JP2015203009A - Tetra-carboxylic acid di-anhydride, polyamic acid, polyimide, and production method thereof, as well as polyamic acid solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide tetra-carboxylic acid di-anhydride that is a raw-material monomer for the production of alicyclic polyimide.SOLUTION: Provided is tetra-carboxylic acid di-anhydride represented by formula (1). [Rto Ris F, H and alkyl group of C1-10; Ris H, C1-10 alkyl group, phenyl group and halogen; and n is an integer of 0 to 12.].

Description

  The present invention relates to a tetracarboxylic dianhydride, a polyamic acid obtained using the tetracarboxylic dianhydride, a polyamic acid solution and a polyimide, and a method for producing the tetracarboxylic dianhydride, the polyamic acid and the polyimide.

  In general, tetracarboxylic dianhydrides are useful as raw materials for producing polyimide resins, curing agents for epoxy resins, and the like. Among such tetracarboxylic dianhydrides, for example, as a raw material for polyimide resins used in the field of electronic equipment and the like, it is possible to form a polyimide resin having sufficient heat resistance, and so on. The system tetracarboxylic dianhydrides have been mainly used.

  However, such an aromatic tetracarboxylic dianhydride is derived from the aromatic nature, and the resulting polyimide resin (fully aromatic polyimide, etc.) is colored. It was not sufficient as a raw material for the polymimide resin used in the above. Actually, as a polyimide resin obtained using such an aromatic tetracarboxylic dianhydride, a wholly aromatic polyimide (for example, trade name “Kapton”, glass transition temperature (Tg): 410 ° C.) However, such a wholly aromatic polyimide has a brown color due to its structure, and cannot be used for optical applications that require transparency.

  Therefore, it has also been proposed to use an aliphatic tetracarboxylic dianhydride as a monomer for producing a highly transparent polyimide used for optical applications and the like. However, when a conventional aliphatic tetracarboxylic dianhydride is used, the obtained polyimide is basically not always sufficient in terms of heat resistance. Therefore, in recent years, research on aliphatic tetracarboxylic dianhydrides has been advanced in order to produce a polyimide having sufficient transparency and sufficient heat resistance. And as an aliphatic tetracarboxylic dianhydride which can manufacture the polyimide which has sufficient transparency and sufficient heat resistance, for example, international publication 2011-99518 (patent document 1) In the following general formula (A):

[In Formula (1), R ^<a> , R ^<b >, R ^<c > shows 1 type selected from the group which consists of a hydrogen atom, a C1-C10 alkyl group, and a fluorine atom each independently, m is 0 An integer of ~ 12 is shown. ]
A tetracarboxylic dianhydride represented by the formula is reported.

International Publication No. 2011-99518

  The tetracarboxylic dianhydride described in Patent Document 1 has high light transmittance and can be used as a raw material monomer for producing polyimide having sufficiently high heat resistance. Moreover, such a tetracarboxylic dianhydride could be efficiently and reliably produced by the method described in Patent Document 1. However, as an aliphatic tetracarboxylic dianhydride that can be used to produce a highly transparent polyimide for use in optical applications, etc., it is equivalent to the tetracarboxylic dianhydride described in Patent Document 1 above. Or the appearance of a new aliphatic tetracarboxylic dianhydride that has more characteristics (light transmission, heat resistance, etc.) and can be more easily produced is desired. ing.

  The present invention has been made in view of the above-mentioned problems of the prior art, and can be used as a raw material monomer for producing an alicyclic polyimide having sufficient light transmittance and sufficiently high heat resistance. A tetracarboxylic dianhydride that can be produced by a simpler method, a polyamic acid obtained using the tetracarboxylic dianhydride, a polyamic acid solution, a polyimide, and the tetracarboxylic dianhydride, the polyamic acid, and It aims at providing the manufacturing method of the said polyimide.

  As a result of intensive studies to achieve the above object, the present inventors have made the compound represented by the following general formula (1) into a tetracarboxylic dianhydride, thereby providing sufficient light transmittance and sufficient. It can be used as a raw material monomer for producing an alicyclic polyimide having high heat resistance, and such a compound can be efficiently produced using a so-called [2 + 2] cycloaddition reaction (cycloaddition reaction). The present invention has been completed by finding that it can be manufactured at a lower cost and with a simpler method.

  That is, the tetracarboxylic dianhydride 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
It is a compound represented by these.

  The method for producing the tetracarboxylic dianhydride of the present invention is represented by the following general formula (2):

[In the formula (2), 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,
n shows the integer of 0-12. ]
A bisspironorbornene compound represented by the following general formula (3):

[In Formula (3), each R ⁴ independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a halogen atom, or two R ⁴ represents one selected from a cycloalkenyl group having 4 to 10 carbon atoms bonded to each other. ]
And a maleic anhydride compound represented by 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the formula is obtained. In such light irradiation, it is preferable to irradiate light having a wavelength of 300 nm to 600 nm.

  The polyimide of the present invention has the following general formula (4):

[In the formula (4), 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
It has the repeating unit represented by these, It is characterized by the above-mentioned. The reason why it is possible to obtain sufficiently high heat resistance by the polyimide having the repeating unit represented by the general formula (4) is not necessarily clear, but the repeating unit inhibits the polymerization reaction. In addition, since the active α-hydrogen does not remain on the carbon atom adjacent to the ketone group, the polyimide has a chemically sufficiently stable structure. The inventors speculate that sufficiently high heat resistance is achieved due to this. Moreover, since the polyimide which has such a repeating unit represented by General formula (4) is an alicyclic polyimide, it can make light transmittance sufficiently high.

Furthermore, in the polyimide of the present invention, R ⁵ in the general formula (4) is represented by the following general formulas (5) to (8):

[In the formula (7), R ⁶ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group,
In the formula (8), Q represents a 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 -SO 2 -C 6 H 4 -O -, - C ( _{CH 3) 2 -C 6 H 4} -C (CH 3) 2 -, - from _{O-C 6 H 4 -C 6} H 4 -O- and _{-O-C 6} group represented by H 4 -O- 1 type selected from the group consisting of ]
It is preferable that it is at least 1 sort (s) of group represented by these.

  The polyamic acid of the present invention has the following general formula (9):

[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
It has the repeating unit represented by these, It is characterized by the above-mentioned. In addition, such a polyamic acid can be utilized as a raw material compound in producing the polyimide of the present invention (can be obtained as a reaction intermediate during polyimide production). Further, as such a polyamic acid, a solution of the polyamic acid having a concentration of 0.5 g / dL obtained by dissolving the polyamic acid in N, N-dimethylacetamide is used and operated under a temperature condition of 30 ° C. The intrinsic viscosity [η] measured with a viscometer is preferably 0.05 to 3.0 dL / g.

In the polyamic acid of the present invention, R ⁵ in the general formula (9) is represented by the following general formulas (5) to (8):

[In the formula (7), R ⁶ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group,
In the formula (8), Q represents a 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 -SO 2 -C 6 H 4 -O -, - C ( _{CH 3) 2 -C 6 H 4} -C (CH 3) 2 -, - from _{O-C 6 H 4 -C 6} H 4 -O- and _{-O-C 6} group represented by H 4 -O- 1 type selected from the group consisting of ]
It is preferable that it is at least 1 sort (s) of group represented by these.

  Moreover, the polyamic acid solution of the present invention contains the polyamic acid of the present invention and an organic solvent. According to such a polyamic acid solution (resin solution: varnish), various forms of polyimide can be efficiently produced.

  The method for producing the polyamic acid of the present invention comprises the following general formula (1) in the presence of an organic solvent:

[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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the following general formula (10):

[In Formula (10), R ⁵ represents an arylene group having 6 to 40 carbon atoms. ]
Is reacted with an aromatic diamine represented by the following general formula (9):

[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
A polyamic acid having a repeating unit represented by the formula:

  The method for producing the polyimide of the present invention has the following general formula (9):

[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
A polyamic acid having a repeating unit represented by general formula (4) is imidized:

[In the formula (4), 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
It is a method characterized by obtaining the polyimide which has a repeating unit represented by these.

  Moreover, in the manufacturing method of the polyimide of the said invention, in presence of an organic solvent, 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the following general formula (10):

[In Formula (10), R ⁵ represents an arylene group having 6 to 40 carbon atoms. ]
It is preferable to further include a step of obtaining a polyamic acid having a repeating unit represented by the general formula (9) by reacting with an aromatic diamine represented by general formula (9). In this case, the polyimide production method of the present invention is represented by the tetracarboxylic dianhydride represented by the general formula (1) and the general formula (10) in the presence of the organic solvent. A step of obtaining a polyamic acid having a repeating unit represented by the above general formula (9) by reacting with an aromatic diamine; and imidation of the polyamic acid to obtain a repeating unit represented by the above general formula (4). And a step of obtaining a polyimide having the above-described process, and a series of steps can efficiently produce polyimide.

  According to the present invention, it can be used as a raw material monomer for producing an alicyclic polyimide having sufficient light transmittance and sufficiently high heat resistance, and can be produced by a simpler method. Tetracarboxylic dianhydride, polyamic acid, polyamic acid solution and polyimide obtained using the tetracarboxylic dianhydride, and method for producing the tetracarboxylic dianhydride, the polyamic acid and the polyimide can be provided. .

2 is a graph showing an FD-MS spectrum of the compound obtained in Example 1. FIG.

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

[Tetracarboxylic dianhydride]
The tetracarboxylic dianhydride 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
(Hereinafter, the compound is sometimes simply referred to as “tetracarboxylic dianhydride represented by the general formula (1)”).

The alkyl group that can be selected as R ¹ in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When such a carbon number exceeds 10, when it uses as a monomer of a polyimide, the heat resistance of the polyimide obtained will fall. As the number of carbon atoms in the alkyl group such can be selected as R ^1, from the viewpoint of high heat resistance when a polyimide was prepared to obtain, preferably 1 to 6, is 1 to 5 Is more preferable, it is still more preferable that it is 1-4, and it is especially preferable that it is 1-3. Such an alkyl group that can be selected as R ¹ may be linear or branched.

R ¹ in the general formula (1) is more preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms from the viewpoint of obtaining a high degree of heat resistance when a polyimide is produced. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group is more preferable from the viewpoint of easy availability of raw materials and easier purification, and a hydrogen atom or methyl group is more preferable. Particularly preferred is a group. In addition, a plurality of R ¹ 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.

  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 of tetracarboxylic dianhydride 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. Thus, it is particularly preferable that n in the general formula (1) is an integer of 2 to 3.

The alkyl group having 1 to 10 carbon atoms R ^2, may be selected as R ³ in the general formula (1) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ¹ described above (And the preferred ones are also the same). As such substituents that can be selected as R ² and R ³ , from the viewpoint of ease of purification, among the above substituents, among the above substituents, a hydrogen atom, a carbon number of 1 to 10 (preferably 1 to 6, more preferably 1). -5, more preferably 1-4, particularly preferably 1-3) alkyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, when there are a plurality of R ² and R ³ in the formula (when n is 2 or more), the plurality of R ² and the plurality of R ³ may be the same or Although they may be different, they are preferably the same from the viewpoint of ease of purification.

Moreover, several R < ⁴ > in such General formula (1) shows 1 type selected from the group which consists of a hydrogen atom, a C1-C10 alkyl group, a phenyl group, and a halogen atom each independently. Or two R ⁴ bonded to adjacent carbon atoms are bonded to each other and are each selected from cycloalkyl groups having 4 to 10 carbon atoms.

Such an alkyl group that can be selected as R ⁴ is an alkyl group having 1 to 10 carbon atoms. If the number of carbon atoms exceeds 10, purification of tetracarboxylic dianhydride becomes difficult. Moreover, as carbon number of such an alkyl group which can be selected as R < ⁴ >, it is preferable that it is 1-6 from a viewpoint that refinement | purification becomes easier, and 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 ⁴ may be linear or branched. Further, the halogen atom that can be selected as R ⁴ in the general formula (1) is not particularly limited, but is preferably a fluorine atom from the viewpoint of stability and the like.

Further, R ⁴ as a plurality of R ⁴ in the general formula (1), which is attached to two carbon atoms in which two R ⁴ attached to adjacent carbon atoms are bonded to (adjacent to each other How to together), together with two carbon atoms to which R ⁴ is bonded respectively may form a cycloalkyl group having 4 to 10 carbon atoms. When the number of carbon atoms of such a cycloalkyl group is less than the lower limit, the compound tends to be unstable, whereas when it exceeds the upper limit, the yield tends to decrease. Moreover, as such a cycloalkyl group, a cycloheptyl group, a cyclohexyl group, and a cyclopentyl group are preferable, and a cyclohexyl group and a cyclopentyl group are more preferable.

R ⁴ in the general formula (1) is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable from the viewpoint of easy availability of raw materials and easier purification. Or it is especially preferable that it is a methyl group. In addition, a plurality of R ⁴ in such a formula may be the same or different from each other, but are preferably the same from the viewpoint of ease of purification and the like. preferable.

  Further, such tetracarboxylic dianhydride of the present invention has a high light transmittance, is sufficiently excellent in solubility in a solvent as compared with wholly aromatic polyimide, etc., and has a sufficiently high heat resistance. As a method for producing such a tetracarboxylic dianhydride of the present invention, the tetracarboxylic dianhydride of the present invention described later can be suitably used as a raw material monomer for producing Since it is also possible to suitably employ this manufacturing method, it is sufficiently inexpensive and can be manufactured by a simpler method. Thus, according to the present invention, it is possible to use as a raw material monomer for producing a polyimide having high light transmittance, sufficiently excellent solubility in a solvent, and sufficiently high heat resistance. In addition, it is possible to provide a tetracarboxylic dianhydride that can be efficiently produced by a simpler method.

[Method for producing tetracarboxylic dianhydride]
The method for producing the tetracarboxylic dianhydride of the present invention is represented by the following general formula (2):

[In the formula (2), 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,
n shows the integer of 0-12. ]
A bisspironorbornene compound represented by the following general formula (3):

[In Formula (3), each R ⁴ independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a halogen atom, or two R ⁴ represents one selected from a cycloalkenyl group having 4 to 10 carbon atoms bonded to each other. ]
The tetracarboxylic dianhydride represented by the above general formula (1) is obtained by subjecting the maleic anhydride compound represented by the formula (I) to a cycloaddition reaction by light irradiation.

Regard bis spiro norbornene compound represented by the general formula (2), R ¹ in the formula (2) is the same as the R ¹ in the general formula (1), the general others that suitable The same as R ¹ in formula (1). Further, ^R 2, ^{R 3} in the general formula (2) are of the general formula (1) in the same manner as ^R 2, ^{R 3} of, ^{R 2} of the preferred ones also in formula (1) , R ³ . Furthermore, n in the general formula (2) is an integer similar to n in the general formula (1), and a suitable value thereof is also the same as n in the general formula (1).

  Examples of the bisspironorbornene compound represented by the general formula (2) include 5-norbornene-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -5 ″ -norbornene ( Also known as “5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ″ -5 ″ -norbornene”), methyl-5-norbornene-2-spiro-α-cyclopentanone— α′-spiro-2 ″-(methyl-5 ″ -norbornene), 5-norbornene-2-spiro-α-cyclohexanone-α′-spiro-2 ″ -5 ″ -norbornene (also known as “5- Norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ″ -5 ″ -norbornene ”) and the like.

  Moreover, the method for producing such a bisspirononorbornene compound represented by the general formula (2) is not particularly limited, and a known method can be appropriately employed. For example, International Publication No. 2011/099518 and JP The method described in 2011-162479 can be used as appropriate.

Regarding the maleic anhydride compound represented by the general formula (3), each R ⁴ in the formula (3) is independently a group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a halogen atom. or represents one selected from, or, represents one of the two R ⁴ is selected bond to the cycloalkenyl group of 4 to 10 carbon atoms with each other.

The alkyl group having 1 to 10 carbon atoms and the halogen atom that can be selected as R ⁴ in the general formula (3) are the same as those described for R ⁴ in the general formula (1). The preferred ones are also the same.

In addition, two R ⁴ in the general formula (3) are bonded to each other to form a cycloalkenyl group having 4 to 10 carbon atoms together with the carbon atom to which the two R ⁴ are bonded. May be. As described above, in the cycloalkenyl group having 4 to 10 carbon atoms that can be selected as R ⁴ in the general formula (3), two R ⁴ are bonded to each other (together), and two R ⁴ are It is a group formed by forming a cyclic structure together with carbon atoms (carbon atoms forming a double bond). If the number of carbon atoms in such a cycloalkenyl group is less than the lower limit, the compound tends to be unstable. On the other hand, if it exceeds the upper limit, the yield of the product tends to decrease. As such a cycloalkenyl group, a cycloheptenyl group, a cyclohexenyl group, and a cyclopentenyl group are preferable, and a cyclohexenyl group and a cyclopentenyl group are more preferable.

R ⁴ in the general formula (3) is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable from the viewpoint of easy availability of raw materials and easier purification. Or it is especially preferable that it is a methyl group. In addition, a plurality of R ⁴ in such a formula may be the same or different from each other, but are preferably the same from the viewpoint of ease of purification and the like. preferable.

  The maleic anhydride compound represented by the general formula (3) is not particularly limited as long as it is represented by the general formula (3). For example, maleic anhydride, Citraconic anhydride, 2,3-dimethylmaleic anhydride, 2-ethylmaleic anhydride, 2,3-diethylmaleic anhydride, 2-isopropylmaleic anhydride, 2,3-diisopropylmaleic anhydride, 2-n-butyl Maleic anhydride, 2,3-di-n-butyl maleic anhydride, 2-t-butyl maleic anhydride, 2,3-di-t-butyl maleic anhydride, 2-phenyl maleic anhydride, 2,3-diphenyl anhydride Maleic acid, 2-fluoromaleic anhydride, 2,3-difluoromaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, 2-bromoanhydride Rainic acid, 2,3-dibromomaleic anhydride, 2-iodomaleic anhydride, 2,3-diiodomaleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, 3,4,5,6-tetra Hydrophthalic anhydride and the like can be used as appropriate. As the maleic anhydride compound represented by the general formula (3), from the viewpoint of easier purification, maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 2-phenyl Maleic anhydride, 2,3-diphenyl maleic anhydride, 2-fluoromaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride are preferred, maleic anhydride, citraconic anhydride, 2,3-dimethyl Maleic anhydride is more preferred. Such maleic anhydride compounds can be used singly or in combination of two or more. Moreover, from the viewpoint of the heat resistance of the resulting polyimide, it is preferable that the maleic anhydride compound is used alone.

  The bisspirornorbornene compound represented by the general formula (2) and the maleic anhydride compound represented by the general formula (3) used in the present invention have been described above, but the production of the tetracarboxylic dianhydride of the present invention has been described. In the method, a step of subjecting the bisspirononorbornene compound represented by the general formula (2) and the maleic anhydride compound represented by the general formula (3) to cycloaddition reaction by light irradiation is performed. In addition, when the outline of such reaction is described in the reaction formula, the following reaction formula (I):

[In the reaction formula (I), the compounds represented by the general formulas (1) to (3) are the same as those described above (the tetracarboxylic dianhydride represented by the above general formula (1), the above general formula, respectively). This is the same as the bisspironorbornene compound represented by (2) and the maleic anhydride compound represented by the general formula (3). ]
It will be something like that.

  As a light source used for light irradiation in such a cycloaddition reaction, light having a wavelength that allows the cycloaddition reaction (so-called [2 + 2] cycloaddition reaction) to proceed (for example, It is not particularly limited as long as it can irradiate ultraviolet light or the like, and a suitable light source can be appropriately selected from known light sources according to the type of raw material compound to be used. it can. As such a light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or the like can be used as appropriate, and the efficiency at the time of light irradiation can be further improved. A mercury lamp is particularly preferred. Moreover, it is preferable to use an internal irradiation type light source for the light irradiation in such a cycloaddition reaction. In the case where such a light source is used, in order to sufficiently control the temperature conditions during the reaction, those equipped with a light source cooling tube can be suitably used. The material of such a light source cooling tube is not particularly limited, and for example, quartz glass and borosilicate glass (hard glass: for example, Pyrex (registered trademark) glass) can be appropriately used.

  Moreover, when performing the cycloaddition reaction by such light irradiation, selection of the wavelength of light becomes important from a viewpoint of making a reaction progress more efficiently. And in this invention, when performing a cycloaddition reaction, although it changes with kinds of raw material compound, it is preferable to irradiate the light with a wavelength of 300 nm-600 nm. When such a wavelength is less than the lower limit, the raw material compound (the bisspirornorbornene compound represented by the general formula (2) and / or the maleic anhydride compound represented by the general formula (3)) is opened. There is a tendency that a reverse reaction in which a polymer (polymerized product) is produced or a maleic anhydride compound is produced from a once produced product tends to proceed. On the other hand, when the above upper limit is exceeded, a cycloaddition reaction occurs. It tends to stop progressing.

  The reaction temperature in such a cycloaddition reaction by light irradiation may be set to a temperature at which the cycloaddition reaction by light irradiation can be performed, and is not particularly limited, but is −20 to 50 ° C. Preferably there is. When such a reaction temperature exceeds the upper limit, by-products such as a polymer tend to be easily generated. On the other hand, when the reaction temperature is lower than the lower limit, the solubility of the maleic anhydride compound in the reaction solution decreases. , Production efficiency tends to decrease. Moreover, as such reaction temperature, the production | generation of a by-product is suppressed significantly and the target compound (The compound (tetracarboxylic dianhydride) represented by the said General formula (1)) is higher selectivity. And from the viewpoint that it can be formed in a yield, it is more preferably −10 to 50 ° C., further preferably −10 to 40 ° C., and particularly preferably 0 to 30 ° C.

  The reaction time in the cycloaddition reaction by such light irradiation is not particularly limited, and may be appropriately set according to the type of light source used, the type of raw material compound, and the like. For example, the cycloaddition reaction may be carried out by setting the reaction time appropriately in accordance with the type of raw material compound and the like, for example, by setting the reaction time in the range of 1 to 50 hours. . The suitable reaction time varies depending on the type of light source used, the type of raw material compound, and the like, but it is usually preferable from a practical viewpoint that the reaction time is 5 to 20 hours. If the reaction time is less than the lower limit, it may be difficult to cause the reaction to proceed sufficiently. On the other hand, if the upper limit is exceeded, the economy tends to be reduced. Moreover, the cycloaddition reaction by the light irradiation may be performed in a batch system or a flow system. Further, the pressure condition in the cycloaddition reaction is not particularly limited, and may be, for example, a normal pressure condition or a pressurized condition.

  Further, when the cycloaddition reaction is carried out by light irradiation, it is preferable to use a solvent. As such a solvent, it is preferable to use an organic solvent capable of dissolving the bisspirononorbornene compound represented by the general formula (2) and the maleic anhydride compound represented by the general formula (3). . As such a solvent, for example, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, ethylene glycol diacetate, methylene chloride, chloroform and the like can be appropriately used. From the viewpoint of having a highly sensitive photosensitizing carbonyl group, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and ethylene glycol diacetate are preferred, methyl acetate, ethyl acetate Is more preferable, and ethyl acetate is particularly preferable. Using such a solvent, the bisspirononorbornene compound represented by the above general formula (2) and the maleic anhydride compound represented by the above general formula (3) are added to the solvent, and the resulting reaction liquid is mixed. By irradiating each of these components with light, the cycloaddition reaction can proceed more efficiently. For example, when light irradiation is performed in a solvent using an internal irradiation type light source or the like, it is possible to further improve the efficiency when irradiating light, which is expressed by the general formula (2). It is possible to carry out the cycloaddition reaction of the bisspirononorbornene compound and the maleic anhydride compound represented by the general formula (3) more efficiently. In addition, such a solvent can be utilized individually by 1 type or in combination of 2 or more types.

  Further, the amount of the bisspirornorbornene compound represented by the general formula (2) and the maleic anhydride compound represented by the general formula (3) used in the cycloaddition reaction is not particularly limited. The molar ratio ([bisspironorbornene compound]: [maleic anhydride compound]) is preferably 1: 0.5 to 1:10 (more preferably 1: 1 to 1: 5). When the molar ratio of the bisspirononorbornene compound is less than the lower limit, the reaction efficiency tends to decrease, and when it exceeds the upper limit, the by-product (polymer) tends to increase. In addition, when the solvent is used, the contents of the bisspirornorbornene compound represented by the general formula (2) and the maleic anhydride compound represented by the general formula (3) are particularly limited. Although it is not, it is preferable to make these total amount contain 1-80 mass% (more preferably 10-30 mass%) in a solvent. When such a content is less than the lower limit, the reaction efficiency tends to decrease. On the other hand, when the content exceeds the upper limit, a by-product (polymer) tends to increase.

  In this way, the bisspirornorbornene compound represented by the above general formula (2) and the maleic anhydride compound represented by the above general formula (3) are subjected to cycloaddition reaction by light irradiation. A tetracarboxylic dianhydride represented by (1) (similar to the tetracarboxylic dianhydride of the present invention) can be obtained. In addition, after obtaining the tetracarboxylic dianhydride represented by the said General formula (1) in this way, you may implement suitably refinement | purification processes, such as recrystallization and sublimation. Such a purification step makes it possible to obtain a tetracarboxylic dianhydride represented by the general formula (1) with higher purity. Such a purification method is not particularly limited, and a known method can be appropriately employed. Moreover, the structure of the tetracarboxylic dianhydride obtained in this way is, for example, FD-MS using an FD-MS measuring instrument (for example, trade name “JMS-700V” manufactured by JEOL Ltd.). This can be confirmed by measuring the MS spectrum.

  Such a tetracarboxylic dianhydride represented by the general formula (1) (the tetracarboxylic dianhydride of the present invention) is particularly useful as a raw material for polyamic acid or a heat-resistant resin such as polyimide. . In addition, when manufacturing a polyimide using the tetracarboxylic dianhydride obtained by this invention (the tetracarboxylic dianhydride of the said invention), the method which can be employ | adopted for the manufacture in particular is not restrict | limited, A known method capable of producing a polyimide using tetracarboxylic dianhydride can be appropriately employed. For example, a tetracarboxylic dianhydride represented by the above general formula (1) in a solvent (the present invention described above) A method of obtaining a polyimide by reacting a tetracarboxylic dianhydride) with a diamine compound and then dehydrating and ring-closing the polyamic acid by heating or acid anhydride may be employed.

  Such a diamine compound is not particularly limited, and a known diamine compound that can be used for production of polyimide or polyamic acid can be appropriately used. For example, aromatic diamine, aliphatic diamine, alicyclic A diamine or the like can be appropriately used. Examples of such aromatic diamines include diaminodiphenylmethane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfonic acid, bis (aminophenoxy) benzene, diaminobiphenyl, and diaminonaphthalene. Examples of the aliphatic diamine include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, and hexamethylene diamine. Examples of the alicyclic diamine include 4,4′-diamino-dicyclohexylmethane, 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, and 3,3′-diethyl-4,4′-. Diamino-dicyclohexylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diamino-dicyclohexylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane, 3,5-diethyl-3 ′, 5′-dimethyl-4,4′-diaminodicyclohexylmethane and the like can be mentioned. In addition, you may use such a diamine compound individually by 1 type or in combination of 2 or more types.

  In addition, the solvent used for the production of the polyimide is not particularly limited, and a known solvent that can be used for the production of polyimide can be used as appropriate. For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfone Xoxide, cresol and the like can be mentioned.

  The amount of the tetracarboxylic dianhydride represented by the general formula (1) (the tetracarboxylic dianhydride of the present invention) and the diamine compound is not particularly limited, but the molar ratio thereof ([general Compound represented by formula (1)]: [diamine compound]) is 0.5: 1.0 to 1.0: 0.5 (more preferably 0.9: 1.0 to 1.0: 0. 9) is preferable. If the amount of the tetracarboxylic dianhydride represented by the general formula (1) is less than the lower limit, the yield tends to decrease. On the other hand, the yield tends to decrease even if the upper limit is exceeded.

  In addition, the temperature condition and the heating time in the step of heating the polyamic acid are not particularly limited, and may be appropriately adjusted to conditions under which polyimide can be produced. For example, the temperature is about 100 to 400 ° C. for 0.1 to 24 hours. Conditions for heating to a certain extent may be employed. Furthermore, the acid anhydride used for the dehydration ring closure of the polyamic acid is not particularly limited as long as it can dehydrate and ring the polyamic acid, and a known acid anhydride can be appropriately used. Examples thereof include propionic anhydride and acetic anhydride. In addition, the method of dehydrating and cyclizing using such an acid anhydride is not particularly limited, and known conditions that can dehydrate and cyclize the polyamic acid may be appropriately employed.

  Further, since the polyimide obtained in this way uses the tetracarboxylic dianhydride represented by the general formula (1) as one of the monomers, an aliphatic tetracarboxylic dianhydride is used. Despite being a polyimide having a monomer as a monomer, it is colorless and transparent while having sufficiently high solvent solubility, and has sufficient heat resistance based on the glass transition temperature (Tg), which is an index of heat resistance. It can be high (it can have a sufficiently high Tg). Therefore, the tetracarboxylic dianhydride of the present invention (tetracarboxylic dianhydride represented by the general formula (1)) is a polyimide for a flexible wiring board, a polyimide for a heat-resistant insulating tape, and a wire enamel. It is particularly useful as a material for producing polyimide, polyimide for semiconductor protective coating, polyimide for liquid crystal alignment film, seamless polyimide belt for copying machines, and the like.

  The tetracarboxylic dianhydride and the production method thereof according to the present invention have been described above. Hereinafter, the polyimide according to the present invention will be described.

[Polyimide]
The polyimide of the present invention has the following general formula (4):

[In the formula (4), 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
It has the repeating unit represented by these, It is characterized by the above-mentioned.

The alkyl group that can be selected as R ¹ , R ² , or R ^{3 in the} general formula (4) 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 (4), 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. A plurality of R ¹ 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. Particularly preferred. In addition, when there are a plurality of R ² and R ³ in the formula (when n is 2 or more), the plurality of R ² and the plurality of R ³ may be the same or Although they may be different, it is particularly preferable that they are the same from the viewpoint of ease of purification and the like.

Such an alkyl group that can be selected as R ⁴ 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 sufficiently high heat resistance cannot be achieved. Moreover, as carbon number of the alkyl group which can be selected as such R < ⁴ >, 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 ⁴ may be linear or branched. The halogen atom that can be selected as R ⁴ in the general formula (4) is not particularly limited, but is preferably a fluorine atom from the viewpoint of stability and the like.

As the plurality of R ⁴ in the general formula (4), adjacent two R ⁴ attached to a carbon atom is (and if R ⁴ are attached respectively to two adjacent carbon atoms) with each other bonded to, together with the carbon atom to which the two R ⁴ are bonded respectively may form a cycloalkyl group having 4 to 10 carbon atoms. When the number of carbon atoms of such a cycloalkyl group is less than the lower limit, the compound tends to be unstable, whereas when it exceeds the upper limit, the yield tends to decrease. Moreover, as such a cycloalkyl group, a cycloheptyl group, a cyclohexyl group, and a cyclopentyl group are preferable, and a cyclohexyl group and a cyclopentyl group are more preferable.

R ⁴ in the general formula (4) is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. Among these, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable from the viewpoint of easy availability of raw materials and easier purification. Or it is especially preferable that it is a methyl group. In addition, a plurality of R ⁴ in such a formula may be the same or different from each other, but are preferably the same from the viewpoint of ease of purification and the like. preferable.

The arylene group that can be selected as R ⁵ in the general formula (4) is an arylene group having 6 to 40 carbon atoms. Moreover, as such carbon number, it is preferable that it is 6-30, and it is more preferable that it is 12-20. When such a carbon number exceeds the upper limit, the heat resistance tends to decrease, and when it is less than the lower limit, the solubility of the obtained polyimide in the solvent tends to decrease.

Moreover, as R < ⁵ > in the said General formula (4), from a viewpoint of the balance of heat resistance and solubility, following General formula (5)-(8):

[In the formula (7), R ⁶ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, and a trifluoromethyl group. In the formula (8), Q represents a 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 -SO 2 -C 6 H 4 -O -, - C (CH 3) 2 -C 6 H 4 -C _{(CH 3)} 2 _-, - it shows the _{O-C 6 H 4 -C 6} H 4 -O- and _{-O-C 6} H 1 kind selected from the group consisting of groups represented by 4 -O-. ]
It is preferable that it is at least 1 sort (s) of group represented by these.

R ⁶ in the general formula (7) 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.

As the Q in the general formula (8), from the viewpoint of solubility of the balance between heat resistance, the _{formula: -O-C 6 H 4 -O} -, - O -, - C (CH 3) 2 - , —CH ₂ —, or —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O—, is preferred, and the formula: —O—C ₆ H ₄ —O— is preferred. Or the group represented by -O- is especially preferable.

Moreover, as group represented by General formula (5)-(8) which can be selected as such R < ⁵ >, from a viewpoint that higher heat resistance is obtained, General formula (7) or (8) The group represented by general formula (8) is more preferable. Furthermore, as groups represented by general formulas (5) to (8) that can be selected as R ⁵ , from the viewpoint that the linear expansion coefficient can be set to a sufficiently low value, the general formula (7 ) Or a group represented by (8) is more preferable. Among these, R ⁵ is a group represented by the general formula (7) from the viewpoint that a sufficiently high heat resistance can be obtained and the linear expansion coefficient can be made lower. Or at least one of the groups represented by the general formula (8) and the Q is represented by —CONH—, —COO—, —CO—, —C ₆ H ₄ — (more preferably —CONH); A group represented by — or —COO—, particularly preferably a group represented by —CONH—. Furthermore, as R ⁵ , from the viewpoint that a higher degree of flexibility (flexibility) can be imparted to the obtained substrate film made of polyimide, a group represented by the general formula (5); At least one of the groups represented by the formula (8) and Q is represented by —O—, —S—, —CH ₂ —, —O—C ₆ H ₄ —O— (more preferably — It is preferable that the group is a group represented by one of the groups represented by O— and —CH ₂ —, more preferably a group represented by —O—.

  Moreover, n in the said General formula (4) shows the integer of 0-12. When such a value of n exceeds the upper limit, purification becomes difficult. Further, the upper limit of the numerical value range of n in the general formula (4) 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 (4) is 1 from the viewpoint of the stability of the tetracarboxylic dianhydride (raw material compound) represented by the general formula (1). More preferably, 2 is particularly preferable. Thus, as n in General formula (4), it is especially preferable that it is an integer of 2-3.

Furthermore, the polyimide has a sufficiently high glass transition temperature, a sufficiently low linear expansion coefficient, and sufficient flexibility (flexibility) of the obtained substrate film, and these characteristics are further enhanced. From the viewpoint of having a more balanced balance, it is preferable to contain a plurality of (two or more) repeating units having different types of R ^{5 in} the general formula (4). Further, from the same viewpoint, since a higher effect is obtained, the polyimide containing the plural types of repeating units is represented by the general formula (4), and R ^{5 in} the formula is the general formula groups represented by the formula (7); and wherein Q is -CONH -, - COO -, - CO -, - C 6 H 4 - 1 kind selected from the group represented by (more preferably, -CONH- A group represented by the general formula (8) which is a group represented by -COO-, particularly preferably a group represented by -CONH-; A unit (A), a group represented by the general formula (4), and wherein R ⁵ is a group represented by the general formula (5); and the Q is —O—, —S—, -CH _{2 -,} - 1 kind of _{O-C 6} H 4 -O-, a group represented by (more preferably -O -, - CH ₂ - A group represented by the general formula (8) which is one of the groups represented, more preferably a group represented by -O-), and a repeating group which is one group selected from the group consisting of What contains a unit (B) is more preferable. Moreover, as such a repeating unit (B), R ⁵ in the general formula (4) is a group represented by the general formula (8) from the viewpoint of easy availability of the monomer at the time of production. And Q in the formula (8) is one of groups represented by —O—, —CH ₂ —, —O—C ₆ H ₄ —O— (more preferably —O—, —CH More preferably, it is one of the groups represented by _2- , more preferably a group represented by -O-.

  Such a polyimide preferably has a 5% weight loss temperature of 350 ° C. or higher, more preferably 450 to 550 ° C. If such a 5% weight loss 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 having such characteristics. It is in. Such 5% weight reduction temperature is obtained by gradually heating from room temperature (25 ° C.) while flowing nitrogen gas in a nitrogen gas atmosphere and measuring the temperature at which the weight of the used sample is reduced by 5%. Can be sought.

  Moreover, as such a polyimide, that whose glass transition temperature (Tg) is 250 degreeC or more is preferable, and the thing of 300-500 degreeC is more preferable. If the glass transition temperature (Tg) 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 having such characteristics. It is in. In addition, such a glass transition temperature (Tg) can be measured using a differential scanning calorimeter (for example, trade name “DSC220” manufactured by SII Nano Technology Co., Ltd.).

  Moreover, as such a polyimide, a thing with a thermal decomposition temperature (Td) of 400 degreeC or more is preferable, and a 450-600 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) is measured using a TG / DTA220 thermogravimetric analyzer (manufactured by SII Nanotechnology Co., Ltd.) in a nitrogen atmosphere under a temperature rising 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

  Furthermore, as a number average molecular weight (Mn) of such a polyimide, it is preferable that it is 1000-1 million in polystyrene conversion, and it is more preferable that it is 10000-100000. When the number average molecular weight is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and when it exceeds the upper limit, processing tends to be difficult.

  Moreover, as a weight average molecular weight (Mw) of such a polyimide, it is preferable that it is 1000-5 million 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 1000, It is still more preferable that it is 5000, It is especially preferable that it is 10,000. Moreover, as an upper limit of the numerical range of a weight average molecular weight (Mw), it is more preferable that it is 5000000, It is further more preferable that it is 500000, It is especially preferable that it is 50000. If the weight average molecular weight is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, processing tends to be 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, molecular weight (Mw or Mn) and molecular weight distribution (Mw / Mn) of such a polyimide are, for example, gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020 /) as a measuring device. 4 columns: manufactured by Tosoh Corporation, trade name: TSK gel GMH _HR, etc.), and data measured using tetrahydrofuran (THF) as a solvent can be obtained by conversion with polystyrene.

  Moreover, as such a polyimide, what mainly contains the repeating unit represented by the said General formula (4) (More preferably content of the repeating unit represented by the said General formula (4) is all repeating units. More preferably, it is 50 to 100 mol%). Such polyimide may contain other repeating units as long as the effects of the present invention are not impaired. Examples of such other repeating units include repeating units derived from other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (1).

  Although the polyimide of the present invention is an alicyclic polyimide, it exhibits a glass transition temperature equivalent to or higher than that of wholly aromatic polyimide (for example, trade name “Kapton”: glass transition temperature 410 ° C.). It is also possible to have such a sufficiently high heat resistance, and it is soluble in a solvent and has a high workability. For example, for a flexible wiring board that requires a very high heat resistance. Polyimide, polyimide for heat-resistant insulating tape, polyimide for wire enamel, polyimide for semiconductor protective coating, polyimide for liquid crystal alignment film, polyimide for organic EL transparent electrode substrate, polyimide for transparent electrode substrate of solar cell, Polyimide for transparent electrode substrate of electronic paper, various gas barrier film substrate materials, transfer belt, interlayer insulation film, sensor It is particularly useful as raw materials for manufacturing the plate or the like.

[Polyamide acid]
The polyamic acid of the present invention has the following general formula (9):

[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
It has the repeating unit represented by these, It is characterized by the above-mentioned.

Such a polyamic acid can be suitably used for producing the polyimide of the present invention (can be obtained as a reaction intermediate (precursor) for producing the polyimide of the present invention. Stuff.) ^R 1 in the general formula ^{(9), R 2, R} 3, R 4, R 1 ^{R 5} and n are the general formula (4) ^{in, R 2, R 3, R} 4, R 5 and It is the same as n, and its preferable one is also the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n in the general formula (4).

  Moreover, as such a polyamic acid, it is preferable that intrinsic viscosity [(eta)] is 0.05-3.0 dL / g, and it is more preferable that it is 0.1-2.0 dL / g. When the intrinsic viscosity [η] is smaller than 0.05 dL / g, when a film-like polyimide is produced using the intrinsic viscosity [η], the resulting film tends to be brittle, while 3.0 dL / g is reduced. When it exceeds, the viscosity is too high and the processability is lowered, and for example, when a film is produced, it is difficult to obtain a uniform film. Such intrinsic viscosity [η] can be measured as follows. That is, first, N, N-dimethylacetamide is used as a solvent, and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL, and a measurement sample (solution) is obtained. obtain. Next, using the measurement sample, the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [η]. As such a kinematic viscometer, THOMAS SCIENTIFIC CO. The brand name “KINEMATIC VISCOMETER TV-5S” manufactured by the company is used.

  Moreover, as such polyamic acid, what mainly contains the repeating unit represented by the said General formula (9) (More preferably, content of the repeating unit represented by the said General formula (9) is all repeating units. More preferably, it is 50 to 100 mol% with respect to. Such a polyamic acid may contain other repeating units as long as the effects of the present invention are not impaired. Examples of such other repeating units include repeating units derived from other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (1).

[Method for producing polyamic acid]
The method for producing the polyamic acid of the present invention comprises the following general formula (1) in the presence of an organic solvent:

[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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the following general formula (10):

[In Formula (10), R ⁵ represents an arylene group having 6 to 40 carbon atoms. ]
The polyamic acid which has a repeating unit represented by the said General formula (9) is obtained by making it react with the aromatic diamine represented by these. Thus, the method for producing a polyamic acid according to the present invention includes a tetracarboxylic dianhydride represented by the general formula (1) and an aromatic represented by the general formula (10) in the presence of an organic solvent. It is a method including a step of obtaining a polyamic acid having a repeating unit represented by the general formula (9) by reacting with a diamine.

The tetracarboxylic dianhydride represented by the general formula (1) used in such a method for producing a polyamic acid is the same as the tetracarboxylic dianhydride of the present invention (the above general formula (1) R ¹ , R ² , R ³ , R ⁴ and n in the tetracarboxylic dianhydride represented by the above formula are the same as those described in the tetracarboxylic dianhydride of the present invention, and The same applies to suitable ones). ^{Incidentally, R 1, R 2, R} 3, R 4 and n in the general formula (1) used in such reactions, ^R 1 in formula (4) ^{in, R 2, R 3, R} 4 And n are preferably the same.

Further, the aromatic diamine represented by general formula (10), R ⁵ of formula (10) is the same as the R ⁵ in the formula described in the polyimide of the present invention (4) The preferred one is also the same as R ⁵ in the general formula (4).

  Examples of the aromatic diamine represented by the general formula (10) include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 3,3′-. Diaminodiphenylethane, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminodiphenyl ether, 3,3′-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 3,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, p-diaminobenzene, m-diaminobenzene, o-diamino Benzene, 4,4′-diaminobiphenyl, 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'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobi Phenyl, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4 -Aminophenoxy) biphenyl, 4,4'-diaminobenzanilide, 9,9'-bis (4-aminophenyl) fluorene, o-tolidine sulfone, 1,3'-bis (4-aminophenoxy) -2,2 -Dimethylpropane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3 ', 5,5'-tetramethylbenzidine, 1,5-bis (4-aminophenoxy) pentane, etc. Can be mentioned.

  It does not restrict | limit especially as a method for manufacturing such an aromatic diamine, A well-known method is employable suitably. Moreover, you may use a commercially available thing suitably as such aromatic diamine.

  Moreover, as said organic solvent, the organic solvent which can melt | dissolve both the tetracarboxylic dianhydride represented by the said General formula (1) and the aromatic diamine represented by the said General formula (10). It is preferable that Examples of such an organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, propylene carbonate, tetramethylurea, 1,3- Aprotic polar solvents such as dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol; tetrahydrofuran, dioxane, cellosolve, glyme And ether solvents such as benzene, toluene and xylene. Such organic solvents may be used singly or in combination of two or more.

  The ratio of the tetracarboxylic dianhydride represented by the general formula (1) and the aromatic diamine represented by the general formula (10) is the aromatic represented by the general formula (10). It is preferable that the acid anhydride group of the tetracarboxylic dianhydride represented by the general formula (1) is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine, and 0.3 to 1 More preferably, it is 2 equivalents. If the use ratio is less than the lower limit, the polymerization reaction does not proceed efficiently, and a high molecular weight polyamic acid tends not to be obtained. On the other hand, if the upper limit is exceeded, a high molecular weight polyamic acid is obtained as described above. There is no tendency.

  Furthermore, as the usage-amount of the said organic solvent, the total amount of the tetracarboxylic dianhydride represented by the said General formula (1) and the aromatic diamine represented by the said General formula (10) is the total amount of a reaction solution. The amount is preferably 0.1 to 50% by mass (more preferably 10 to 30% by mass). If the amount of the organic solvent used is less than the lower limit, the polyamic acid tends not to be obtained efficiently. On the other hand, if it exceeds the upper limit, stirring tends to be difficult due to the increase in viscosity.

  Further, when the tetracarboxylic dianhydride represented by the above general formula (1) and the aromatic diamine represented by the above general formula (10) are reacted, a polyamic acid having an improved reaction rate and a high polymerization degree is added. From the viewpoint of obtaining, a basic compound may be further added to the organic solvent. Examples of such basic compounds include, but are not limited to, triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, α-picoline, and the like. Can be mentioned. Moreover, it is preferable that the usage-amount of such a basic compound shall be 0.001-10 equivalent with respect to 1 equivalent of tetracarboxylic dianhydrides represented by the said General formula (1), 0.01 It is more preferable to set it to -0.1 equivalent. When the amount of such a basic compound used is less than the lower limit, the effect of addition tends to decrease, and when it exceeds the upper limit, it tends to cause coloring or the like.

  Moreover, the reaction temperature at the time of making the tetracarboxylic dianhydride represented by the said General formula (1) and the aromatic diamine represented by the said General formula (10) react these compounds. What is necessary is just to adjust suitably to possible temperature, Although it does not restrict | limit in particular, It is preferable to set it as 15-30 degreeC. Moreover, as a method of making the tetracarboxylic dianhydride represented by the said General formula (1) and the aromatic diamine represented by the said General formula (10) react, a tetracarboxylic dianhydride and aromatic diamine are mentioned. Any known method capable of carrying out the polymerization reaction can be used as appropriate, and is not particularly limited. For example, an aromatic diamine is dissolved in a solvent at atmospheric pressure and under an inert atmosphere such as nitrogen, helium, and argon. Then, the method of adding the tetracarboxylic dianhydride represented by the said General formula (1) at the said reaction temperature, and making it react for 10 to 48 hours after that may be employ | adopted suitably. 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, in the presence of an organic solvent, the tetracarboxylic dianhydride represented by the above general formula (1) is reacted with the aromatic diamine represented by the above general formula (10), and the above general A polyamic acid having a repeating unit represented by the formula (9) can be obtained. The polyamic acid having a repeating unit represented by the general formula (9) thus obtained is the same as that described in the polyamic acid of the present invention (in the general formula (9) above). ^{R 1, R 2, R 3} , R 4, R 5 and n are same as ^{R 1, R 2, R 3} , R 4, R 5 and n of formula (9) in which described in the polyamic acid of the present invention The preferable thing is also the same.) Therefore, the method for producing a polyamic acid of the present invention can be suitably used as a method for producing the polyamic acid of the present invention.

  In addition, when the polyamic acid obtained by the present invention contains other repeating units together with the repeating unit represented by the general formula (9), the above general acid is used in the production of the polyamic acid. You may employ | adopt the method of making these react with the said aromatic diamine using another tetracarboxylic dianhydride with the tetracarboxylic dianhydride represented by Formula (1). Other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (1) include butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid. Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid Anhydride, 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-di 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 Aliphatic or alicyclic tetracarboxylic dianhydrides such as 1,3,5,6-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid Water, 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 dianhydride, Bis (phthalic acid) phenylphospho Finoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether Examples thereof include dianhydrides and aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride. In addition, when using aromatic tetracarboxylic acid, in order to prevent coloring by intramolecular CT, the amount used thereof is appropriately changed within a range in which the obtained polyimide can have sufficient transparency. It is preferable.

  In addition, when the polyamic acid having the repeating unit represented by the general formula (9) is isolated from the organic solvent after the step is performed, the isolation method is not particularly limited, and the polyamic acid is simply used. A known method that can be separated can be appropriately employed, and for example, a method of isolating as a reprecipitate may be employed.

[Polyamic acid solution]
The polyamic acid solution of the present invention includes the polyamic acid of the present invention and an organic solvent. As the organic solvent used in such a polyamic acid solution, the same organic solvent as that used in the method for producing a polyamic acid of the present invention can be suitably used. Therefore, the polyamic acid solution of the present invention may be prepared by carrying out the above-described method for producing a polyamic acid of the present invention and using the reaction solution obtained after the reaction as it is as a polyamic acid solution. That is, the polyamic acid solution of the present invention comprises a tetracarboxylic dianhydride represented by the general formula (1) and an aromatic diamine represented by the general formula (10) in the presence of the organic solvent. You may make it react, producing the polyamic acid which has a repeating unit represented by the said General formula (9), and obtaining the solution containing the said polyamic acid and the said organic solvent.

  The content of the polyamic acid in such a polyamic acid solution is not particularly limited, but is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. If such a content is less than the lower limit, the molecular weight of the polyamic acid tends to decrease. On the other hand, if the content exceeds the upper limit, it tends to be difficult to produce polyimide. Such a polyamic acid solution can be suitably used for producing the polyimide of the present invention.

[Production method of polyimide]
The method for producing a polyimide of the present invention is characterized by imidizing a polyamic acid having a repeating unit represented by the general formula (9) to obtain a polyimide having a repeating unit represented by the general formula (4). It is a method.

  The polyamic acid having a repeating unit represented by the general formula (9) used in such a polyimide production method is the same as that described in the polyamic acid of the present invention.

  Such an imidization method is not particularly limited as long as it is a method capable of imidizing polyamic acid, and a known method can be appropriately employed. For example, the repetition represented by the above general formula (9) A method of imidizing a polyamic acid having a unit by heat treatment at a temperature of 60 to 400 ° C. (more preferably 60 to 350 ° C., still more preferably 150 to 350 ° C., particularly preferably 150 ° C. to 250 ° C.). Alternatively, a method of imidization using a so-called “imidating agent” can be suitably employed.

  In the case of adopting a method for imidizing by performing such heat treatment, the reaction tends to be delayed if the heating temperature is less than 60 ° C., and on the other hand, if the upper limit is exceeded, coloring or thermal decomposition may occur. There is a tendency for molecular weight to decrease. Moreover, it is preferable that reaction time (heating time) in the case of employ | adopting the method to imidize by heat-processing shall be 0.5 to 5 hours. If such a reaction time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if it exceeds the upper limit, it tends to be colored or decrease in molecular weight due to thermal decomposition.

  When a method of imidizing using a so-called “imidating agent” is adopted, polyamic acid having a repeating unit represented by the above general formula (9) is imidized in a solvent in the presence of an imidizing agent. It is preferable to do. As such a solvent, the thing similar to the organic solvent used for the manufacturing method of the polyamic acid of the said invention can be used suitably.

  Further, as such an imidizing agent, a known imidizing agent can be used as appropriate, for example, acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, pyridine, collidine, lutidine, triethylamine. And tertiary amines such as N-methylpiperidine. Moreover, it is preferable that the reaction temperature in the case of imidation in the case of imidating by adding an imidizing agent is 0-180 degreeC, and it is more preferable that it is 60-150 degreeC. The reaction time is preferably 0.1 to 48 hours. If the reaction temperature or 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, the mixing probability of a substance (such as oxygen) that degrades the polymer increases, and the molecular weight increases. It tends to decrease. The amount of the imidizing agent used is not particularly limited, and is from several millimoles to several moles (preferably 0.00 mol) with respect to 1 mole of the repeating unit represented by the general formula (9) in the polyamic acid. (About 05-4.0 moles).

  In such a method for producing a polyimide of the present invention, the polyamic acid having a repeating unit represented by the general formula (9) is obtained by the method for producing a polyamic acid of the present invention. Is preferred.

  Furthermore, as a method for producing the polyimide of the present invention, in the presence of an organic solvent, a tetracarboxylic dianhydride represented by the general formula (1), an aromatic diamine represented by the general formula (10), and It is preferable to further include a step of obtaining a polyamic acid having a repeating unit represented by the general formula (9) by reacting In addition, this process is the same process as the process of obtaining the polyamic acid demonstrated in the manufacturing method of the polyamic acid of the said invention (The organic solvent to be used, tetracarboxylic dianhydride, aromatic diamine, reaction conditions, etc. are the above-mentioned. This is the same as described in the method for producing a polyamic acid of the present invention.) Thus, as a manufacturing method of the polyimide of this invention, in presence of an organic solvent, the tetracarboxylic dianhydride represented by the said General formula (1), and the aromatic represented by the said General formula (10) A step (I) of obtaining a polyamic acid having a repeating unit represented by the above general formula (9) by reacting with a diamine, and an imidation of the polyamic acid, and a repeating represented by the above general formula (4) It is preferable that the method includes a step (II) of obtaining a polyimide having a unit. Thus, when the manufacturing method of the polyimide of this invention is made into the method containing process (I) and process (II), it is possible to manufacture a polyimide more efficiently in a series of processes.

  In addition, when using the method including such a process (I) and process (II), and employ | adopting the method of imidating by performing heat processing in the said imidation, the said process ( The tetracarboxylic dianhydride represented by the above general formula (1) in an organic solvent without isolating the polyamic acid having the repeating unit represented by the above general formula (9) after carrying out I) And a reaction liquid obtained by reacting the aromatic diamine represented by the general formula (10) (a reaction liquid containing a polyamic acid having a repeating unit represented by the general formula (9)) as it is. It is also possible to employ a method in which the reaction solution is subjected to a treatment (drying treatment) for removing the solvent by evaporation (drying treatment) to remove the solvent, and then imidized by performing the heat treatment. By the treatment for evaporating and removing the solvent, it is possible to isolate the polyamic acid having the repeating unit represented by the general formula (9) in the form of a film, and then perform a heat treatment. . In the treatment for evaporating and removing the solvent, the temperature condition for evaporating the solvent is preferably 0 to 180 ° C, and more preferably 40 to 150 ° C. If such a temperature condition is less than the lower limit, the solvent tends not to evaporate (dry). On the other hand, if it exceeds the upper limit, the solvent tends to boil and a film containing bubbles and voids tends to be formed. In this case, for example, in the case of producing a film-like polyimide, the reaction solution obtained may be applied as it is on a substrate (for example, a glass plate), and the solvent may be removed by evaporation and heat treatment, It becomes possible to produce a film-like polyimide 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. In addition, when isolating and using the polyamic acid which has a repeating unit represented by the said General formula (9) from the said reaction liquid, it does not restrict | limit especially as an isolation method, It is possible to isolate a polyamic acid. Such known methods can be employed as appropriate, and for example, a method of isolating as a reprecipitate may be employed.

  Moreover, when using the method including step (I) and step (II) and adopting a method of imidizing using an “imidizing agent”, an “imide” using an “imidizing agent” In the first place, it is preferable to imidize in a solvent (more preferably, the organic solvent described in the method for producing a polyamic acid of the present invention), so for example, in the organic solvent, the general formula ( 1) a reaction solution obtained by reacting the tetracarboxylic dianhydride represented by the above general formula (10) with the aromatic diamine represented by the above general formula (10) (the repeating unit represented by the above general formula (9)). Without using the reaction solution containing the polyamic acid having the same structure (without isolating the polyamic acid having the repeating unit represented by the general formula (9) from the reaction solution after performing the step (I). Using the reaction solution as it is), the method of imidation by adding the imidization agent to the reaction solution can be suitably employed.

  In addition, when the polyimide obtained by this invention shall contain another repeating unit with the repeating unit represented by the said General formula (4), the polyamic acid used for the manufacture is made into the said general formula ( It is good also as what contains another repeating unit with the repeating unit represented by 9). For example, when the method for producing a polyimide of the present invention is a method including the steps (I) and (II), the tetracarboxylic dianhydride represented by the general formula (1) in the step (I) In addition, other tetracarboxylic dianhydrides may be used and reacted with the aromatic diamine, followed by step (II). As other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (1), the same ones as described in the method for producing a polyamic acid of the present invention are appropriately used. Can be used.

The polyimide having the repeating unit represented by the general formula (4) thus obtained is the same as that described in the polyimide of the present invention (R ¹ , R ² in the formula (4), R ³ , R ⁴ , R ⁵ and n are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n described in the polyimide of the present invention, and the preferred ones are also the same. .) Therefore, the method for producing a polyimide of the present invention is a method that can be suitably used as a method for producing the polyimide of the present invention. Moreover, since the polyimide obtained in this way is obtained using an alicyclic tetracarboxylic dianhydride (aliphatic tetracarboxylic dianhydride), it has a very high transparency. It becomes. Therefore, such polyimides are flexible wiring board films, heat-resistant insulating tapes, wire enamels, semiconductor protective coating agents, liquid crystal alignment films, transparent conductive films for organic EL, flexible board films, flexible transparent conductive films, organic Transparent conductive film for thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, film for touch panel, transparent electrode substrate (transparent electrode substrate for organic EL, transparent electrode substrate for solar cell, electronic paper This is particularly useful as a material for producing a transparent electrode substrate, a transfer belt, an interlayer insulating film, a sensor substrate, and the like. As described above, according to the present invention, a polyimide that has a high light transmittance and a sufficiently high heat resistance, and a polyimide that can efficiently and reliably produce the polyimide. A manufacturing method can be provided.

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

  In the following, the molecular structure of the compounds obtained in the examples is identified by measuring the FD-MS spectrum using an FD-MS measuring instrument (manufactured by JEOL Ltd., trade name: JMS-700V). It went by.

(Example 1)
A 100 W high-pressure mercury lamp manufactured by Sen Special Light Source Co., Ltd. as a light source (trade name “HL100C” manufactured by Sen Special Light Source Co., Ltd .: a high-pressure mercury lamp disposed in a light source cooling tube), and a reaction vessel made of quartz glass An apparatus (an internal irradiation type photochemical reaction apparatus) equipped with a 100 W high-pressure mercury lamp equipped with a light source cooling tube at the center of the two-necked flask was prepared. Next, the following general formula (11):

And maleic anhydride (3.92 g, 40.0 mmol) represented by the following general formula (12):

A bisspirononorbornene compound represented by the formula (4.81 g, 20.0 mmol) and ethyl acetate (50 mL) were introduced, stirred at room temperature (25 ° C.), the maleic anhydride and the bis A spironorbornene compound was dissolved to obtain a reaction solution. The bisspirononorbornene compound represented by the general formula (12) was synthesized by adopting the same method as that described in Example 1 of JP2011-162479A.

  Next, the outer wall of the two-necked flask as the reaction vessel was covered with aluminum foil, and tap water was allowed to flow through the light source cooling tube. Next, while stirring the reaction liquid in the two-necked flask, under a room temperature (25 ° C.) condition, a light source (100 W high-pressure mercury lamp with the light source cooling tube) existing inside (center part) of the two-necked flask ) To light (including light having a wavelength in the range of 300 to 600 nm) was started. After continuously irradiating light from the light source for 15 hours in this way, the solid content generated in the flask is recovered by filtration, and left to stand at 60 ° C. for 3 hours under vacuum conditions to remove the solvent from the solid content. This gave the product (8.32 g).

  In order to confirm the structure of the product (compound) thus obtained, FD-MS measurement was performed. The FD-MS spectrum of the compound thus obtained is shown in FIG.

  As is clear from the results shown in FIG. 1, by irradiating the reaction liquid with light as described above, the following general formula (13):

It was confirmed that a compound represented by the formula (tetracarboxylic dianhydride: target compound) was obtained. That is, in the FD-MS spectrum shown in FIG. 1, a peak was confirmed at a position corresponding to the mass number (436) of the target compound (tetracarboxylic dianhydride represented by the general formula (13)). It was confirmed that the tetracarboxylic dianhydride represented by the general formula (13) was obtained.

  In addition, the polyamic acid which has a repeating unit represented by the said General formula (9) can be obtained by making such tetracarboxylic dianhydride and the said aromatic diamine react in presence of an organic solvent, Moreover, the polyimide which has a repeating unit represented by the said General formula (1) can be obtained by imidating this polyamic acid by a well-known method.

As described above, according to the present invention, it can be used as a raw material monomer for producing an alicyclic polyimide having sufficient light transmittance and sufficiently high heat resistance, and is a simpler method. A tetracarboxylic dianhydride that can be produced by the method, a polyamic acid obtained using the tetracarboxylic dianhydride, a polyamic acid solution and a polyimide, and a method for producing the tetracarboxylic dianhydride, the polyamic acid, and the polyimide are provided. It becomes possible to do.
Thus, the tetracarboxylic dianhydride of the present invention can be more easily produced, and can impart sufficiently high heat resistance when an alicyclic polyimide is produced using the tetracarboxylic dianhydride. Therefore, for example, polyimide for flexible wiring board, polyimide for heat-resistant insulating tape, polyimide for electric wire enamel, polyimide for semiconductor protective coating, polyimide for liquid crystal alignment film, organic EL transparent electrode substrate It is particularly useful as a material (raw material monomer) for producing polyimide, polyimide for a transparent electrode substrate of a solar cell, polyimide for a transparent electrode substrate of electronic paper, various gas barrier film substrate materials, and the like.

Claims (10)

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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride, which is a compound represented by the formula: The following general formula (2):
[In the formula (2), 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,
n shows the integer of 0-12. ]
A bisspironorbornene compound represented by the following general formula (3):
[In Formula (3), each R ⁴ independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a halogen atom, or two R ⁴ represents one selected from a cycloalkenyl group having 4 to 10 carbon atoms bonded to each other. ]
And a maleic anhydride compound represented by 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
The tetracarboxylic dianhydride represented by these is obtained, The manufacturing method of the tetracarboxylic dianhydride characterized by the above-mentioned. The following general formula (4):
[In the formula (4), 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
The polyimide characterized by having the repeating unit represented by these. R ⁵ in the general formula (4) is represented by the following general formulas (5) to (8):
[In the formula (7), R ⁶ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group,
In the formula (8), Q represents a 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 -SO 2 -C 6 H 4 -O -, - C ( _{CH 3) 2 -C 6 H 4} -C (CH 3) 2 -, - from _{O-C 6 H 4 -C 6} H 4 -O- and _{-O-C 6} group represented by H 4 -O- 1 type selected from the group consisting of ]
The polyimide according to claim 3, which is at least one of the groups represented by the formula: The following general formula (9):
[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
The polyamic acid characterized by having the repeating unit represented by these. R ⁵ in the general formula (9) is represented by the following general formulas (5) to (8):
[In the formula (7), R ⁶ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group,
In the formula (8), Q represents a 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 -SO 2 -C 6 H 4 -O -, - C ( _{CH 3) 2 -C 6 H 4} -C (CH 3) 2 -, - from _{O-C 6 H 4 -C 6} H 4 -O- and _{-O-C 6} group represented by H 4 -O- 1 type selected from the group consisting of ]
The polyamic acid according to claim 5, wherein the polyamic acid is at least one of the groups represented by the formula:   A polyamic acid solution comprising the polyamic acid according to claim 5 or 6 and an organic solvent. In the presence of an organic solvent, 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the following general formula (10):
[In Formula (10), R ⁵ represents an arylene group having 6 to 40 carbon atoms. ]
Is reacted with an aromatic diamine represented by the following general formula (9):
[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
A process for producing a polyamic acid, comprising obtaining a polyamic acid having a repeating unit represented by the formula: The following general formula (9):
[In the formula (9), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
A polyamic acid having a repeating unit represented by general formula (4) is imidized:
[In the formula (4), 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
R ⁵ represents an arylene group having 6 to 40 carbon atoms,
n shows the integer of 0-12. ]
A method for producing a polyimide, comprising obtaining a polyimide having a repeating unit represented by the formula: In the presence of an organic solvent, 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,
R ⁴ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group and a halogen atom, or 2 bonded to an adjacent carbon atom. One R ⁴ is bonded to each other and represents one selected from cycloalkyl groups having 4 to 10 carbon atoms;
n shows the integer of 0-12. ]
A tetracarboxylic dianhydride represented by the following general formula (10):
[In Formula (10), R ⁵ represents an arylene group having 6 to 40 carbon atoms. ]
The process for producing a polyimide according to claim 9, further comprising a step of reacting with an aromatic diamine represented by formula (9) to obtain a polyamic acid having a repeating unit represented by the general formula (9). .