KR102429867B1 - Polyimide precursor resin composition - Google Patents

Abstract

a polyimide precursor resin which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule and diamine; Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by C-P; and at least one additive compound selected from the group consisting of quaternary amine compounds; A polyimide precursor resin composition containing a solvent.

Description

Polyimide precursor resin composition

The present invention relates to a polyimide precursor resin composition.

In the field of display devices such as displays and liquid crystal displays using organic electroluminescent elements, the appearance of a material having high light transmittance such as glass and sufficiently high heat resistance as a material used for a substrate or the like has been demanded. And, in recent years, polyimide has been paid attention to as a material used for glass replacement applications, etc., and in order to manufacture such a polyimide, various polyimide precursor resin compositions are disclosed.

For example, in International Publication No. 2011/099518 (Patent Document 1), a reaction solution containing a polyamic acid having a repeating unit described by a specific general formula and a solvent is disclosed. The polyimide obtained by using the same reaction solution (composition) as described in Patent Document 1 has high light transmittance and sufficiently high heat resistance, and can be applied to various fields.

International Publication No. 2011/099518

However, the reaction solution (composition) as described in Patent Document 1 efficiently and reliably produces polyimide having higher toughness while maintaining properties such as coefficient of linear expansion, glass transition temperature, and total light transmittance at a sufficiently high level. It was not necessarily sufficient from a manufacturing point of view.

The present invention has been made in view of the problems of the prior art, and while maintaining properties such as coefficient of linear expansion, glass transition temperature, and total light transmittance at a sufficiently high level, polyimide having higher toughness can be efficiently and reliably manufactured It aims at providing the polyimide precursor resin composition which can do this.

As a result of intensive research to achieve the above object, the present inventors have prepared a polyimide precursor resin composition with at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule. a polyimide precursor resin which is a polymer of a species and a diamine; Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by C-P; and at least one additive compound selected from the group consisting of quaternary amine compounds; By containing a solvent, it becomes possible to efficiently and reliably manufacture a polyimide having higher toughness while maintaining properties such as coefficient of linear expansion, glass transition temperature and total light transmittance at a sufficiently high level using it. Found and completed the present invention.

That is, the polyimide precursor resin composition of the present invention is

a polyimide precursor resin which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule and diamine;

Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by C-P; and at least one additive compound selected from the group consisting of quaternary amine compounds;

menstruum

will contain

In the polyimide precursor resin composition of the present invention, at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule is represented by the following general formula (1):

(1)

(One)

[In formula (1), R ¹ , R ² , R ³ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n represents an integer of 0 to 12 ]

a compound represented by ; The following general formula (2):

(2)

(2)

[In Formula (2), A represents 1 type selected from the group which consists of a divalent aromatic group which may have a substituent and the number of carbon atoms which form an aromatic ring is 6-30, R< ⁴ > is a hydrogen atom each independently and one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, and R ⁵ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms]

a compound represented by ; The following general formula (3):

(3)

(3)

[In formula (3), R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or two R ⁶ bonded to the same carbon atom. may form a methylidene group as one of these, and R ⁷ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms]

a compound represented by; The general formula (4):

(4)

(4)

a compound represented by ; And it is preferable that it is at least 1 sort(s) selected from the group which consists of derivatives of these compounds (compounds represented by general formula (1)-(4)).

In addition, in the polyimide precursor resin composition of the present invention, the polyimide precursor resin has the following general formula (I):

(I)

(I)

[In formula (I), X ¹ is the following general formula (I-1):

(I-1)

(I-1)

[In formula (I-1), R ¹ , R ² , R ³ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is an integer of 0 to 12 represents, and the symbols *1 to *4 indicate which of the four bonds bonded to X ¹ in the formula (I), respectively]

a tetravalent group represented by ; The general formula (I-2):

(I-2)

(I-2)

[In formula (I-2), A represents one selected from the group consisting of a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent and form an aromatic ring, and R ⁴ is each independently Represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, R ⁵ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, symbol *1 to *4 indicates that the bond to which the symbol is attached is any of the four bonds bonded to X ¹ in formula (I)]

a tetravalent group represented by ; The general formula (I-3):

(I-3)

(I-3)

[In formula (I-3), R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or two groups bonded to the same carbon atom. R ⁶ may become one to form a methylidene group, R ⁷ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and symbols *1 to *4 indicate that the symbol is indicates that the attached bond is any of the four bonds bonded to X ¹ in the formula (I)]

At least one selected from the group consisting of a tetravalent group represented by

R ¹⁰ represents an arylene group having 6 to 50 carbon atoms,

Y ¹ and Y ² each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkylsilyl group having 3 to 9 carbon atoms]

repeating units represented by ; and the general formulas (II) to (III):

(II)

(II)

(III)

(III)

[In formulas (II) to (III), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkylsilyl having 3 to 9 carbon atoms represents one selected from the group consisting of groups]

It is preferable to have at least one type of repeating unit selected from the group consisting of repeating units represented by .

Moreover, in the polyimide precursor resin composition of the said this invention, it is preferable that the said addition compound is triphenylphosphine.

According to the present invention, there is provided a polyimide precursor resin composition capable of efficiently and reliably producing polyimide having higher toughness while maintaining properties such as coefficient of linear expansion, glass transition temperature and total light transmittance at a sufficiently high level. it becomes possible to do

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the preferable embodiment.

[Polyimide Precursor Resin Composition]

The polyimide precursor resin composition of the present invention comprises:

a polyimide precursor resin (first component) which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule and diamine;

Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by C-P; and at least one additive compound (second component) selected from the group consisting of quaternary amine compounds;

solvent (third component)

will contain Hereinafter, each component is divided and demonstrated.

<Polyimide precursor resin composition (first component)>

The polyimide precursor resin composition (1st component) which concerns on this invention is a polymer of at least 1 sort(s) and diamine selected from the group which consists of tetracarboxylic dianhydride which has two norbornane skeletons in a molecule|numerator, and its derivative(s). Here, the tetracarboxylic dianhydride used as a monomer component of a polymer, its derivative(s), and diamine are separately demonstrated.

<Tetracarboxylic dianhydride and its derivatives>

The tetracarboxylic dianhydride used as the monomer component of the polymer has two norbornane skeletons in the molecule. Here, the norbornane skeleton is represented by the following general formula (i):

(i)

(i)

It may have a structure represented by , and a hydrogen atom, an atom other than a hydrogen atom, a substituent other than a hydrogen atom, etc. may be bonded to each carbon atom forming this skeleton. As described above, the tetracarboxylic dianhydride according to the present invention may have two structural moieties (skeletons) represented by the general formula (i) in the molecule, and the structure thereof is not particularly limited. In addition, as a derivative of tetracarboxylic dianhydride, what is necessary is just to be obtained using the said tetracarboxylic dianhydride, It is not restrict|limited in particular, For example, diester dicarboxylic acid obtained by modifying|denaturing tetracarboxylic dianhydride, and diester dicarboxylic acid dichloride.

As such tetracarboxylic dianhydride and derivatives thereof, from the viewpoint of transparency and heat resistance of the polyimide obtained using the component, compounds represented by the above general formulas (1) to (4) and derivatives thereof are preferred. , the compounds represented by the general formulas (1) to (3) and their derivatives are more preferable. Hereinafter, the compounds represented by the said General formulas (1) - (4) and their derivatives which can be suitably used as tetracarboxylic dianhydride concerning this invention are divided and demonstrated.

(Compound represented by the general formula (1))

With respect to the compound represented by the general formula (1), R ¹ , R ² , and R ³ in the general formula (1) are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. A species is represented, and n represents the integer of 0-12.

The alkyl group which may be selected as R ¹ , R ² , and R ³ in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When this carbon number exceeds 10, a glass transition temperature will fall and it will become impossible to achieve sufficiently high heat resistance. Further, the number of carbon atoms of the alkyl group that can be selected as R ¹ , R ² , and R ³ is preferably 1 to 6, more preferably 1 to 5, and more preferably 1 to 4 from the viewpoint of further facilitation of purification. It is more preferable, and it is especially preferable that it is 1-3. In addition, the alkyl group which can be selected as such R< ¹ >, R< ² >, R< ³ > may be linear or branched may be sufficient as it. Moreover, as such an alkyl group, a methyl group and an ethyl group are more preferable from a viewpoint of easiness of refinement|purification.

In addition, as R ¹ , R ² , R ³ in the general formula (1), from the viewpoint of obtaining higher heat resistance than when a polyimide is produced, each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more Preferably, among them, from the viewpoint of easy availability of raw materials and easier purification, each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group is more preferable, and a hydrogen atom or a methyl group is particularly desirable. In addition, a plurality of R ¹ , R ² , and R ³ in the formula are particularly preferably the same from the viewpoint of easiness of purification or the like.

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

In addition, it does not restrict|limit as a method in particular for manufacturing the tetracarboxylic dianhydride represented by such General formula (1), A well-known method can be employ|adopted suitably, for example, as described in International Publication No. 2011/099517 You may employ|adopt the method, the method of international publication 2011/099518, etc. are employ|adopted.

(Compound represented by the general formula (2))

With respect to the compound represented by the general formula (2), in the general formula (2), A may have a substituent and is selected from the group consisting of a divalent aromatic group in which the number of carbon atoms forming an aromatic ring is 6 to 30. R ⁴ independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ is each independently a group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. 1 type selected from

A in the general formula (2) is a divalent aromatic group which may have a substituent as described above, and the number of carbons forming an aromatic ring contained in the aromatic group (in addition, the number of carbon atoms forming an aromatic ring "Number of carbons" means only the number of carbons in the aromatic ring in the aromatic group, not including the number of carbons in the substituent, when the aromatic group has a substituent containing carbon (such as a hydrocarbon group). , in the case of a 2-ethyl-1,4-phenylene group, the number of carbons forming an aromatic ring is 6) is 6 to 30. Thus, A in General formula (1) may have a substituent and is a divalent group (divalent aromatic group) which has a C6-C30 aromatic ring. When the number of carbons forming such an aromatic ring exceeds the above upper limit, when a polyimide is prepared using a polyimide precursor resin having such a repeating unit, it tends to be difficult to sufficiently suppress the coloring of the polyimide. Moreover, as for the number of carbons which form the aromatic ring of the said divalent aromatic group from a viewpoint of transparency and easiness of refinement|purification, it is more preferable that it is 6-18, and it is still more preferable that it is 6-12.

The divalent aromatic group is not particularly limited as long as it satisfies the conditions for the number of carbons described above. For example, benzene, naphthalene, terphenyl, anthracene, phenanthrene, triphenylene, pyrene, chrysene, biphenyl , terphenyl, quaterphenyl, a residue from which two hydrogen atoms are removed from an aromatic compound such as quinquiphenyl ene group, 2,6-naphthylene group, 2,7-naphthylene group, 4,4'-biphenylene group, 9,10-anthracenylene group, etc.); and a group in which at least one hydrogen atom in the residue is substituted with a substituent (eg, 2,5-dimethyl-1,4-phenylene group, 2,3,5,6-tetramethyl-1,4-phenylene group) etc. can be used appropriately. Moreover, in such a residue, the position of the hydrogen atom to be released as described above is not particularly limited, and, for example, when the residue is a phenylene group, any position of the ortho-position, the meta-position, and the para-position may be used.

As such a divalent aromatic group, a phenylene group which may have a substituent or a phenylene group which may have a substituent from the viewpoint that the solubility of the polyimide in a solvent is more excellent and higher workability is obtained when a polyimide is prepared. A biphenylene group, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, and a terphenylene group which may have a substituent are preferable. That is, as such a divalent aromatic group, a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and a terphenylene group which may each have a substituent are preferable. Further, among these divalent aromatic groups, from the viewpoint of obtaining a higher effect from the above point of view, a phenylene group, a biphenylene group, and a naphthylene group which may each have a substituent are more preferable, and a phenylene group which may each have a substituent, A biphenylene group is more preferable, and the phenylene group which may have a substituent is most preferable.

In addition, in A in general formula (2), it does not restrict|limit as a substituent which the said divalent aromatic group may have, For example, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned. Among the substituents that such a divalent aromatic group may have, an alkyl group having 1 to 10 carbon atoms and a carbon number An alkoxy group of 1-10 is more preferable. When carbon number of the alkyl group and alkoxy group suitable as such a substituent exceeds 10 and it uses as a monomer of a polyimide, there exists a tendency for the heat resistance of the polyimide obtained to fall. Further, the number of carbon atoms of the alkyl group and the alkoxy group suitable as such a substituent is preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4 from the viewpoint of obtaining higher heat resistance than when polyimide is produced. It is more preferable, and it is especially preferable that it is 1-3. In addition, the alkyl group and the alkoxy group which can be selected as such a substituent may be linear or branched may be sufficient as them respectively.

Moreover, among these divalent aromatic groups, when polyimide is manufactured, the solubility with respect to the solvent of a polyimide becomes more excellent, and from a viewpoint of obtaining more advanced processability, the phenylene group which may have a substituent, respectively, biphenyl A phenylene group, a naphthylene group, an anthracenylene group, or a terphenylene group is preferable, and it is more preferable that they are a phenylene group, a biphenylene group, or a naphthylene group, which may each have a substituent, and a phenylene group which may each have a substituent; It is more preferable that it is a biphenylene group, and the most preferable is the phenylene group which may have a substituent.

Moreover, among these divalent aromatic groups, from the viewpoint of obtaining higher heat resistance, it is preferable that they are a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and a terphenylene group, each of which may have a substituent. It is more preferable that they are a phenylene group, a biphenylene group, a naphthylene group, or a terphenylene group which may have a substituent, and it is still more preferable that they are a phenylene group, a biphenylene group, and a naphthylene group which may have a substituent, respectively, and the most preferable It is a phenylene group which may have a substituent.

In addition, in A in General formula (2), it does not restrict|limit especially as a substituent which the said divalent aromatic group may have, For example, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned. Among the substituents that the divalent aromatic group may have, when a polyimide is prepared, the solubility of the polyimide in a solvent is more excellent, and from the viewpoint of obtaining a higher workability, an alkyl group having 1 to 10 carbon atoms, carbon number An alkoxy group of 1 to 10 is more preferable. When carbon number of the alkyl group and alkoxy group suitable as such a substituent exceeds 10, when a polyimide is prepared, there exists a tendency for the heat resistance of this polyimide to fall. In addition, the number of carbon atoms of the alkyl group and the alkoxy group suitable as such a substituent is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, from the viewpoint of obtaining higher heat resistance. to 3 are particularly preferred. In addition, the alkyl group and the alkoxy group which can be selected as such a substituent may be linear or branched may be sufficient as them respectively.

In addition, ^R4 in the said General formula (2) is 1 type selected from the group which each independently consists of a hydrogen atom and a C1-C10 alkyl group. When the number of carbon atoms of the alkyl group that can be selected as such R ⁴ exceeds 10, a sufficiently high heat resistance cannot be achieved. Further, the alkyl group that can be selected as R ⁴ is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and more preferably 1 to 6 from the viewpoint of obtaining higher heat resistance. 3 is particularly preferred. In addition, the alkyl group which can be selected as such R< ⁴ > may be linear or branched may be sufficient as it.

R ⁴ in the general formula (2) is each independently a hydrogen atom, a methyl group, an ethyl group, n - It is more preferable that they are a propyl group and an isopropyl group, It is especially preferable that they are a hydrogen atom and a methyl group. In addition, although R< ⁴ > in such Formula (2) may be the same or different, respectively, from viewpoints, such as easiness of refinement|purification, if it is the same, it is preferable. Moreover, it is especially preferable that all of some R< ⁴ > in the said General formula (2) is a hydrogen atom. As described above, when all of the substituents represented by R ⁴ in the repeating unit represented by the general formula (2) are hydrogen atoms, higher heat resistance tends to be obtained.

In addition, the alkyl group which can be selected as R< ⁵ > in the said General formula (2) is a C1-C10 alkyl group. When such carbon number exceeds 10, a sufficiently high heat resistance cannot be achieved. Further, the number of carbon atoms in the alkyl group that can be selected as R ⁵ is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, from the viewpoint of further facilitation of purification. to 3 are particularly preferred. In addition, the alkyl group which can be selected as such R< ⁵ > may be linear or branched may be sufficient as it. Moreover, as such an alkyl group, a methyl group and an ethyl group are more preferable from a viewpoint of easiness of refinement|purification.

As R ⁵ in the general formula (2), each independently hydrogen atom from the viewpoint of obtaining higher heat resistance than when polyimide is produced, easy availability of raw materials, easier purification, and the like; It is more preferable that they are a methyl group, an ethyl group, n-propyl group, or isopropyl group, and it is especially preferable that they are a hydrogen atom or a methyl group. In addition, although some R< ⁵ > in this formula may be the same or different, respectively, from a viewpoint of easiness of refinement|purification, etc., if it is the same, it is preferable.

It does not restrict|limit especially as a method for manufacturing the compound represented by such general formula (2), A well-known method can be employ|adopted suitably, For example, you may employ|adopt the method etc. which were described in International Publication No. 2015/163314.

(Compound represented by the general formula (3))

With respect to the compound represented by the general formula (3), in the general formula (3), R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group. Or, two R ⁶ bonded to the same carbon atom may become one to form a methylidene group, and R ⁷ are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. indicates.

R ⁶ in the general formula (3) each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or two R ⁶ bonded to the same carbon atom These become one to form a methylidene group.

The alkyl group which may be selected as R ⁶ in the general formula (3) is an alkyl group having 1 to 10 carbon atoms. When such carbon number exceeds 10, a sufficiently high heat resistance cannot be achieved. Further, the number of carbon atoms in the alkyl group that can be selected as R ⁶ is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, from the viewpoint of further facilitation of purification. to 3 are particularly preferred. In addition, the alkyl group which can be selected as such R< ⁶ > may be linear or branched may be sufficient as it. Moreover, as such an alkyl group, a methyl group and an ethyl group are more preferable from a viewpoint of easiness of refinement|purification.

In addition, among some R< ⁶ > in this general formula (3), two R< ⁶ > couple|bonded with the same carbon atom may become one and form a methylidene group ( ₌ CH2). That is, two R ⁶ bonded to the same carbon atom in the general formula (3) become one, and the corresponding carbon atom (a carbon atom to which two R ⁶ bonds are formed among the carbon atoms forming the norbornane ring structure). ) by a double bond as a methylidene group (methylene group).

As a plurality of R ⁶ in the general formula (3), each independently hydrogen atom, It is more preferable that they are a methyl group, an ethyl group, n-propyl group, or isopropyl group, and it is especially preferable that they are a hydrogen atom or a methyl group. In addition, although some R< ⁶ > in such a formula may be the same or different, respectively, from a viewpoint of easiness of purification, etc., if it is the same, it is preferable.

In addition, R< ⁷ > in the said General formula (3) is 1 type selected from the group which each independently consists of a hydrogen atom and a C1-C10 alkyl group. When the number of carbon atoms of the alkyl group that can be selected as R ⁷ exceeds 10, the heat resistance of the polymer is lowered. Further, the alkyl group that can be selected as R ⁷ is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and more preferably 1 to 6 from the viewpoint of obtaining higher heat resistance. 3 is particularly preferred. In addition, the alkyl group which can be selected as such R< ⁷ > may be linear or branched may be sufficient as it.

In addition, R ⁷ in the general formula (3) is each independently a hydrogen atom from the viewpoint of obtaining a higher heat resistance when the polymer is produced, easy availability of raw materials, easier purification, and the like; It is more preferable that they are a methyl group, an ethyl group, n-propyl group, and isopropyl group, It is especially preferable that they are a hydrogen atom and a methyl group. In addition, although R< ⁷ > in such Formula (3) may be the same or different, respectively, from a viewpoint of easiness of refinement|purification, etc., if it is the same, it is preferable.

Moreover, it is especially preferable that some R<^6> and R< ⁷ > in the said General formula (3) are all a hydrogen atom. As described above, when the substituents represented by R ⁶ and R ⁷ in the repeating unit represented by the general formula (3) are both hydrogen atoms, the yield of the compound is improved and a higher degree of heat resistance tends to be obtained. .

It does not restrict|limit especially as a method for manufacturing the compound represented by such general formula (3), A well-known method can be employ|adopted suitably, For example, you may employ|adopt the method etc. which were described in International Publication No. 2017/030019.

(Compound represented by the general formula (4))

It does not restrict|limit especially as a compound represented by such General formula (4), You may use a commercial item suitably. In addition, it does not restrict|limit especially as a method for manufacturing the compound represented by such general formula (4), A well-known method is employable suitably.

(Derivatives of compounds represented by the general formulas (1) to (4))

The derivatives of the compounds represented by the general formulas (1) to (4) are not particularly limited, but diester dicarboxylic acids and diester dicarboxylic acids that are modified products of the compounds represented by the general formulas (1) to (4) Acid dichloride is more preferable. That is, when a derivative of the compound represented by the general formulas (1) to (4) is used, the compound represented by the general formulas (1) to (4) is replaced with the corresponding diester dicarboxylic acid or diester dicarboxylic acid. It is preferable to use after denaturation with carboxylic acid dichloride.

It does not restrict|limit especially as a preparation method of such a derivative|guide_body, A well-known method can be employ|adopted suitably. For example, as a method for preparing a diester dicarboxylic acid suitable as a derivative of the compound represented by the general formulas (1) to (4), the compound represented by the general formulas (1) to (4) is optional. A method of obtaining the corresponding diesterdicarboxylic acid by reacting with an alcohol of Moreover, a polyimide precursor can be obtained by carrying out solution polymerization of the diester dicarboxylic acid obtained in this way with diamine in condensing agent presence. Further, as a method for preparing diester dicarboxylic acid dichloride suitable as a derivative of the compound represented by the general formulas (1) to (4), for example, a compound represented by the general formulas (1) to (4) A method of obtaining the corresponding diester dicarboxylic acid dichloride by reacting with an arbitrary alcohol to obtain a diester dicarboxylic acid and then reacting with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) may be employed. have. Moreover, a polyimide precursor can be obtained by stirring these diester dicarboxylic acid dichloride and diamine in the range of -20 degreeC - 100 degreeC (more preferably 5-80 degreeC) for 1 to 72 hours. Thus, the obtained polyimide precursor tends to be more excellent in storage stability than the case where the compound represented by the said General formula (1)-(4) is used as it is.

<About diamine>

As such diamine, what is necessary is just to be able to use it for manufacture of a polyimide, It does not restrict|limit, An aliphatic diamine or an aromatic diamine may be sufficient. As such diamine, an aromatic diamine is preferable from the viewpoint of heat resistance and convenience of polymerization method, and among them, the following general formula (ii):

HY ¹ NR ¹⁰ -NY ² H (ii)

[In formula (ii), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² each independently represent one selected from the group consisting of a hydrogen atom and an alkylsilyl group having 3 to 9 carbon atoms]

The aromatic diamine represented by is more preferable.

The arylene group which may be selected as R ¹⁰ in the general formula (ii) has 6 to 50 carbon atoms, but the arylene group preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, more preferably 12 to 50 carbon atoms. 20 is more preferable. If the number of carbon atoms is less than the lower limit, heat resistance tends to decrease when the polyimide obtained is prepared, while when the carbon number exceeds the upper limit, the solubility of the polyimide in a solvent tends to decrease when the polyimide is prepared.

As R ¹⁰ in the general formula (ii), the following general formulas (a) to (d) from the viewpoint of obtaining higher heat resistance and mechanical strength when polyimide is prepared:

[In formula (c), R ¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a hydroxyl group and a trifluoromethyl group, and in the formula (d), Q is 9,9-flu an orenylidene group; Formula: -O-, -S-, -CO-, -CONH-, -SO ₂ -, -C(CF ₃ ) ₂ -, -OC ₆ H ₄ -O-, -C(CH ₃ ) ₂ -, -CH ₂ -, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -C(CF ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -, -OC ₆ H ₄ -C ₆ H ₄ -O-, - groups represented by CONH-C ₆ H ₄ -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -C ₆ H ₄ -, and -OC ₆ H ₄ -O-, -COO-, -OCO-; and the general formula (e):

(In formula (e), each R ^a independently represents any one of an alkyl group having 1 to 10 carbon atoms, a phenyl group and a tolyl group, and y represents an integer of 1 to 18)

represents one selected from the group consisting of a group represented by

It is preferable that it is at least 1 sort(s) of the group represented by.

As R ¹¹ in this general formula (c), a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is more preferable from a heat resistant viewpoint, and a hydrogen atom is especially preferable. Moreover, as R< ¹¹ > in General formula (c), it is more preferable that they are a methyl group, a hydroxyl group, or a trifluoromethyl group from a viewpoint of a linear expansion coefficient.

In addition, in the group represented by the general formula (e) which may be selected as Q in the general formula (d), R ^a is each independently any one of an alkyl group having 1 to 10 carbon atoms, a phenyl group and a tolyl group. When carbon number of such an alkyl group exceeds the said upper limit, when a polyimide is prepared, there exists a tendency for the heat resistance and transparency of this polyimide to fall. As such R ^a , it is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group or a tolyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. Moreover, y in the said General formula (e) represents the integer of 1-15, It is more preferable that it is 3-12, It is more preferable that it is 5-10. Moreover, when y is less than the said lower limit, there exists a tendency for mechanical strength to fall, on the other hand, when it exceeds the said upper limit, when a polyimide is prepared, there exists a tendency for the heat resistance and transparency of the polyimide to fall.

Further, as Q in the general formula (d), a 9,9-fluorenylidene group, or a formula: -CONH-, -OC ₆ H ₄ -O-, -O-, -C(CH ₃ ) ₂ -, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -CH ₂ -, -OC A group represented by ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -SO ₂ -, -OCO- or -COO- is preferred. and 9,9-fluorenylidene group, or a formula: -CONH-, -CH ₂ -, -OC ₆ H ₄ -O-, -OC ₆ H ₄ -C ₆ H ₄ -O-, -SO ₂ - , -OCO-, -COO- or -O- is particularly preferable, and a 9,9-fluorenylidene group, or a formula: -CONH-, -SO ₂ -, -OCO-, -COO-, - The group represented by CH ₂ - or -O- is most preferred. Moreover, as Q in the said general formula (d), it is preferable that it is a group represented by the said general formula (e) from a viewpoint of adhesiveness and laser releasability, From a viewpoint of a linear expansion coefficient and heat resistance, formula: -OCO-, -COO- , the group represented by -CONH- is preferable.

Further, as such R ¹⁰ , 4,4'-diaminobenzanilide (DABAN), 4,4'-, from the viewpoint that it becomes possible to obtain a polyimide having a better balance at a sufficient level with heat resistance, transparency, and mechanical strength. Diaminodiphenyl ether (DDE), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 9,9'-bis(4-aminophenyl)fluorene (FDA), p-diaminobenzene ( PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (alias: m-tolidine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4-amino Benzoic acid (BAAB), 4,4'-bis(4-aminobenzamide)-3,3'-dihydroxybiphenyl (BABB), 3,3'-diaminodiphenylsulfone (3,3'-DDS) ), and at least one aromatic diamine selected from the group consisting of 4,4'-diaminodiphenylsulfone (4,4'-DDS), a divalent group (arylene group) excluding two amino groups is preferable, 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 9,9'-bis Two amino groups from at least one aromatic diamine selected from the group consisting of (4-aminophenyl)fluorene (FDA), p-diaminobenzene (PPD) and 4-aminophenyl-4-aminobenzoic acid (BAAB) It is more preferably a divalent group (arylene group) except for 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), and 2,2'-bis(trifluoro It is more preferable that it is a divalent group (arylene group) obtained by removing two amino groups from at least one aromatic diamine selected from the group consisting of romethyl)benzidine (TFMB).

The alkylsilyl group which may be selected as Y ¹ , Y ² in the general formula (ii) has 3 to 9 carbon atoms. The alkylsilyl group that can be selected as such Y ¹ and Y ² is more preferably a trimethylsilyl group or a t-butyldimethylsilyl group.

Moreover, it is more preferable that both Y< ¹ > and Y< ² > in this formula (ii) are a hydrogen atom from a viewpoint of the simplicity of polyimide synthesis|combination. That is, as an aromatic diamine represented by said Formula ( _ii ), the aromatic diamine represented by Formula: ^H2NR10 _- NH2 is more preferable.

It does not restrict|limit especially as an aromatic diamine represented by such _a formula: ^H2NR10 _- NH2, A well-known thing can be used suitably, You may use a commercially available thing suitably. Examples of the aromatic diamine include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenyl Ethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-dia minodiphenyl ether, 2,2-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[ 4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl , 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4-aminophenyl)fluorene, p-diaminobenzene, m-diaminobenzene, o-dia Minobenzene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3 '-diaminobiphenyl, 2,2'-diaminobiphenyl, 3,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene , 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline , 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminodiphenylsulfone, 4,4' -diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4 ,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 9,9'-bis(4-aminophenyl)fluorene, o-tolidinesulfone, 2,3,5,6-tetramethyl -1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 1,5-bis(4-aminophenoxy)pentane, 2,2-bis(4-aminophenoxyphenyl) Hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 4-aminophenyl-4-aminobenzoic acid, 4,4'-bis(4-aminobenzamide)-3,3'-dihydro Roxybiphenyl etc. are mentioned. In addition, you may use these aromatic diamine individually by 1 type or in combination of 2 or more type.

In the case of using two or more aromatic diamines in combination, 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis(trifluoro Romethyl) benzidine (TFMB), 9,9'-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD), 2,2'-dimethyl-4,4'-diaminobi Phenyl (alias: m-tolidine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4,4'-bis(4-aminobenzamide) -3,3'-dihydroxybiphenyl (BABB), 3,3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'- DDS) is preferably used, and 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis(trifluoro Romethyl) benzidine (TFMB), 9,9'-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD), 4-aminophenyl-4-aminobenzoic acid (BAAB), 3, It is preferable to use at least two types selected from 3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'-DDS). In addition, when two or more aromatic diamines are used in combination, a combination of 4,4'-diaminobenzanilide (DABAN) and 4,4'-diaminodiphenyl ether (DDE), 4,4'-diaminobenz a combination of anilide (DABAN) with 2,2'-bis(trifluoromethyl)benzidine (TFMB), a combination of 4,4'-diaminobenzanilide (DABAN) with p-diaminobenzene (PPD), 3, Combination of 3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'-DDS), 4-aminophenyl-4-aminobenzoic acid (BAAB) at least one selected from a combination of 2,2'-bis(trifluoromethyl)benzidine (TFMB) and a combination of 4-aminophenyl-4-aminobenzoic acid (BAAB) and p-diaminobenzene (PPD) It is more preferable to include a combination.

Further, at least one of the aromatic diamines represented by the general formula (ii) (HY ¹ NR ¹⁰ -NY ² H: Y ¹ and Y ² ) other than the aromatic diamine represented by the formula: H ₂ NR ¹⁰ -NH ₂ is a hydrogen atom Examples of the silylated diamine obtained by reacting the aromatic diamine represented by the formula: H ₂ NR ¹⁰ -NH ₂ with a silylating agent as the other) are exemplified. Examples of such silylated diamine include bis(4-trimethylsilylaminophenyl)ether and 1,4-bis(trimethylsilylamino)benzene. Examples of the silylating agent include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane.

In addition, the method in particular for manufacturing such a diamine is not restrict|limited, either, A well-known method can be employ|adopted suitably. In addition, as such diamine, you may use a commercial item suitably.

<About polymer>

Polyimide precursor resin which concerns on this invention is a polymer of the said diamine and at least 1 sort(s) selected from the group which consists of tetracarboxylic dianhydride which has two norbornane skeletons in the said molecule|numerator, and its derivative(s). As such a polymer, it is more preferable to have at least 1 sort(s) of repeating unit selected from the group which consists of repeating units represented by the said general formula (I)-(III).

(About the repeating unit represented by the general formula (I))

With respect to the repeating unit represented by the general formula (I), X ¹ in the general formula (I) is a tetravalent group represented by the general formulas (I-1) to (I-3). R ¹ , R ² , R ³ , and n in the general formula (I-1) have the same meaning as R ¹ , R ² , R ³ , n in the general formula (1), and their suitability is also the above general formula (1). ) in R ¹ , R ² , R ³ , and n), and A, R ⁴ , and R ⁵ in the general formula (I-2) are A, R ⁴ , R ⁵ in the general formula (2). It has the same meaning as (its suitable also has the same meaning as A, R ⁴ , and R ⁵ in the above general formula (2)). In addition, R ^{6 and R 7 in the general formula (I-3) have the same meaning as R 6 , R 7 in the general} formula ( ³ ). have the same meaning).

In addition, X ¹ in the general formula (I) is a tetravalent group (organic group) represented by the general formulas (I-1) to (I-3) as described above, and the general formula (I-1) Symbols *1 to *4 in (I-3) to (I-3) indicate that the bond to which the symbol is attached is any of the four bonds bonded to X ¹ in the formula (1), respectively. By using the tetravalent organic group represented by such general formulas (I-1) to (I-3) for the site of X ¹ , it becomes possible to achieve higher levels of transparency, heat resistance and dimensional stability. In addition, among the bonds to which these symbols *1 to *4 are attached, any of the bonds to which the symbols *1 to *2 are attached is a bond bonded to the formula in the general formula (I): -COOY ¹ , and any of the bonds to which the symbols *3 to *4 are attached is a bond bonded to the formula in the general formula (I): -COOY ² , or any of the bonds to which the symbols *1 to *2 are attached A bond which is a bond bonded to -COOY ² in the formula (I), and any of the bonds to which the symbols *3 to *4 are attached to the formula in the general formula (I): -COOY ¹ It is preferable that it is a hand.

In addition, R< ¹⁰ > in the said general formula (I) represents a C6-C50 arylene group. R ¹⁰ in the general formula (I) is the same as R ¹⁰ in the general formula (ii), and its suitability is the same as that of R ⁴ in the general formula (ii).

Y ¹ and Y ² in the general formula (I) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), or an alkylsilyl group having 3 to 9 carbon atoms. Such Y ¹ and Y ² can be changed by appropriately changing the type of the substituent and the introduction rate of the substituent by appropriately changing the production conditions (the type of diamine to be used, etc.). When both of these Y ¹ and Y ² are hydrogen atoms (the so-called repeating unit of polyamic acid), the production tends to be easier when a polyimide is produced using this.

Moreover, when Y< ¹ >, Y< ² > in General formula (I) is a C1-C6 (preferably C1-C3) alkyl group, there exists a tendency for the storage stability of polyimide precursor resin to become more excellent. Further, when Y ¹ and Y ² are an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), Y ¹ and Y ² are more preferably a methyl group or an ethyl group.

Moreover, when Y< ¹ >, Y< ² > in General formula (I) is a C3-C9 alkylsilyl group, there exists a tendency for the solubility of polyimide precursor resin to become more excellent. Thus, when Y ¹ , Y ² is an alkylsilyl group having 3 to 9 carbon atoms, Y ¹ , Y ² is more preferably a trimethylsilyl group or a t-butyldimethylsilyl group.

In addition, with respect to Y ¹ , Y ² in the repeating unit represented by the general formula (I), the introduction rate of groups other than hydrogen atoms (alkyl group and/or alkylsilyl group) is not particularly limited, Y ¹ , Y ² When at least a part of these is an alkyl group and/or an alkylsilyl group, 25% or more (more preferably 50% or more, still more preferably 75% or more) of the total amount of Y ¹ and Y ² in the entire repeating unit is an alkyl group and/or Or it is preferable to set it as an alkylsilyl group (in this case, Y ¹ and Y ² other than an alkyl group and/or an alkylsilyl group become a hydrogen atom). In addition, when 25% or more of the total amount of each of Y ¹ and Y ² in the repeating unit represented by the general formula (I) is an alkyl group and/or an alkylsilyl group, the storage stability of the polyimide precursor tends to be more excellent. have.

The repeating unit represented by the general formula (I) is a compound represented by the general formulas (1) to (3) (tetracarboxylic dianhydride) and diester dicarboxylic acids and diesters which are derivatives of these compounds It can form easily by making at least 1 sort(s) of dicarboxylic acid dichloride react with the aromatic diamine (HY ¹ NR ¹⁰ -NY ² H) represented by the said General formula (ii). In this way, by appropriately selecting the monomer component according to the intended design, it is possible to form a polymer having a repeating unit represented by the general formula (I). From this point of view, the polymer (polyimide precursor resin) having a repeating unit represented by the general formula (I) is a compound represented by the general formulas (1) to (3) (tetracarboxylic dianhydride) and those It can be said that it is a polymer of at least one type of diester dicarboxylic acid and diester dicarboxylic acid dichloride which are derivatives of a compound, and the aromatic diamine (HY ¹ NR ¹⁰ -NY ² H) represented by the said general formula (ii). .

(with respect to the repeating unit represented by the general formulas (II) to (III))

With respect to the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III), R ¹⁰ in these formulas (II) to (III) represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkylsilyl group having 3 to 9 carbon atoms. R ^{10 , Y 1 , and Y 2 in the general formula (II) have the same meaning as R 10 , Y 1 , Y 2 in the general} formula (I) ^{. 1} , has the same meaning as Y ² ).

The repeating units represented by the general formulas (II) to (III) include the compound represented by the general formula (4) (tetracarboxylic dianhydride) and the diester dicarboxylic acid and diester derivatives of the compound It can form easily by making at least 1 sort(s) of dicarboxylic acid dichloride and the aromatic diamine (Y2NR10 _- ^NY2 ) represented by the said General formula ( _ii ) react. In this way, by appropriately selecting the monomer component according to the intended design, it is possible to form a polymer having a repeating unit represented by the general formulas (II) to (III). From this point of view, the polymer (polyimide precursor resin) having repeating units represented by the general formulas (II) to (III) is a compound represented by the general formula (4) and a diester dicarr which is a derivative of the compound. It can be said that it is a polymer of at least 1 sort(s) of an acid and diester dicarboxylic acid dichloride, and the aromatic diamine (HY ¹ NR ¹⁰ -NY ² H) represented by the said general formula (ii).

Further, the polyimide precursor resin (polymer) according to the present invention contains at least one repeating unit selected from the group consisting of repeating units represented by the general formulas (I) to (III) as described above. polymers are preferred. Further, among the repeating units represented by the general formulas (I) to (III), from the viewpoint of dimensional stability of the polyimide obtained, X ¹ in the formula (I) is a tetravalent group represented by the general formula (I-1). A repeating unit is preferable, and from the viewpoint of solvent solubility of the polyimide obtained, a repeating unit in which X ¹ in the formula (I) is a tetravalent group represented by the general formula (I-2) is preferable, and the obtained polyimide has low dielectric properties A repeating unit in which X ¹ in the formula (I) is a tetravalent group represented by the general formula (I-3) is preferred from the viewpoint of In addition, from the viewpoint of the mechanical properties of the polyimide obtained, among the repeating units represented by the general formula (I), the repeating unit in which X ¹ in the formula (I) is a tetravalent group represented by the general formula (I-1) is particularly desirable.

Moreover, as a repeating unit represented by the said general formula (I), it is more preferable from ^a viewpoint of the simplicity of imidation that it is a repeating unit (a repeating unit of polyamic acid) in which ^both Y1 and Y2 are hydrogen atoms.

In addition, when this polyimide precursor resin (polymer) contains the repeating unit represented by the said general formula (I)-(III), it may contain, for example, 1 type selected from the group which consists of these repeating units. Or it may contain 2 or more types of repeating units selected from the group which consists of these repeating units.

In addition, when this polyimide precursor resin (polymer) contains the repeating units represented by the said general formulas (I) to (III), the total amount (content amount) of these repeating units represented by these general formulas (I) to (III) of 20 to 100 mol% (more preferably 30 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 50 to 100 mol%, particularly preferably 60 to 100 mol%) is preferred. Further, with respect to the total amount (total amount) of the repeating units represented by the general formulas (I) to (III), the lower limit of the numerical range is more preferably 70 mol%, still more preferably 80 mol%, and 90 Most preferably, it is mol%. When the total amount (total amount) of such repeating units is less than the above lower limit, it tends to be difficult to achieve a higher level of heat resistance based on the glass transition temperature (Tg).

In addition, the polyimide precursor resin suitable as the polyimide precursor resin according to the present invention and containing any of the repeating units represented by the above general formulas (I) to (III) further contains other repeating units depending on the use, etc. may be doing It does not restrict|limit especially as such another repeating unit, A well-known repeating unit etc. which can be used as a repeating unit of polyimide precursor resin are mentioned. As such other repeating units, for example, tetracarboxylic dianhydrides other than those represented by the general formulas (1) to (4) are used, and these are represented by the above formula: HY ¹ NR ⁴ -NY ² H It is good also as a repeating unit etc. which are formed by making it react with the aromatic diamine used.

It is not limited to the tetracarboxylic dianhydride which has two norbornane skeletons in a molecule|numerator as such another tetracarboxylic dianhydride, The well-known tetracarboxylic dianhydride which can be used for preparation of a polyamic acid and a polyimide. Water can be used suitably, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride , 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-fura nyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetra Hydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuryl)-3-methyl Aliphatic such as -3-cyclohexene-1,2-dicarboxylic acid dianhydride and bicyclo[2,2,2]-octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride or alicyclic tetracarboxylic dianhydride; Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5 ,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-dimethyldi Phenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylsulfide 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, 2,2',3, 3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride and aromatic tetracarboxylic dianhydrides such as bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride. .

As such other repeating units, from the viewpoint that it becomes possible to obtain a cured product having properties such as heat resistance, transparency, mechanical strength and solvent solubility at a sufficient level and in a better balance when a polyimide is finally formed, among them, 1 ,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-bi Phenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride and 4,4'-(2,2-hexafluoro A repeating unit formed by reacting at least one tetracarboxylic dianhydride selected from the group consisting of leoisopropylidene)diphthalic dianhydride with an aromatic diamine represented by the formula: H ₂ NR ⁴ -NH ₂ 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride at least one selected from the group consisting of tetracarboxylic acid dianhydride It is more preferable that it is a repeating unit formed by making carboxylic dianhydride react with the aromatic diamine represented by _the said Formula: ^H2NR4 _- NH2.

Moreover, when such polyimide precursor resin is a polyamic acid, it is preferable that the intrinsic viscosity [η] 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] of this polyamic acid is less than 0.05 dL/g, when a film-like polyimide is produced using it, the resulting film tends to become brittle, while when it exceeds 3.0 dL/g, When a viscosity is too high and workability falls, for example, when a film is manufactured, it becomes difficult to obtain a uniform film. In addition, the intrinsic viscosity [η] of such a polyamic acid 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 at a concentration of 0.5 g/dL to obtain a measurement sample (solution). 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 employed as the intrinsic viscosity [η]. In addition, as such a kinematic viscometer, the automatic viscosity measuring apparatus (trade name "VMC-252") manufactured by Rigo Corporation is used.

In the method for producing such a polyimide precursor resin (polymer), in order to form a polymer of tetracarboxylic dianhydride and diamine as described above, tetracarboxylic dianhydride and diamine as described above may be used, and known The preparation method (polymerization method) of the used polyimide precursor resin (polymer) can be used suitably. For example, when using the compound represented by the said General formula (1) as said tetracarboxylic dianhydride, the method for manufacturing the polyamic acid described in International Publication No. 2011/099518, etc. are suitably employ|adopted In the case of using the compound represented by the general formula (2) as the tetracarboxylic dianhydride, the method for producing a polyamic acid described in International Publication No. 2015/163314 may be appropriately employed. do. Thus, according to the kind of monomer (the said tetracarboxylic dianhydride and the said diamine) to be used, you may prepare polyimide precursor resin (polymer) using polymerization conditions etc. which are described in well-known literature suitably.

<Additional compound (second component)>

The additive compound (second component) according to the present invention contains a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in the molecule: It is at least 1 sort(s) of compound selected from the group which consists of a quaternary phosphorus compound containing the structure represented by C-P, and a quaternary amine compound.

Examples of such tertiary phosphorus compounds include triphenylphosphine, triparatolylphosphine, tritertiarybutylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, and 1,4-bisdiphenylphosphine. butane and the like. As such a tertiary phosphorus compound, triphenylphosphine, triparatolylphosphine, and tricyclohexylphosphine are more preferable from a viewpoint of the mechanical characteristic of the polyimide obtained, and triphenylphosphine and triparatolylphosphine are still more preferable. and triphenylphosphine is particularly preferred.

Moreover, as such a quaternary phosphorus compound, benzyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide, normal butyl triphenyl phosphonium chloride, normal butyl triphenyl phosphonium dicyanamide phenacetyl triphenyl phosphonium is, for example, Chloride, hexyltriphenylphosphonium bromide, octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, benzyltriphenylphosphonium bromide, 2-methylbenzyl and quaternary phosphorus salts such as triphenylphosphonium bromide, methyltriphenylphosphonium iodide, phenacetyltriphenylphosphonium chloride, aryltriphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate. As such a quaternary phosphorus compound, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride, tetraphenylphosphonium bromide from the viewpoints of the mechanical properties of the resulting polyimide and solubility in solvents. , tetraphenylphosphonium tetraphenylborate is more preferable, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate are still more preferable, benzyltriphenylphosphonium chloride, benzyltriphenylphospho Ponium bromide is particularly preferred.

Moreover, as said quaternary amine compound, For example, the organic acid salt of 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) (For example, the octylic acid salt of DBU, p of DBU) -Toluenesulfonate, DBU formate, DBU orthophthalate, etc.), DBU phenolic resin salt, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) phenolic resin salt, acid child and quaternary amine salts such as U-CAT 5002 from Proze, tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium hydrochloride, tetraethylammonium hydrochloride, and tetramethylammonium tetraphenylborate. Among these quaternary amine compounds, from the viewpoint of obtaining higher heat resistance and mechanical strength when polyimide is produced, an organic acid salt of DBU is preferable, and a phenol salt of DBU and an octylate salt of DBU are more preferable.

In addition, among these additive compounds (second component), when polyimide is prepared, flame retardancy can be imparted to polyimide, storage stability of polyimide precursor solution is not affected, etc. Compounds are particularly preferred, and triphenylphosphine is most preferred. In addition, as such a compound (2nd component), you may use individually by 1 type, or may use it in combination of 2 or more type.

<Solvent (third component)>

It does not restrict|limit especially as a solvent (3rd component) which concerns on this invention, For example, what can be used for the resin solution of polyamic acid can be used suitably. Examples of such a solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, γ -Caprolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, tetramethylurea, 1, aprotic polar solvents such as 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, and pyridine; phenolic solvents such as m-cresol, p-cresol, xylenol, phenol, and halogenated phenol; ether solvents such as tetrahydrofuran, dioxane, cellosolve, and glyme; aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as cyclopentanone and cyclohexanone; Nitrile solvents such as acetonitrile and benzonitrile; Acetate ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and propylene glycol methyl acetate; methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; Ketone solvents, such as methyl ethyl ketone and acetone, etc. are mentioned.

In addition, as such a solvent, from the viewpoint of solubility, film-forming property, productivity, industrial availability, the presence or absence of existing equipment, and price, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butyro Lactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferred, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butyrolactone , tetramethylurea is more preferable, and N,N-dimethylacetamide, N-methyl-2-pyrrolidone and tetramethylurea are particularly preferable. In addition, you may use these solvent individually by 1 type or in combination of 2 or more type.

Moreover, the polyimide precursor resin composition of this invention may contain other components other than the said polyimide precursor resin (1st component), the said addition compound (2nd component), and the said solvent (3rd component). Although it does not restrict|limit especially as these other components, For example, antioxidant (phenol type, phosphite type, thioether type, etc.), ultraviolet absorber, hindered amine type light stabilizer, nucleating agent, resin additive (filler, talc, glass fiber, etc.) ), a flame retardant, a workability improving agent, a lubricant, and the like. Moreover, it does not restrict|limit especially as these other components (antioxidant etc.), A well-known thing can be used suitably, and a commercially available thing may be used.

<About composition, etc. of the composition>

The polyimide precursor resin composition of this invention contains the said polyimide precursor resin (1st component), the said addition compound (2nd component), and the said solvent (3rd component).

In such a polyimide precursor resin composition, the content of the polyimide (first component) and the content of the additive compound (second component) are not particularly limited, but the content of the second component with respect to 100 parts by mass of the first component is It is preferable that it is 0.1-25 mass parts, and it is more preferable that it is 0.5-15 mass parts. When the content of the additive compound (second component) is less than the above lower limit, the mechanical strength of the polyimide tends to decrease when polyimide is produced, whereas when the above upper limit is exceeded, polyimide is produced when polyimide is produced. There is a tendency for the heat resistance of the mid to fall.

Moreover, content in particular of such a solvent is although it does not restrict|limit, It is preferable that it is 50-99 mass %, It is more preferable that it is 50-90 mass %, It is more preferable that it is 60-90 mass %, It is 70-90 mass % It is particularly preferred. When the content of the solvent is less than the above lower limit, it tends to be difficult to make the polyimide precursor resin sufficiently dissolved in the solvent, and it tends to be difficult to obtain a uniform varnish composition. On the other hand, when the above upper limit is exceeded, the polyimide precursor resin When the resin is imidized and cured to produce a polyimide, the mechanical strength of the polyimide tends to decrease.

<About the method for producing the composition>

The method for producing the polyimide precursor resin composition of the present invention is not particularly limited, and the polyimide precursor resin (first component), the additive compound (second component), and the solvent (third component) are mixed. It is not particularly limited as long as it is a method capable of producing a polyimide precursor resin composition containing at least one selected from the group consisting of tetracarboxylic dianhydrides other than tetracarboxylic dianhydrides having two norbornane skeletons in the molecule) and derivatives thereof; The diamine (preferably a compound represented by the above formula (ii) (HY ¹ NR ¹⁰ -NY ² H), more preferably a compound represented by the formula: H ₂ NR ¹⁰ -NH ₂ ) is reacted (a polymerization reaction advancing) to form a polymer of the diamine with at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivatives, and in the above step, the tetracarboxylic dianhydride and any step in reacting the diamine with at least one selected from the group consisting of a derivative thereof [before the reaction, during the reaction (in addition, during the reaction referred to herein), consisting of the tetracarboxylic dianhydride and its derivatives. In the case of further advancing the polymerization reaction using the reaction solution obtained after reacting at least one selected from the group and the diamine once, the step before or during the polymerization reaction using the reaction solution is also included), after the reaction any step], a method including a step of adding the additive compound (hereinafter, this method is simply referred to as "method (I)" for convenience) can be suitably employed. In addition, the tetracarboxylic dianhydride and its derivative(s), diamine, solvent, and addition compound used in this method (I) are the same as those previously described (its suitable thing is also the same).

In this method (I), in the presence of a solvent, in the presence of a solvent, Specific conditions for reacting the diamine with at least one selected from the group consisting of) and derivatives thereof are not particularly limited, and the conditions are adjusted so that the polymerization reaction proceeds according to the type of component used. Just set it appropriately. Moreover, as this method (I), at least 1 sort(s) selected from the group which consists of said tetracarboxylic dianhydride and its derivative(s), it is a compound represented by the said General formula (1) - (4) (other tetramethyls as needed). The presence of the solvent by using at least one selected from the group consisting of carboxylic acid dianhydride) and derivatives thereof, and using the aromatic diamine represented by the general formula (ii) as the diamine. Hereinafter, at least one selected from the group consisting of the compounds represented by the general formulas (1) to (4) and derivatives thereof and the aromatic diamine represented by the general formula (ii) are reacted to obtain a first reaction solution. a polyimide precursor resin having at least one repeating unit selected from the group consisting of repeating units represented by the general formulas (I) to (III) by adding the additive compound to the reaction solution; It is preferable to employ|adopt method (I-1) including the 2nd process of obtaining the polyimide precursor resin composition containing an additive compound and the said solvent.

In addition, as in this method (I-1), in the step of applying the varnish to the substrate and forming a film by adding the additive compound in the second process after the polymerization reaction is performed once in the first process, the additive compound It becomes possible to further improve the molecular weight of polyimide using As such, in the case of obtaining a polyimide film using the additive compound in the film forming step, in the presence of the solvent, selected from the group consisting of the compounds represented by the general formulas (1) to (4) and their derivatives. When at least one kind is reacted with the aromatic diamine represented by the general formula (ii) to obtain a polyimide film without using the additive compound (when the additive compound is not used in any step of preparing the polyimide) ), it is advantageous in that the obtained polyimide film has excellent mechanical properties. Hereinafter, method (I-1) suitable as such method (I) will be described.

First, a 1st process is demonstrated. The first step is a step of reacting at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivatives with the aromatic diamine in the presence of a solvent to obtain a reaction solution containing a polyimide precursor resin. In addition, "at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof" used in this first step is composed of the compounds represented by the general formulas (1) to (4) and their derivatives. At least 1 type selected from the group may be included, and at least 1 type selected from the group which consists of other tetracarboxylic dianhydride and its derivative(s) other than that may be included as needed.

Although the solvent mentioned above can be used suitably as a solvent used for such a 1st process, Especially, it is preferable that it is a solvent which can melt|dissolve both the said tetracarboxylic dianhydride and the said aromatic diamine. These solvents may be used individually by 1 type or in mixture of 2 or more types.

In addition, in this method, the amount of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof (component reacted with the aromatic diamine represented by the general formula (ii)) used (the above general formula ( The total amount of the compounds represented by 1) to (4), other tetracarboxylic dianhydrides and derivatives thereof), and the amount of the aromatic diamine represented by the above general formula (ii) (formula: HY ¹ NR ⁴ - The ratio of the total amount of the compound represented by NY ² H) is not particularly limited, but when the above derivative is used, it is assumed (converted) that the derivative is tetracarboxylic dianhydride before induction, the aromatic diamine is All acid anhydrides in the tetracarboxylic dianhydride used in the reaction (when the above derivative is used, it is assumed that all of the derivatives are tetracarboxylic dianhydride before induction (before modification)) with respect to 1 equivalent of the amino group having It is preferable to set it as the quantity used as 0.5-2 equivalents, and it is more preferable to set it as 0.8-1.2 equivalents of groups. When at least one selected from the group consisting of such tetracarboxylic dianhydride and derivatives thereof and the aromatic diamine are used in a suitable ratio below the lower limit, the polymerization reaction does not proceed efficiently and a high molecular weight polyamic acid cannot be obtained. On the other hand, when the above upper limit is exceeded, polyamic acid having a high molecular weight tends not to be obtained similarly to the above.

In addition, the usage-amount of the solvent used in the said 1st process is an amount of at least 1 sort(s) selected from the group which consists of tetracarboxylic dianhydride used for reaction and its derivative(s) (the said General formula (1) - (4) The total amount of the represented compound, the other tetracarboxylic dianhydrides and their derivatives) and the amount of the aromatic diamine (the total amount of the compound represented by the formula: HY ¹ NR ⁴ -NY ² H) (reactant [substrate] ] is 1 to 80 mass % (more preferably 5 to 50 mass %) based on the total amount of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, aromatic diamine, and solvent It is preferably sheep. If the amount of the solvent used is less than the above lower limit, it tends to be impossible to efficiently obtain polyamic acid. On the other hand, if the amount exceeds the above upper limit, stirring becomes difficult due to increase in viscosity, and there is a tendency that a high molecular weight product cannot be obtained.

Further, in the first step, the reaction temperature at the time of reacting the aromatic diamine with at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivatives is a temperature at which these compounds can be reacted. Although it does not restrict|limit especially if it adjusts suitably, It is preferable to set it as -20-100 degreeC (more preferably 5-80 degreeC).

Further, in the first step, as a method of reacting at least one selected from the group consisting of tetracarboxylic dianhydride and its derivatives with the aromatic diamine, from the group consisting of tetracarboxylic dianhydride and its derivatives A method capable of conducting a polymerization reaction of at least one selected type with an aromatic diamine can be appropriately used and is not particularly limited, but for example, at atmospheric pressure, in an inert atmosphere such as nitrogen, helium, or argon, at the reaction temperature, It is preferable to employ|adopt the method of adding the said tetracarboxylic dianhydride and the said aromatic diamine in a solvent, and making it react for about 1 to 72 hours after that. If the reaction temperature or reaction time is less than the above lower limit, the molecular weight of the polyimide precursor tends not to be sufficiently improved. On the other hand, if it exceeds the above upper limit, depolymerization of the polyimide precursor proceeds and the molecular weight tends to decrease. In this way, the said reaction liquid can be obtained by making the said tetracarboxylic dianhydride and the said aromatic diamine react in a 1st process.

In the method (I-1), in the second step, the addition compound is added to the reaction solution obtained in the first step.

In this way, by adding the addition compound (second component) to the reaction solution in the second step, at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivatives (the general formula (1) ) to the compounds represented by (4) and other tetracarboxylic dianhydrides and derivatives thereof added as needed), and an aromatic diamine represented by the general formula (ii) (the formula: HY ¹ NR ⁴ -NY ² ) Polyimide having at least one repeating unit selected from the group consisting of repeating units represented by the general formulas (I) to (III), which is a polymer of at least one selected from the group consisting of compounds represented by H). It becomes possible to obtain the polyimide precursor resin composition containing a precursor resin, the said addition compound, and the said solvent.

Moreover, when the polyimide precursor resin composition obtained in this way is heated, it becomes possible to heat the polyimide precursor resin in the presence of the said additive compound (the said 2nd component) and a solvent, In the heating process, the said additive compound (the said 2nd component) Since the second component) acts as a catalyst for accelerating the reaction, it is also possible to improve the molecular weight of the finally obtained polyimide.

In addition, the usage-amount of this addition compound (the said 2nd component) is at least 1 sort(s) selected from the group which consists of said tetracarboxylic dianhydride and its derivative(s) used in method (I-1) (the said general formula ( (total amount of the compounds represented by 1) to (4) and other tetracarboxylic dianhydrides and derivatives thereof added as necessary) and the aromatic represented by the above general formula (ii) used in method (I-1) With respect to the total amount of the diamine amount (the total amount of the compound represented by Y ₂ NR ⁴ -NY ₂ ) and the amount of the additive compound (the second component) used in the method (I-1), the additive compound It is preferable that it is the quantity used as 0.1-30 mass %, and it is more preferable that it is the quantity used as 0.5-10 mass % of ratio (addition amount). If the content of such an additive compound (the second component) is less than the lower limit, it becomes difficult to improve the molecular weight of the polyimide in the case of forming a polyimide using the obtained polyimide precursor resin composition, and such a composition is used. The heat resistance and mechanical strength of the polyimide tend to decrease even when the polyimide is produced by using is no longer obtained, and various physical properties of the obtained polyimide tend to decrease. In addition, in order to adjust the ratio (addition amount) of the said addition compound, you may add a solvent again simultaneously when adding an addition compound.

In this way, a polyimide precursor resin having at least one repeating unit selected from the group consisting of repeating units represented by the general formulas (I) to (III), the polyimide precursor resin, the additive compound, and the solvent. A mid precursor resin composition can be obtained.

Further, in this method (I-1), when the tetracarboxylic dianhydride is used and the compound represented by the formula: H ₂ NR ⁴ -NH ₂ is used as the aromatic diamine, the general formula Contains polyamic acids having at least one repeating unit selected from the group consisting of repeating units represented by (I) to (III), and wherein Y ¹ and Y ² in the general formula of the repeating unit are both hydrogen atoms. A polyimide precursor resin composition containing the polyimide precursor resin to be used, the additive compound, and the solvent can be obtained.

As mentioned above, although the method for producing the polyimide precursor resin composition of the present invention has been described based on methods (I) and (I-1) which are suitable methods thereof, the method for producing the polyimide precursor resin composition of the present invention is not limited to the above method, polyimide precursor resin which is a polymer of diamine and at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule; Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by C-P, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by C-P; and at least one additive compound selected from the group consisting of quaternary amine compounds; If it is a method which can obtain the polyimide precursor resin composition containing a solvent, it can employ|adopt suitably.

Moreover, the polyimide precursor resin composition of this invention obtained by doing in this way uses this as a varnish (resin solution) for polyimide preparation, and imidizes the said polyimide precursor resin composition, The polyimide resin composition (polyimide and the said composition containing an additive compound) can be obtained.

The method in particular for obtaining such a polyimide resin composition is not restrict|limited, A well-known method which can imidate the polyimide precursor resin in the said polyimide resin composition to make a polyimide is employable suitably. It does not restrict|limit especially as such imidation method, A well-known method which can imidate the said polyimide precursor resin can be employ|adopted suitably, For example, when polyimide precursor resin is polyamic acid, International Publication No. 2011/ The imidization method described in 099518, the imidization method described in International Publication No. 2015/163314, the imidization method described in International Publication No. 2017/030019, etc. are suitably employable. . Moreover, as a method of such imidation, a so-called chemical imidation method (a method of imidating a polyimide precursor resin (preferably polyamic acid) in the polyimide precursor resin composition of the present invention is imidized using a known imidizing agent) , The polyimide precursor resin in the polyimide precursor resin composition (preferably poly It is preferable to employ a method of imidizing amic acid) or the like.

Further, when a polyimide precursor resin having a repeating unit represented by the general formula (I) is imidized to prepare a polyimide, the following general formula (I'):

(I')

(I')

[wherein, X ¹ represents at least one selected from the group consisting of tetravalent groups represented by the general formulas (I-1) to (I-3), and R ¹⁰ represents an arylene group having 6 to 50 carbon atoms. ]

A polyimide having a repeating unit represented by can be obtained. In addition, X ¹ and R ¹⁰ in the general formula (I') have the same meanings as X ¹ and R ¹⁰ in the general formula (I), and their suitability is also the same.

Further, when a polyimide is prepared by imidizing a polyimide precursor resin having at least one of the repeating units represented by the general formulas (II) to (III), the following general formula (II'):

(II')

(II')

[wherein, R ¹⁰ represents an arylene group having 6 to 50 carbon atoms]

A polyimide having a repeating unit represented by can be obtained. ^In addition, R10 in the said general formula (II') has the same meaning as ^R10 in the said general formula (II), and its suitability is also the same.

In addition, when a polyimide resin composition is prepared using the polyimide precursor resin composition of the present invention as a varnish (resin solution) for polyimide preparation (when an imidized product of the polyimide precursor resin composition of the present invention is prepared), , it becomes possible to efficiently and reliably manufacture polyimides having higher toughness while maintaining properties such as coefficient of linear expansion, glass transition temperature and total light transmittance at a sufficiently high level. In addition, the polyimide obtained by using the polyimide precursor resin composition of the present invention in this way is, from the characteristics thereof, for example, a film for flexible wiring boards, a heat-resistant insulating tape, an electric wire enamel, a protective coating agent for semiconductors, and an insulating film for rewiring of semiconductors. , liquid crystal aligning film, transparent conductive film for organic EL, flexible substrate film, flexible transparent conductive film, transparent conductive film for organic thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, film for touch panel, flat panel detector TFT substrate films for photocopiers, seamless polyimide belts for copiers (so-called transfer belts), transparent electrode substrates (transparent electrode substrates for organic EL, transparent electrode substrates for solar cells, transparent electrode substrates for electronic paper, etc.), interlayer insulating film, sensor substrates, images Sensor substrate, light emitting diode (LED) reflector (LED light reflector: LED reflector), LED light cover, LED reflector light cover, coverlay film, highly flexible composite substrate, semiconductor resist, lithium ion battery, organic memory It is particularly useful as a material for manufacturing a substrate, a substrate for an organic transistor, a substrate for an organic semiconductor, a color filter substrate, and the like. In addition, the polyimide obtained by using such a polyimide precursor resin composition of the present invention can be used in addition to the above-mentioned uses by making the shape into a powdery body or various molded bodies, for example, automobile parts, aerospace, etc. It is also possible to use it suitably for parts for use in applications, bearing parts, sealing materials, bearing parts, gear wheels, valve parts, and the like.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Synthesis Example 1: Synthesis of CpODA)

Based on the methods described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, the following general formula (A):

Tetracarboxylic acid dianhydride represented by (norbornane-2-spiro-α-cyclopentanone-α′-spiro-2′′-norbornane-5,5′′,6,6′′-tetra Carboxylic dianhydride: Hereinafter, tetracarboxylic dianhydride represented by the general formula (A) is referred to as "CpODA") was synthesized.

(Synthesis Example 2: Synthesis of BNBDA)

According to the method described in Examples 1 to 2 of International Publication No. 2017/030019, the following general formula (B):

A tetracarboxylic dianhydride represented by (hereinafter referred to as "BNBDA") was synthesized.

(Synthesis Example 3: Synthesis of BzDA)

According to the method described in Example 1 of International Publication No. 2015/163314, the general formula (C):

A tetracarboxylic dianhydride represented by (hereinafter referred to as "BzDA") was prepared.

(Synthesis Example 4: Synthesis of DNDA)

According to the method described on pages 1117 to 1123 of Macromolecules (Vol. 27), published in 1994, the following general formula (D):

(D)

(D)

A tetracarboxylic dianhydride represented by (hereinafter referred to as "DNDA") was prepared.

<About abbreviations such as monomers>

About the tetracarboxylic dianhydride, aromatic diamine, and addition compound used in the following Examples etc., the abbreviation etc. are described below. In addition, the following abbreviation etc. are used for description in an Example as needed.

(1) tetracarboxylic dianhydride

CpODA: tetracarboxylic dianhydride represented by the general formula (A) (Synthesis Example 1)

BNBDA: tetracarboxylic dianhydride represented by the general formula (B) (Synthesis Example 2)

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

BzDA: tetracarboxylic dianhydride represented by the general formula (C) (Synthesis Example 3)

DNDA: tetracarboxylic dianhydride represented by the general formula (D) (Synthesis Example 4)

(2) aromatic diamines

DABAN: 4,4'-diaminobenzanilide (manufactured by Junsei Yakuhin, Japan)

PPD: 1,4-paraphenylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by Seika Kogyo Co., Ltd.)

DDE: 4,4'-diaminodiphenyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

m-Tol: m-tolidine (alias; 2,2'-dimethylbenzidine, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(3) additive compounds

Tertiary phosphorus compound (A): triphenylphosphine (trade name "TPP": manufactured by Hokko Chemical Co., Ltd.)

Tertiary phosphorus compound (B): triparatolylphosphine (trade name "TPTP": manufactured by Hokko Chemical Co., Ltd.)

Quaternary amine compound (A): tetramethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)

Quaternary phosphorus compound (A): benzyltriphenylphosphonium bromide (trade name "U-cat 5003": manufactured by San Apro Corporation)

(Example 1)

<First step>

In a nitrogen atmosphere, 4.54 g (20.00 mmol) of DABAN was introduced as an aromatic diamine into a 100 mL screw tube, and 7.69 g (20.00 mmol) of CpODA was introduced as a tetracarboxylic dianhydride. Next, 48.9 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 5.92 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 1.99 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and triphenylphos as the addition compound were added to the reaction solution. After adding 0.118 g of fin (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours, and the polyamic acid which is a polymer of CpODA and DABAN, the tertiary phosphorus compound (A), and a solvent (dimethylacetate) A polyimide precursor resin composition containing amide) was obtained.

(Example 2)

Using the reaction solution obtained in the first step of Example 1, 3.07 g of the reaction solution was aliquoted and introduced into a 10 mL screw tube, and then dimethylacetamide (N,N-dimethylacetamide) as a solvent in the reaction solution was added. After adding 1.01 g and 0.029 g of triparatolylphosphine (tertiary phosphorus compound (B)), the mixture was stirred under room temperature conditions for 6 hours to obtain polyamic acid, which is a polymer of CpODA and DABAN, and a tertiary phosphorus compound (B). ) and a solvent (dimethylacetamide) to obtain a polyimide precursor resin composition.

(Example 3)

<First step>

In a nitrogen atmosphere, 1.70 g (7.50 mmol) of DABAN and 0.27 g (2.50 mmol) of PPD as aromatic diamines were introduced into a 50 mL screw tube, and 3.84 g (10.00 mmol) of CpODA as tetracarboxylic dianhydride was introduced. did. Next, 23.3 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 3.91 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 1.30 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and triphenylphos as the addition compound were added to the reaction solution. After adding 0.077 g of fin (tertiary phosphorus compound (A)), the mixture was stirred for 6 hours under room temperature conditions, polyamic acid, which is a polymer of CpODA, DABAN, and PPD, tertiary phosphorus compound (A), and a solvent ( A polyimide precursor resin composition containing dimethylacetamide) was obtained.

(Example 4)

<First step>

In a nitrogen atmosphere, 1.14 g (5.00 mmol) of DABAN and 0.541 g (5.00 mmol) of PPD as aromatic diamines were introduced into a 50 mL screw tube, and 3.84 g (10.0 mmol) of CpODA as tetracarboxylic dianhydride were introduced. did. Next, 22.1 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

4.41 g of the reaction solution prepared in the first step was aliquoted and introduced into a 10 mL screw tube. After adding 0.086 g of fin (tertiary phosphorus compound (A)), the mixture was stirred for 6 hours under room temperature conditions, polyamic acid, which is a polymer of CpODA, DABAN, and PPD, tertiary phosphorus compound (A), and a solvent ( A polyimide precursor resin composition containing dimethylacetamide) was obtained.

(Example 5)

<First step>

In a nitrogen atmosphere, 1.14 g (5.00 mmol) of DABAN and 1.60 g (5.00 mmol) of TFMB as aromatic diamines were introduced into a 50 mL screw tube, and 3.84 g (10.0 mmol) of CpODA as tetracarboxylic dianhydride were introduced. did. Next, 26.3 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 3.52 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 1.28 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and triphenylphos as the addition compound were added to the reaction solution. After adding 0.073 g of fin (tertiary phosphorus compound (A)), the mixture was stirred for 6 hours under room temperature conditions, polyamic acid, which is a polymer of CpODA, DABAN, and TFMB, tertiary phosphorus compound (A), and a solvent ( A polyimide precursor resin composition containing dimethylacetamide) was obtained.

(Example 6)

<First step>

In a nitrogen atmosphere, 0.909 g (4.00 mmol) of DABAN and 0.200 g (1.00 mmol) of DDE as aromatic diamines were introduced into a 50 mL screw tube, and 1.65 g (5.00 mmol) of BNBDA as tetracarboxylic dianhydride was introduced. did. Next, 11.0 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

4.65 g of the reaction solution prepared in the first step was aliquoted and introduced into a 10 mL screw tube, and 1.69 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and triphenylphos as the addition compound were added to the reaction solution. After adding 0.093 g of fin (tertiary phosphorus compound (A)), the mixture was stirred for 6 hours under room temperature conditions, polyamic acid which is a polymer of BNBDA, DABAN, and DDE, tertiary phosphorus compound (A), and a solvent ( A polyimide precursor resin composition containing dimethylacetamide) was obtained.

(Example 7)

<First step>

In a nitrogen atmosphere, 0.909 g (4.00 mmol) of DABAN and 0.320 g (1.00 mmol) of TFMB were introduced into a 50 mL screw tube as aromatic diamine, and 1.65 g (5.00 mmol) of BNBDA was introduced as tetracarboxylic dianhydride. did. Next, 11.5 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

4.65 g of the reaction solution prepared in the first step was aliquoted and introduced into a 10 mL screw tube, and 1.50 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and triphenylphosph as the addition compound were added to the reaction solution. After adding 0.099 g of fin (tertiary phosphorus compound (A)), the mixture was stirred for 6 hours under room temperature conditions, and then polyamic acid, which is a polymer of BNBDA, DABAN and TFMB, tertiary phosphorus compound (A), and a solvent ( A polyimide precursor resin composition containing dimethylacetamide) was obtained.

(Comparative Example 1)

The reaction solution obtained in the first step of Example 1 was used as it is as a polyimide precursor resin composition for comparison.

(Comparative Example 2)

Using the reaction solution obtained in the first step of Example 1, 4.53 g of the reaction solution was aliquoted and introduced into a 10 mL screw tube, and then dimethylacetamide (N,N-dimethylacetamide) as a solvent in the reaction solution was added. A polyimide precursor resin composition comprising 1.65 g and 0.091 g of trimethyl phosphite, followed by stirring for 6 hours under room temperature temperature conditions, polyamic acid, which is a polymer of CpODA and DABAN, trimethyl phosphite, and a solvent (dimethylacetamide) got

[Evaluation of properties of polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2]

<Preparation of polyimide>

The polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were used as polyamic acid varnishes for polyimide production, respectively, and films containing polyimide were prepared as follows. That is, first, the polyimide precursor resin composition is spin-coated on a large slide glass (trade name "S9213" manufactured by Matsunami Glass Kogyo Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm), and on a glass plate A coating film of the polyimide precursor resin composition was formed. Thereafter, the glass plate on which the coating film is formed is put into an oven, the temperature condition is 70° C., and the temperature condition is set to stand for 2 hours in a nitrogen atmosphere, then the temperature condition is changed to 135° C. By changing to the final heating temperature (Example 1 and Comparative Example 1: 370 ° C., Examples 2 to 7 and Comparative Example 2: 350 ° C.) shown in Table 1 for each type of the mid precursor resin composition, the temperature conditions of the final heating temperature The coating film was cured by standing for 30 minutes under Next, the polyimide-coated glass thus obtained was taken out from the oven, the polyimide-coated glass was immersed in hot water at 90° C. for 0.5 hours, and the film was peeled and recovered from the glass substrate to obtain a film containing polyimide. . Moreover, when all the films containing the obtained polyimide were visually confirmed the color, it was confirmed that it was colorless and transparent. In addition, the thickness of the film containing the obtained polyimide is shown in Table 1.

<Measurement of coefficient of linear expansion (CTE)>

Using the polyimide-containing films (imidized products of the polyimide precursor resin composition) obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 as described above, respectively, The coefficient of linear expansion of the obtained polyimide was measured as follows. That is, first, from the film containing the polyimide, a film for measurement having a size of length: 20 mm and width: 5 mm was formed. Because it does not affect the film thickness of each example as it is). Then, after vacuum-drying the obtained film for a measurement (120 degreeC, 1 hour), the measurement sample (dry film) was prepared by heat-processing at 200 degreeC in nitrogen atmosphere for 1 hour. Next, using the obtained measurement sample (dry film), using a thermomechanical analysis apparatus (trade name "TMA8311" manufactured by Rigaku) as a measurement apparatus, in a nitrogen atmosphere, in a tension mode (49 mN), a temperature increase rate of 5° C./min. It was measured by adopting the conditions, measuring the change in length of the sample at 50°C to 200°C, and finding the average value of the change in length per 1°C in the temperature range of 100°C to 200°C.

<Measurement of glass transition temperature (Tg)>

Using the polyimide-containing films (imidized products of the polyimide precursor resin composition) obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 as described above, respectively, The value (unit: degreeC) of the glass transition temperature (Tg) of the obtained polyimide was measured as follows. That is, as a measurement sample, a sample having a length of 20 mm and a width of 5 mm cut out from the film containing the polyimide (the thickness of such a sample does not affect the measured value, so the thickness of the film obtained in Examples is the same) Also, using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) as a measuring device, measurement was performed under nitrogen atmosphere, tension mode (49 mN), and a temperature increase rate of 5 ° C./min to obtain a TMA curve, , The value of the glass transition temperature (Tg) of the polyimide constituting the film obtained in each Example (unit: ° C.) was obtained by extrapolating the curves before and after the inflection point of the TMA curve resulting from the glass transition. The obtained results are shown in Table 1.

<Measurement of 5% weight loss temperature (Td5%)>

The 5% weight loss temperature of the polyimide is a film containing the polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 4, Examples 6 and Comparative Examples 1 and 2, respectively (the polyimide precursor resin composition is already A sample of about 10 mg was prepared using each of the compounds), placed in an aluminum sample pan, and a thermogravimetric analyzer as a measuring device (trade name "TG/DTA7200" manufactured by SI Nanotechnology Co., Ltd.) was obtained by measuring the temperature at which the weight of the sample used was reduced by 5% by setting the scanning temperature from 40°C to 550°C under a nitrogen gas atmosphere, heating at a temperature increase rate of 10°C/min.

<Measurement of total light transmittance and yellowness (YI)>

Using the polyimide-containing films (imidized products of the polyimide precursor resin composition) obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 as described above, respectively, The total light transmittance (unit: %) and yellowness (YI) of the obtained polyimide were measured as follows. That is, the film containing the polyimide is used as it is as a measurement sample, and as a measuring device, a product name "Hazemeter NDH-5000" manufactured by Nippon Denshoku Kogyo Co., Ltd., a trade name "Nippon Denshoku Kogyo Co., Ltd." The total light transmittance (unit: %) and yellowness (YI) of the polyimide resin composition constituting the film obtained in each example etc. were respectively calculated|required by performing measurement using each of the spectrocolorimeter SD6000". In addition, at the time of such a measurement, the total light transmittance was measured with the brand name "Hazemeter NDH-5000" made by Nippon Denshoku Kogyo Co., Ltd., and yellow with the trade name "Spectrophotometer SD6000" made by Nippon Denshoku Kogyo Co., Ltd. degrees were measured. In addition, the total light transmittance was calculated|required by performing the measurement based on JISK7361-1 (published in 1997), and yellowness (YI) was calculated|required by performing the measurement based on ASTME313-05 (issued in 2005). The obtained results are shown in Table 1.

<Measurement of toughness>

Using the polyimide-containing films (imidized products of the polyimide precursor resin composition) obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 as described above, respectively, Toughness was judged by touch. The index of judgment is shown below. In addition, the determination result is shown in Table 1.

(evaluation of toughness)

A: It can be judged that the film is very tough from the touch, and it is confirmed that the toughness is very high.

B: From the touch, it can be judged that the film is good as it is, and the toughness is confirmed to be moderate.

In addition, in Table 1, the kind of acid dianhydride, diamine, and addition compound used in each Example is shown together. In addition, with respect to the description of the acid dianhydride and the diamine in Table 1, 2 types of components are described in one frame, the numerical value in parentheses shows the molar ratio of these 2 types of components.

As is clear from the results shown in Table 1, all of the films containing polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 had a coefficient of linear expansion of 23 ppm/K or less. Since a sufficiently low value is shown, the glass transition temperature is sufficiently high as 333° C. or higher, and the total light transmittance is 87% or higher, properties such as the coefficient of linear expansion, the glass transition temperature and the total light transmittance are all It was confirmed that it was at a sufficiently high level.

In addition, the film containing the polyimide obtained by using the polyimide precursor resin composition obtained in Examples 1 to 7, respectively, is a film containing the polyimide obtained using the polyimide precursor resin composition obtained in Comparative Examples 1 to 2; By comparison, it was found that the toughness was higher.

From these results, according to the polyimide precursor resin compositions (Examples 1 to 7) of the present invention, while maintaining properties such as coefficient of linear expansion, glass transition temperature and total light transmittance at a sufficiently high level, the polyimide having higher toughness It was confirmed that it was possible to efficiently and reliably manufacture a mid|mid.

(Example 8)

<First step>

In a nitrogen atmosphere, 2.12 g (10.0 mmol) of m-Tol was introduced as an aromatic diamine into a 50 mL screw tube, and 3.84 g (10.0 mmol) of CpODA was introduced as a tetracarboxylic dianhydride. Next, 24.9 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 5.67 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 0.083 g of triphenylphosphine (tertiary phosphorus compound (A)) as the addition compound was added to the reaction solution, A polyimide precursor resin composition containing a polyamic acid which is a polymer of CpODA and m-Tol, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) was obtained by stirring under room temperature conditions for 6 hours.

In this way, using the polyimide precursor resin composition obtained in Example 8, except that the final heating temperature was set to 350 ° C., the above-described “Properties of the polyimide precursor resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 3” A film (film thickness: 14 µm) containing polyimide was prepared by employing a method similar to the method employed for "Evaluation of", and the glass transition temperature, total light transmittance, YI, and toughness were measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 8 had a glass transition temperature of 334° C., a total light transmittance of 88%, a YI of 4.0, and the evaluation result of toughness was A. . As described above, according to the polyimide precursor resin composition of the present invention, while maintaining various physical properties such as glass transition temperature, total light transmittance, and YI at a sufficiently high level, it is possible to efficiently and reliably produce a polyimide having higher toughness. found that it was possible

(Example 9)

<First step>

In a nitrogen atmosphere, 3.20 g (10.0 mmol) of TFMB as an aromatic diamine was introduced into a 50 mL screw tube, and 1.92 g (5.00 mmol) of CpODA and 2.22 g (5.00 mmol) of 6FDA were introduced as tetracarboxylic dianhydride. did. Next, 29.5 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 7.20 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 0.143 g of triphenylphosphine (tertiary phosphorus compound (A)) as the addition compound was added to the reaction solution, The polyimide precursor resin composition containing the polyamic acid which is a polymer of CpODA, 6FDA, and TFMB, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) was obtained by stirring under the temperature condition of room temperature for 6 hours.

Thus, using the polyimide precursor resin composition obtained in Example 9, except that the final heating temperature was set to 350° C., the above-described “Properties of the polyimide precursor resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 3” A film (film thickness: 7 µm) containing polyimide was prepared by employing the same method as the method employed for “Evaluation of measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 9 had a glass transition temperature of 360°C, a 5% weight loss temperature of 480°C, a total light transmittance of 91%, and YI was 1.9, and the evaluation result of toughness was A. As described above, according to the polyimide precursor resin composition of the present invention, while maintaining various physical properties such as glass transition temperature, total light transmittance, and YI at a sufficiently high level, it is possible to efficiently and reliably produce a polyimide having higher toughness. found that it was possible

(Example 10)

<First step>

In a nitrogen atmosphere, 3.2023 g (10.00 mmol) of TFMB was introduced as an aromatic diamine into a 50 mL screw tube, and 3.8438 g (10.00 mmol) of CpODA was introduced. Then, 28.18 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred under nitrogen atmosphere under the temperature conditions of room temperature for 6 hours, and the reaction liquid was obtained.

<Second process>

After aliquoting 4.7316 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 0.0941 g of tetramethylammonium bromide (quaternary amine compound (A)) was added to the reaction solution, and then temperature conditions at room temperature. The polyimide precursor resin composition containing the polyamic acid which is a polymer of CpODA and TFMB, a quaternary amine compound (A), and a solvent (dimethylacetamide) was obtained by stirring under the conditions for 6 hours.

In this way, using the polyimide precursor resin composition obtained in Example 10, except that the final heating temperature was set to 350 ° C. A film (film thickness: 10 µm) containing polyimide was prepared by employing a method similar to the method employed for As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 10 had a glass transition temperature of 355° C., a total light transmittance of 90%, a YI of 1.2, and the evaluation result of toughness was A. . As described above, according to the polyimide precursor resin composition of the present invention, while maintaining various physical properties such as glass transition temperature, total light transmittance, and YI at a sufficiently high level, it is possible to efficiently and reliably produce a polyimide having higher toughness. found that it was possible

(Example 11)

First, the same process as the 1st process employ|adopted in Example 1 was employ|adopted and the reaction liquid was obtained. Next, 5.21 g of the obtained reaction solution was aliquoted and introduced into a 10 mL screw tube, and 1.76 g of dimethylacetamide (N,N-dimethylacetamide) as a solvent and benzyltriphenylphosphonium bromide as the added compound were added to the reaction solution. (Quaternary phosphorus compound (A)) 104 mg was added and stirred for 6 hours under room temperature conditions, polyamic acid, which is a polymer of CpODA and DABAN, quaternary phosphorus compound (A), and a solvent (dimethylacetamide) A polyimide precursor resin composition containing

Thus, using the polyimide precursor resin composition obtained in Example 11, except that the final heating temperature was set to 370° C., the above-described “Properties of the polyimide precursor resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 3 A film (film thickness: 27 µm) containing polyimide was prepared by employing a method similar to the method employed for "Evaluation of", and the coefficient of linear expansion, total light transmittance, YI, and toughness were measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 11 had a coefficient of linear expansion of 7 ppm/K, a total light transmittance of 87%, a YI of 3.1, and the evaluation result of toughness was A. . As described above, according to the polyimide precursor resin composition of the present invention, it is possible to efficiently and reliably produce a polyimide having higher toughness while making various physical properties such as coefficient of linear expansion, total light transmittance and YI at a sufficiently high level. found it possible

(Example 12)

<First step>

In a nitrogen atmosphere, 9.8 g of dimethylacetamide (N,N-dimethylacetamide) and 1.00 g (5.00 mmol) of DDE as an aromatic diamine were introduced into a 50 mL screw tube and heated to 80°C. Then, 2.03 g (5.00 mmol) of BzDA as tetracarboxylic dianhydride was added into the screw tube, and then 3.5 g of dimethylacetamide (N,N-dimethylacetamide) was used to wash the BzDA attached to the wall surface of the screw tube. It was added while letting it flow out to obtain a mixed solution. Thereafter, the mixture was stirred at 80° C. under a nitrogen atmosphere for 3.5 hours to obtain a uniform solution. Then, the obtained solution was cooled to room temperature, and stirring was continued for one more day to obtain a reaction solution.

<Second process>

After aliquoting 2.75 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 55.0 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the added compound is added, followed by temperature conditions at room temperature The polyimide precursor resin composition containing the polyamic acid which is a polymer of BzDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) was obtained by stirring under the conditions for 6 hours.

Thus, using the polyimide precursor resin composition obtained in Example 12, the atmosphere at the time of heating in the oven was made a reduced pressure atmosphere instead of a nitrogen atmosphere (after putting the glass plate on which the coating film was formed into the oven, the temperature of 70 ° C. From the step of standing still at the temperature condition for 2 hours to the step of standing at the final heating temperature for 30 minutes, heating in a reduced pressure atmosphere) and the final heating temperature of 350 ° C. A film (film thickness: 18 µm) containing polyimide was prepared by employing a method similar to the method employed for “evaluation of properties of polyimide precursor resin composition obtained in steps 1 to 3”, glass transition temperature, 5% Weight loss temperature, total light transmittance, YI and toughness were measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 12 had a glass transition temperature of 317°C, a 5% weight loss temperature of 462°C, a total light transmittance of 89%, and YI was 3.5, and the evaluation result of toughness was A. As described above, according to the polyimide precursor resin composition of the present invention, various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI are made at a sufficiently high level, and a polyimide having higher toughness can be obtained. It turned out that it is possible to manufacture efficiently and reliably.

(Example 13)

<First step>

In a nitrogen atmosphere, 1.00 g (5.00 mmol) of DDE was introduced as an aromatic diamine in a 50 mL screw tube, and 1.51 g (5.00 mmol) of DNDA was introduced as a tetracarboxylic dianhydride. Next, 10.0 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained liquid mixture was stirred for one day under a nitrogen atmosphere under room temperature conditions to obtain a reaction liquid.

<Second process>

After aliquoting 2.21 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 44.1 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the added compound was added, followed by temperature conditions at room temperature. The polyimide precursor resin composition containing the polyamic acid which is a polymer of DNDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) was obtained by stirring under the conditions for 6 hours.

Thus, using the polyimide precursor resin composition obtained in Example 13, the atmosphere at the time of heating in the oven was made a reduced pressure atmosphere instead of a nitrogen atmosphere (after putting the glass plate on which the coating film was formed into the oven, the temperature of 70 ° C. Heating under a reduced pressure atmosphere from the step of standing at the temperature condition for 2 hours to the step of standing at the final heating temperature for 30 minutes), and the final heating temperature of 350 ° C. A film (film thickness: 17 µm) containing polyimide was prepared by employing a method similar to the method employed for “Evaluation of the properties of the polyimide precursor resin composition obtained in Steps 3 to 3”, glass transition temperature, 5% weight Decreasing temperature, total light transmittance, YI and toughness were measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 13 has a glass transition temperature of 367° C., a 5% weight loss temperature of 435° C., a total light transmittance of 89%, and YI 1.2, and the evaluation result of toughness was A. As described above, according to the polyimide precursor resin composition of the present invention, various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI are made at a sufficiently high level, and polyimide having higher toughness can be obtained. It turned out that it is possible to manufacture efficiently and reliably.

(Example 14)

<First step>

In a nitrogen atmosphere, 1.60 g (5.00 mmol) of TFMB was introduced as an aromatic diamine in a 50 mL screw tube, and 1.51 g (5.00 mmol) of DNDA was introduced as tetracarboxylic dianhydride. Next, 12.5 g of dimethylacetamide (N,N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Then, the obtained liquid mixture was stirred for 30 minutes under a nitrogen atmosphere under a temperature condition of 60°C to obtain a uniform solution. Then, the obtained solution was cooled to room temperature and stirred for 1 day to obtain a reaction solution.

<Second process>

After aliquoting 2.43 g of the reaction solution prepared in the first step and introducing it into a 10 mL screw tube, 48.7 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the added compound was added, followed by temperature conditions at room temperature The polyimide precursor resin composition containing the polyamic acid which is a polymer of DNDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) was obtained by stirring under the conditions for 6 hours.

Thus, using the polyimide precursor resin composition obtained in Example 14, the atmosphere at the time of heating in the oven was changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (after putting the glass plate on which the coating film was formed into the oven, the temperature was 70 ° C. Heating under a reduced pressure atmosphere from the step of standing at the temperature condition for 2 hours to the step of standing at the final heating temperature for 30 minutes), and the final heating temperature of 350 ° C. A film (film thickness: 15 µm) containing polyimide was prepared by employing the same method as the method employed for "Evaluation of the properties of the polyimide precursor resin composition obtained in steps 3 to 3", and the coefficient of linear expansion, the glass transition temperature, The 5% weight loss temperature, total light transmittance, YI and toughness were measured. As a result of these measurements, the polyimide obtained using the polyimide precursor resin composition obtained in Example 14 had a coefficient of linear expansion of 27 ppm/K, a glass transition temperature of 278° C., a 5% weight loss temperature of 415° C., and total light The transmittance was 91%, YI was 1.0, and the evaluation result of toughness was A. As described above, according to the polyimide precursor resin composition of the present invention, various physical properties such as coefficient of linear expansion, glass transition temperature, 5% weight loss temperature, total light transmittance, and YI are at a sufficiently high level while having higher toughness. It turned out that it is possible to manufacture polyimide efficiently and reliably.

As described above, according to the present invention, a polyimide capable of efficiently and reliably manufacturing a polyimide having higher toughness while maintaining properties such as a coefficient of linear expansion, a glass transition temperature and a total light transmittance at a sufficiently high level. It becomes possible to provide a precursor resin composition.

Therefore, the polyimide precursor resin composition of the present invention is suitable for producing various polyimide-containing products such as various films, automobile parts, aerospace parts, bearing parts, sealing materials, bearing parts, gear wheels and valve parts. It is particularly useful as a material for

Claims (4)

a polyimide precursor resin which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof having two norbornane skeletons in the molecule and diamine;
Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound having a structure represented by CP, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a quaternary phosphorus compound having a structure represented by CP; and at least one additive compound selected from the group consisting of quaternary amine compounds;
menstruum
containing, a polyimide precursor resin composition. According to claim 1, wherein at least one member selected from the group consisting of tetracarboxylic dianhydride having two norbornane skeletons in the molecule and derivatives thereof, the following general formula (1):

(One)
[In formula (1), R ¹ , R ² , R ³ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n represents an integer of 0 to 12 ]
a compound represented by ; The following general formula (2):

(2)
[In Formula (2), A represents 1 type selected from the group which consists of a divalent aromatic group which may have a substituent and the number of carbon atoms which form an aromatic ring is 6-30, R< ⁴ > is a hydrogen atom each independently and one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, and R ⁵ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms]
a compound represented by ; The following general formula (3):

(3)
[In formula (3), R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or two R ⁶ bonded to the same carbon atom. may form a methylidene group as one of these, and R ⁷ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms]
a compound represented by ; The general formula (4):

(4)
a compound represented by ; And the polyimide precursor resin composition which is at least 1 sort(s) selected from the group which consists of derivatives of these compounds. 3. The polyimide precursor resin according to claim 1 or 2, wherein the polyimide precursor resin has the following general formula (I):

(I)
[In formula (I), X ¹ is the following general formula (I-1):

(I-1)
[In formula (I-1), R ¹ , R ² , R ³ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is an integer of 0 to 12 represents, and the symbols *1 to *4 indicate which of the four bonds bonded to X ¹ in the formula (I), respectively]
a tetravalent group represented by ; The general formula (I-2):

(I-2)
[In formula (I-2), A represents one selected from the group consisting of a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent and form an aromatic ring, and R ⁴ is each independently Represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, R ⁵ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, symbol *1 to *4 indicates that the bond to which the symbol is attached is any of the four bonds bonded to X ¹ in formula (I)]
a tetravalent group represented by ; The general formula (I-3):

(I-3)
[In formula (I-3), R ⁶ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group and a nitro group, or two groups bonded to the same carbon atom. R ⁶ may become one to form a methylidene group, R ⁷ each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and symbols *1 to *4 indicate that the symbol is indicates that the attached bond is any of the four bonds bonded to X ¹ in the formula (I)]
At least one selected from the group consisting of a tetravalent group represented by
R ¹⁰ represents an arylene group having 6 to 50 carbon atoms,
Y ¹ and Y ² each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkylsilyl group having 3 to 9 carbon atoms]
repeating units represented by ; and the general formulas (II) to (III):

(II)

(III)
[In formulas (II) to (III), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkylsilyl having 3 to 9 carbon atoms represents one selected from the group consisting of groups]
A polyimide precursor resin composition having at least one repeating unit selected from the group consisting of repeating units represented by The polyimide precursor resin composition according to claim 1 or 2, wherein the additive compound is triphenylphosphine.