorless transparent film (polyimide film) made of a polyimide resin composition was produced. Thus, the film thickness of the obtained film was 40 micrometers in any Example. Table 1 shows the types of tetracarboxylic dianhydrides, aromatic diamines and additives used in the production of films in Examples 1 to 13, and the amounts of additives used. Moreover, the numerical value in the parenthesis regarding tetracarboxylic dianhydride and aromatic diamine in Table 1 shows the molar ratio of tetracarboxylic dianhydride and aromatic diamine.

(Example 14)
Instead of using DDE as an aromatic diamine, 2.27 g (10.0 mmol) of DABAN was used, the reaction time was changed from 3 hours to 6 hours, and the amount of dimethylacetamide (N, N-dimethylacetamide) used was changed. A varnish composition was produced in the same manner as in Example 1 except that the amount was changed to 7.36 g and the amount of γ-butyrolactone used was changed to 7.44 g, and then a colorless and transparent film comprising a polyimide resin composition ( Polyimide film) was produced. The film thickness thus obtained was 30 μm.

(Example 15)
A varnish composition was produced in the same manner as in Example 14 except that 0.13 g (0.50 mmol) of the tertiary phosphorus compound (A) was used instead of the tertiary amine compound (A) as an additive. Then, the colorless and transparent film (polyimide film) which consists of a polyimide resin composition was manufactured, respectively. The film thickness thus obtained was 30 μm.

(Example 16)
As an aromatic diamine, a varnish composition was prepared in the same manner as in Example 15 except that a mixture of DABAN 1.14 g (5.00 mmol) and DDE 1.00 g (5.00 mmol) was used instead of DABAN alone. After the production, a colorless and transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 30 μm.

(Example 17)
As an aromatic diamine, instead of using DABAN alone, a mixture of 1.14 g (5.00 mmol) of DABAN and 1.60 g (5.00 mmol) of TFMB is used, and the amount of dimethylacetamide (N, N-dimethylacetamide) used is reduced. After changing to 7.90g and changing the usage-amount of (gamma) -butyrolactone to 7.90g, after manufacturing a varnish composition like Example 15, the colorless and transparent film which consists of a polyimide resin composition ( Polyimide film) was produced. The film thickness thus obtained was 30 μm.

(Example 18)
A varnish composition was produced in the same manner as in Example 16 except that 0.050 g (0.50 mmol) of the tertiary amine compound (A) was used instead of the tertiary phosphorus compound (A) as an additive. Then, the colorless and transparent film (polyimide film) which consists of a polyimide resin composition was manufactured, respectively. The film thickness thus obtained was 30 μm.

(Example 19)
A varnish composition was produced in the same manner as in Example 17, except that 0.050 g (0.50 mmol) of the tertiary amine compound (A) was used instead of the tertiary phosphorus compound (A) as an additive. Then, the colorless and transparent film (polyimide film) which consists of a polyimide resin composition was manufactured, respectively. The film thickness thus obtained was 30 μm.

(Example 20)
As an aromatic diamine, instead of using DABAN alone, a mixture of DABAN 2.05 g (9.00 mmol) and PPD 0.11 g (1.00 mmol) was used, and the amount of dimethylacetamide (N, N-dimethylacetamide) used was reduced. After changing to 7.25 g and changing the usage-amount of (gamma) -butyrolactone to 7.25 g, after manufacturing a varnish composition like Example 14, the colorless and transparent film which consists of a polyimide resin composition ( Polyimide film) was produced. The film thickness thus obtained was 30 μm.

(Example 21)
As an aromatic diamine, instead of using DDE, 3.48 g (10.0 mmol) of FDA was used, the amount of dimethylacetamide (N, N-dimethylacetamide) was changed to 8.70 g, and γ-butyrolactone was used. A varnish composition was produced in the same manner as in Example 1 except that the amount was changed to 9.02 g, and then a colorless transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 30 μm.

(Example 22)
Instead of using DDE as an aromatic diamine, 2.48 g (10.0 mmol) of 4,4′-DDS was used, and the amount of dimethylacetamide (N, N-dimethylacetamide) used was changed to 7.60 g. Except having changed the usage-amount of (gamma) -butyrolactone to 7.60 g, after manufacturing a varnish composition like Example 1, the colorless and transparent film (polyimide film) which consists of a polyimide resin composition was each manufactured. . The film thickness thus obtained was 30 μm.

(Example 23)
As an aromatic diamine, instead of using DDE, 3.48 g (10.0 mmol) of 3,3′-DDS was used, and the amount of dimethylacetamide (N, N-dimethylacetamide) used was changed to 7.60 g. Except having changed the usage-amount of (gamma) -butyrolactone to 7.60 g, after manufacturing a varnish composition like Example 1, the colorless and transparent film (polyimide film) which consists of a polyimide resin composition was each manufactured. . The film thickness thus obtained was 30 μm.

(Example 24)
As an aromatic diamine, instead of using DDE alone, a mixture of 4,4′-DDS 1.24 g (5.00 mmol) and 3,3′-DDS 1.24 g (5.00 mmol) was used, and dimethylacetamide (N N-dimethylacetamide) was changed to 7.60 g, and the amount of γ-butyrolactone was changed to 7.60 g. Each colorless transparent film (polyimide film) made of the resin composition was produced. The film thickness thus obtained was 30 μm.

(Example 25)
Instead of using DDE as an aromatic diamine, 1.98 g (10.0 mmol) of DDM is used, the amount of dimethylacetamide (N, N-dimethylacetamide) used is changed to 7.04 g, and the use of γ-butyrolactone A varnish composition was produced in the same manner as in Example 1 except that the amount was changed to 7.04 g, and then a colorless transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 30 μm.

(Example 26)
Instead of using DDE as an aromatic diamine, 2.28 g (10.0 mmol) of BAAB is used, the amount of dimethylacetamide (N, N-dimethylacetamide) used is changed to 7.37 g, and γ-butyrolactone is used. A varnish composition was produced in the same manner as in Example 1 except that the amount was changed to 7.37 g, and then a colorless transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 30 μm.

(Example 27)
Instead of using DDE as an aromatic diamine, use 4.54 g (10.0 mmol) of BABB, change the amount of dimethylacetamide (N, N-dimethylacetamide) to 10.0 g, and use γ-butyrolactone A varnish composition was produced in the same manner as in Example 1 except that the amount was changed to 10.0 g, and then a colorless transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 30 μm.

  Table 2 shows the types of tetracarboxylic dianhydrides, aromatic diamines, additives, and the like used for the production of films in Examples 14 to 27. Moreover, the numerical value in the parenthesis regarding tetracarboxylic dianhydride and aromatic diamine in Table 2 shows the molar ratio of tetracarboxylic dianhydride and aromatic diamine.

(Example 28)
As a tetracarboxylic dianhydride, instead of using BzDA alone, a mixture of CpODA 5.76 g (15.0 mmol), s-BPDA 2.21 g (7.5 mmol) and HPMDA 1.68 g (7.5 mmol) was used. Instead of using DDE as an aromatic diamine, 9.61 g (30.0 mmol) of TFMB is used, the amount of dimethylacetamide (N, N-dimethylacetamide) used is changed to 39.2 g, and the use of γ-butyrolactone is used. After producing a varnish composition in the same manner as in Example 1 except that the amount was changed to 39.4 g and the amount of the tertiary amine compound (A) used was changed to 0.149 g (1.47 mmol). A colorless and transparent film (polyimide film) made of a polyimide resin composition was produced. The film thickness thus obtained was 38 μm.

(Example 29)
As a tetracarboxylic dianhydride, a mixture of 2.88 g (7.5 mmol) of CpODA, 2.21 g (7.5 mmol) of s-BPDA and 3.36 g (15.0 mmol) of HPMDA was used, and dimethylacetamide (N, N-dimethyl) was used. Acetamide) was changed to 36.0 g and γ-butyrolactone was changed to 36.0 g, except that a varnish composition was produced in the same manner as in Example 20, and then the polyimide resin composition was used. A colorless transparent film (polyimide film) was produced. The film thickness thus obtained was 50 μm.

(Example 30)
A varnish composition was produced in the same manner as in Example 20 except that 0.386 g (1.47 mmol) of the tertiary phosphorus compound (A) was used instead of the tertiary amine compound (A) as an additive. Then, a colorless and transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 29 μm.

(Example 31)
A varnish composition was produced in the same manner as in Example 20, except that 0.637 g (1.47 mmol) of the quaternary phosphate (C) was used instead of the tertiary amine compound (A) as an additive. Then, a colorless and transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 38 μm.

(Example 32)
As tetracarboxylic dianhydride, instead of using BzDA alone, a mixture of CpODA 1.15 g (3.0 mmol), s-BPDA 0.88 g (3.0 mmol) and BzDA 1.63 g (4.0 mmol) was used, As an aromatic diamine, instead of using DDE, 3.2 g (10.0 mmol) of TFMB is used, the amount of dimethylacetamide (N, N-dimethylacetamide) used is changed to 9.1 g, and γ-butyrolactone is used. A varnish composition was produced in the same manner as in Example 1 except that the amount used was changed to 6.86 g, and then a colorless transparent film (polyimide film) made of the polyimide resin composition was produced. The film thickness thus obtained was 90 μm.

(Example 33)
As tetracarboxylic dianhydride, instead of using BzDA alone, a mixture of BNBDA 3.30 g (10.0 mmol), s-BPDA 1.47 g (5.000 mmol) and HPMDA 1.12 g (5.0 mmol) was used, Instead of using DDE as an aromatic diamine, 6.45 g (20.1 mmol) of TFMB was used, the amount of dimethylacetamide (N, N-dimethylacetamide) used was changed to 24.8 g, and the use of γ-butyrolactone was used. After producing a varnish composition in the same manner as in Example 1 except that the amount was changed to 24.7 g and the amount of the tertiary amine compound (A) was changed to 0.101 g (1.00 mmol). A colorless and transparent film (polyimide film) made of a polyimide resin composition was produced. The film thickness thus obtained was 16 μm.

  Table 3 shows the types of tetracarboxylic dianhydrides, aromatic diamines and additives used in the production of films in Examples 28 to 33. Moreover, the numerical value in the parenthesis regarding tetracarboxylic dianhydride and aromatic diamine in Table 3 shows the molar ratio of tetracarboxylic dianhydride and aromatic diamine.

[Evaluation of Film Properties of Polyimide Resin Compositions Obtained in Examples 1-33]
<Measurement of glass transition temperature (Tg)>
The value (unit: ° C.) of the glass transition temperature (Tg) of the polyimide resin composition constituting the film obtained in each example was measured as follows. That is, using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) as a measuring device, 20 mm in length cut out from a film (cured product of polyimide resin composition) obtained in each example or the like as a measurement sample, Using a sample having a width of 5 mm (the thickness of the sample does not affect the measured value, so the film thickness obtained in the example is kept as it is), and in a nitrogen atmosphere, a tensile mode (49 mN) The TMA curve is obtained by measuring at a temperature rising rate of 5 ° C./min, and extrapolated before and after the inflection point of the TMA curve resulting from the glass transition. The glass transition temperature (Tg) value (unit: ° C.) of the polyimide resin composition constituting the obtained film was determined. The obtained results are shown in Table 4. <Measurement of total light transmittance and yellowness (YI)>
The total light transmittance (unit:%) and yellowness (YI) of the polyimide resin composition constituting the film obtained in each example were measured as follows. That is, the film (cured product of the polyimide resin composition) obtained in each example etc. was used as it was as a sample for measurement, and the trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measuring device. The total light transmittance (unit: unit :) of the polyimide resin composition constituting the film obtained in each example or the like by performing measurement using a product name “spectral colorimeter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. %) And yellowness (YI) were determined. In this measurement, the total light transmittance was measured with a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd., and the product name “Spectral Color Meter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. Yellowness was measured. Further, the total light transmittance is obtained by performing measurement in accordance with JIS K7361-1 (issued in 1997), and the yellowness (YI) is measured in accordance with ASTM E313-05 (issued in 2005). Was determined by The obtained results are shown in Table 4. <Measurement method of elongation at break>
The elongation at break (unit:%) of the polyimide resin composition constituting the film obtained in each example was determined according to the method described in “JIS K7161” of Japanese Industrial Standards, with a tensile speed of 5 mm / min. Measured under conditions. In such a measurement, an Instron tensile tester is used as a measuring device, and a JIS K-7139A22 compliant punch is used as a measurement sample, which is obtained by processing from the film obtained in each example. Using a dumbbell-shaped test piece, the measurement sample (dumbbell-shaped test piece) was set in the measuring apparatus and measured. Table 4 shows the obtained results.

  As is clear from the results shown in Table 4, any of the polyimide resin compositions (cured products) constituting the films obtained in each example can be used for glass replacement applications from the values of total light transmittance and YI. It has become clear that it has a sufficiently high light transmittance. Also, it is understood that all of the polyimide resin compositions (cured products) constituting the films obtained in each Example have a Tg of 348 ° C. or higher and have sufficiently high heat resistance based on Tg. It was. Furthermore, it was also found that any polyimide resin composition (cured product) constituting the film obtained in each example had sufficiently excellent mechanical strength from the value of elongation at break.

  As described above, according to the present invention, the cured product has sufficient light transmittance that can be used for glass replacement applications, and has sufficiently high heat resistance and sufficiently excellent mechanical strength. It is possible to provide a polyimide resin composition that can be suitably used for manufacturing a cured product of such a polyimide resin composition and such a polyimide.

  Therefore, the polyimide resin composition of the present invention is particularly useful as a material for producing various films, automotive parts, aerospace parts, bearing parts, seal materials, bearing parts, gear wheels, valve parts and the like. .

Claims (2)

The following general formula (1):
[In the formula (1), R ¹ , R ² and R ³ each independently represents 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 is 0 to 12 R ⁴ represents an arylene group having 6 to 50 carbon atoms. ]
A repeating unit (A) represented by the following general formula (2):
[In Formula (2), A may have a substituent and is 1 type selected from the group which consists of a bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30. R ⁴ represents an arylene group having 6 to 50 carbon atoms, and a plurality of R ⁵ each independently represents one type selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. ]
And a repeating unit (B) represented by the following general formula (3):
[In Formula (3), R ⁴ represents an arylene group having 6 to 50 carbon atoms, and a plurality of R ⁶ are independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ⁶ bonded to the same carbon atom may be combined to form a methylidene group, and R ⁷ and R ⁸ are each independently a hydrogen atom and 1 type selected from the group which consists of a C1-C10 alkyl group is shown. ]
A polyimide containing at least one repeating unit selected from the group consisting of repeating units (C) represented by:
At least one compound selected from the group consisting of an imidazole compound, a phosphorus compound, and an amine compound;
The polyimide resin composition characterized by including.   A polyimide varnish comprising the polyimide resin composition according to claim 1, further comprising a solvent.