WO2019163703A1

WO2019163703A1 - Polyimide precursor resin composition

Info

Publication number: WO2019163703A1
Application number: PCT/JP2019/005814
Authority: WO
Inventors: 大輔渡部; 亜紗子京武
Original assignee: Ｊｘｔｇエネルギー株式会社
Priority date: 2018-02-21
Filing date: 2019-02-18
Publication date: 2019-08-29
Also published as: KR102429867B1; CN111742012A; KR20200123172A; TW201936720A; JPWO2019163703A1; JP7203082B2

Abstract

A polyimide precursor resin composition which contains: a polyimide precursor resin which is a polymer of a diamine and at least one substance that is selected from the group consisting of tetracarboxylic acid dianhydrides having two norbornane skeletons in each molecule and derivatives of the tetracarboxylic acid dianhydrides; at least one additive compound that is selected from the group consisting of tertiary phosphorus compounds containing a structure which is represented by formula C-P, wherein a phosphorus atom and a carbon atom are directly bonded to each other, in each molecule, quaternary phosphorus compounds containing a structure which is represented by formula C-P, wherein a phosphorus atom and a carbon atom are directly bonded to each other, in each molecule, and quaternary amine compounds; and 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 using organic electroluminescence elements and liquid crystal displays, materials such as glass that have high light transmission and sufficiently high heat resistance have emerged as materials used for substrates and the like. It has been sought. In recent years, polyimide has attracted attention as a material used for glass substitute applications and the like, and various polyimide precursor resin compositions have been disclosed for producing such polyimide.

For example, International Publication No. 2011/099518 (Patent Document 1) discloses a reaction solution containing a polyamic acid having a repeating unit described by a specific general formula and a solvent. Polyimide obtained by using such a reaction liquid (composition) as described in Patent Document 1 has high light transmittance and sufficiently high heat resistance, and can be applied to various fields. It was something.

International Publication No. 2011/099518

However, the reaction liquid (composition) described in Patent Document 1 is a polyimide having higher toughness while maintaining characteristics such as a linear expansion coefficient, a glass transition temperature, and a total light transmittance at a sufficiently high level. Is not always sufficient from the viewpoint of efficiently and reliably producing the material.

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

As a result of intensive studies to achieve the above object, the present inventors have selected a polyimide precursor resin composition from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof. A polyimide precursor resin which is a polymer of at least one selected from diamine and a diamine; a tertiary phosphorus compound containing a structure represented by the formula: CP in which a phosphorus atom and a carbon atom are directly bonded in the molecule; A compound in which a phosphorus atom and a carbon atom are directly bonded to each other: at least one additive compound selected from the group consisting of a quaternary phosphorus compound containing a structure represented by CP and a quaternary amine compound; a solvent; By using this, a polyimid having higher toughness can be used while maintaining properties such as the linear expansion coefficient, glass transition temperature and total light transmittance at a sufficiently high level. It found that it is possible to manufacture efficiently and reliably, 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 dianhydrides having two norbornane skeletons in the molecule and derivatives thereof;
Formula in which phosphorus atom and carbon atom are directly bonded in the molecule: tertiary phosphorus compound including structure represented by CP, Formula in which phosphorus atom and carbon atom are directly bonded in molecule: Represented by CP At least one additive compound selected from the group consisting of a quaternary phosphorus compound containing a structure and a quaternary amine compound;
With a solvent;
It contains.

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

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

[In the formula (2), A represents one kind selected from the group consisting of a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. Each of 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 each R ⁵ independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. One species selected from the group is shown. ]
A compound represented by the following general formula (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 bonded to the same carbon atom. Two R ⁶ groups together may form a methylidene group, and each R ⁷ 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 (4):

And at least one selected from the group consisting of these compounds (derivatives of the compounds represented by the general formulas (1) to (4)).

In the polyimide precursor resin composition of the present invention, the polyimide precursor resin is represented by the following general formula (I):

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

[In Formula (I-1), R ¹ , R ² and R ³ each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 Represents an integer of ~ 12, and the symbols * 1 to * 4 are each ^one of the four bonds that are bonded to X1 in the formula (I). Indicates. ]
A tetravalent group represented by the following general formula (I-2):

[In Formula (I-2), A is 1 selected from the group consisting of a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. R ⁴ represents one type independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents each independently a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. Each of the bonds selected from the group consisting of four bonds, each of which is bonded to X ¹ in the formula (I). Indicates either. ]
A tetravalent group represented by the following general formula (I-3):

[In the formula (I-3), each R ⁶ 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 the same carbon atom. And two R ⁶ bonded to each other may form a methylidene group, and each R ⁷ is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. Symbols * 1 to * 4 indicate that each of the bonds to which the symbols are attached is any one of four bonds that are bonded to X ¹ in the formula (I). ]
At least one selected from the group consisting of tetravalent groups 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. ]
And the following general formulas (II) to (III):

[In the formulas (II) to (III), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number 3 1 type selected from the group consisting of ˜9 alkylsilyl groups. ]
It is preferable to have at least one repeating unit selected from the group consisting of:

Furthermore, in the polyimide precursor resin composition of the present invention, the additive compound is preferably triphenylphosphine.

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

Hereinafter, the present invention will be described in detail on the basis of preferred embodiments thereof.

[Polyimide precursor resin composition]
The polyimide precursor resin composition of the present invention is
A polyimide precursor resin (first component) which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof;
Formula in which phosphorus atom and carbon atom are directly bonded in the molecule: tertiary phosphorus compound including structure represented by CP, Formula in which phosphorus atom and carbon atom are directly bonded in molecule: Represented by CP At least one additive compound (second component) selected from the group consisting of a quaternary phosphorus compound containing a structure and a quaternary amine compound;
A solvent (third component);
It contains. Hereinafter, each component will be described separately.

<Polyimide precursor resin composition (first component)>
The polyimide precursor resin composition (first component) according to the present invention is a compound comprising at least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof and a diamine. It is a coalescence. Here, the tetracarboxylic dianhydride and its derivative used as a monomer component of the polymer, and the diamine will be described separately.

<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 means the following general formula (i):

And a carbon atom that forms such a skeleton may be bonded to a hydrogen atom, an atom other than a hydrogen atom, a substituent other than a hydrogen atom, and the like. As described above, the tetracarboxylic dianhydride according to the present invention may have two structural parts (skeletons) represented by the general formula (i) in the molecule, and the structure is not particularly limited. . The tetracarboxylic dianhydride derivative is not particularly limited as long as it is obtained using the tetracarboxylic dianhydride. For example, the tetracarboxylic dianhydride may be modified by modifying the tetracarboxylic dianhydride. And diester dicarboxylic acid and diester dicarboxylic acid dichloride obtained.

Such tetracarboxylic dianhydrides and derivatives thereof are represented by the above general formulas (1) to (4) from the viewpoints of transparency and heat resistance of polyimides obtained using the components. And the compounds represented by the general formulas (1) to (3) and the derivatives thereof are more preferable. Hereinafter, the compounds represented by the above general formulas (1) to (4) that can be suitably used as the tetracarboxylic dianhydride according to the present invention and their derivatives will be described separately.

(Compound represented by the general formula (1))
Regarding the compound represented by the general formula (1), R ¹ , R ² and R ^{3 in the} general formula (1) are each independently a 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.

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

In addition, R ¹ , R ² , and R ^{3 in the} general formula (1) are each independently a hydrogen atom or a carbon number of 1 to 10 from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. In particular, from the viewpoints of easy availability of raw materials and easier purification, each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. It is more preferably a group, and particularly preferably a hydrogen atom or a methyl group. Moreover, it is especially preferable that several R < ¹ >, R < ² >, R < ³ > in such a formula is the same from viewpoints, such as the ease of refinement | purification.

In the general formula (1), n represents an integer of 0 to 12. When such a value of n exceeds the upper limit, purification becomes difficult. Further, the upper limit value of the numerical value range of n in the general formula (1) is more preferably 5 and particularly preferably 3 from the viewpoint of easier purification. Further, the lower limit of the numerical range of n in the general formula (1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material compound. Thus, n in the general formula (1) is particularly preferably an integer of 2 to 3.

The method for producing the tetracarboxylic dianhydride represented by the general formula (1) is not particularly limited, and a known method can be appropriately employed. For example, International Publication No. You may employ | adopt the method as described in 2011/099517, the method as described in international publication 2011/099518, etc.

(Compound represented by the general formula (2))
Regarding the compound represented by the general formula (2), in the general formula (2), A is a divalent group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. R ⁴ represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents each independently selected from the group consisting of the following aromatic groups: Represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.

As described above, A in the general formula (2) is a divalent aromatic group which may have a substituent, and is a carbon that forms an aromatic ring contained in the aromatic group. (“The number of carbons forming the aromatic ring” herein means that when the aromatic group has a substituent containing carbon (such as a hydrocarbon group), the carbon in the substituent is The number of carbon atoms in the aromatic ring in the aromatic group is not included, and for example, in the case of a 2-ethyl-1,4-phenylene group, the number of carbon atoms forming the aromatic ring is 6. ) Is from 6 to 30. Thus, A in the general formula (1) is a divalent group (divalent aromatic group) which may have a substituent and has an aromatic ring having 6 to 30 carbon atoms. is there. When the number of carbons forming such an aromatic ring exceeds the above upper limit, it is difficult to sufficiently suppress coloring of the polyimide when a polyimide is prepared using a polyimide precursor resin having such a repeating unit. It tends to be. From the viewpoint of transparency and ease of purification, the number of carbon atoms forming the aromatic ring of the divalent aromatic group is more preferably 6-18, and further preferably 6-12. preferable.

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

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

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

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

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

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

In the general formula (2), each R ⁴ is independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms of the alkyl group that can be selected as R ⁴ exceeds 10, sufficiently high heat resistance cannot be achieved. In addition, the alkyl group that can be selected as R ⁴ is preferably 1 to 6, more preferably 1 to 5, and more preferably 1 to 4 from the viewpoint of obtaining higher heat resistance. Is more preferable, and 1 to 3 is particularly preferable. Such an alkyl group that can be selected as R ⁴ may be linear or branched.

In addition, R ⁴ in the general formula (2) is independently from the viewpoints that higher heat resistance is obtained, that raw materials are easily obtained, that purification is easier, and the like. A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a hydrogen atom and a methyl group are particularly preferable. In addition, R ⁴ in the formula (2) may be the same or different from each other, but they are the same from the viewpoint of ease of purification. Is preferred. In addition, it is particularly preferable that a plurality of R ⁴ in the general formula (2) are all hydrogen atoms. Thus, when all 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.

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

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

The method for producing such a compound represented by the general formula (2) is not particularly limited, and a known method can be appropriately employed. For example, as described in International Publication No. 2015/163314 A method or the like may be adopted.

(Compound represented by the general formula (3))
Regarding the compound represented by the general formula (3), in the general formula (3), each R ⁶ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. One R or two R ⁶ bonded to the same carbon atom may form a methylidene group, and each R ⁷ independently represents a hydrogen atom and a carbon number of 1 to 10 1 type selected from the group consisting of the following alkyl groups.

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

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

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

As the plurality of R ⁶ in the general formula (3), it is possible to obtain higher heat resistance, easier acquisition (preparation) of raw materials, easier purification, and the like. 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 preferable. In addition, the plurality of R ⁶ in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.

In the general formula (3), R ⁷ is each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. 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 decreases. The alkyl group that can be selected as R ⁷ is preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4 from the viewpoint of obtaining higher heat resistance. Is more preferable, and 1 to 3 is particularly preferable. Further, such an alkyl group that can be selected as R ⁷ may be linear or branched.

Further, R ⁷ in the general formula (3) is a viewpoint that a higher degree of heat resistance can be obtained when the polymer is produced, that raw materials are easily obtained, and that purification is easier. Therefore, independently of each other, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a hydrogen atom and a methyl group are particularly preferable. In addition, R ⁷ in the formula (3) may be the same or different from each other, but they are the same from the viewpoint of ease of purification and the like. Is preferred.

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

A method for producing such a compound represented by the general formula (3) is not particularly limited, and a known method can be appropriately employed. For example, as described in International Publication No. 2017/030019 A method or the like may be adopted.

(Compound represented by the general formula (4))
The compound represented by the general formula (4) is not particularly limited, and a commercially available product may be appropriately used. Moreover, 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 above general formulas (1) to (4))
The derivatives of the compounds represented by the general formulas (1) to (4) are not particularly limited, but a diester dicarboxylic acid that is a modified product of the compounds represented by the general formulas (1) to (4), and Diester dicarboxylic acid dichloride is more preferable. That is, when the derivatives of the compounds represented by the general formulas (1) to (4) are used, the compounds represented by the general formulas (1) to (4) are converted into the corresponding diester dicarboxylic acid or diester. It is preferably used after being modified to dicarboxylic acid dichloride.

The method for preparing such a derivative is not particularly limited, and a known method can be appropriately employed. For example, as a method for preparing a diester dicarboxylic acid suitable as a derivative of the compounds represented by the general formulas (1) to (4), the compounds represented by the general formulas (1) to (4) may be arbitrarily selected. A method of obtaining the corresponding diester dicarboxylic acid by reacting with alcohol can be employed. In addition, a polyimide precursor can be obtained by solution-polymerizing the diester dicarboxylic acid thus obtained with a diamine in the presence of a condensing agent. Examples of a method for preparing a diester dicarboxylic acid dichloride suitable as a derivative of the compounds represented by the general formulas (1) to (4) include, for example, the compounds represented by the general formulas (1) to (4). A method of obtaining a 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.), etc. it can. A polyimide precursor can be obtained by stirring such a diester dicarboxylic acid dichloride and diamine in the range of −20 ° C. to 100 ° C. (more preferably 5 to 80 ° C.) for 1 to 72 hours. The polyimide precursor thus obtained tends to have better storage stability than when the compounds represented by the general formulas (1) to (4) are used as they are.

<About diamine>
Such a diamine is not particularly limited as long as it can be used for the production of polyimide, and may be an aliphatic diamine or an aromatic diamine. As such a diamine, an aromatic diamine is preferable from the viewpoint of heat resistance and simplicity of the polymerization method, and among them, the following general formula (ii):
HY ¹ N—R ¹⁰ —NY ² H (ii)
[In the formula (ii), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² are each independently selected from the group consisting of a hydrogen atom and an alkylsilyl group having 3 to 9 carbon atoms. One type is shown. ]
The aromatic diamine represented by these is more preferable.

The arylene group that can be selected as R ¹⁰ in the general formula (ii) has 6 to 50 carbon atoms, and the aryl group preferably has 6 to 40 carbon atoms, It is more preferably 6 to 30, and further preferably 12 to 20. If the number of carbon atoms is less than the lower limit, the heat resistance tends to decrease when the resulting polyimide is prepared.On the other hand, if the upper limit is exceeded, the polyimide has a solubility in a solvent when prepared. It tends to decrease.

R ¹⁰ in the general formula (ii) is represented by the following general formulas (a) to (d): from the viewpoint that higher heat resistance and mechanical strength can be obtained when a polyimide is prepared.

[In the formula (c), R ¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a hydroxyl group, and a trifluoromethyl group, and in the formula (d), Q is , 9,9-fluorenylidene group; formula: —O—, —S—, —CO—, —CONH—, —SO ₂ —, —C (CF ₃ ) ₂ —, —O—C ₆ H ₄ —O— , —C (CH ₃ ) ₂ —, —CH ₂ —, —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O—, —O—C ₆ H ₄ —C (CF ₃ ) ₂ -C ₆ H ₄ -O-, -O-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -C (CH ₃ ) ₂ -C ₆ H ₄ -C (CH ₃ ) _2- _{_{_{_{, -O-C 6 H 4 -C}}}} 6 H 4 -O -, - CONH-C 6 H 4 -NHCO -, - NHCO-C 6 H 4 -CONH -, - C 6 H 4 - and, -O- C Groups represented by ₆ H ₄ —O—, —COO—, —OCO—; and the following general formula (e):

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

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

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

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

Moreover, as such R ¹⁰ , 4,4′-diaminobenzanilide (from the viewpoint that it is possible to obtain a polyimide having a sufficient balance of heat resistance, transparency and mechanical strength at a sufficient level. DABAN), 4,4′-diaminodiphenyl ether (DDE), 2,2′-bis (trifluoromethyl) benzidine (TFMB), 9,9′-bis (4-aminophenyl) fluorene (FDA), p-diamino Benzene (PPD), 2,2′-dimethyl-4,4′-diaminobiphenyl (also known as m-tolidine), 4,4′-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid ( BAAB), 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl (BABB), 3,3′-diaminodiphenyl 2 obtained by removing two amino groups from at least one aromatic diamine selected from the group consisting of luphone (3,3′-DDS) and 4,4′-diaminodiphenylsulfone (4,4′-DDS) Valent group (arylene group) is preferable, 4,4′-diaminobenzanilide (DABAN), 4,4′-diaminodiphenyl ether (DDE), 2,2′-bis (trifluoromethyl) benzidine (TFMB), 9 , 9'-bis (4-aminophenyl) fluorene (FDA), p-diaminobenzene (PPD) and 4-aminophenyl-4-aminobenzoic acid (BAAB) It is more preferably a divalent group (arylene group) obtained by removing two amino groups from diamine, and 4,4′-diaminobenzanilide (DABAN) Two amino groups are removed from at least one aromatic diamine selected from the group consisting of 4,4′-diaminodiphenyl ether (DDE) and 2,2′-bis (trifluoromethyl) benzidine (TFMB) More preferably, it is a divalent group (arylene group).

The alkylsilyl group that can be selected as Y ¹ and Y ² in the general formula (ii) is one having 3 to 9 carbon atoms. Examples of the alkylsilyl group that can be selected as Y ¹ and Y ² include A trimethylsilyl group or a t-butyldimethylsilyl group is more preferable.

In addition, Y ¹ and Y ² in the formula (ii) are more preferably hydrogen atoms from the viewpoint of simplicity of polyimide synthesis. That is, the aromatic diamine represented by the formula (ii) is more preferably an aromatic diamine represented by the formula: H ₂ N—R ¹⁰ —NH ₂ .

The aromatic diamine represented by the formula: H ₂ N—R ¹⁰ —NH ₂ is not particularly limited, and known ones can be used as appropriate, and commercially available ones may be used as appropriate. Examples of such aromatic diamines include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 3,3′-diaminodiphenylethane, and 4,4′-. Diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl Sulfone, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 4,4'-diamino Biphenyl, 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′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4- Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 9,9'-bis (4-aminophenyl) fluorene , O-tolidine sulfone, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3 ′, 5,5′-tetramethylbenzidine, 1,5-bis (4-aminophenoxy) pentane 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, 4-aminopheny 4-aminobenzoic acid, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl, and the like. Such aromatic diamines may be used singly or in combination of two or more.

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

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

In addition, the method for producing such a diamine is not particularly limited, and a known method can be appropriately employed. Moreover, you may utilize a commercial item suitably as such diamine.

<About polymer>
The polyimide precursor resin according to the present invention is a polymer of the diamine and at least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof. As such a polymer, those having at least one repeating unit selected from the group consisting of repeating units represented by the above general formulas (I) to (III) are more preferable.

(Repeating unit represented by general formula (I))
Regarding the repeating unit represented by the general formula (I), X ¹ in the general formula (I) is a tetravalent group represented by the above general formulas (I-1) to (I-3). is there. The general formula (I-1) ^R 1 ^in, R ^{2, R} 3, n has the same meaning as ^R ^1, R ^{2, R} 3, n in the general formula (1) (as its preferred Are the same as R ¹ , R ² , R ³ and n in the general formula (1)), and A, R ⁴ and R ⁵ in the general formula (I-2) are the same as those in the general formula (2). ) Are the same as A, R ⁴ and R ^{5 in the} general formula (2), and the preferred ones are also the same as A, R ⁴ and R ^{5 in the} general formula (2). In addition, R in the general formula (I-3) ^R 6, ^{R 7} in has the same meaning as ^R 6, ^{R 7} in the general formula (3) (the preferred ones also Formula (3) ^6, ^{R 7} as synonymous).

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. Symbols * 1 to * 4 in the general formulas (I-1) to (I-3) are four bonds in which the bonds to which the symbols are attached are each bonded to X ¹ in the formula (1). It is one of these. By utilizing such a tetravalent organic group represented by the general formulas (I-1) to (I-3) as the X ¹ site, transparency, heat resistance and dimensional stability are improved. It becomes possible. Further, among the bonds having the symbols * 1 to * 4 attached thereto, any of the bonds having the symbols * 1 to * 2 is represented by the general formula (I). Formula: -COOY ¹ is a bond that bonds to ^one of the bonds marked with symbols * 3 to * 4, and the bond in formula (I) is represented by the formula: -COOY ² It is a bond that bonds, or any one of the bonds marked with symbols * 1 to * 2 is a bond that bonds to the formula: -COOY ² in the general formula (I) In addition, any of the bonds to which symbols * 3 to * 4 are attached is preferably a bond that bonds to the formula: —COOY ¹ in the general formula (I).

In the general formula (I), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms. R ¹⁰ such in the general formula (I) are the same as the R ¹⁰ in the general formula (ii), is the same as R ⁴ in the general formula (ii) as its preferred.

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 alkylsilyl having 3 to 9 carbon atoms. One of the groups. Such Y ¹ and Y ² can change the kind of the substituent and the introduction rate of the substituent by appropriately changing the production conditions (type of diamine used, etc.). When such Y ¹ and Y ² are both hydrogen atoms (when they become so-called polyamic acid repeating units), when they are used to produce polyimide, the production tends to be easier. is there.

Further, when Y ¹ and Y ² in the general formula (I) are an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), the polyimide precursor resin has more excellent storage stability. Tend to be. When Y ¹ and Y ² are alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), Y ¹ and Y ² are more preferably methyl groups or ethyl groups.

Further, when Y ¹ and Y ² in the general formula (I) are alkylsilyl groups having 3 to 9 carbon atoms, the solubility of the polyimide precursor resin tends to be more excellent. Thus, when Y ¹ and Y ² are alkylsilyl groups having 3 to 9 carbon atoms, Y ¹ and Y ² are more preferably trimethylsilyl groups or t-butyldimethylsilyl groups.

Moreover, regarding Y ¹ and Y ² in the repeating unit represented by the general formula (I), the introduction rate of a group other than a hydrogen atom (an alkyl group and / or an alkylsilyl group) is not particularly limited, but Y ¹ In the case where at least a part of Y ² is an alkyl group and / or an alkylsilyl group, 25% or more (more preferably 50% or more, still more preferably 75%) of the total amount of Y ¹ and Y ² in all repeating units. % Or more) is preferably an alkyl group and / or an alkylsilyl group (in this case, Y ¹ and Y ² other than the alkyl group and / or the alkylsilyl group are hydrogen atoms). Moreover, about each of Y < ¹ >, Y < ² > in the repeating unit represented by the said general formula (I), 25% or more of total amount is made into an alkyl group and / or an alkylsilyl group, The preservation stability of a polyimide precursor Tend to be more excellent.

Such a repeating unit represented by the general formula (I) includes a diester dicarboxylic acid which is a compound (tetracarboxylic dianhydride) represented by the above general formulas (1) to (3) or a derivative of those compounds. And at least one of diester dicarboxylic acid dichloride and the aromatic diamine (HY ¹ N—R ¹⁰ —NY ² H) represented by the above general formula (ii) can be easily formed. Can do. Thus, the polymer which has a repeating unit represented by general formula (I) can be formed by selecting a monomer component suitably according to target design. From such a viewpoint, the polymer (polyimide precursor resin) having a repeating unit represented by the above general formula (I) is a compound represented by the above general formula (1) to (3) (tetracarboxylic acid dicarboxylic acid). Anhydride) and at least one of diester dicarboxylic acid and diester dicarboxylic acid dichloride which are derivatives of these compounds, and aromatic diamines (HY ¹ N—R ¹⁰ —NY ² H) represented by the above general formula (ii) It can be said that it is a polymer.

(Repeating units represented by general formulas (II) to (III))
Regarding 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) is an arylene 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. ^R 10 in the general formula ^{^{(II), Y 1, Y}} 2 is the formula ^R ^10, Y 1 in (I), the same meaning as ^{Y 2} (also Formula those its preferred (I And R ¹⁰ , Y ¹ and Y ^{2 in the} same meaning).

Such repeating units represented by the general formulas (II) to (III) include the compound represented by the above general formula (4) (tetracarboxylic dianhydride) and a diester dicarboxylic acid which is a derivative of the compound, and It can be easily formed by reacting at least one of diester dicarboxylic acid dichlorides with an aromatic diamine (Y ₂ N—R ¹⁰ —NY ₂ ) represented by the above general formula (ii). . Thus, a polymer having repeating units represented by the general formulas (II) to (III) can be formed by appropriately selecting the monomer components in accordance with the target design. From such a viewpoint, the polymer (polyimide precursor resin) having the repeating units represented by the above general formulas (II) to (III) is a compound represented by the above general formula (4) and a derivative of the compound. It can be said that the polymer is a polymer of at least one of diester dicarboxylic acid and diester dicarboxylic acid dichloride which is the aromatic diamine (HY ¹ N—R ¹⁰ —NY ² H) represented by the general formula (ii). .

In addition, as described above, the polyimide precursor resin (polymer) according to the present invention is selected from the group consisting of repeating units represented by the above general formulas (I) to (III). Polymers containing at least one repeating unit are preferred. Among the repeating units represented by the general formulas (I) to (III), X ¹ in the formula (I) is represented by the general formula (I-1) from the viewpoint of dimensional stability of the obtained polyimide. In view of solvent solubility of the resulting polyimide, X ¹ in the formula (I) is preferably a tetravalent group represented by the above general formula (I-2). From the viewpoint of the low dielectric properties of the resulting polyimide, a repeating unit that is a group is preferably a repeating unit in which X ^{1 in the} formula (I) is a tetravalent group represented by the general formula (I-3). preferable. From the viewpoint of the mechanical properties of the resulting polyimide, among the repeating units represented by the general formula (I), X ^{1 in the} formula (I) is represented by the general formula (I-1). A repeating unit which is a tetravalent group is particularly preferred.

As the repeating unit represented by the general formula (I), from the viewpoint of ease of imidization, it Y ¹ and Y ² are repeating units each a hydrogen atom (repeating unit of polyamic acid) Is more preferable.

Further, when such a polyimide precursor resin (polymer) contains the repeating units represented by the above general formulas (I) to (III), for example, it is selected from the group consisting of these repeating units. It may contain 1 type, or may contain 2 or more types of repeating units selected from the group consisting of these repeating units.

Further, when such a polyimide precursor resin (polymer) contains a repeating unit represented by the above general formulas (I) to (III), it is represented by these general formulas (I) to (III). The total amount of repeating units (the total content) is 20 to 100 mol% (more preferably 30 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 50 to 100 mol%) based on all repeating units. And particularly preferably 60 to 100 mol%). Further, regarding the total amount (total amount) of the repeating units represented by the general formulas (I) to (III), the lower limit value of the numerical range is more preferably 70 mol%, and 80 mol%. More preferably, it is most preferable that it is 90 mol%. When the total amount (total amount) of such repeating units is less than the lower limit, it tends to be difficult to make the heat resistance based on the glass transition temperature (Tg) a higher level.

In addition, the polyimide precursor resin containing any one of the repeating units represented by the above general formulas (I) to (III), which is suitable as the polyimide precursor resin according to the present invention, may be used depending on the application to be used. The repeating unit may be further included. Such other repeating units are not particularly limited, and include known repeating units that can be used as the repeating units of the polyimide precursor resin. As such other repeating units, for example, other tetracarboxylic dianhydrides other than the compounds represented by the general formulas (1) to (4) are used, and these are represented by the above formula: HY ¹ N— It may be a repeating unit formed by reacting with an aromatic diamine represented by R ⁴ —NY ² H.

Such other tetracarboxylic dianhydrides are not limited to tetracarboxylic dianhydrides having two norbornane skeletons in the molecule, but are known tetracarboxylic acid dianhydrides that can be used for the preparation of polyamic acid and polyimide. Carboxylic dianhydrides can be used as appropriate, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride, 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- , 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene- Aliphatic or cycloaliphatic tetracarboxylic such as 1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Acid dianhydride; pyromellitic dianhydride, 3,3 ', 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′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4 , 4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3, 3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 3,3 ', 4,4'- Biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether Examples thereof include dianhydrides and aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride.

As such other repeating units, when a polyimide is finally formed, it is possible to obtain a cured product having a sufficient balance of characteristics such as heat resistance, transparency, mechanical strength and solvent solubility. In particular, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and 4,4 ' - (2,2-hexafluoroisopropylidene) at least one tetracarboxylic dianhydride selected from diphthalic dianhydride group consisting anhydride and, the _formula: with H ^{₂ N-R} 4 -NH ² It is preferably a repeating unit formed by reacting with an aromatic diamine, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyl Formed by reacting at least one tetracarboxylic dianhydride selected from the group consisting of tetracarboxylic dianhydrides with an aromatic diamine represented by the above formula: H ₂ N—R ⁴ —NH ₂ More preferred is a repeating unit.

When such a polyimide precursor resin is a polyamic acid, the intrinsic viscosity [η] is preferably 0.05 to 3.0 dL / g, and preferably 0.1 to 2.0 dL / g. Is more preferable. When the intrinsic viscosity [η] of such a polyamic acid is less than 0.05 dL / g, when a film-like polyimide is produced using the polyamic acid, the resulting film tends to become brittle, while 3.0 dL When it exceeds / g, the viscosity is too high and the processability is lowered. For example, when a film is produced, it is difficult to obtain a uniform film. The intrinsic viscosity [η] of such 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 so as to have a concentration of 0.5 g / dL, and a measurement sample (solution) is obtained. obtain. Next, using the measurement sample, the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [η]. In addition, as such a kinematic viscometer, an automatic viscosity measuring device (trade name “VMC-252”) manufactured by Kouaisha is used.

In order to form a polymer of tetracarboxylic dianhydride and diamine as described above, a method for producing such a polyimide precursor resin (polymer) is obtained by using tetracarboxylic dianhydride and diamine as described above. What is necessary is just to utilize, The preparation method (polymerization method) of a well-known polyimide precursor resin (polymer) can be utilized suitably. For example, when the compound represented by the general formula (1) is used as the tetracarboxylic dianhydride, a method for producing a polyamic acid described in International Publication No. 2011/099518 is used. When the compound represented by the general formula (2) is used as the tetracarboxylic dianhydride, a polyamic acid described in International Publication No. 2015/163314 is produced. The method for the above may be adopted as appropriate. In this way, a polyimide precursor resin (polymer) is prepared by appropriately using the polymerization conditions described in known literature depending on the types of monomers (tetracarboxylic dianhydride and diamine) used. May be.

<Additive compound (second component)>
The additive compound (second component) according to the present invention includes a tertiary phosphorus compound having a structure represented by the formula: CP in which a phosphorus atom and a carbon atom are directly bonded in the molecule, and a phosphorus atom and a carbon atom in the molecule. Is at least one compound selected from the group consisting of a quaternary phosphorus compound containing a structure represented by the formula: CP and a quaternary amine compound.

Examples of such tertiary phosphorus compounds include triphenylphosphine, triparatolylphosphine, tritertiarybutylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, 1,4-bisdiphenylphosphinobutane, and the like. As such a tertiary phosphorus compound, from the viewpoint of mechanical properties of the resulting polyimide, triphenylphosphine, tripalatolylphosphine, and tricyclohexylphosphine are more preferable, triphenylphosphine, and triparatolylphosphine are more preferable, and triphenylphosphine Is particularly preferred.

Examples of such quaternary phosphorus compounds include benzyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, normal butyltriphenylphosphonium chloride, normal butyltriphenylphosphonium dicyanamide phenacetyltriphenylphosphonium chloride, hexyltriphenyl. Phosphonium bromide, octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, benzyltriphenylphosphonium bromide, 2-methylbenzyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, phenacetiltri Phenylphosphoni Mukuroraido, allyl triphenylphosphonium bromide, quaternary phosphorus salts such as tetraphenylphosphonium tetraphenyl borate, and the like. Examples of such quaternary phosphorus compounds include benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride, tetraphenylphosphonium from the viewpoint of the mechanical properties of the resulting polyimide and solubility in solvents. Bromide and tetraphenylphosphonium tetraphenylborate are more preferred, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate are more preferred, and benzyltriphenylphosphonium chloride and benzyltriphenylphosphonium bromide are particularly preferred.

Further, as the quaternary amine compound, for example, an organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) (for example, octylate of DBU, p-toluenesulfone of DBU) Acid salt, DBU formate, DBU orthophthalate, etc.), phenol resin salt of DBU, phenol resin salt of 1,5-diazabicyclo [4.3.0] none-5-ene (DBN), manufactured by San Apro Quaternary amine salts such as U-CAT 5002, tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium hydrochloride, tetraethylammonium hydrochloride, tetramethylammonium tetraphenylborate; and the like. Among such quaternary amine compounds, when a polyimide is produced, an organic acid salt of DBU is preferable from the viewpoint of obtaining higher heat resistance and mechanical strength, and a phenol salt of DBU and an octylate salt of DBU are preferable. More preferred.

In addition, among these additive compounds (second component), when polyimide is prepared, it is possible to impart flame retardancy to the polyimide, and it does not affect the storage stability of the polyimide precursor solution. The tertiary phosphorus compound is particularly preferable, and triphenylphosphine is most preferable. In addition, as such a compound (second component), one kind may be used alone, or two or more kinds may be used in combination.

<Solvent (third component)>
It does not restrict | limit especially as a solvent (3rd component) concerning this invention, For example, what can be utilized for the resin solution of a polyamic acid can be utilized suitably. Examples of such solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, γ-modified prolactone, δ Valerolactone, γ-Prolactone, ε-Prolactone, α-methyl-γ-butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, Aprotic polar solvents such as hexamethylphosphoric triamide and pyridine; phenolic solvents such as m-cresol, p-cresol, xylenol, phenol and halogenated phenol; ethers such as tetrahydrofuran, dioxane, cellosolve and glyme solvent; Aromatic solvents such as benzene, toluene and xylene; Ketone solvents such as cyclopentanone and cyclohexanone; Nitrile solvents such as acetonitrile and benzonitrile; Acetic esters such as ethyl acetate, butyl acetate, isobutyl acetate and propylene glycol methyl acetate Examples thereof include ketone solvents such as system solvents, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, and acetone.

Examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ from the viewpoints of solubility, film formability, productivity, industrial availability, presence / absence of existing equipment, and price. -Butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferred, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, tetramethylurea are more preferred, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and tetramethylurea are particularly preferred. In addition, you may utilize such a solvent individually by 1 type or in combination of 2 or more types.

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

<Composition of composition>
The polyimide precursor resin composition of the present invention includes the polyimide precursor resin (first component), the additive compound (second component), and the solvent (third 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 second component relative to 100 parts by mass of the first component The content is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 15 parts by mass. When the content of such an additive compound (second component) is less than the lower limit, when the polyimide is produced, the mechanical strength of the polyimide tends to decrease. On the other hand, when the upper limit is exceeded, the polyimide is produced. In addition, the heat resistance of polyimide tends to decrease.

Further, the content of such a solvent is not particularly limited, but is preferably 50 to 99% by mass, more preferably 50 to 90% by mass, still more preferably 60 to 90% by mass, It is particularly preferably 70 to 90% by mass. When the content of the solvent is less than the lower limit, it is difficult to make the polyimide precursor resin sufficiently dissolved in the solvent, and it tends to be difficult to obtain a uniform varnish composition. When the above upper limit is exceeded, the polyimide precursor resin tends to be imidized and cured to produce a polyimide, whereby the mechanical strength of the polyimide tends to decrease.

<About the method for manufacturing a composition>
The method for producing such a 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 (first component). There is no particular limitation as long as it is a method capable of producing a polyimide precursor resin composition containing three components). For example, in the presence of a solvent, a tetracarboxylic acid dicarboxylate having two norbornane skeletons in the molecule is used. It is selected from the group consisting of anhydrides (which may contain other tetracarboxylic dianhydrides other than tetracarboxylic dianhydrides having two norbornane skeletons in the molecule as necessary) and derivatives thereof At least one; and the above diamine (preferably the compound represented by the above formula (ii) (HY ¹ N—R ¹⁰ —NY ² H), more preferably the formula: H ₂ N—R ¹⁰ —N A compound represented by H ₂ ); and a polymer of the diamine and at least one selected from the group consisting of the tetracarboxylic dianhydride and derivatives thereof. Any step of reacting at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative with the diamine in the step [before reaction, during reaction (Note that the term “during reaction” here refers to the use of a reaction solution obtained after once reacting at least one selected from the group consisting of the tetracarboxylic dianhydride and derivatives thereof with the diamine. In the case of further proceeding the polymerization reaction, including any stage before or during the polymerization reaction using the reaction solution), any stage after the reaction] A method including a step of adding a compound (hereinafter, this method is simply referred to as “method (I)” for convenience) can be suitably employed. The tetracarboxylic dianhydride and its derivative, diamine, solvent, and additive compound used in such method (I) are the same as those already described (the preferred ones are also the same). is there).

In such a method (I), in the presence of a solvent, the tetracarboxylic dianhydride (if necessary, other tetracarboxylic acid other than tetracarboxylic dianhydride having two norbornane skeletons in the molecule) Specific conditions for reacting the diamine with at least one selected from the group consisting of dianhydrides (which may contain dianhydrides) and derivatives thereof are not particularly limited, depending on the types of components used The conditions may be set as appropriate so that the polymerization reaction proceeds. In addition, as such a method (I), at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative is used as a compound represented by the general formulas (1) to (4) ( Other tetracarboxylic dianhydrides may be included if necessary) and at least one selected from the group consisting of derivatives thereof, and the diamine represented by the above general formula (ii). At least one selected from the group consisting of the compounds represented by the general formulas (1) to (4) and derivatives thereof in the presence of the solvent, and the above general formula A first step of obtaining a reaction liquid by reacting with the aromatic diamine represented by (ii), and adding the additive compound to the reaction liquid to represent the above general formulas (I) to (III) Group of repeating units A method (I-1) comprising a polyimide precursor resin having at least one repeating unit selected from the above, a second step of obtaining a polyimide precursor resin composition containing the additive compound and the solvent. It is preferable to do.

As in the method (I-1), after the polymerization reaction is once advanced in the first step, the additive compound is added in the second step, so that the varnish is applied to the substrate to form a film. In this stage, the molecular weight of the polyimide can be further improved using the additive compound. As described above, when a polyimide film is obtained by using the additive compound in the film forming stage, it is composed of the compounds represented by the general formulas (1) to (4) and derivatives thereof in the presence of the solvent. When at least one selected from the group is reacted with the aromatic diamine represented by the general formula (ii) to obtain a polyimide film without using the additive compound (in any stage of preparing the polyimide) Is advantageous in that the mechanical properties of the resulting polyimide film are superior to those in the case where the additive compound is not used. Hereinafter, the method (I-1) suitable as the method (I) will be described.

First, the first step will be described. In the first step, in the presence of a solvent, at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative and the aromatic diamine are reacted to prepare a reaction solution containing a polyimide precursor resin. It is a process to obtain. The “at least one selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof” used in the first step is the compounds represented by the general formulas (1) to (4) and those And at least one selected from the group consisting of other tetracarboxylic dianhydrides and derivatives thereof, as long as it contains at least one selected from the group consisting of these derivatives. You may go out.

As the solvent used in the first step, the above-mentioned solvents can be used as appropriate. Among them, the solvent can dissolve both the tetracarboxylic dianhydride and the aromatic diamine. preferable. Such solvents may be used alone or in combination of two or more.

In such a method, the amount of at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative (a component to be reacted with the aromatic diamine represented by the general formula (ii)) is used. (The total amount of the compounds represented by the general formulas (1) to (4), other tetracarboxylic dianhydrides and their derivatives), and the aromatic diamine represented by the general formula (ii) usage: the ratio of the (expression amount of HY 1 ^N-R 4 ^-NY compounds represented by, 2 ^H) is not particularly limited, when using the derivatives, before induction derivatives thereof either tetracarboxylic Assuming that it is an acid dianhydride (converted), the tetracarboxylic dianhydride used in the reaction is equivalent to 1 equivalent of the amino group of the aromatic diamine. The amount of all acid anhydride groups in the body is assumed to be 0.5 to 2 equivalents of the tetracarboxylic dianhydride before induction (before modification). Preferably, it is 0.8 to 1.2 equivalent. When at least one selected from the group consisting of such tetracarboxylic dianhydrides and derivatives thereof and a suitable use ratio of the aromatic diamine is less than the lower limit, the polymerization reaction does not proceed efficiently and the high molecular weight polyamic acid. On the other hand, if the upper limit is exceeded, a high molecular weight polyamic acid tends to be not obtained as described above.

Further, the amount of the solvent used in the first step is at least one amount selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof used in the reaction (the above general formulas (1) to (4)). And the amount of the aromatic diamine (formula: HY ¹ N—R ⁴ —NY ² H) and the other tetracarboxylic dianhydrides and their derivatives) 1 to 80 mass based on the total amount of the aromatic diamine and the solvent, wherein the total amount (total amount of the reactant [substrate]) is at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof % (More preferably 5 to 50% by mass). If the amount of the solvent used is less than the lower limit, it tends to be difficult to obtain polyamic acid efficiently. On the other hand, if the amount exceeds the upper limit, stirring tends to be difficult due to the increase in viscosity, and a high molecular weight product tends not to be obtained. It is in.

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 derivatives thereof is to react these compounds. The temperature can be adjusted to a temperature that can be adjusted appropriately, and is not particularly limited, but is preferably −20 to 100 ° C. (more preferably 5 to 80 ° C.).

In the first step, the aromatic diamine may be reacted with at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative from tetracarboxylic dianhydride and its derivative. A method capable of performing a polymerization reaction of at least one selected from the group consisting of aromatic diamines can be used as appropriate, and is not particularly limited. For example, in an atmospheric pressure, under an inert atmosphere such as nitrogen, helium, or argon In the method, it is preferable to employ a method in which the tetracarboxylic dianhydride and the aromatic diamine are added to the solvent at the reaction temperature and then reacted for about 1 to 72 hours. If the reaction temperature or reaction time is less than the lower limit, the molecular weight of the polyimide precursor tends not to be sufficiently improved. On the other hand, if the upper limit is exceeded, depolymerization of the polyimide precursor proceeds and the molecular weight tends to decrease. It is in. Thus, 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 additive compound is added to the reaction solution obtained in the first step.

In this way, in the second step, at least one selected from the group consisting of the tetracarboxylic dianhydride and derivatives thereof by adding the additive compound (second component) to the reaction solution ( The compounds represented by the general formulas (1) to (4) and other tetracarboxylic dianhydrides and derivatives thereof added as necessary, and the fragrance represented by the general formula (ii). A polymer with a group diamine (at least one selected from the group consisting of compounds represented by the above formula: HY ¹ N—R ⁴ —NY ² H). It is possible to obtain a polyimide precursor resin composition comprising a polyimide precursor resin having at least one type of repeating unit selected from the group consisting of repeating units represented by formula (II), the additive compound, and the solvent. It made.

When the polyimide precursor resin composition thus obtained is heated, the polyimide precursor resin can be heated in the presence of the additive compound (second component) and a solvent, and the heating step Since the additive compound (second component) serves as a catalyst for promoting the reaction, the molecular weight of the finally obtained polyimide can be improved.

In addition, the amount of the additive compound (second component) used is at least one amount selected from the group consisting of the tetracarboxylic dianhydride and derivatives thereof used in Method (I-1) ( The compound represented by the above general formulas (1) to (4) and other tetracarboxylic dianhydrides and their derivatives added as necessary, and the method (I-1). The amount of the aromatic diamine represented by the general formula (ii) (the total amount of the compound represented by the formula: Y ₂ N—R ⁴ —NY ₂ ) and the additive compound used in the method (I-1) ( The amount of the additive compound (addition amount) is preferably 0.1 to 30% by mass, and preferably 0.5 to 10% by mass with respect to the total amount of the second component). More preferably, it is an amount. If the content of such an additive compound (second component) is less than the lower limit, it is difficult to improve the molecular weight of the polyimide when forming the polyimide using the resulting polyimide precursor resin composition, Even if a polyimide is produced using such a composition, the heat resistance and mechanical strength of the polyimide tend to be reduced. On the other hand, if the upper limit is exceeded, the polyimide precursor resin composition obtained is used to obtain a polyimide. The side reaction proceeds during the production of the product, a uniform polyimide cannot be obtained, and the physical properties of the resulting polyimide tend to be reduced. In addition, in order to adjust the ratio (addition amount) of the additive compound, the solvent may be added again when the additive compound is added.

Thus, a polyimide precursor resin having at least one repeating unit selected from the group consisting of the repeating units represented by the general formulas (I) to (III), the additive compound, the solvent, The polyimide precursor resin composition containing can be obtained.

In such a method (I-1), the tetracarboxylic dianhydride was used, and the compound represented by the above formula: H ₂ N—R ⁴ —NH ₂ was used as the aromatic diamine. In this case, it has at least one repeating unit selected from the group consisting of repeating units represented by the above general formulas (I) to (III), and Y ^{1 in} the general formula of the repeating unit and A polyimide precursor resin composition comprising a polyimide precursor resin composed of a polyamic acid in which all Y ² are hydrogen atoms, the additive compound, and the solvent can be obtained.

The method for producing the polyimide precursor resin composition of the present invention has been described based on the preferred methods (I) and (I-1). The polyimide precursor resin composition of the present invention has been described above. The method for producing the product is not limited to the above-described method, and is a mixture of at least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof and a diamine. A polyimide precursor resin that is a polymer; a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: a tertiary phosphorus compound including a structure represented by CP; a phosphorus atom and a carbon atom are directly bonded in a molecule A polyimide precursor containing: 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 solvent; As long as the method capable of obtaining a fat composition, it may be employed as appropriate.

Moreover, the polyimide precursor resin composition of the present invention obtained in this way is used as a varnish (resin solution) for polyimide preparation, and the polyimide precursor resin composition is imidized to obtain a polyimide resin. A composition (a composition containing polyimide and the additive compound) can be obtained.

The method for obtaining such a polyimide resin composition is not particularly limited, and a known method capable of imidizing the polyimide precursor resin in the polyimide resin composition to form a polyimide can be appropriately adopted. it can. The imidization method is not particularly limited, and a known method capable of imidizing the polyimide precursor resin can be appropriately employed. For example, when the polyimide precursor resin is a polyamic acid. , Imidation method described in International Publication No. 2011/099518, imidization method described in International Publication No. 2015/163314, imidation described in International Publication No. 2017/030019 These methods can be employed as appropriate. Further, as such an imidization method, a so-called chemical imidization method (a polyimide precursor resin (preferably a polyamic acid) in the polyimide precursor resin composition of the present invention described above is converted into an imide using a known imidizing agent). And the polyimide precursor resin composition of the present invention is heated at a temperature of 60 to 450 ° C. (more preferably 80 to 400 ° C.) to give a polyimide precursor in the polyimide precursor resin composition. It is preferable to employ a method of imidizing a body resin (preferably polyamic acid).

When a polyimide is prepared by imidizing a polyimide precursor resin having a repeating unit represented by the above general formula (I), the following general formula (I ′):

[Wherein, X ¹ represents at least one selected from the group consisting of tetravalent groups represented by the above general formulas (I-1) to (I-3), and R ¹⁰ has 6 to 50 carbon atoms. An arylene group of ]
The polyimide which has a repeating unit represented by this can be obtained. Incidentally, ^{X 1} and ^{R 10} in the general formula (I ') has the same meaning as ^{X 1} and ^{R 10} in the formula (I), is the same as the preferable examples.

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 ′):

[Wherein R ¹⁰ represents an arylene group having 6 to 50 carbon atoms. ]
The polyimide which has a repeating unit represented by this can be obtained. In addition, R < ¹⁰ > in the said general formula (II ') is synonymous with R < ¹⁰ > in the said general formula (II), The suitable thing is also the same.

In addition, when a polyimide resin composition is prepared using such a polyimide precursor resin composition of the present invention as a varnish (resin solution) for polyimide preparation (an imidized product of the polyimide precursor resin composition of the present invention). When prepared, it is possible to efficiently and reliably produce polyimide having higher toughness while maintaining characteristics such as linear expansion coefficient, glass transition temperature and total light transmittance at a sufficiently high level. Become. In addition, the polyimide obtained by using the polyimide precursor resin composition of the present invention in this way has, for example, a film for a flexible wiring board, a heat-resistant insulating tape, a wire enamel, a semiconductor protective coating agent, and a semiconductor protective coating. Insulating film for rewiring, liquid crystal alignment 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, TFT substrate film for flat panel detector, seamless polyimide belt for copying machine (so-called transfer belt), transparent electrode substrate (transparent electrode substrate for organic EL, transparent electrode substrate for solar cell, electronic paper Transparent electrode substrate), interlayer insulation film, Sensor substrate, image sensor substrate, light emitting diode (LED) reflector (LED illumination reflector: LED reflector), LED illumination cover, LED reflector illumination cover, coverlay film, high ductility composite substrate It is particularly useful as a material for producing resists for semiconductors, lithium ion batteries, organic memory substrates, organic transistor substrates, organic semiconductor substrates, color filter base materials and the like. Moreover, the polyimide obtained by using such a polyimide precursor resin composition of the present invention can have a shape other than the above-described uses, such as a powdered body, various molded bodies, etc. It can also be used as appropriate for automobile parts, aerospace parts, bearing parts, seal materials, bearing parts, gear wheels, valve parts, and the like.

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

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

A tetracarboxylic dianhydride represented by the formula (norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic acid Anhydride: The tetracarboxylic dianhydride represented by the general formula (A) is hereinafter referred to as “CpODA”).

(Synthesis Example 2: Synthesis of BNBDA)
In accordance with the method described in Examples 1-2 of WO2017 / 030019, the following general formula (B):

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

(Synthesis Example 3: Synthesis of BzDA)
In accordance with the method described in Example 1 of WO2015 / 163314, the following general formula (C):

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

(Synthesis Example 4: Synthesis of DNDA)
In accordance with the method described on pages 1117 to 1123 of Macromolecules (Vol. 27) published in 1994, the following general formula (D):

A tetracarboxylic dianhydride represented by the formula (hereinafter referred to as “DNDA”) was prepared.

<About abbreviations of monomers, etc.>
Abbreviations and the like are described below for the tetracarboxylic dianhydrides, aromatic diamines, and additive compounds used in the following Examples and the like. In addition, the following abbreviations etc. are utilized for the description in an Example depending on the case.

(1) Tetracarboxylic dianhydride CpODA: tetracarboxylic dianhydride represented by the above general formula (A) (Synthesis Example 1)
BNBDA: tetracarboxylic dianhydride represented by the above general formula (B) (Synthesis Example 2)
6FDA: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
BzDA: tetracarboxylic dianhydride represented by the above general formula (C) (Synthesis Example 3)
DNDA: tetracarboxylic dianhydride represented by the above general formula (D) (Synthesis Example 4)
(2) Aromatic diamine DABAN: 4,4'-diaminobenzanilide (manufactured by Nippon Pure Chemicals Co., Ltd.)
PPD: 1,4-paraphenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
TFMB: 2,2′-bis (trifluoromethyl) benzidine (manufactured by Seika Industry Co., Ltd.)
DDE: 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
m-Tol: m-tolidine (also known as 2,2′-dimethylbenzidine, manufactured by Tokyo Chemical Industry Co., Ltd.)
(3) Additive Compound Tertiary Phosphorus Compound (A): Triphenylphosphine (trade name “TPP”: manufactured by Hokuko Chemical Industries)
Tertiary phosphorus compound (B): Triparatolylphosphine (trade name “TPTP”: manufactured by Hokuko Chemical Industries)
Quaternary amine compound (A): Tetramethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
Quaternary phosphorus compound (A): benzyltriphenylphosphonium bromide (trade name “U-cat 5003”: San Apro Co., Ltd.).

Example 1
<First step>
Under a nitrogen atmosphere, DABAN 4.54 g (20.00 mmol) was introduced as an aromatic diamine into a 100 mL screw tube, and CpODA 7.69 g (20.00 mmol) 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 mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After separating 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 the additive compound were added to the reaction solution. After adding 0.118 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring at room temperature for 6 hours, polyamic acid which is a polymer of CpODA and DABAN and tertiary phosphorus compound A polyimide precursor resin composition containing (A) and a solvent (dimethylacetamide) was obtained.

(Example 2)
Using the reaction solution obtained in the first step of Example 1, 3.07 g of the reaction solution was separated and introduced into a 10 mL screw tube, and then dimethylacetamide (N, N-dimethyl) as a solvent was added to the reaction solution. After adding 1.01 g of acetamide) and 0.029 g of triparatolylphosphine (tertiary phosphorus compound (B)), the mixture is stirred at room temperature for 6 hours, thereby polyamic acid which is a polymer of CpODA and DABAN Then, a polyimide precursor resin composition containing a tertiary phosphorus compound (B) and a solvent (dimethylacetamide) was obtained.

(Example 3)
<First step>
Under a nitrogen atmosphere, 1.70 g (7.50 mmol) of DABAN and 0.27 g (2.50 mmol) of PPD as aromatic diamine were introduced into a 50 mL screw tube, and 3.84 g (10.10 of CpODA as tetracarboxylic dianhydride). 00 mmol) was introduced. Next, 23.3 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After separating 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 the additive compound were added to the reaction solution. After adding 0.077 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid which is a polymer of CpODA, DABAN and PPD, and tertiary A polyimide precursor resin composition containing a phosphorus compound (A) and a solvent (dimethylacetamide) was obtained.

Example 4
<First step>
Under a nitrogen atmosphere, DABAN 1.14 g (5.00 mmol) and PPD 0.541 g (5.00 mmol) are introduced as aromatic diamines into a 50 mL screw tube, and CpODA 3.84 g (10. 0 mmol) was introduced. Next, 22.1 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After 4.41 g of the reaction solution prepared in the first step was introduced into a 10 mL screw tube, 1.48 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the additive compound were added to the reaction solution. After adding 0.086 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid which is a polymer of CpODA, DABAN and PPD, and tertiary A polyimide precursor resin composition containing a phosphorus compound (A) and a solvent (dimethylacetamide) was obtained.

(Example 5)
<First step>
Under a nitrogen atmosphere, DABAN 1.14 g (5.00 mmol) and TFMB 1.60 g (5.00 mmol) were introduced as aromatic diamines into a 50 mL screw tube, and CpODA 3.84 g (10. 0 mmol) was introduced. Next, 26.3 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After separating 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 the additive compound were added to the reaction solution. After adding 0.073 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid which is a polymer of CpODA, DABAN and TFMB, and tertiary A polyimide precursor resin composition containing a phosphorus compound (A) and a solvent (dimethylacetamide) was obtained.

(Example 6)
<First step>
Under a nitrogen atmosphere, DABAN 0.909 g (4.00 mmol) and DDE 0.200 g (1.00 mmol) were introduced as aromatic diamines into a 50 mL screw tube, and BNBDA 1.65 g (5. 00 mmol) was introduced. Next, 11.0 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After 4.65 g of the reaction liquid prepared in the first step was separated and introduced into a 10 mL screw tube, 1.69 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the additive compound were added to the reaction liquid. After adding 0.093 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid, which is a polymer of BNBDA, DABAN and DDE, and tertiary A polyimide precursor resin composition containing a phosphorus compound (A) and a solvent (dimethylacetamide) was obtained.

(Example 7)
<First step>
Under a nitrogen atmosphere, DABAN 0.909 g (4.00 mmol) and TFMB 0.320 g (1.00 mmol) were introduced as aromatic diamines into a 50 mL screw tube, and BNBDA 1.65 g (5. 00 mmol) was introduced. Next, 11.5 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
4.65 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, and then 1.50 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the additive compound were added to the reaction solution. After adding 0.099 g of triphenylphosphine (tertiary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid which is a polymer of BNBDA, DABAN and TFMB, and tertiary A polyimide precursor resin composition containing a phosphorus compound (A) and a solvent (dimethylacetamide) was obtained.

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

(Comparative Example 2)
Using the reaction liquid obtained in the first step of Example 1, 4.53 g of the reaction liquid was separated and introduced into a 10 mL screw tube, and then dimethylacetamide (N, N-dimethyl) as a solvent was added to the reaction liquid. Acetamide) 1.65 g and trimethyl phosphite 0.091 g were added, and the mixture was stirred at room temperature for 6 hours, so that polyamic acid, which is a polymer of CpODA and DABAN, trimethyl phosphite, A polyimide precursor resin composition containing a solvent (dimethylacetamide) was obtained.

[Evaluation of characteristics of polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2]
<Preparation of polyimide>
Using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as polyamic acid varnishes for producing polyimide, films made of polyimide were prepared as follows. That is, first, the polyimide precursor resin composition was spin-coated on a large slide glass (trade name “S9213” manufactured by Matsunami Glass Industrial Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm), and then on a glass plate. A coating film of the polyimide precursor resin composition was formed. Thereafter, the glass plate on which the coating film has been formed is put into an oven, the temperature condition is set to 70 ° C., and the mixture is allowed to stand for 2 hours in a nitrogen atmosphere. Furthermore, the temperature conditions were changed to the final heating temperatures shown in Table 1 (Example 1 and Comparative Example 1: 370 ° C., Examples 2 to 7 and Comparative Example 2: 350 ° C.) for each type of polyimide precursor resin composition. A polyimide-coated glass in which the coating film is cured by being changed and allowed to stand for 30 minutes under the temperature condition of the final heating temperature, and a thin film made of polyimide (a film made of polyimide) is coated on the glass substrate Got. Next, the polyimide-coated glass thus obtained is taken out of the oven, and the polyimide-coated glass is immersed in hot water at 90 ° C. for 0.5 hours, and the film is peeled off and collected from the glass substrate. A film consisting of In addition, as for the film which consists of obtained polyimide, when the color was confirmed visually, it was confirmed that it is colorless and transparent. In addition, Table 1 shows the thickness of the obtained film made of polyimide.

<Measurement of linear expansion coefficient (CTE)>
A film made of polyimide obtained by using each of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above (an imidized polyimide precursor resin composition) was obtained. Using each, the linear expansion coefficient of the obtained polyimide was measured as follows. That is, first, a film for measurement having a size of 20 mm in length and 5 mm in width was formed from the polyimide film (in the case of the thickness range shown in Table 1, the thickness is a measured value. The film thickness of each example was used as it was. Next, the obtained film for measurement was vacuum-dried (120 ° C., 1 hour), and then heat-treated at 200 ° C. for 1 hour in a nitrogen atmosphere to prepare a measurement sample (dry film). Next, using the obtained measurement sample (dry film), using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) as a measuring device, in a nitrogen atmosphere, in a tensile mode (49 mN), a rate of temperature increase Using the condition of 5 ° C./min, measuring the change in length of the sample from 50 ° C. to 200 ° C., and calculating the average value of the change in length per 1 ° C. in the temperature range of 100 ° C. to 200 ° C. Measured by seeking.

<Measurement of glass transition temperature (Tg)>
A film made of polyimide obtained by using each of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above (an imidized polyimide precursor resin composition) was obtained. Using each, the value (unit: ° C) of the glass transition temperature (Tg) of the obtained polyimide was measured as follows. That is, a sample having a length of 20 mm and a width of 5 mm cut out from the polyimide film as a measurement sample (the thickness of the sample does not affect the measured value, so the thickness of the film obtained in the example remains the same. And using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) as a measuring device, under a nitrogen atmosphere, in a tensile mode (49 mN), at a temperature rising rate of 5 ° C./min. The TMA curve is obtained by measurement and the glass transition temperature of the polyimide constituting the film obtained in each example is obtained by extrapolating the curve before and after the inflection point of the TMA curve resulting from the glass transition. The value (unit: ° C.) of (Tg) was determined. The obtained results are shown in Table 1.

<Measurement of 5% weight loss temperature (Td 5%)>
The 5% weight loss temperature of polyimide was determined by the films made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 4, Example 6 and Comparative Examples 1 and 2, respectively (polyimide precursor). A sample of about 10 mg was prepared using each of the imidized resin compositions), put in an aluminum sample pan, and a thermogravimetric analyzer (trade name “TG” manufactured by SII Nano Technology Co., Ltd.) as a measuring device. / DTA7200 ”), the scanning temperature is set from 40 ° C. to 550 ° C. in a nitrogen gas atmosphere, and heating is performed at a temperature rising rate of 10 ° C./min, and the weight of the sample used is reduced by 5%. It was determined by measuring the temperature.

<Measurement of total light transmittance and yellowness (YI)>
A film made of polyimide obtained by using each of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above (an imidized polyimide precursor resin composition) was obtained. Using each, the total light transmittance (unit:%) and yellowness (YI) of the obtained polyimide were measured as follows. That is, the film made of the polyimide is used as it is as a sample for measurement, and as a measuring device, a trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. The total light transmittance (unit:%) and yellowness (YI) of the polyimide resin composition constituting the film obtained in each example and the like were respectively determined by performing measurement using “total SD6000”. In this measurement, the total light transmittance was measured with a trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. Yellowness was measured. Further, the total light transmittance is obtained by measuring in accordance with JIS K7361-1 (issued in 1997), and the yellowness (YI) is measured in accordance with ASTM E313-05 (issued in 2005). Was determined by The obtained results are shown in Table 1.

<Measurement of toughness>
A film made of polyimide obtained by using each of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above (an imidized polyimide precursor resin composition) was obtained. Using each, the toughness was determined by tactile sensation. The index of determination is shown below. The determination results are shown in Table 1.
(Toughness evaluation)
A: From the tactile sensation, it can be judged that the film is very tough, and it is recognized that the toughness is very high.
B: It can be judged from the touch that the film is reasonably strong, and the toughness is moderate.

Table 1 also shows the types of acid dianhydride, diamine, and additive compound used in each example. In addition, in the description of the acid dianhydride and diamine in Table 1, the numerical values in parentheses indicate the molar ratio of the two types of components with respect to those in which two types of components are described in one frame.

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

In addition, films made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7, respectively, use the polyimide precursor resin compositions obtained in Comparative Examples 1 and 2. It was found that the toughness was higher than that of the obtained polyimide film.

From these results, according to the polyimide precursor resin compositions of the present invention (Examples 1 to 7), the characteristics such as the linear expansion coefficient, the glass transition temperature, and the total light transmittance are maintained at a sufficiently high level. It was confirmed that polyimide having higher toughness can be produced efficiently and reliably.

(Example 8)
<First step>
Under a nitrogen atmosphere, m-Tol 2.12 g (10.0 mmol) was introduced as an aromatic diamine and CpODA 3.84 g (10.0 mmol) was introduced as a tetracarboxylic dianhydride into a 50 mL screw tube. Next, 24.9 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
5.67 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, and then 0.083 g of triphenylphosphine (tertiary phosphorus compound (A)) as the additive compound was added to the reaction solution. After that, the polyimide precursor containing polyamic acid, which is a polymer of CpODA and m-Tol, tertiary phosphorus compound (A), and solvent (dimethylacetamide) is stirred for 6 hours at room temperature. A body resin composition was obtained.

Thus, using the polyimide precursor resin composition obtained in Example 8, the final heating temperature was set to 350 ° C., and the above-mentioned “Examples 1 to 7 and Comparative Examples 1 to 3” were obtained. By adopting a method similar to the method adopted for “evaluation of properties of the polyimide precursor resin composition”, a film made of polyimide (film thickness: 14 μm) is prepared, glass transition temperature, total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 8 has a glass transition temperature of 334 ° C., a total light transmittance of 88%, and YI. The toughness evaluation result was A. Thus, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently obtained while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at a sufficiently high level. It was also found that it can be reliably manufactured.

Example 9
<First step>
Under 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 of 6FDA as a tetracarboxylic dianhydride (5. 00 mmol) was introduced. Next, 29.5 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
7.20 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, and then 0.143 g of triphenylphosphine (tertiary phosphorus compound (A)) as the additive compound was added to the reaction solution. Then, the polyimide precursor containing polyamic acid which is a polymer of CpODA, 6FDA and TFMB, tertiary phosphorus compound (A) and solvent (dimethylacetamide) is stirred for 6 hours at room temperature. A body resin composition was obtained.

Thus, using the polyimide precursor resin composition obtained in Example 9, the final heating temperature was set to 350 ° C., and the above-mentioned “Examples 1 to 7 and Comparative Examples 1 to 3” were obtained. A film (film thickness: 7 μm) made of polyimide was prepared by adopting the same method as that adopted for the “evaluation of characteristics of the polyimide precursor resin composition”, a glass transition temperature, a 5% weight reduction temperature. The total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 9 has a glass transition temperature of 360 ° C. and a 5% weight loss temperature of 480 ° C., The total light transmittance was 91%, YI was 1.9, and the toughness evaluation result was A. Thus, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently obtained while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at a sufficiently high level. It was also found that it can be reliably manufactured.

(Example 10)
<First step>
Under a nitrogen atmosphere, TFMB 3.2023 g (10.00 mmol) was introduced as an aromatic diamine and CpODA 3.8438 g (10.00 mmol) was introduced into a 50 mL screw tube. Next, 28.18 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, the obtained mixed liquid was stirred for 6 hours under a nitrogen atmosphere at room temperature to obtain a reaction liquid.

<Second step>
After separating 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 added. The polyimide precursor resin composition containing polyamic acid which is a polymer of CpODA and TFMB, a quaternary amine compound (A), and a solvent (dimethylacetamide) by stirring for 6 hours at room temperature. Got.

Thus, using the polyimide precursor resin composition obtained in Example 10, the polyimide obtained in Examples 1 to 9 and Comparative Example 1 was used except that the final heating temperature was 350 ° C. By adopting a method similar to the method employed for “evaluation of properties of precursor resin composition”, a film made of polyimide (film thickness: 10 μm) is prepared, and glass transition temperature, total light transmittance, YI and Toughness was measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 10 has a glass transition temperature of 355 ° C., a total light transmittance of 90%, and YI. The toughness evaluation result was A. Thus, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently obtained while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at a sufficiently high level. It was also found that it can be reliably manufactured.

(Example 11)
First, a reaction solution was obtained by adopting the same process as the first process employed in Example 1. Next, 5.21 g of the obtained reaction liquid was separated and introduced into a 10 mL screw tube, and then 1.76 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and benzyltrimethyl as an additive compound were added to the reaction liquid. After adding 104 mg of phenylphosphonium bromide (quaternary phosphorus compound (A)) and stirring for 6 hours at room temperature, polyamic acid which is a polymer of CpODA and DABAN and quaternary phosphorus compound (A ) And a solvent (dimethylacetamide), a polyimide precursor resin composition was obtained.

Thus, using the polyimide precursor resin composition obtained in Example 11, the final heating temperature was set to 370 ° C., except that “obtained in the above-mentioned“ Examples 1 to 7 and Comparative Examples 1 to 3 ”. By adopting the same method as that adopted for “evaluation of properties of the polyimide precursor resin composition”, a film made of polyimide (film thickness: 27 μm) was prepared, and the linear expansion coefficient, total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 11 has a linear expansion coefficient of 7 ppm / K, a total light transmittance of 87%, YI was 3.1, and the evaluation result of toughness was A. As described above, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently obtained while maintaining various physical properties such as linear expansion coefficient, total light transmittance, and YI to a sufficiently high level. It was also found that it can be reliably manufactured.

(Example 12)
<First step>
Under 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. Next, 2.0 g (5.00 mmol) of BzDA as tetracarboxylic dianhydride was added into the screw tube, and 3.5 g of dimethylacetamide (N, N-dimethylacetamide) was then applied to the wall surface of the screw tube. BzDA was added while washing and pouring to obtain a mixed solution. Then, when the mixed solution was stirred at 80 ° C. for 3.5 hours under a nitrogen atmosphere, a uniform solution was obtained. Next, the resulting solution was cooled to room temperature, and further stirred for 1 day to obtain a reaction solution.

<Second step>
After 2.75 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, 55.0 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the additive compound was added, 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) is obtained by stirring for 6 hours under the temperature conditions of It was.

In this way, using the polyimide precursor resin composition obtained in Example 12, the atmosphere when heating in the oven was changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (a glass plate with a coating film formed thereon). After being put in the oven, it is heated in a reduced pressure atmosphere from the stage of standing at 70 ° C. for 2 hours to the stage of standing at the final heating temperature for 30 minutes), and the final heating temperature is 350 ° C. A film made of polyimide by adopting the same method as that adopted for the above-mentioned “evaluation of characteristics of polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3” ( Film thickness: 18 μm) was prepared, and the glass transition temperature, 5% weight loss temperature, total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 12 has a glass transition temperature of 317 ° C. and a 5% weight loss temperature of 462 ° C., The total light transmittance was 89%, YI was 3.5, and the toughness evaluation result was A. As described above, according to the polyimide precursor resin composition of the present invention, the toughness is increased while maintaining various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI to a sufficiently high level. It has been found that it is possible to efficiently and reliably produce a polyimide having

(Example 13)
<First step>
Under a nitrogen atmosphere, 1.00 g (5.00 mmol) of DDE as an aromatic diamine was introduced into 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 mixed solution was stirred for 1 day under a nitrogen atmosphere at room temperature to obtain a reaction solution.

<Second step>
After 2.21 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, 44.1 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the additive compound was added, 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) is obtained by stirring for 6 hours under the temperature conditions of It was.

Thus, using the polyimide precursor resin composition obtained in Example 13, the atmosphere during heating in the oven was changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (a glass plate on which a coating film was formed). After being put in the oven, it is heated in a reduced pressure atmosphere from the stage of standing at 70 ° C. for 2 hours to the stage of standing at the final heating temperature for 30 minutes), and the final heating temperature is 350 ° C. A film made of polyimide by adopting the same method as that adopted for the above-mentioned “evaluation of characteristics of polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3” ( Film thickness: 17 μm) was prepared, and the glass transition temperature, 5% weight loss temperature, total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 13 has a glass transition temperature of 367 ° C. and a 5% weight loss temperature of 435 ° C., The total light transmittance was 89%, YI was 1.2, and the toughness evaluation result was A. As described above, according to the polyimide precursor resin composition of the present invention, the toughness is increased while maintaining various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI to a sufficiently high level. It has been found that it is possible to efficiently and reliably produce a polyimide having

(Example 14)
<First step>
Under a nitrogen atmosphere, 1.60 g (5.00 mmol) of TFMB as an aromatic diamine was introduced into a 50 mL screw tube, and 1.51 g (5.00 mmol) of DNDA was introduced as a tetracarboxylic dianhydride. Next, 12.5 g of dimethylacetamide (N, N-dimethylacetamide) was added into the screw tube to obtain a mixed solution. Next, when the obtained mixed liquid was stirred for 30 minutes under a nitrogen atmosphere at a temperature of 60 ° C., a uniform solution was obtained. Next, the obtained solution was cooled to room temperature and stirred for 1 day to obtain a reaction solution.

<Second step>
After 2.43 g of the reaction solution prepared in the first step was separated and introduced into a 10 mL screw tube, 48.7 mg of triphenylphosphine (tertiary phosphorus compound (A)) as the additive compound was added, 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) is obtained by stirring for 6 hours under the temperature conditions of It was.

Thus, using the polyimide precursor resin composition obtained in Example 14, instead of changing the atmosphere when heating in the oven to a nitrogen atmosphere, a reduced pressure atmosphere (a glass plate on which a coating film was formed) After being put in the oven, it is heated in a reduced pressure atmosphere from the stage of standing at 70 ° C. for 2 hours to the stage of standing at the final heating temperature for 30 minutes), and the final heating temperature is 350 ° C. A film made of polyimide by adopting the same method as that adopted for the above-mentioned “evaluation of characteristics of polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3” ( Film thickness: 15 μm) was prepared, and the linear expansion coefficient, glass transition temperature, 5% weight loss temperature, total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained using the polyimide precursor resin composition obtained in Example 14 has a linear expansion coefficient of 27 ppm / K, a glass transition temperature of 278 ° C., 5 % Weight reduction temperature was 415 ° C., total light transmittance was 91%, YI was 1.0, and the toughness evaluation result was A. Thus, according to the polyimide precursor resin composition of the present invention, various physical properties such as a linear expansion coefficient, a glass transition temperature, a 5% weight loss temperature, a total light transmittance, and a YI are sufficiently advanced. It has been found that a polyimide having higher toughness can be produced efficiently and reliably.

As described above, according to the present invention, a polyimide having higher toughness is efficiently and reliably produced while maintaining characteristics such as a linear expansion coefficient, a glass transition temperature, and a total light transmittance at a sufficiently high level. It is possible to provide a polyimide precursor resin composition that can be used.

Therefore, the polyimide precursor resin composition of the present invention produces products made of various polyimides such as various films, automotive parts, aerospace parts, bearing parts, seal materials, bearing parts, gear wheels and valve parts. It is particularly useful as a material for the purpose.

Claims

A polyimide precursor resin which is a polymer of at least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof;
Formula in which phosphorus atom and carbon atom are directly bonded in the molecule: tertiary phosphorus compound including structure represented by CP, Formula in which phosphorus atom and carbon atom are directly bonded in molecule: Represented by CP At least one additive compound selected from the group consisting of a quaternary phosphorus compound containing a structure and a quaternary amine compound;
With a solvent;
Containing a polyimide precursor resin composition.
At least one selected from the group consisting of tetracarboxylic dianhydrides having two norbornane skeletons in the molecule and derivatives thereof has the following general formula (1):

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

[In the formula (2), A represents one kind selected from the group consisting of a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. Each of 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 each R 5 independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. One species selected from the group is shown. ]
A compound represented by the following general formula (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 bonded to the same carbon atom. Two R 6 groups together may form a methylidene group, and each R 7 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 (4):

The polyimide precursor resin composition according to claim 1, wherein the polyimide precursor resin composition is at least one selected from the group consisting of:
The polyimide precursor resin has the following general formula (I):

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

[In Formula (I-1), R 1 , R 2 and R 3 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 Represents an integer of ~ 12, and the symbols * 1 to * 4 are each one of the four bonds that are bonded to X1 in the formula (I). Indicates. ]
A tetravalent group represented by the following general formula (I-2):

[In Formula (I-2), A is 1 selected from the group consisting of a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. R 4 represents one type independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R 5 represents each independently a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. Each of the bonds selected from the group consisting of four bonds, each of which is bonded to X 1 in the formula (I). Indicates either. ]
A tetravalent group represented by the following general formula (I-3):

[In the formula (I-3), each R 6 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 the same carbon atom. And two R 6 bonded to each other may form a methylidene group, and each R 7 is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. Symbols * 1 to * 4 indicate that each of the bonds to which the symbols are attached is any one of four bonds that are bonded to X 1 in the formula (I). ]
At least one selected from the group consisting of tetravalent groups 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. ]
And the following general formulas (II) to (III):

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