JPWO2019163703A1 - Polyimide precursor resin composition - Google Patents

Abstract

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

Description

The present invention relates to a polyimide precursor resin composition.

In the field of display devices such as displays and liquid crystal displays that use organic electroluminescence elements, materials with high light transmission and sufficiently high heat resistance, such as glass, have emerged as materials used for substrates and the like. I have been asked. In recent years, polyimide has attracted attention as a material used as a substitute for glass, and various polyimide precursor resin compositions have been disclosed for producing such a polyimide.

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

International Publication No. 2011/099518

However, the reaction solution (composition) as described in Patent Document 1 is a polyimide having higher toughness while maintaining characteristics such as coefficient of linear expansion, glass transition temperature and total light transmittance at sufficiently high levels. It was not always sufficient from the viewpoint of efficient and reliable production.

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 coefficient of linear expansion, glass transition temperature and total light transmittance at sufficiently high levels. It is an object of the present invention to provide a polyimide precursor resin composition capable of efficiently and surely producing the above.

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 a tetracarboxylic acid dianhydride having two norbornan skeletons in the molecule and a derivative thereof. A polyimide precursor resin which is a polymer of at least one of the diamines; a tertiary phosphorus compound containing a structure represented by CP, in which a phosphorus atom and a carbon atom are directly bonded in the molecule. Formula in which a phosphorus atom and a carbon atom are directly bonded to a polyimide: 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; By using this, a polyimide having higher toughness can be efficiently and surely maintained while maintaining characteristics such as linear expansion coefficient, glass transition temperature and total light transmittance at sufficiently high levels. We have found that it is possible to manufacture the present invention, and have 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 a tetracarboxylic dianhydride having two norbornane skeletons in the molecule and a derivative thereof and a diamine;
Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: A tertiary phosphorus compound containing a structure represented by CP, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: represented by CP With at least one additive compound selected from the group consisting of a quaternary phosphorus compound containing a structure and a quaternary amine compound;
With solvent;
Is contained.

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

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

[In formula (2), A is one selected from the group consisting of divalent aromatic groups which may have a substituent and have 6 to 30 carbon atoms forming an aromatic ring. Shown, R ⁴ is each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ is independently composed of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, respectively. Shows one species selected from the group. ]
Compound represented by; the following general formula (3):

[In formula (3), 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 is bonded to the same carbon atom. shows a may form a methylidene group, R ⁷ is one selected from each independently consisting of hydrogen atom and alkyl group having 1 to 10 carbon atoms in the group two R ⁶ are taken together .. ]
Compound represented by; the following general formula (4):

It is preferable that the compound is at least one selected from the group consisting of the compounds represented by the above; and derivatives of those compounds (compounds represented by the general formulas (1) to (4)).

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

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

[In formula (I-1), R ¹ , R ² , and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is 0. Indicates an integer of ~ 12, and the symbols * 1 to * 4 indicate that the connecting hands with the symbols are any of the four joining hands that are connected to X ¹ in the formula (I), respectively. Is shown. ]
Tetravalent group represented by; the following general formula (I-2):

[In formula (I-2), A is selected from the group consisting of divalent aromatic groups which may have a substituent and have 6 to 30 carbon atoms forming an aromatic ring. Species are indicated, R ⁴ represents one species independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ indicates an alkyl group having a hydrogen atom and 1 to 10 carbon atoms independently, respectively. represents one selected from the group consisting of the symbol * 1 * 4 of four coupling hands of bond that is attached with No.該記is bonded to X ¹ in each formula (I) Indicates that it is either. ]
Tetravalent group represented by; the following general formula (I-3):

[In formula (I-3), 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. bound two R ⁶ are taken together to may form a methylidene group, R ⁷ is one selected from each independently hydrogen and the group consisting of alkyl group having 1 to 10 carbon atoms it is shown, indicating that the symbol * 1 * 4 is either four coupling hands of bond that is attached with No.該記is bonded to X ¹ in each formula (I). ]
Indicates 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. ]
Repeat unit represented by; and the following general formulas (II) to (III):

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

Further, in the polyimide precursor resin composition of the present invention, it is preferable that the added compound is triphenylphosphine.

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

Hereinafter, the present invention will be described in detail according to its preferred embodiment.

[Polyimide precursor resin composition]
The polyimide precursor resin composition of the present invention
A polyimide precursor resin (first component) which is a polymer of at least one selected from the group consisting of a tetracarboxylic dianhydride having two norbornane skeletons in the molecule and a derivative thereof and a diamine;
Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: A tertiary phosphorus compound containing a structure represented by CP, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: represented by CP With 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;
With solvent (third component);
Is contained. 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 weight of at least one selected from the group consisting of a tetracarboxylic dianhydride having two norbornan skeletons in the molecule and a derivative thereof, and a diamine. It is a coalescence. Here, the tetracarboxylic dianhydride and its derivative used as the 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 is the following general formula (i):

It suffices to have a structure represented by, and each carbon atom forming such a skeleton may have a hydrogen atom, an atom other than a hydrogen atom, a substituent other than a hydrogen atom, or the like bonded. As described above, the tetracarboxylic dianhydride according to the present invention may have two structural portions (skeletons) represented by the general formula (i) in the molecule, and the structure is not particularly limited. .. The derivative of the tetracarboxylic dianhydride may be any one obtained by using the tetracarboxylic dianhydride, and is not particularly limited. For example, the tetracarboxylic dianhydride is modified. Examples thereof include diesterdicarboxylic acid and diesterdicarboxylic acid dichloride obtained.

Such tetracarboxylic dianhydrides and their derivatives are represented by the above general formulas (1) to (4) from the viewpoint of the transparency and heat resistance of the polyimide obtained by using the component. Compounds and derivatives thereof are preferable, and compounds represented by the above general formulas (1) to (3) and derivatives thereof are more preferable. Hereinafter, the compounds represented by the above general formulas (1) to (4) and derivatives thereof which can be suitably used as the tetracarboxylic dianhydride according to the present invention 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 independently composed of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, respectively. Indicates one type selected from, and n indicates an integer from 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. If the number of carbon atoms exceeds 10, the glass transition temperature drops and a sufficiently high degree of heat resistance cannot be achieved. Further, the number of carbon atoms of the alkyl group that can be selected as R ¹ , R ² , and R ³ is preferably 1 to 6 and preferably 1 to 5 from the viewpoint of facilitating purification. Is more preferable, 1 to 4 is more preferable, and 1 to 3 is particularly preferable. Further, the alkyl group that can be selected as such R ¹ , R ² and R ³ may be linear or branched. Further, as such an alkyl group, a methyl group and an ethyl group are more preferable from the viewpoint of easiness of purification.

Further, R ¹ , R ² and R ^{3 in the} general formula (1) are independently hydrogen atoms or 1 to 10 carbon atoms from the viewpoint of obtaining higher heat resistance when the polyimide is produced. It is more preferable that it is an alkyl group of, and above all, from the viewpoint of easy availability of raw materials and easier purification, each independently has a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or isopropyl. It is more preferably a group, and particularly preferably a hydrogen atom or a methyl group. Further, it is particularly preferable that a plurality of R ¹ , R ² , and R ^{3 in} such a formula are the same from the viewpoint of ease of purification and the like.

Further, n in the general formula (1) represents an integer of 0 to 12. If such a value of n exceeds the upper limit, purification becomes difficult. Further, the upper limit of the numerical range of n in the general formula (1) is more preferably 5 and particularly preferably 3 from the viewpoint of facilitating 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. As described above, it is particularly preferable that n in the general formula (1) is 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 adopted. The method described in 2011/099517, the method described in International Publication No. 2011/099518, and the like may be adopted.

(Compound represented by the general formula (2))
Regarding the compound represented by the general formula (2), in the above general formula (2), A may have a substituent and the number of carbon atoms forming an aromatic ring is 6 to 30. Indicates one species selected from the group consisting of aromatic groups of, R ⁴ indicates one species independently selected from the group consisting of an alkyl group having a hydrogen atom and 1 to 10 carbon atoms, and R ⁵ is independent of each other. Shows 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 such a general formula (2) is a divalent aromatic group that may have a substituent, and is a carbon that forms an aromatic ring contained in the aromatic group. (Note that the "number of carbons forming an aromatic ring" here means that if the aromatic group has a substituent containing carbon (such as a hydrocarbon group), the carbon in the substituent is used. Does not include the number of carbons, and refers only to the number of carbons contained in the aromatic ring in the aromatic group. For example, in the case of a 2-ethyl-1,4-phenylene group, the number of carbons forming the aromatic ring is 6. ) Are 6 to 30. As described above, 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 the coloring of the polyimide when the polyimide is prepared using the polyimide precursor resin having such a repeating unit. It tends to be. Further, from the viewpoint of transparency and ease of purification, the number of carbons forming the aromatic ring of the divalent aromatic group is more preferably 6 to 18, and further preferably 6 to 12. preferable.

The divalent aromatic group may be any one that satisfies the above conditions for the number of carbon atoms, and is not particularly limited. For example, benzene, naphthalene, terphenyl, anthracene, phenylene, triphenylene, pyrene, etc. Residues in which two hydrogen atoms are desorbed from aromatic compounds such as chrysen, biphenyl, terphenyl, quaterphenyl, and kinkphenyl (Note that, as such residues, the position of the desorbed hydrogen atom is 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.); A group 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). ) Etc. can be used as appropriate. In such a residue, as described above, the position of the hydrogen atom to be eliminated is not particularly limited. For example, when the residue is a phenylene group, any of the ortho position, the meta position and the para position. It may be in the position of.

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 more excellent and a higher degree of processability can be obtained. It has 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. A terphenylene group may be preferable. That is, as such a divalent aromatic group, a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and a terphenylene group, each of which may have a substituent, are preferable. Further, among such divalent aromatic groups, a phenylene group, a biphenylene group, and a naphthylene group, each of which may have a substituent, are more preferable because a higher effect can be obtained from the above viewpoint. A phenylene group or a biphenylene group which may have a substituent is more preferable, and a phenylene group which may have a substituent is most preferable.

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

Further, among such divalent aromatic groups, each substituent is obtained from the viewpoint that the solubility of the polyimide in a solvent becomes more excellent when the polyimide is produced and a higher degree of processability can be obtained. It is preferably a phenylene group, a biphenylene group, a naphthylene group, an anthrasenylene group, or a terphenylene group, and may have a substituent, respectively, a phenylene group, a biphenylene group, or a naphthylene group. More preferably, it is more preferably a phenylene group and a biphenylene group which may have a substituent, respectively, and most preferably, a phenylene group which may have a substituent.

Further, among such divalent aromatic groups, from the viewpoint of obtaining a higher degree of heat resistance, each may have a substituent, such as a phenylene group, a biphenylene group, a naphthylene group, and an anthracenylene group. 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, and each of them may have a substituent. A phenylene group, a biphenylene group, and a naphthylene group are more preferable, and a phenylene group which may have a substituent is most preferable.

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

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

Further, R ⁴ in the general formula (2) is independently obtained from the viewpoints of obtaining higher heat resistance, easy availability of raw materials, easier purification, and the like. It is more 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. Further possible, R ⁴ in such equation (2), respectively, may be one even or different which are identical ones but, from the viewpoint of easiness of purification is identical ones Is preferable. Further, a plurality of R ⁴ in the general formula (2) is particularly preferably both hydrogen atoms. Thus, when the substituents represented by R ⁴ is in the repeating unit represented by the general formula (2) are both a hydrogen atom tends to higher heat resistance can be obtained.

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

Aspect R ⁵ is preferably of the general formula (2), when a polyimide was prepared, more advanced that the heat resistance can be obtained, that raw material is easily available, it purification is easier, such as equal Therefore, it is more 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. Further, a plurality of R ⁵ in such formulas, respectively, or may be even or different which are identical ones but, from the viewpoint of easiness of purification, it is the same thing preferable.

The method for producing the compound represented by the general formula (2) is not particularly limited, and a known method can be appropriately adopted. For example, as described in International Publication No. 2015/1633314. 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), 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, respectively. or represents one or may form the same methylidene group two R ⁶ attached to a carbon atom together, R ⁷ hydrogen atoms and carbon atoms are each independently 1 to 10 It shows one kind selected from the group consisting of the alkyl group of.

R ^{6 in} such a general formula (3) 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. two R ⁶ bonded to 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. If the number of carbon atoms exceeds 10, a sufficiently high degree of heat resistance cannot be achieved. 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, and 1 to 5 from the viewpoint of facilitating purification. It is more preferably 4 and particularly preferably 1 to 3. Further, the alkyl group that can be selected as such R ⁶ may be linear or branched. Further, as such an alkyl group, a methyl group and an ethyl group are more preferable from the viewpoint of easiness 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₎ You may be. That is, the two R ⁶ are attached to the same carbon atom in the general formula (3) together, of the carbon atoms forming the carbon atom (norbornane ring structure, R ⁶ are two binding It may be bonded as a methylidene group (methylene group) to the carbon atom) by a double bond.

As the general formula (3) a plurality of R ⁶ in the more advanced the heat resistance can be obtained, that availability of raw materials (Preparation) is easier, it purification is easier, from the viewpoint of equal , Each independently, is more 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. Further, a plurality of R ⁶ in such formulas, respectively, or may be even or different which are identical ones but, from the viewpoint of easiness of purification, it is the same thing preferable.

Further, R ⁷ in the general formula (3) is one type independently 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 is lowered. Further, the alkyl group that can be selected as R ⁷ is preferably 1 to 6, more preferably 1 to 5, and 1 to 4 from the viewpoint of obtaining a higher heat resistance. Is more preferable, and 1 to 3 is particularly preferable. Further, the alkyl group that can be selected as such R ⁷ may be linear or branched.

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

Further, it is particularly preferable that each of the plurality of R ⁶ and R ⁷ in the general formula (3) is a hydrogen atom. As described above, in the repeating unit represented by the general formula (3), when the substituents represented by R ⁶ and R ⁷ are all hydrogen atoms, the yield of the compound is improved, and more. There is a tendency to obtain a high degree of heat resistance.

The method for producing the compound represented by the general formula (3) is not particularly limited, and a known method can be appropriately adopted. For example, it is 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. Further, the method for producing the compound represented by the general formula (4) is not particularly limited, and a known method can be appropriately adopted.

(Derivatives of compounds represented by the above general formulas (1) to (4))
The derivative of the compound represented by the general formulas (1) to (4) is not particularly limited, but is a diesterdicarboxylic acid which is a modified product of the compound represented by the general formulas (1) to (4), and , Diester dicarboxylic acid dichloride is more preferred. 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 replaced with the corresponding diester dicarboxylic acid or diester. It is preferable to use it after denaturing it with a dicarboxylic acid dichloride.

The method for preparing such a derivative is not particularly limited, and a known method can be appropriately adopted. For example, as a method for preparing a diesterdicarboxylic acid suitable as a derivative of the compounds represented by the general formulas (1) to (4), any of the compounds represented by the general formulas (1) to (4) can be used. A method of obtaining the corresponding diester dicarboxylic acid by reacting with an alcohol can be adopted. A polyimide precursor can be obtained by solution-polymerizing the diesterdicarboxylic acid thus obtained with a diamine in the presence of a condensing agent. Further, as a method for preparing a diesterdicarboxylic acid dichloride suitable as a derivative of the compounds represented by the general formulas (1) to (4), for example, the compounds represented by the general formulas (1) to (4). Is reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid, and then reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a corresponding diester dicarboxylic acid dichloride. it can. A polyimide precursor can be obtained by stirring such a diester dicarboxylic acid dichloride and a diamine in a 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 more excellent storage stability than the case where the compounds represented by the above general formulas (1) to (4) are used as they are.

<About diamine>
The diamine may be any diamine that can be used for producing polyimide, and is not particularly limited, 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 formula (ii), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² are independently selected from the group consisting of a hydrogen atom and an alkylsilyl group having 3 to 9 carbon atoms. Shows one type. ]
The aromatic diamine represented by is more preferable.

The general formula (ii) an arylene group which may be selected as R ¹⁰ in is the number of carbon atoms is of from 6 to 50 carbon atoms of such aryl group is preferably 6 to 40, It is more preferably 6 to 30, and even more preferably 12 to 20. If the number of carbon atoms is less than the lower limit, the heat resistance tends to decrease when the obtained polyimide is prepared, while if it exceeds the upper limit, the solubility of the polyimide in the solvent becomes high when the polyimide is prepared. It tends to decrease.

The R ¹⁰ in such a general formula (ii), there may from the viewpoint of high heat resistance and mechanical strength by when prepared polyimide is obtained by the following general formula (a) ~ (d):

[In formula (c), R ¹¹ represents one selected from the group consisting of hydrogen atom, fluorine atom, methyl group, ethyl group, hydroxyl group, and trifluoromethyl group, and in 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 ₆ H _4- Groups represented by -O-, -COO-, -OCO-; and the following general formula (e):

(In the formula (e), R ^a is independently an alkyl group containing 1 to 10 carbon atoms, indicates either one of a phenyl group and tolyl group, y is an integer of 1 to 18.)
Indicates one species selected from the group consisting of groups represented by; ]
It is preferably at least one of the groups represented by.

As R ^{11 in} such a general formula (c), a hydrogen atom, a fluorine atom, a methyl group or an ethyl group is more preferable, and a hydrogen atom is particularly preferable, from the viewpoint of heat resistance. Further, 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 coefficient of linear expansion.

Further, in the group represented by the general formula (e) which can be selected as Q in the general formula (d), ^Ra is independently among an alkyl group having 1 to 10 carbon atoms, a phenyl group and a tolyl group. It is one of the above. When the number of carbon atoms of such an alkyl group exceeds the upper limit, the heat resistance and transparency of the polyimide tend to decrease when the polyimide is prepared. 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. Further, y in the general formula (e) represents an integer of 1 to 15, and is more preferably 3 to 12 and even more preferably 5 to 10. If y is less than the lower limit, the mechanical strength tends to decrease, while if y exceeds the upper limit, the heat resistance and transparency of the polyimide tend to decrease when the polyimide is prepared.

Further, as Q in the above general formula (d), from the viewpoint that it is possible to obtain a cured product having heat resistance, transparency and mechanical strength at a sufficient level in a more balanced manner, 9, 9- Fluolenilidene group, or formula: -CONH-, -O-C ₆ H _4- O-, -O-, -C (CH ₃ ) _2- , -O-C ₆ H _4- SO _2- C ₆ H _{4 -O -, - CH 2 -,} - O-C 6 H 4 -C 6 H 4 -O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - SO ₂ -, - OCO-, or, preferably a group represented by -COO-, 9,9-fluorenylidene group, or the _{formula: -CONH -, - CH 2 -} , - O-C 6 H 4 -O- _{, -O-C 6 H 4 -C} 6 H 4 -O -, - SO 2 -, - OCO -, - COO-, or particularly preferably a group represented by -O-, 9,9-fluorenylidene group, Alternatively, the groups represented by the formulas: -CONH-, -SO _2- , -OCO-, -COO-, -CH _2- or -O- are most preferable. Further, the Q in the general formula (d) is preferably a group represented by the general formula (e) from the viewpoint of adhesiveness and laser peeling property, and from the viewpoint of linear expansion coefficient and heat resistance. From the above, groups represented by the formulas: -OCO-, -COO-, -CONH- are preferable.

Further, as such R ¹⁰ , from the viewpoint that it becomes possible to obtain a polyimide having heat resistance, transparency and mechanical strength at a sufficient level in a more balanced manner, 4,4'-diaminobenzanilide ( 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-trizine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid ( BAAB), 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl (BABB), 3,3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4'- A divalent group (arylene group) obtained by removing two amino groups from at least one aromatic diamine selected from the group consisting of diaminodiphenylsulfone (4,4'-DDS) is preferable, and 4,4'-diamino Benzenelide (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 9,9'-bis (4-aminophenyl) fluorene (FDA), A divalent group (arylene group) obtained by removing two amino groups from at least one aromatic diamine selected from the group consisting of p-diaminobenzene (PPD) and 4-aminophenyl-4-aminobenzoic acid (BAAB). ), Which is composed of 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), and 2,2'-bis (trifluoromethyl) benzidine (TFMB). It is more preferably a divalent group (arylene group) obtained by removing two amino groups from at least one aromatic diamine selected from the group.

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

Further, it is more preferable that Y ¹ and Y ² in the formula (ii) are all hydrogen atoms from the viewpoint of easiness of polyimide synthesis. That is, as the aromatic diamine represented by the above formula (ii), the aromatic diamine represented by the formula: H ₂ N-R ^10- NH ₂ is more preferable.

The aromatic diamine represented by such a formula: H ₂ N-R ^10- NH ₂ is not particularly limited, and known ones can be appropriately used, and commercially available ones may be appropriately used. 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 ] Sulphon, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis (4-aminophenyl) Fluolene, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3 '-Dimethylbiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 3,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-[1,3-phenylenebis (1-methyl-ethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methyl-ethylidene)] bisaniline, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide , 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 9,9' -Bis (4-aminophenyl) fluorene, o-trizine 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 ( Examples thereof include trifluoromethyl) benzidine, 4-aminophenyl-4-aminobenzoic acid, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl and the like. Further, such an aromatic diamine may be used alone or in combination of two or more.

When two or more kinds of 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-) Trizine), 4,4'-diphenyldiaminomethane (DDM), 4-aminophenyl-4-aminobenzoic acid (BAAB), 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl ( BABB), at least two selected from 3,3'-diaminodiphenylsulfone (3,3′-DDS) and 4,4′-diaminodiphenylsulfone (4,4′-DDS) can be utilized. Preferably, 4,4'-diaminobenzanilide (DABAN), 4,4'-diaminodiphenyl ether (DDE), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 9,9'-bis (4-). Aminophenyl) Fluolene (FDA), p-diaminobenzene (PPD), 4-aminophenyl-4-aminobenzoic acid (BAAB), 3,3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4 It is preferable to utilize at least two selected from'-diaminodiphenylsulfone (4,4'-DDS). When two or more kinds of aromatic diamines are used in combination, a combination of 4,4'-diaminobenzanilide (DABAN) and 4,4'-diaminodiphenyl ether (DDE) and 4,4'-diaminobenzanilide (DABAN) are used. ) And 2,2'-bis (trifluoromethyl) benzidine (TFMB), 4,4'-diaminobenzanilide (DABAN) and p-diaminobenzene (PPD), 3,3'-diaminodiphenylsulfone Combination of (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'-DDS), 4-aminophenyl-4-aminobenzoic acid (BAAB) and 2,2'-bis (tri) It is more likely to contain at least one combination selected from a combination of fluoromethyl) benzidine (TFMB) and a combination of 4-aminophenyl-4-aminobenzoic acid (BAAB) and p-diaminobenzene (PPD). preferable.

Further, the aromatic diamine represented by the above 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), it is silylated obtained by reacting an aromatic diamine represented by the formula: H ₂ N-R ^10- NH ₂ with a silylating agent. Examples include diamine. 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.

The method for producing such a diamine is not particularly limited, and a known method can be appropriately adopted. Further, as such a diamine, a commercially available product may be appropriately used.

<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 dianhydride 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 the repeating units represented by the above general formulas (I) to (III) are more preferable.

(About the repeating unit represented by the general formula (I))
With respect to such a repeating unit represented by the general formula (I), X ¹ in the general formula (I) is a tetravalent group represented by the general formulas (I-1) to (I-3). 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 Is synonymous with 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 general formula (2). ^a, in) the same meaning as R 4, ^{R 5} (the preferred ones also the general formula (2) in ^a, the same meaning as ^R 4, R ^5). 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).

Further, X ^{1 in} such a general formula (I) is a tetravalent group (organic group) represented by the above general formulas (I-1) to (I-3) as described above. formula (I-1) ~ (I -3) 4 pieces of bonds the symbol * 1 * 4 bond that is attached with No.該記is bonded to X ¹ of the respective formulas (1) in Indicates that it is one of the following. The general formula (I-1) ~ (I -3) by the tetravalent organic group represented utilized at the site of the X ^1, the transparency, those more sophisticated heat resistance and dimensional stability It becomes possible to. Further, among the bonders having such symbols * 1 to * 4 attached with the symbol, any of the bonders with the symbols * 1 to * 2 is included in the general formula (I). Formula: A bond that binds to -COOY ¹ and any of the bonds with symbols * 3 to * 4 is the formula in general formula (I): -COOY ² . It is a connecting hand that joins, or any of the joining hands with the symbols * 1 to * 2 is a joining hand that binds to the formula: -COOY ² in the general formula (I). , And any of the bonds with the symbols * 3 to * 4 is preferably a bond that binds to the formula: -COOY ¹ in the general formula (I).

Further, R ¹⁰ in the general formula (I) 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 independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), or alkylsilyls having 3 to 9 carbon atoms. It is one of the groups. Such Y ¹ and Y ² can be changed by appropriately changing the type of the substituent and the introduction rate of the substituent by appropriately changing the production conditions (type of diamine to be used, etc.). When both Y ¹ and Y ² are hydrogen atoms (when they are so-called repeating units of polyamic acid), the production tends to be easier when polyimide is produced using them. is there.

Further, when Y ¹ and Y ² in the general formula (I) are alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), the storage stability of the polyimide precursor resin is more excellent. It tends to be. Further, 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. As described above, when Y ¹ and Y ² are alkylsilyl groups having 3 to 9 carbon atoms, it is more preferable that Y ¹ and Y ² are trimethylsilyl groups or t-butyldimethylsilyl groups.

The introduction rate of groups other than hydrogen atoms (alkyl groups and / or alkylsilyl groups) is not particularly limited with respect to Y ¹ and Y ² in the repeating unit represented by the general formula (I), but Y ¹ When 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} the total repeating unit. % or higher) is preferably a alkyl group and / or an alkyl silyl group (in this case, Y ^1, Y ² other than the alkyl group and / or an alkylsilyl group is a hydrogen atom). Further, for each of Y ¹ and Y ^{2 in} the repeating unit represented by the general formula (I), 25% or more of the total amount is an alkyl group and / or an alkylsilyl group to stabilize the storage of the polyimide precursor. The sex tends to be better.

Such a repeating unit represented by the general formula (I) is a compound (tetracarboxylic acid dianhydride) represented by the above general formulas (1) to (3) and a diesterdicarboxylic acid which is a derivative of the compound. And at least one of the diesterdicarboxylic acid dichlorides and the aromatic diamine represented by the above general formula (ii) (HY ¹ N-R ^10- NY ² H) can be easily formed. Can be done. As described above, by appropriately selecting the monomer component according to the target design, a polymer having a repeating unit represented by the general formula (I) can be formed. From this point of view, the polymer (polyimide precursor resin) having the repeating unit represented by the general formula (I) is a compound (tetracarboxylic acid di) represented by the general formulas (1) to (3). Anhydrous) and at least one of diester dicarboxylic acid and diester dicarboxylic acid dichloride which are derivatives of those compounds and aromatic diamine (HY ¹ N-R ^10- NY ² H) represented by the above general formula (ii). ) Can be said to be a polymer.

(Regarding repeating units represented by general formulas (II) to (III))
With respect to such a repeating unit represented by the general formula (II) and a 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. The groups are shown, and 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 ) Is synonymous with R ¹⁰ , Y ¹ , and Y ² ).

Such repeating units represented by the general formulas (II) to (III) include the compound represented by the general formula (4) (tetracarboxylic dianhydride) and the diesterdicarboxylic acid which is a derivative of the compound. It can be easily formed by reacting at least one of the diesterdicarboxylic acid dichlorides with the aromatic diamine (Y ₂ N-R ^10- NY ₂ ) represented by the above general formula (ii). .. As described above, by appropriately selecting the monomer component according to the target design, a polymer having repeating units represented by the general formulas (II) to (III) can be formed. From this point of view, the polymer (polyimide precursor resin) having the repeating unit represented by the general formulas (II) to (III) is the compound represented by the general formula (4) and a derivative of the compound. It can be said that it is a polymer of at least one of the diester dicarboxylic acid and the diester dicarboxylic acid dichloride and the aromatic diamine (HY ¹ N-R ^10- NY ² H) represented by the above general formula (ii). ..

Further, 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) as described above. Polymers containing at least one repeating unit are preferred. Further, among the repeating units represented by the general formulas (I) to (III), X ¹ in the formula (I) is the general formula (I-1) from the viewpoint of the dimensional stability of the obtained polyimide. A repeating unit which is a tetravalent group represented by the above formula (I-2) is preferable, and from the viewpoint of solvent solubility of the obtained polyimide, X ¹ in the formula (I) is the tetravalent unit represented by the above general formula (I-2). A repeating unit as a group is preferable, and from the viewpoint of the low dielectric property of the obtained polyimide, a repeating unit in which X ^{1 in the} formula (I) is a tetravalent group represented by the above general formula (I-3) is used. preferable. Further, from the viewpoint of the mechanical properties of the obtained 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). Repeating units, which are tetravalent groups, are particularly preferred.

Further, the repeating unit represented by the above general formula (I) is a repeating unit in which both Y ¹ and Y ² are hydrogen atoms (repeating unit of polyamic acid) from the viewpoint of simplicity of imidization. Is more preferable.

Further, when such a polyimide precursor resin (polymer) contains 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 one type, or may contain two or more types of repeating units selected from the group consisting of these repeating units.

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

Further, a polyimide precursor resin containing any 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 intended use and the like. May further include a repeating unit of. Such other repeating units are not particularly limited, and examples thereof include known repeating units that can be used as repeating units for the polyimide precursor resin. As such other repeating units, for example, tetracarboxylic dianhydrides other than the compounds represented by the general formulas (1) to (4) are used, and these are used in the above formula: HY ¹ N-. It may be a repeating unit or the like formed by reacting with an aromatic diamine represented by R ^4- NY ² H.

Such other tetracarboxylic acid dianhydrides are not limited to tetracarboxylic acid dianhydrides having two norbornan skeletons in the molecule, but known tetras that can be used for the preparation of polyamic acid and polyimide. Carous acid dianhydride can be appropriately used, for example, butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic hydride, 1,2,3,4-cyclopentanetetracarboxylic hydride. Anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetichydride, 3,5,6-tricarboxynorbornan-2-acetate dianhydride, 2,3,4,5- tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1, 2-c] -Fran-1,3-dione, 1,3,3a,4,5,9b-Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -Fran-1,3-dione, 1,3,3a,4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -Fran-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [2, 2,2] -Octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, or other aliphatic or alicyclic tetracarboxylic acid dianhydride; pyromellitic acid dianhydride, 3, 3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride , 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3, 3', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furtetracarboxylic acid 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'-Perfluoroisopropyridenediphthalic acid dianhydride, 4,4'-(2,2-hexafluoroisopropyridene) diphthalic acid dianhydride, 3,3', 4,4'-biphenyl Tetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine Oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dian Examples thereof include anhydrides and aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

As such another repeating unit, when a polyimide is finally formed, it is possible to obtain a cured product having properties such as heat resistance, transparency, mechanical strength and solvent solubility at a sufficient level in a more balanced manner. Among them, 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' At least one tetracarboxylic dianhydride selected from the group consisting of- (2,2-hexafluoroisopropyridene) diphthalic dianhydride and the above formula: H ₂ N-R ^4- NH _2. It is preferably a repeating unit formed by reacting with an aromatic diamine, and is preferably 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetra. It is formed by reacting at least one tetracarboxylic dianhydride selected from the group consisting of carboxylic acid dianhydride with an aromatic diamine represented by the above formula: H ₂ N-R ^4- NH _2. More preferably, it is a repeating unit.

When such a polyimide precursor resin is a polyamic acid, its intrinsic viscosity [η] is preferably 0.05 to 3.0 dL / g, preferably 0.1 to 2.0 dL / g. Is more preferable. If the intrinsic viscosity [η] of such a polyamic acid is less than 0.05 dL / g, the obtained film tends to be brittle when a film-shaped polyimide is produced using the polyamic acid, while 3.0 dL. If it exceeds / g, the viscosity is too high and the processability is lowered, and it becomes difficult to obtain a uniform film, for example, when a film is produced. Further, the intrinsic viscosity [η] of such a polyamic acid can be measured as follows. That is, first, N, N-dimethylacetamide is used as a solvent, and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL to prepare a measurement sample (solution). obtain. Next, using the measurement sample, the viscosity of the measurement sample is measured using a kinematic viscosity meter under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [η]. As such a kinematic viscometer, an automatic viscosity measuring device (trade name "VMC-252") manufactured by Rigosha is used.

In such a method for producing a polyimide precursor resin (polymer), in order to form a polymer of tetracarboxylic acid dianhydride and diamine as described above, the tetracarboxylic acid dianhydride and diamine as described above are used. It may be used, and a known method for preparing a polyimide precursor resin (polymer) (polymerization method) can be appropriately used. For example, when a compound represented by the general formula (1) is used as the tetracarboxylic dianhydride, the method for producing a polyamic acid described in International Publication No. 2011/099518 may be used. It may be appropriately adopted, and when the compound represented by the general formula (2) is used as the tetracarboxylic dianhydride, the polyamic acid described in International Publication No. 2015/1633314 is produced. The method for this may be appropriately adopted. In this way, a polyimide precursor resin (polymer) is prepared by appropriately utilizing the polymerization conditions and the like described in known documents according to the type of the monomer (the tetracarboxylic dianhydride and the diamine) used. You may.

<Additional compound (second component)>
The additive compound (second component) according to the present invention is 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, and the phosphorus atom and the carbon atom in the molecule. Formula: At least one compound selected from the group consisting of a quaternary phosphorus compound containing a structure represented by CP and a quaternary amine compound.

Examples of such tertiary phosphorus compounds include triphenylphosphine, triparatrilphosphine, tritersial butylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, 1,4-bisdiphenylphosphinobtan and the like. As such a tertiary phosphorus compound, triphenylphosphine, triparatrilphosphine, and tricyclohexylphosphine are more preferable, and triphenylphosphine and triparatrilphosphine are further preferable, and triphenylphosphine is more preferable from the viewpoint of the mechanical properties of the obtained polyimide. Is particularly preferable.

Examples of such quaternary phosphorus compounds include benzyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide, normal butyl triphenyl phosphonium chloride, normal butyl triphenyl phosphonium disianamide phenacetyl triphenyl phosphonium chloride, and hexyl triphenyl. Phosphonium bromide, octyldiphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, benzyltriphenylphosphonium bromide, 2-methylbenzyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, phenacetili Examples thereof include quaternary phosphorus salts such as phenylphosphonium chloride, allyltriphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate. Such quaternary phosphorus compounds include benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride, and tetraphenylphosphonium from the viewpoint of the mechanical properties of the obtained polyimide and the solubility in a solvent. Bromide and tetraphenylphosphonium tetraphenyl borate are more preferable, benzyl triphenyl phosphonium chloride, benzyl triphenyl phosphonium bromide and tetraphenyl phosphonium tetraphenyl borate are further preferable, and benzyl triphenyl phosphonium chloride and benzyl triphenyl phosphonium bromide are particularly preferable.

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.), DBU phenolic resin salt, 1,5-diazabicyclo [4.3.0] none-5-ene (DBN) phenolic resin salt, manufactured by San-Apro Examples thereof include U-CAT 5002, tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium hydrochloride, tetraethylammonium hydrochloride, quaternary amine salts such as tetramethylammonium tetraphenylborate; and the like. Among such quaternary amine compounds, DBU organic acid salts are preferable, and DBU phenol salts and DBU octyl salts are preferable from the viewpoint that higher heat resistance and mechanical strength can be obtained when polyimide is produced. More preferred.

Further, among such additive compounds (second component), it is possible to impart flame retardancy to the polyimide when the polyimide is prepared, 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. 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)>
The solvent (third component) according to the present invention is not particularly limited, and for example, a solvent that can be used in a resin solution of polyamic acid can be preferably used. Examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, γ-modified prolactone, δ. -Valerolactone, γ-modified prolactone, ε-modified prolactone, α-methyl-γ-butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, Aproton polar solvents such as hexamethylphosphoric triamide and pyridine; phenolic solvents such as m-cresol, p-cresol, xylenol, phenol and halogenated phenol; ether solvents such as tetrahydrofuran, dioxane, cellosolve and glyme. Solvents; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as cyclopentanone and cyclohexanone; nitrile solvents such as acetonitrile and benzonitrile, ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol methyl acetate and the like. Examples thereof include acetate-based solvents, methylisobutylketone, diisobutylketone, cyclopentanone, cyclohexanone, methylethylketone, and ketone-based solvents such as acetone.

In addition, such solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and γ from the viewpoints of solubility, film forming property, productivity, industrial availability, presence / absence of existing equipment, and price. -Butyrolactone, propylene carbonate, tetramethylurea, 1,3-dimethyl-2-imidazolidinone are preferable, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone and tetramethylurea are more preferable. N, N-dimethylacetamide, N-methyl-2-pyrrolidone and tetramethylurea are particularly preferred. It should be noted that such a solvent may be used alone or in combination of two or more.

Further, 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). May be good. Such other components are not particularly limited, but are, 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, lubricants, etc. Further, the other components (antioxidants and the like) are not particularly limited, and known ones can be appropriately used, and commercially available ones may be used.

<Composition of composition, etc.>
The polyimide precursor resin composition of the present invention contains 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 added compound (second component) are not particularly limited, but the content of the second component with respect to 100 parts by mass of the first component is not particularly limited. The content is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 15 parts by mass. If the content of such an additive compound (second component) is less than the lower limit, the mechanical strength of the polyimide tends to decrease when the polyimide is produced, while if it exceeds the upper limit, the polyimide is produced. In addition, the heat resistance of polyimide tends to decrease.

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, and even more preferably 60 to 90% by mass. It is particularly preferably 70 to 90% by mass. If the content of such a solvent is less than the above lower limit, it tends to be difficult to make the polyimide precursor resin sufficiently dissolved in the solvent, and it tends to be difficult to obtain a uniform varnish composition. When the above upper limit is exceeded, the mechanical strength of the polyimide tends to decrease when the polyimide precursor resin is imidized and cured to produce a polyimide.

<About the method for producing the 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) are not particularly limited. It is not particularly limited as long as it is a method capable of producing a polyimide precursor resin composition containing (three components), and is, for example, a tetracarboxylic acid having two norbornan skeletons in the molecule in the presence of a solvent. It is selected from the group consisting of an anhydride (if necessary, other tetracarboxylic acid dianhydride other than the tetracarboxylic acid dianhydride having two norbornan skeletons in the molecule may be contained) and a derivative thereof. With at least one; the above diamine (preferably the compound represented by the above formula (ii) (HY ¹ N-R ^10- NY ² H), more preferably represented by the formula: H ₂ N-R ^10- NH _2). Compound) and; are reacted (progressing the polymerization reaction) to form a polymer of at least one selected from the group consisting of the tetracarboxylic acid dianhydride and its derivative and the diamine. In addition, in the above-mentioned step, any step in reacting the above-mentioned diamine with at least one selected from the group consisting of the above-mentioned tetracarboxylic acid dianhydride and its derivatives [Before the reaction, during the reaction (note here). The term “during the reaction” means that the polymerization reaction is further advanced using the reaction solution obtained after reacting at least one selected from the group consisting of the tetracarboxylic acid dianhydride and its derivative with the diamine once. A method including a step of adding the above-mentioned additive compound in any of the steps before or during the polymerization reaction using the reaction solution in the case of squeezing] and after the reaction] (hereinafter, such a method is referred to as a convenience. , Simply referred to as "method (I)") can be preferably adopted. The tetracarboxylic dianhydride and its derivatives, diamines, solvents, and added compounds 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, a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride having two norbornan skeletons in the molecule) The specific conditions for reacting the diamine with at least one selected from the group consisting of (may contain dianhydride) and its derivatives are not particularly limited, and depend on the type of component used. The conditions may be appropriately set so that the polymerization reaction proceeds. Further, as such a method (I), at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative is a compound represented by the general formulas (1) to (4) (1). If necessary, other tetracarboxylic dianhydride may be contained) and at least one selected from the group consisting of derivatives thereof is utilized, and the diamine is represented by the above general formula (ii). In the presence of the solvent, at least one selected from the group consisting of the compounds represented by the general formulas (1) to (4) and derivatives thereof, and the above general formula The first step of reacting with the aromatic diamine represented by (ii) to obtain a reaction solution, and the addition of the additive compound to the reaction solution are represented by the above general formulas (I) to (III). A method comprising a second step of obtaining a polyimide precursor resin composition containing the polyimide precursor resin having at least one repeating unit selected from the group consisting of repeating units, the additive compound, and the solvent (I). It is preferable to adopt -1).

As in the method (I-1), the polymerization reaction is allowed to proceed once in the first step, and then the additive compound is added in the second step to apply the varnish to the substrate to form a film. At this stage, the molecular weight of the polyimide can be further improved by utilizing the added compound. As described above, when the polyimide film is obtained by using the added compound in the film forming step, it is composed of the compounds represented by the general formulas (1) to (4) and their derivatives in the presence of the solvent. When at least one selected from the group is reacted with an aromatic diamine represented by the above general formula (ii) to obtain a polyimide film without using the additive compound (at any stage of preparing polyimide). It is also advantageous in that the mechanical properties of the obtained polyimide film are excellent as compared with the case where the additive compound is not used). Hereinafter, a method (I-1) suitable as such a 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 is reacted with the aromatic diamine to prepare a reaction solution containing a polyimide precursor resin. This is the process of obtaining. In addition, "at least one selected from the group consisting of tetracarboxylic dianhydride and its derivative" used in such a first step is a compound represented by the general formulas (1) to (4) and them. It suffices to contain at least one selected from the group consisting of derivatives of the above, and if necessary, contains at least one selected from the group consisting of other tetracarboxylic dianhydrides and derivatives thereof. You may be.

As the solvent used in such a first step, the above-mentioned solvent can be appropriately used, and among them, it is a solvent capable of dissolving both the tetracarboxylic dianhydride and the aromatic diamine. preferable. Such a solvent may be used alone or in combination of two or more.

Further, in such a method, the amount of at least one selected from the group consisting of the tetracarboxylic acid dianhydride and its derivative (the component to react with the aromatic diamine represented by the above general formula (ii)) is used. (The total amount of the compounds represented by the general formulas (1) to (4), other tetracarboxylic acid dianhydrides and their derivatives) and the aromatic diamine represented by the general formula (ii). The ratio with the amount of the compound used (formula: total amount of the compound represented by HY ¹ N-R ^4- NY ² H) is not particularly limited, but when the above derivative is used, all the derivatives are tetracarboxylic before induction. Assuming (converted) to be an acid dianhydride, the tetracarboxylic acid dianhydride used in the reaction (when the derivative is used, the derivative thereof) is based on 1 equivalent of the amino group of the aromatic diamine. It is preferable that the amount of all the acid anhydride groups in each of them is 0.5 to 2 equivalents before the induction (assuming that the tetracarboxylic acid dianhydride is used). More preferably, the amount is 0.8 to 1.2 equivalents. If at least one selected from the group consisting of such tetracarboxylic dianhydrides and derivatives thereof and the preferable usage ratio of the aromatic diamine are 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 not to be obtained as described above.

Further, the amount of the solvent used in the first step is at least one selected from the group consisting of the tetracarboxylic dianhydride used in the reaction and its derivative (the general formulas (1) to (4)). Of the compound represented by, the total amount of other tetracarboxylic dianhydrides and their derivatives) and the amount of the aromatic diamine (formula: HY ¹ N-R ^4- NY ² H). The total amount (total amount of reactant [substrate]) with (total amount) is 1 to 80 mass with respect to the total amount of at least one selected from the group consisting of tetracarboxylic dianhydride and its derivative, aromatic diamine and solvent. The amount is preferably such that it becomes% (more preferably 5 to 50% by mass). If the amount of such a solvent used is less than the lower limit, it tends to be impossible to efficiently obtain polyamic acid, while if it exceeds the upper limit, stirring becomes difficult due to high viscosity and a high molecular weight substance cannot be obtained. It is in.

Further, in the first step, the reaction temperature at the time of reacting the aromatic diamine with at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative is to react these compounds. The temperature may be appropriately adjusted, and is not particularly limited, but is preferably -20 to 100 ° C. (more preferably 5 to 80 ° C.).

Further, in the first step, as a method of reacting at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative with the aromatic diamine, the tetracarboxylic dianhydride and its derivative are used. A method capable of carrying out a polymerization reaction of an aromatic diamine with at least one selected from the group can be appropriately used, and is not particularly limited, but is, for example, in an atmospheric pressure, in an inert atmosphere such as nitrogen, helium, or argon. In the above, it is preferable to adopt a method in which the tetracarboxylic dianhydride and the aromatic diamine are added to the solvent at the reaction temperature, and then the reaction is carried out 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, while if it exceeds the upper limit, depolymerization of the polyimide precursor proceeds and the molecular weight tends to decrease. It is in. In this way, the reaction solution can be obtained by reacting the tetracarboxylic dianhydride with the aromatic diamine in the first step.

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

In this way, in the second step, by adding the added compound (second component) to the reaction solution, at least one selected from the group consisting of the tetracarboxylic dianhydride and its derivative ( The compounds represented by the general formulas (1) to (4), other tetracarboxylic dianhydrides added as necessary, and derivatives thereof) and the fragrance represented by the general formula (ii). The general formulas (I) to (III), which are polymers of the group diamine (the above formula: at least one selected from the group consisting of the compounds represented by HY ¹ N-R ^4- NY ² H). ), A polyimide precursor resin having at least one repeating unit selected from the group consisting of repeating units represented by), the additive compound, and the solvent can be obtained. Become.

When the polyimide precursor resin composition thus obtained is heated, the polyimide precursor resin can be heated in the presence of the added compound (the second component) and a solvent, and the heating step thereof. Since the added compound (the second component) acts as a catalyst for accelerating the reaction, it is possible to improve the molecular weight of the finally obtained polyimide.

Further, the amount of such an added compound (the second component) used is at least one selected from the group consisting of the tetracarboxylic dianhydride used in the method (I-1) and a derivative thereof (the amount of the second component). The total amount of the compounds represented by the general formulas (1) to (4), other tetracarboxylic dianhydrides added as necessary, and their derivatives), and the method (I-1). The amount of aromatic diamine represented by the general formula (ii) (total amount of compounds represented by the formula: Y ₂ N-R ^4- NY ₂ ) and the added compound used in the method (I-1) ( The ratio (addition amount) of the added compound is preferably 0.1 to 30% by mass with respect to the total amount with the amount of the second component), and is 0.5 to 10% by mass. More preferably, it is an amount. If the content of such an added compound (the second component) is less than the lower limit, it becomes difficult to improve the molecular weight of the polyimide when the polyimide is formed by using the obtained 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 decrease, and on the other hand, when the above upper limit is exceeded, the polyimide precursor resin composition obtained is used for polyimide. A side reaction proceeds during the production of the above, and a uniform polyimide cannot be obtained, and various physical properties of the obtained polyimide tend to deteriorate. In addition, in order to adjust the ratio (addition amount) of the added compound, the solvent may be added again at the time of adding the added compound.

In this way, the 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 added compound, and the solvent. A polyimide precursor resin composition containing the above can be obtained.

Incidentally, in such a way (I-1), using the tetracarboxylic dianhydride and the above formula as the aromatic diamine: using a compound represented by H _{2 N-R} ⁴ -NH 2 In the case, it has at least one repeating unit selected from the group consisting of the repeating units represented by the above general formulas (I) to (III), and Y ¹ and Y ^{1 in} the general formula of the repeating unit. A polyimide precursor resin composition containing a polyimide precursor resin composed of a polyamic acid in which Y ² is a hydrogen atom, 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 above based on the preferred methods (I) and (I-1), but 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 method, and at least one selected from the group consisting of tetracarboxylic dianhydride having two norbornan skeletons in the molecule and a derivative thereof and diamine. Polyimide precursor resin which is a polymer; formula in which phosphorus atom and carbon atom are directly bonded in the molecule: Tertiary phosphorus compound containing a structure represented by CP, phosphorus atom and carbon atom are directly bonded in the molecule. Formula: Polyimide precursor resin composition containing 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; and a solvent. Any method that can be obtained can be appropriately adopted.

Further, the polyimide precursor resin composition of the present invention thus obtained is used as a varnish (resin solution) for preparing polyimide, and the polyimide precursor resin composition is imidized to form 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 obtain 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 adopted. For example, when the polyimide precursor resin is a polyamic acid. , The imidization method described in International Publication No. 2011/099518, the imidization method described in International Publication No. 2015/1633314, and the imidization method described in International Publication No. 2017/030019. Method, etc. can be adopted as appropriate. Further, as such an imidization method, a so-called chemical imidization method (the polyimide precursor resin (preferably polyamic acid) in the polyimide precursor resin composition of the present invention described above is imidized by using a known imidizing agent. The polyimide precursor in the polyimide precursor resin composition is subjected to a treatment of heating the polyimide precursor resin composition of the present invention under a temperature condition of 60 to 450 ° C. (more preferably 80 to 400 ° C.). It is preferable to adopt a method of imidizing the body resin (preferably polyimide).

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

[In the formula, 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. Indicates the Allylene group of. ]
A polyimide having a repeating unit represented by is 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 precursor resin having at least one of the repeating units represented by the above general formulas (II) to (III) is imidized to prepare a polyimide, the following general formula (II'):

[In the formula, R ¹⁰ represents an arylene group having 6 to 50 carbon atoms. ]
A polyimide having a repeating unit represented by is obtained. Note that R ¹⁰ in the general formula (II') has the same meaning as R ¹⁰ in the general formula (II), and the same applies to suitable ones.

Further, when a polyimide resin composition is prepared by using such a polyimide precursor resin composition of the present invention as a varnish (resin solution) for preparing a polyimide (imimided product of the polyimide precursor resin composition of the present invention). (When prepared), it is possible to efficiently and reliably produce polyimide with higher toughness while maintaining characteristics such as linear expansion coefficient, glass transition temperature, and total light transmittance at sufficiently high levels. Become. The polyimide thus obtained by using the polyimide precursor resin composition of the present invention has, for example, a film for a flexible wiring substrate, a heat-resistant insulating tape, an electric wire enamel, a protective coating agent for a semiconductor, and a semiconductor. Insulation 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 type solar cell, transparent conductive film for dye sensitized solar cell , Flexible gas barrier film, Touch panel film, 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, etc.), interlayer insulating 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 ductivity composite substrate, semiconductor resist, lithium ion battery, organic memory substrate, organic transistor substrate, organic semiconductor substrate, color filter substrate, etc. are particularly useful as materials for manufacturing. .. In addition to the above-mentioned uses, the polyimide obtained by using the polyimide precursor resin composition of the present invention may be formed into a powdery body or various molded bodies, for example. It can also be appropriately used for automobile parts, aerospace parts, bearing parts, sealing materials, bearing parts, gear wheels, valve parts and the like.

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

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

Tetracarboxylic dianhydride represented by (norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic dianhydride Anhydride: Hereinafter, the tetracarboxylic dianhydride represented by the above general formula (A) is referred to as "CpODA").

(Synthesis Example 2: BNBDA Synthesis)
In accordance with the method described in Examples 1 and 2 of International Publication No. 2017/030019, the following general formula (B):

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

(Synthesis Example 3: Synthesis of BzDA)
In accordance with the method described in Example 1 of International Publication No. 2015/1633314, 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 (Volume 27) published in 1994, the following general formula (D):

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

<Abbreviations for monomers, etc.>
The abbreviations and the like of the tetracarboxylic dianhydride, the aromatic diamine, and the added compound used in the following examples are described below. The following abbreviations and the like may be used in the description in the examples.

(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'-(hexafluoroisopropyridene) 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 Chemical Industries, Ltd.)
PPD: 1,4-para-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
TFMB: 2,2'-bis (trifluoromethyl) benzidine (manufactured by Seika Kogyo Co., Ltd.)
DDE: 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
m-Tol: m-trizine (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 Industry Co., Ltd.)
Tertiary phosphorus compound (B): tripalatrilphosphine (trade name "TPTP": manufactured by Hokuko Chemical Industry Co., Ltd.)
Quadruple amine compound (A): Tetramethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tertiary phosphorus compound (A): benzyltriphenylphosphonium bromide (trade name "U-cat 5003": manufactured by San-Apro Co., Ltd.).

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

<Second process>
After introducing 5.92 g of the reaction solution prepared in the first step into a 10 mL screw tube, 1.99 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the added compound are added to the reaction solution. After adding 0.118 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain polyamic acid, which is a polymer of CpODA and DABAN, and a tertiary phosphorus compound. 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 separately introduced into a 10 mL screw tube, and then dimethylacetamide (N, N-dimethyl) as a solvent was introduced into the reaction solution. After adding 1.01 g of acetamide) and 0.029 g of triparatrilphosphine (tertiary phosphorus compound (B)), the polyamic acid which is a polymer of CpODA and DABAN is stirred under the temperature condition of room temperature for 6 hours. A polyimide precursor resin composition containing the tertiary phosphorus compound (B) and a solvent (dimethylacetamide) was obtained.

(Example 3)
<First process>
Under a nitrogen atmosphere, 1.70 g (7.50 mmol) of DABAN and 0.27 g (2.50 mmol) of PPD were introduced as aromatic diamines into a 50 mL screw tube, and 3.84 g (10.) 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

<Second process>
After 3.91 g of the reaction solution prepared in the first step was introduced into a 10 mL screw tube, 1.30 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the added compound were added to the reaction solution. After adding 0.077 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain 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 process>
In a nitrogen atmosphere, 1.14 g (5.00 mmol) of DABAN and 0.541 g (5.00 mmol) of PPD were introduced as aromatic diamines into a 50 mL screw tube, and 3.84 g (10.) CpODA as tetracarboxylic dianhydride. 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

<Second process>
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 added compound were added to the reaction solution. After adding 0.086 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain 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 process>
Under a nitrogen atmosphere, 1.14 g (5.00 mmol) of DABAN and 1.60 g (5.00 mmol) of TFMB as aromatic diamines were introduced into a 50 mL screw tube, and 3.84 g (10.) CpODA as tetracarboxylic dianhydride. 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

<Second process>
After introducing 3.52 g of the reaction solution prepared in the first step into a 10 mL screw tube, 1.28 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the added compound are added to the reaction solution. After adding 0.073 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain 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 process>
Under a nitrogen atmosphere, 0.909 g (4.00 mmol) of DABAN and 0.200 g (1.00 mmol) of DDE were introduced as aromatic diamines into a 50 mL screw tube, and 1.65 g (5.) BNBDA as tetracarboxylic dianhydride. 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

<Second process>
After 4.65 g of the reaction solution prepared in the first step was introduced into a 10 mL screw tube, 1.69 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the added compound were added to the reaction solution. After adding 0.093 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain 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 process>
Under a nitrogen atmosphere, 0.909 g (4.00 mmol) of DABAN and 0.320 g (1.00 mmol) of TFMB as aromatic diamines were introduced into a 50 mL screw tube, and 1.65 g (5.) BNBDA as tetracarboxylic dianhydride. 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

<Second process>
After 4.65 g of the reaction solution prepared in the first step was introduced into a 10 mL screw tube, 1.50 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and the added compound were added to the reaction solution. After adding 0.099 g of triphenylphosphine (tertiary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain 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 solution obtained in the first step of Example 1, 4.53 g of the reaction solution was separately introduced into a 10 mL screw tube, and then dimethylacetamide (N, N-dimethyl) as a solvent was introduced into the reaction solution. After adding 1.65 g of acetamide) and 0.091 g of trimethyl phosphate, the mixture was stirred at room temperature for 6 hours to obtain polyamic acid, which is a polymer of CpODA and DABAN, and trimethyl phosphate. 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>
The polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were used as varnishes for polyamic acid for producing polyimide, respectively, to prepare a film made of polyimide as follows. That is, first, the polyimide precursor resin composition is spin-coated on a large slide glass (trade name "S9213" manufactured by Matsunami Glass Industry 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 on the surface. After that, the glass plate on which the coating film was formed was put into an oven and allowed to stand for 2 hours in a nitrogen atmosphere at a temperature condition of 70 ° C., and then allowed to stand for 30 minutes at a temperature condition of 135 ° C. Further, the temperature conditions are set 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. By changing and allowing it to stand for 30 minutes under the temperature condition of the final heating temperature, the coating film is cured, 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 from the oven, the polyimide-coated glass is immersed in hot water at 90 ° C. for 0.5 hours, and the film is peeled off from the glass substrate to recover the polyimide. Obtained a film consisting of. When the colors of all the obtained polyimide films were visually confirmed, it was confirmed that they were colorless and transparent. Table 1 shows the thickness of the obtained polyimide film.

<Measurement of coefficient of linear expansion (CTE)>
A film (imidized product of the polyimide precursor resin composition) made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above, respectively. Using each of them, the linear expansion coefficient of the obtained polyimide was measured as follows. That is, first, from the film made of the polyimide, a film for measurement having a size of 20 mm in length and 5 mm in width was formed (in the range of the thickness as shown in Table 1, the thickness is the measured value. Since it does not particularly affect the film thickness, the film thickness of each example was adopted as it is). Next, the obtained measurement film was vacuum dried (120 ° C. for 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) and using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) as a measurement device, a tension mode (49 mN) and a temperature rise rate under a nitrogen atmosphere. Taking the condition of 5 ° C./min, the change in length of the sample from 50 ° C. to 200 ° C. is measured, and the average value of the change in length per 1 ° C. in the temperature range of 100 ° C. to 200 ° C. Measured by determination.

<Measurement of glass transition temperature (Tg)>
A film (imidized product of the polyimide precursor resin composition) made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above, respectively. Using each of them, the value (unit: ° C.) of the glass transition temperature (Tg) of the obtained polyimide was measured as follows. That is, as a measurement sample, a sample having a size of 20 mm in length and 5 mm in width cut out from the film made of the polyimide (since the thickness of such a sample does not affect the measured value, the thickness of the film obtained in the example remains unchanged. In a nitrogen atmosphere, in a tensile mode (49 mN), and at a temperature rise rate of 5 ° C./min, using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) as a measuring device. 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 curves before and after the turning point of the TMA curve due to the glass transition. The value (unit: ° C.) of (Tg) was determined. The results obtained are shown in Table 1.

<Measurement of 5% weight loss temperature (Td5%)>
The 5% weight loss temperature of the polyimide is a film made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 4, 6 and Comparative Examples 1 and 2, respectively (polyimide precursor). Prepare a sample of about 10 mg using each of the imidized resin compositions), put this in an aluminum sample pan, and use a thermogravimetric analyzer (trade name "TG" manufactured by SII Nanotechnology Co., Ltd.) as a measuring device. / DTA7200 "), the scanning temperature is set from 40 ° C. to 550 ° C. under a nitrogen gas atmosphere, and heating is performed under the condition of a heating 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 (imidized product of the polyimide precursor resin composition) made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above, respectively. Using each of them, 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 the product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. and the product name "Spectrocolor Color" manufactured by Nippon Denshoku Industries Co., Ltd. are used as measuring devices. The total light transmittance (unit:%) and yellowness (YI) of the polyimide resin composition constituting the film obtained in each example and the like were determined by performing the measurement using each of the total SD6000. In such measurement, the total light transmittance was measured with the product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd., and the product name "Spectrocolorimeter SD6000" manufactured by Nippon Denshoku Industries Co., Ltd. was used. The yellowness was measured. The total light transmittance is determined 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). I asked for it. The results obtained are shown in Table 1.

<Measurement of toughness>
A film (imidized product of the polyimide precursor resin composition) made of polyimide obtained by using the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 as described above, respectively. Each was used to determine toughness by tactile sensation. The index of judgment is shown below. The determination results are shown in Table 1.
(Evaluation of toughness)
A: It can be judged from the tactile sensation that the film is very tough, and it is recognized that the film has very high toughness.
B: From the tactile sensation, it can be judged that the film is tough as it is, and it is recognized that the toughness is moderate.

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

As is clear from the results shown in Table 1, 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 are all lines. The coefficient of expansion is 23 ppm / K or less, which is a sufficiently low value, the glass transition temperature is 333 ° C. or more, which is a sufficiently high temperature, and the total light transmittance is 87% or more. It was confirmed that the characteristics such as expansion coefficient, glass transition temperature and total light transmittance are all at sufficiently high levels.

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

From these results, according to the polyimide precursor resin composition of the present invention (Examples 1 to 7), the characteristics such as the coefficient of linear expansion, the glass transition temperature and the total light transmittance are maintained at sufficiently high levels. It was confirmed that it is possible to efficiently and surely produce a polyimide having higher toughness.

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

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

The polyimide precursor resin composition thus obtained in Example 8 was used to obtain the above-mentioned "Examples 1 to 7 and Comparative Examples 1 to 3" except that the final heating temperature was set to 350 ° C. A film made of polyimide (thickness: 14 μm) was prepared by adopting the same method as that used for "evaluation of the characteristics of the polyimide precursor resin composition", and the glass transition temperature, total light transmittance, and so on. YI and toughness were measured. As a result of such measurement, the polyimide obtained by 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. Was 4.0, 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 produced while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at sufficiently high levels. And it was found that it can be manufactured reliably.

(Example 9)
<First process>
In a nitrogen atmosphere, 3.20 g (10.0 mmol) of TFMB as an aromatic diamine was introduced into a 50 mL screw tube, and 1.92 g (5.00 mmol) of CpODA and 2.22 g (5.) of 6FDA as tetracarboxylic dianhydride. 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

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

The polyimide precursor resin composition thus obtained in Example 9 was used to obtain the above-mentioned "Examples 1 to 7 and Comparative Examples 1 to 3" except that the final heating temperature was set to 350 ° C. A film made of polyimide (thickness: 7 μm) was prepared by adopting the same method as that used for "evaluation of the characteristics of the polyimide precursor resin composition", and the glass transition temperature and 5% weight loss temperature were obtained. , Total light transmittance, YI and toughness were measured. As a result of such measurement, the polyimide obtained by 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%, the YI was 1.9, and the toughness evaluation result was A. As described above, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently produced while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at sufficiently high levels. And it was found that it can be manufactured reliably.

(Example 10)
<First process>
In 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 solution was stirred under a nitrogen atmosphere at room temperature for 6 hours to obtain a reaction solution.

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

Using the polyimide precursor resin composition obtained in Example 10 in this manner, the polyimides obtained in Examples 1 to 9 and Comparative Example 1 described above are used except that the final heating temperature is set to 350 ° C. A film made of polyimide (thickness: 10 μm) was prepared by adopting the same method as the method adopted for "evaluation of the characteristics of the precursor resin composition", and the glass transition temperature, total light transmittance, YI and The toughness was measured. As a result of such measurement, the polyimide obtained by 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. Was 1.2, 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 produced while maintaining various physical properties such as glass transition temperature, total light transmittance and YI at sufficiently high levels. And it was found that it can be manufactured reliably.

(Example 11)
First, a reaction solution was obtained by adopting the same steps as the first step adopted in Example 1. Next, 5.21 g of the obtained reaction solution was taken out and introduced into a 10 mL screw tube, and then 1.76 g of dimethylacetamide (N, N-dimethylacetamide) as a solvent and benzyltri as the additive compound were added to the reaction solution. After adding 104 mg of phenylphosphonium bromide (quaternary phosphorus compound (A)), the mixture was stirred under room temperature conditions for 6 hours to obtain polyamic acid, which is a polymer of CpODA and DABAN, and a quaternary phosphorus compound (A). ) And a solvent (dimethylacetamide) to obtain a polyimide precursor resin composition.

The polyimide precursor resin composition thus obtained in Example 11 was used to obtain the above-mentioned "Examples 1 to 7 and Comparative Examples 1 to 3" except that the final heating temperature was set to 370 ° C. A film made of polyimide (thickness: 27 μm) was prepared by adopting the same method as that used for "evaluation of the characteristics of the polyimide precursor resin composition", and the coefficient of linear expansion, total light transmittance, and so on. YI and toughness were measured. As a result of such measurement, the polyimide obtained by using the polyimide precursor resin composition obtained in Example 11 has a linear expansion coefficient of 7 ppm / K and a total light transmittance of 87%. The YI was 3.1 and the toughness evaluation result was A. As described above, according to the polyimide precursor resin composition of the present invention, a polyimide having higher toughness can be efficiently produced while keeping various physical properties such as coefficient of linear expansion, total light transmittance and YI at sufficiently high levels. And it was found that it can be manufactured reliably.

(Example 12)
<First process>
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, 2.03 g (5.00 mmol) of BzDA as a tetracarboxylic dianhydride was added to the screw tube, and then 3.5 g of dimethylacetamide (N, N-dimethylacetamide) was applied to the wall surface of the screw tube. The BzDA was added while being washed and poured to obtain a mixed solution. Then, the mixed solution was stirred at 80 ° C. for 3.5 hours under a nitrogen atmosphere to obtain a uniform solution. Then, the obtained solution was cooled to room temperature, and stirring was continued for 1 day to obtain a reaction solution.

<Second process>
2.75 g of the reaction solution prepared in the first step is taken out and introduced into a 10 mL screw tube, and then 55.0 mg of the additive compound triphenylphosphine (tertiary phosphorus compound (A)) is added, and then at room temperature. By stirring for 6 hours under the above temperature conditions, a polyimide precursor resin composition containing a polyamic acid which is a polymer of BzDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) is obtained. It was.

Using the polyimide precursor resin composition obtained in Example 12 in this manner, the atmosphere when heating in the oven is changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (a glass plate on which a coating film is formed). After putting it in the oven, it is heated in a reduced pressure atmosphere from the stage of standing for 2 hours under the temperature condition of 70 ° C. to the stage of standing for 30 minutes at the final heating temperature), 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 the characteristics of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3". The 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 by 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%, the 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, various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI are set to sufficiently high levels, and higher toughness is achieved. It was found that it is possible to efficiently and surely produce the polyimide having the above.

(Example 13)
<First process>
Under a nitrogen atmosphere, 1.00 g (5.00 mmol) of DDE was introduced as an aromatic diamine and 1.51 g (5.00 mmol) of DNDA was introduced as a tetracarboxylic dianhydride in a 50 mL screw tube. 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 under a nitrogen atmosphere at room temperature for one day to obtain a reaction solution.

<Second process>
After 2.21 g of the reaction solution prepared in the first step was introduced into a 10 mL screw tube, 44.1 mg of the additive compound triphenylphosphine (tertiary phosphorus compound (A)) was added, and then the temperature at room temperature. By stirring for 6 hours under the above temperature conditions, a polyimide precursor resin composition containing a polyamic acid which is a polymer of DNDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) is obtained. It was.

Using the polyimide precursor resin composition obtained in Example 13 in this manner, the atmosphere when heating in the oven is changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (a glass plate on which a coating film is formed). After putting it in the oven, it is heated in a reduced pressure atmosphere from the stage of standing for 2 hours under the temperature condition of 70 ° C. to the stage of standing for 30 minutes at the final heating temperature), 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 the characteristics of the polyimide precursor resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3". The 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 by 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%, the 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, various physical properties such as glass transition temperature, 5% weight loss temperature, total light transmittance and YI are set to sufficiently high levels, and higher toughness is achieved. It was found that it is possible to efficiently and surely produce the polyimide having the above.

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

<Second process>
2.43 g of the reaction solution prepared in the first step was taken out and introduced into a 10 mL screw tube, and then 48.7 mg of the additive compound triphenylphosphine (tertiary phosphorus compound (A)) was added, and then at room temperature. By stirring for 6 hours under the above temperature conditions, a polyimide precursor resin composition containing a polyamic acid which is a polymer of DNDA and DDE, a tertiary phosphorus compound (A), and a solvent (dimethylacetamide) is obtained. It was.

Using the polyimide precursor resin composition obtained in Example 14 in this manner, the atmosphere when heating in the oven is changed to a reduced pressure atmosphere instead of a nitrogen atmosphere (a glass plate on which a coating film is formed). After putting it in the oven, it is heated in a reduced pressure atmosphere from the stage of standing for 2 hours under the temperature condition of 70 ° C. to the stage of standing for 30 minutes at the final heating temperature), 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 the characteristics of the 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 by 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., and 5 The% weight loss temperature was 415 ° C., the total light transmittance was 91%, the YI was 1.0, and the toughness evaluation result was A. As described above, according to the polyimide precursor resin composition of the present invention, various physical properties such as linear expansion coefficient, glass transition temperature, 5% weight loss temperature, total light transmittance and YI are kept at sufficiently high levels. It was found that it is possible to efficiently and reliably produce a polyimide having higher toughness.

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

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

Claims (4)

A polyimide precursor resin which is a polymer of at least one selected from the group consisting of a tetracarboxylic dianhydride having two norbornane skeletons in the molecule and a derivative thereof and a diamine;
Formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: A tertiary phosphorus compound containing a structure represented by CP, a formula in which a phosphorus atom and a carbon atom are directly bonded in a molecule: represented by CP With at least one additive compound selected from the group consisting of a quaternary phosphorus compound containing a structure and a quaternary amine compound;
With solvent;
A polyimide precursor resin composition containing. At least one selected from the group consisting of tetracarboxylic dianhydride having two norbornane skeletons in the molecule and derivatives thereof is the following general formula (1):
[In formula (1), R ¹ , R ² , and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is 0 to 12. Indicates an integer of. ]
Compound represented by; the following general formula (2):
[In formula (2), A is one selected from the group consisting of divalent aromatic groups which may have a substituent and have 6 to 30 carbon atoms forming an aromatic ring. Shown, R ⁴ is each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ is independently composed of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, respectively. Shows one species selected from the group. ]
Compound represented by; the following general formula (3):
[In formula (3), 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 is bonded to the same carbon atom. shows a may form a methylidene group, R ⁷ is one selected from each independently consisting of hydrogen atom and alkyl group having 1 to 10 carbon atoms in the group two R ⁶ are taken together .. ]
Compound represented by; the following general formula (4):
The polyimide precursor resin composition according to claim 1, which is at least one selected from the group consisting of the compound represented by the above; and the derivative of the compound. The polyimide precursor resin has the following general formula (I):
[In the formula (I), X ¹ is the following general formula (I-1):
[In formula (I-1), R ¹ , R ² , and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n is 0. Indicates an integer of ~ 12, and the symbols * 1 to * 4 indicate that the connecting hands with the symbols are any of the four joining hands that are connected to X ¹ in the formula (I), respectively. Is shown. ]
Tetravalent group represented by; the following general formula (I-2):
[In formula (I-2), A is selected from the group consisting of divalent aromatic groups which may have a substituent and have 6 to 30 carbon atoms forming an aromatic ring. Species are indicated, R ⁴ represents one species independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R ⁵ indicates an alkyl group having a hydrogen atom and 1 to 10 carbon atoms independently, respectively. represents one selected from the group consisting of the symbol * 1 * 4 of four coupling hands of bond that is attached with No.該記is bonded to X ¹ in each formula (I) Indicates that it is either. ]
Tetravalent group represented by; the following general formula (I-3):
[In formula (I-3), 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. bound two R ⁶ are taken together to may form a methylidene group, R ⁷ is one selected from each independently hydrogen and the group consisting of alkyl group having 1 to 10 carbon atoms it is shown, indicating that the symbol * 1 * 4 is either four coupling hands of bond that is attached with No.該記is bonded to X ¹ in each formula (I). ]
Indicates 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. ]
Repeat unit represented by; and the following general formulas (II) to (III):
[In formulas (II) to (III), R ¹⁰ represents an arylene group having 6 to 50 carbon atoms, and Y ¹ and Y ² independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 3 carbon atoms. Shown is one selected from the group consisting of alkylsilyl groups of ~ 9. ]
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 repeating unit represented by. The polyimide precursor resin composition according to any one of claims 1 to 3, wherein the added compound is triphenylphosphine.