JP2018123297A - Polyimide precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide precursor composition which is excellent in transparency, has good mechanical characteristics such as tensile strength, and provides a film containing an alicyclic polyimide resin; a method for producing a polyimide film using the polyimide precursor composition; and a permanent film which is excellent in transparency, has good mechanical characteristics such as tensile strength, and contains an alicyclic polyimide resin.SOLUTION: A polyimide precursor composition contains a resin precursor component (B) selected from a diamine compound having a predetermined structure, a monomer component containing alicyclic tetracarboxylic dianhydride having a predetermined structure, and a polyamide acid containing an alicyclic tetracarboxylic skeleton having a predetermined structure, an imidazole compound (A) having a predetermined structure, and a solvent (S).SELECTED DRAWING: None

Description

  The present invention relates to a polyimide precursor composition containing a polyimide resin precursor component, a method for producing a polyimide film using the polyimide precursor composition, and a permanent film.

  The polyimide resin has excellent heat resistance, mechanical strength, insulation, and low dielectric constant characteristics. For this reason, the polyimide resin is widely used as an insulating material and a protective material in various elements and electrical / electronic components such as an electronic substrate such as a multilayer wiring board.

  In addition, since it has excellent mechanical properties and heat resistance, a wholly aromatic polyimide (for example, trade name “Kapton”) has been used in advanced industries such as space and aviation. Such a wholly aromatic polyimide is synthesized by a reaction between an aromatic tetracarboxylic dianhydride and an aromatic diamine. For example, it is known that the above-mentioned kapton has the highest heat resistance (glass transition temperature (Tg): 410 ° C.) among the heat-resistant polymers (see Non-Patent Document 1).

  However, such wholly aromatic polyimides exhibit a brown color due to charge transfer (CT) between the aromatic ring-based tetracarboxylic dianhydride unit and the aromatic ring-based diamine unit. For this reason, application to uses, such as an optical use in which the transparency of wholly aromatic polyimide is required, was difficult.

Therefore, in order to produce a polyimide that can be used for optical applications and the like, research on alicyclic polyimides that do not generate CT and have high light transmittance has been advanced.
Such an alicyclic polyimide is obtained by a reaction between an alicyclic tetracarboxylic dianhydride and an alicyclic diamine, or a reaction between an alicyclic tetracarboxylic dianhydride and an aromatic diamine. And three types of resins obtained by the reaction of aromatic tetracarboxylic dianhydride and alicyclic diamine.

  However, among these alicyclic polyimides, it has been difficult to increase the molecular weight of polyimides obtained using alicyclic diamines. The basicity of the alicyclic diamine is 100 times higher than the basicity of the aromatic diamine. For this reason, aliphatic diamine and aromatic diamine are completely different in polymerization behavior. As a result, when an aliphatic diamine is used, high molecular weight is unlikely to proceed due to precipitation of the salt produced during polymerization.

  On the other hand, alicyclic polyimides obtained by combining alicyclic tetracarboxylic dianhydrides and aromatic diamines are easy to increase in molecular weight because general synthetic methods for wholly aromatic polyimides can be applied as they are. . Therefore, in recent years, alicyclic polyimides obtained by combining alicyclic tetracarboxylic dianhydrides and aromatic diamines among alicyclic polyimides have attracted attention. Then, alicyclic polyimides using monocyclic, bicyclocyclic, tricyclocyclic, tetracyclocyclic or spirocyclic alicyclic tetracarboxylic dianhydrides have been studied.

Engineering Plastics, Kyoritsu Shuppan, published in 1987, p88 Macromolecules, 27, published in 1994, p1117

However, when a film made of alicyclic polyimide is formed, a film having excellent transparency is obtained, but there is a problem that it is difficult to obtain a film having good mechanical properties such as tensile strength. Mechanical properties such as tensile strength are important mechanical properties in the membrane.
Therefore, there is a need for a polyimide precursor composition that provides a film containing an alicyclic polyimide resin that has excellent transparency and excellent mechanical properties such as tensile strength.

  The present invention has been made in view of the above problems, and is a polyimide precursor composition that is excellent in transparency, has excellent mechanical properties such as tensile strength, and provides a film containing an alicyclic polyimide resin. And a method for producing a polyimide film using the polyimide precursor composition, and a permanent film having excellent transparency and mechanical properties such as tensile strength and including an alicyclic polyimide resin. Objective.

  The present inventors selected from a monomer component containing a diamine compound having a predetermined structure and an alicyclic tetracarboxylic dianhydride having a predetermined structure, and a polyamic acid containing an alicyclic skeleton having a predetermined structure. The above-mentioned problem is solved by using a polyimide precursor composition in which a resin precursor component (B), an imidazole compound (A) having a predetermined structure, and a solvent (S) are blended, The present invention has been completed. Specifically, the present invention provides the following.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基であり、Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。）
で表される化合物であり、
樹脂前駆体成分（Ｂ）が、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を同一分子内に１つ以上有するジアミン化合物（Ｂ−Ｉａ）を含むジアミン成分（Ｂ−Ｉ）と、下記式（ｂ２）：

（式（ｂ２）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍは０以上１２以下の整数を示す。）
で表されるノルボルナン−２−スピロ−α−シクロアルカノン−α’−スピロ−２’’−ノルボルナン−５，５’’，６，６’’−テトラカルボン酸二無水物類（Ｂ−ＩＩ）とを含有するモノマー成分、及び下記式（ｂ３）：

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。）
で表される繰り返し単位を有するポリアミド酸（Ｂ−ＩＩＩ）からなる群より選択される少なくとも１つである、ポリイミド前駆体組成物である。 The first aspect of the present invention contains an imidazole compound (A), a resin precursor component (B), and a solvent (S),
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
A diamine containing a diamine compound (B-Ia) in which the resin precursor component (B) has at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond in the same molecule Component (BI) and the following formula (b2):

(In the formula (b2), R ^b1 , R ^b2 , and R ^b3 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, m represents an integer of 0 or more and 12 or less.)
Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydrides (B-II) And a monomer component containing the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
It is a polyimide precursor composition which is at least 1 selected from the group which consists of the polyamic acid (B-III) which has a repeating unit represented by these.

The second aspect of the present invention is a forming step of forming a coating film comprising the polyimide precursor composition according to the first aspect;
And a ring-closing step of ring-closing the polyamic acid derived from the resin precursor component (B) in the coating film by heating the coating film.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基であり、Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。）
で表される化合物であり、
ポリイミド樹脂が、下記式（ｂ３）：

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。）
で表される繰り返し単位を主成分とするポリアミド酸（Ｂ−ＩＩＩ）が閉環した樹脂である、永久膜である。 The third aspect of the present invention includes an imidazole compound (A) and a polyimide resin,
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
The polyimide resin has the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
It is a permanent film | membrane which is resin which ring-closed the polyamic acid (B-III) which has as a main component the repeating unit represented by these.

  A fourth aspect of the present invention is a polyimide film obtained by curing the polyimide precursor composition according to the first aspect.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基であり、Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。）
で表される化合物であり、
ポリイミド樹脂が下記式（ｂ３）：

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。）
で表される繰り返し単位を主成分とするポリアミド酸（Ｂ−ＩＩＩ）が閉環した樹脂である、ポリイミド膜である。 A fifth aspect of the present invention includes an imidazole compound (A) and a polyimide resin,
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
The polyimide resin is represented by the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
It is a polyimide film which is a resin in which the polyamic acid (B-III) whose main component is a repeating unit represented by

  According to the present invention, a polyimide precursor composition that is excellent in transparency, has good mechanical properties such as tensile strength, and provides a film containing an alicyclic polyimide resin, and the polyimide precursor composition are used. It is possible to provide a method for producing a polyimide film, and a permanent film having excellent transparency and mechanical properties such as tensile strength and containing an alicyclic polyimide resin.

≪Polyimide precursor composition≫
The polyimide precursor composition which is the first aspect of the present invention contains an imidazole compound (A), a resin precursor component (B), and a solvent (S).
Hereinafter, essential or optional components contained in the polyimide precursor composition will be described in order.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基を示す。Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。） <Imidazole compound (A)>
The imidazole compound (A) is represented by the following formula (0). When the polyimide precursor composition contains the imidazole compound (A), a polyimide film excellent in mechanical properties such as transparency and tensile strength can be formed using the polyimide precursor composition.

(In Formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ represents a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms. R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)

In Formula (0), R ² is an aromatic group that may have a substituent. The aromatic group that may have a substituent may be an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent.

  The type of the aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, and may be two or more aromatic hydrocarbon groups. May be formed by a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

  The kind of the aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.

  Examples of the substituent that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, and organic group. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

  When the substituent that the aromatic group has is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

  When the aromatic group has a substituent on the adjacent carbon atom, the two substituents bonded on the adjacent carbon atom may combine to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

  When the substituent that the aromatic group has is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes an oxygen atom, a nitrogen atom, a silicon atom, and the like. A bond containing a hetero atom may be included. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, a carboxylic acid ester bond, a carboxylic acid amide bond, a urethane bond, an imino bond (—N═C (—R) —, -C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

  As the bond containing a hetero atom that the organic group may have, from the viewpoint of heat resistance of the compound represented by the formula (0), an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, a carboxylic acid ester bond, Carboxylic acid amide bond, amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (-N = C (-R)-, -C (= NR)-: R Represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

  When the organic group is a substituent other than a hydrocarbon group, the type of substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than hydrocarbon groups include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups. , Alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether group and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

  Examples of the substituent that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 carbon atom. Preferred are an alkoxy group having 12 or less, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.

R ² is preferably a phenyl group, a furyl group, or a thienyl group, each of which may have a substituent, from the viewpoint of the effect of the present invention.

（式（０−１）中、Ｒ^１は水素原子又はアルキル基であり、Ｒ^３は、置換基を有してもよいアルキレン基である。＊は結合手である。） In formula (0), R ³⁰ represents a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms. When R ³⁰ is a monovalent substituent having 1 to 40 carbon atoms, the monovalent substituent for R ³⁰ is not particularly limited, but may have 1 to 40 carbon atoms which may have a substituent. Examples thereof include the following alkyl groups or π-conjugated groups having 4 to 40 carbon atoms which may have a substituent. Examples of the substituent that these alkyl groups or π-conjugated groups may have include a carboxy group, an alkyloxycarbonyl group, an alkyl group, an aryl group, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, and a silanol group. Nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonate group and the like. As R < ³⁰ >, the alkyl group which may have a substituent is preferable, and the monovalent group represented by a following formula (0-1) is preferable.

(In Formula (0-1), R ¹ is a hydrogen atom or an alkyl group, R ³ is an alkylene group which may have a substituent. * Is a bond.)

In formula (0-1), R ¹ is a hydrogen atom or an alkyl group. When R ¹ is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

Specific examples of the alkyl group suitable as R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

In formula (0-1), R ³ is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, and a halogen atom. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably a methylene group. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent that is bonded to the alkylene group.

  The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

  The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or dialkylamino group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

Specific examples of the alkylene group suitable as R ³ include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, and n-butane. -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl Group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group N-octadecane-1,18-diyl group, n -Nonadecane-1,19-diyl group and n-icosane-1,20-diyl group are mentioned.

In formula (0), R ⁴ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group. , N is an integer of 0 or more and 3 or less. When n is 2 or 3, the plurality of R ⁴ may be the same or different from each other.

When R ⁴ is an organic group, the organic group is the same as the organic group that the aromatic group may have as a substituent for R ² .

When R ⁴ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. As the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable. A furyl group and a thienyl group are more preferable.

When R ⁴ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably any of the 2-position, 4-position, and 5-position, and more preferably the 2-position. When R ⁴ is an aromatic hydrocarbon group or an aromatic heterocyclic group, the bonding position of these groups on imidazole is preferably the 2-position.

Among the compounds represented by the above formula (0), a compound represented by the following formula (0-1-1) is preferable from the viewpoint of excellent effects of the present invention, and is represented by the formula (0-1-1). And a compound in which R ³⁰ is the above formula (0-1) is more preferable.

（式（０−１−１）中、Ｒ^３０、Ｒ^４、及びｎは、式（０）と同様であり、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。）

(In formula (0-1-1), R ³⁰ , R ⁴ , and n are the same as in formula (0), and R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently , Hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group An ammonio group or an organic group.)

In Formula (0-1-1), it is preferable that at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a group other than a hydrogen atom. It is preferable in terms of solvent solubility.
When R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are organic groups, the organic group is the same as the organic group that R ² in Formula (0) has as a substituent. R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably a hydrogen atom from the viewpoint of solubility of the imidazole compound in a solvent.

Among them, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ is preferably the following substituent, and R ⁹ is particularly preferably the following substituent. When R ⁹ is the following substituent, R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms.
-O-R ¹⁰
(R ¹⁰ is a hydrogen atom or an organic group.)

When R ¹⁰ is an organic group, the organic group is the same as the organic group that R ² in Formula (0) has as a substituent. R ¹⁰ is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

（式（０−１−１−１）において、Ｒ^３０、Ｒ^４、及びｎは、式（０）と同様であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５は、それぞれ独立に、水素原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。） Among the compounds represented by the above formula (0-1-1), a compound represented by the following formula (0-1-1-1) is preferable.

(In the formula (0-1-1-1), R ³⁰ , R ⁴ , and n are the same as in the formula (0), and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are respectively Independently, hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, Ammonio group or organic group.)

In Formula (0-1-1-1), at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is preferably a group other than a hydrogen atom.
Among the compounds represented by the formula (0-1-1-1), at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is represented by the aforementioned —O—R ^10. A group is preferable, and R ¹⁵ is particularly preferably a group represented by —O—R ¹⁰ . When R ¹⁵ is a group represented by —O—R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are preferably hydrogen atoms.

  The method for synthesizing the compound represented by the formula (0) is not particularly limited. For example, the halogen-containing carboxylic acid derivative represented by the following formula (I) and the imidazole compound represented by the following formula (II) are reacted according to a conventional method to perform imidazolylation, whereby the above formula (0) Can be synthesized.

（式（Ｉ）及び式（ＩＩ）中、Ｒ^２、Ｒ^３０、Ｒ^４及びｎは、式（０）と同様である。式（Ｉ）において、Ｈａｌはハロゲン原子である。）

(In formula (I) and formula (II), R ² , R ³⁰ , R ⁴ and n are the same as in formula (0). In formula (I), Hal is a halogen atom.)

Preferable specific examples of the compound represented by the formula (0) include the following.

  Content of the imidazole compound (A) in a polyimide precursor composition is not specifically limited in the range which does not inhibit the objective of this invention. Content of an imidazole compound (A) is 1 mass part or more, for example with respect to 100 mass parts of below-mentioned resin precursor components (B), and although an upper limit is not specifically limited, For example, it is 60 mass parts or less. The content of the imidazole compound (A) is more preferably 5 parts by mass or more and 50 parts by mass or less, and particularly preferably 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin precursor component (B). By using the amount of the imidazole compound (A) in such a range, it is easy to form a polyimide film having excellent transparency and mechanical properties such as tensile strength.

<Resin precursor component (B)>
The resin precursor component (B) includes a predetermined diamine component (BI) and norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″-represented by the following formula (b2). A monomer component containing norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (B-II), and a polyamic acid having a repeating unit represented by the following formula (b3) ( At least one selected from the group consisting of B-III).

（式（ｂ２）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍは０以上１２以下の整数を示す。）

(In the formula (b2), R ^b1 , R ^b2 , and R ^b3 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, m represents an integer of 0 or more and 12 or less.)

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。）

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )

  Hereinafter, the monomer component and the polyamic acid will be described.

(Monomer component)
When the resin precursor component (B) contains a monomer component, the monomer component includes the diamine component (BI), norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″. -Norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (B-II) (hereinafter also referred to as “tetracarboxylic dianhydride (B-II)”). .
Hereinafter, essential or optional components that the monomer component may contain will be described.

(Diamine component (BI))
The diamine component (BI) includes a diamine compound (BIa) having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond in the same molecule. A diamine compound (B-Ia) may be used individually by 1 type, and may be used in combination of 2 or more type.
The ratio of the mass of the diamine compound (B-Ia) to the mass of the diamine component (BI) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 50% by mass or more, and 70% by mass. The above is particularly preferable.

In the diamine compound (B-Ia), a bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond may be contained in a position to be a side chain in the generated polyimide resin. You may contain in the position used as the principal chain in the polyimide resin to produce | generate.
For example, when the diamine compound (B-Ia) is 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 4-aminophenyl-4-aminobenzoate, etc., sulfone bond, carboxylic acid A bond selected from an ester bond and a carboxylic acid amide bond is included in the diamine compound (B-Ia) at a position to be a main chain in the generated polyimide resin.
Also, the diamine compound (B-Ia) is 2-phenylcarbamoyl-1,4-phenylenediamine, 2-benzoylamino-1,4-phenylenediamine, 2-phenoxycarbonyl-1,4-phenylenediamine, 2-benzoyl. In the case of oxy-1,4-phenylenediamine, 2-phenylsulfonyl-1,4-phenylenediamine and the like, the bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond is a diamine compound (B- In Ia), it is contained in a position to be a side chain in the produced polyimide resin.
A bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond is preferably included in the diamine compound (B-Ia) at a position to be a main chain in the polyimide resin to be formed.

Such a diamine compound (B-Ia) corresponds to a compound represented by the following formula (1).
H ₂ N—R ^F1 —NH ₂ (1)
(In Formula (1), R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond.)

In the formula (1), in the divalent organic group as R ^F1 , the portion other than the sulfone bond, the carboxylic acid ester bond, and the carboxylic acid amide bond may be an aromatic group or an aliphatic group. . The aliphatic group may be a linear group, a branched group, a cyclic group, or a group having a combination of these structures.
In the divalent organic group as R ^F1 , the portion other than the sulfone bond, the carboxylic acid ester bond, and the carboxylic acid amide bond may be a hydrocarbon group and includes a hetero atom other than a carbon atom and a hydrogen atom. May be.
R ^F1 is at least one selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond because the reactivity of the monomer component is good and it is easy to form a polyimide resin having excellent mechanical properties. It is preferably composed of a species bond and an aromatic group. The aromatic group may be an arylene group (aromatic hydrocarbon group) or a heteroarylene group (aromatic heterocyclic group).

In the case where R ^F1 in formula (1) is composed of a bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and an arylene group, one or more arylene groups contained in R ^F1 The total number of carbon atoms is preferably 12 or more and 40 or less, more preferably 12 or more and 30 or less, and particularly preferably 12 or more and 25 or less.
When the total number of carbon atoms of the arylene group exceeds 40, the heat resistance of the resulting polyimide resin tends to decrease. When the number of carbon atoms of the arylene group is less than 12, the solubility of the resulting polyimide resin in the solvent tends to be reduced.

（式（ｂ１ａ）中、Ｒ^Ｆ１０〜Ｒ^Ｆ１２は置換基を有していてもよい２価の炭化水素基であり、Ｚ^ｂは独立にスルホン結合、カルボン酸エステル結合、又はカルボン酸アミド結合である。）
で表される化合物と、下記式（ｂ１ｂ）：

（式（ｂ１ｂ）中、Ｒ^Ｆ１３、及びＲ^Ｆ１４は置換基を有していてもよい２価の炭化水素基であり、Ｚ^ｂはスルホン結合、カルボン酸エステル結合、又はカルボン酸アミド結合である。）
で表される化合物とが好ましい。
式（ｂ１ａ）で表される化合物としては、下記式（ｂ１−１）：

（式（ｂ１−１）中、Ｒ^Ｆ１０〜Ｒ^Ｆ１２は置換基を有していてもよい２価の炭化水素基であり、Ｚは独立に酸素原子又はＮＨである。）
で表される化合物が好ましい。
式（ｂ１ｂ）で表される化合物としては、下記式（ｂ１−２）：

（式（ｂ１−２）中、Ｒ^Ｆ１３、及びＲ^Ｆ１４は置換基を有していてもよい２価の炭化水素基であり、Ｚは酸素原子又はＮＨである。）
で表される化合物が好ましい。 As a diamine compound represented by the formula (1), the following formula (b1a):

(In Formula (b1a), R ^{F10 to} R ^F12 are divalent hydrocarbon groups which may have a substituent, and Z ^b is independently a sulfone bond, a carboxylic acid ester bond, or a carboxylic acid amide bond. is there.)
And a compound represented by the following formula (b1b):

(In Formula (b1b), R ^F13 and R ^F14 are divalent hydrocarbon groups which may have a substituent, and Z ^b is a sulfone bond, a carboxylic acid ester bond, or a carboxylic acid amide bond. .)
The compound represented by these is preferable.
As a compound represented by the formula (b1a), the following formula (b1-1):

(In Formula (b1-1), R ^{F10 to} R ^F12 are divalent hydrocarbon groups which may have a substituent, and Z is independently an oxygen atom or NH.)
The compound represented by these is preferable.
As a compound represented by the formula (b1b), the following formula (b1-2):

(In Formula (b1-2), R ^F13 and R ^F14 are divalent hydrocarbon groups which may have a substituent, and Z is an oxygen atom or NH.)
The compound represented by these is preferable.

R ^{F10 to} R ^F14 in the formula (b1a), the formula (b1b), the formula (b1-1), and the formula (b1-2) are divalent hydrocarbon groups that may have a substituent. From the viewpoint of the balance between the heat resistance of the resulting polyimide resin and the solubility in a solvent, R ^{F10 to} R ^F14 are each independently at least one of the groups represented by the following formulas (3) to (6). Preferably it is a seed.

（式（３）〜（６）中、Ｒ^１１は、水素原子、フッ素原子、クロロ原子、ブロモ原子、水酸基、炭素原子数１以上５以下のアルキル基、及び炭素原子数１以上５以下のフッ素化アルキル基よりなる群から選択される１種を示す。式（６）中、Ｑは、９，９−フルオレニリデン基、又は、式：−Ｃ_６Ｈ_４−、−ＣＯＮＨ−Ｃ_６Ｈ_４−ＮＨＣＯ−、−ＮＨＣＯ−Ｃ_６Ｈ_４−ＣＯＮＨ−、−Ｏ−Ｃ_６Ｈ_４−ＣＯ−Ｃ_６Ｈ_４−Ｏ−、−ＯＣＯ−Ｃ_６Ｈ_４−ＣＯＯ−、−ＯＣＯ−Ｃ_６Ｈ_４−Ｃ_６Ｈ_４−ＣＯＯ−、−ＯＣＯ−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＮＨ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＦ_３）_２−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−Ｃ_６Ｈ_４−ＳＯ_２−Ｃ_６Ｈ_４−Ｏ−、−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−、−Ｏ−Ｃ_６Ｈ_４−Ｃ_６Ｈ_４−Ｏ−、及び−Ｏ−Ｃ_６Ｈ_４−Ｏ−で表される基よりなる群から選択される１種を示す。）
式（３）〜（６）の定義の説明において、−Ｃ_６Ｈ_４−で表される基は、ｏ−フェニレン基でも、ｍ−フェニレン基でも、ｐ−フェニレン基でもよく、ｍ−フェニレン基、及びｐ−フェニレン基が好ましく、ｐ−フェニレン基がより好ましい。

(In formulas (3) to (6), R ¹¹ represents a hydrogen atom, a fluorine atom, a chloro atom, a bromo atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, and fluorine having 1 to 5 carbon atoms. In formula (6), Q is a 9,9-fluorenylidene group or a formula: —C ₆ H ₄ —, —CONH—C ₆ H ₄ —. _{NHCO -, - NHCO-C 6} H 4 -CONH -, - O-C 6 H 4 -CO-C 6 H 4 -O -, - OCO-C 6 H 4 -COO -, - OCO-C 6 H 4 _{-C 6 H 4 -COO -, -} OCO -, - O -, - S -, - CO -, - CONH -, - SO 2 -, - C (CF 3) 2 -, - C (CH 3) 2 _{-, - CH 2 -, -} O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - O-C 6 H _{-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 ( 1 type selected from the group consisting of CH ₃ ) ₂ —, —O—C ₆ H ₄ —C ₆ H ₄ —O—, and —O—C ₆ H ₄ —O—. )
In the description of the definitions of the formulas (3) to (6), the group represented by —C ₆ H ₄ — may be an o-phenylene group, an m-phenylene group, a p-phenylene group, or an m-phenylene group. And a p-phenylene group are preferred, and a p-phenylene group is more preferred.

R ¹¹ in the formulas (3) to (6) is preferably a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group from the viewpoint of heat resistance of the resulting polyimide resin, and a trifluoromethyl group Is more preferable.

As Q in the formula (6), from the viewpoint of the balance between the heat resistance of the resulting polyimide resin, and solubility in solvents, 9,9-fluorenylidene _{group, -C 6 H 4 -, -} O-C 6 H ₄ —O—, —O—, —C (CH ₃ ) ₂ —, —CH ₂ —, or —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O—, —CONH -, preferably, _{-O-C 6} H 4 -O- or -O- is particularly preferred.

  Among the groups represented by the formulas (3) to (6), a group represented by the formula (5) or the formula (6) is more preferable from the viewpoint of easily obtaining a polyimide resin having more excellent heat resistance. The group represented by 6) is particularly preferred.

As said R ^<F10 > -R ^<F14> , group represented by a following formula is preferable.

Among the above groups, R ^{F10 to} R ^F14 are more preferably groups represented by the following formulae.

Among the above groups, as R ^F11 , R ^F12 and R ^F13 , groups represented by the following formulas are particularly preferable.

Preferable examples of the compound represented by the formula (b1a) include the following compounds.

Preferable examples of the compound represented by the above formula (b1b) include the following compounds.

The diamine component (B-I) is only a diamine compound (B-Ib) having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond in the same molecule. Or a combination containing only two or more of the above diamine compounds (B-Ia), or a diamine compound (B-Ia) other than the above diamine compound (B-Ia) and the above diamine compound (B-Ia) -Ic) are preferred.
The diamine compound (B-Ia) is as described above, and the diamine compound (B-Ib) is selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond among the diamine compound (B-Ia). In particular, a diamine compound represented by the formula (b1a) is preferable, and a diamine compound represented by the formula (b1-1) is more preferable.
As a combination containing 2 or more types of said diamine compound (B-Ia), it contains 2 or more types of diamine compounds represented by Formula (b1a), or 2 or more types of diamine compounds represented by Formula (b1b). Or a combination of each diamine compound represented by the formula (b1a) and the formula (b1b) is preferable, and a case where two or more diamine compounds represented by the formula (b1b) are included is preferable.

As diamine compound (B-Ic) other than said diamine compound (B-Ia), the compound represented by following formula (7) is preferable.
H ₂ N—R ^{F 2} —NH ₂ (7)
(In Formula (7), R ^F2 is a divalent organic group that is a group other than R ^F1 described above.)
In Formula (7), R ^F2 is a group other than R ^F1 . That is, R ^F2 is a divalent organic group having no at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond.

R ^F2 in formula (7) is preferably at least one of the groups represented by the following formulas (8) to (11).

（式（８）〜（１１）中、Ｒ^１１は、水素原子、フッ素原子、クロロ原子、ブロモ原子、水酸基、炭素原子数１以上５以下のアルキル基、及び炭素原子数１以上５以下のフッ素化アルキル基よりなる群から選択される１種を示す。式（１１）中、Ｑ’は、９，９−フルオレニリデン基、又は、式：−Ｃ_６Ｈ_４−、−Ｏ−Ｃ_６Ｈ_４−ＣＯ−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＦ_３）_２−Ｃ_６Ｈ_４−Ｏ−、−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−、−Ｏ−Ｃ_６Ｈ_４−Ｃ_６Ｈ_４−Ｏ−、及び−Ｏ−Ｃ_６Ｈ_４−Ｏ−で表される基よりなる群から選択される１種を示す。）
式（８）〜（１１）の定義の説明において、−Ｃ_６Ｈ_４−で表される基は、ｏ−フェニレン基でも、ｍ−フェニレン基でも、ｐ−フェニレン基でもよく、ｍ−フェニレン基、及びｐ−フェニレン基が好ましく、ｐ−フェニレン基がより好ましい。

(In the formulas (8) to (11), R ¹¹ represents a hydrogen atom, a fluorine atom, a chloro atom, a bromo atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, and fluorine having 1 to 5 carbon atoms. In formula (11), Q ′ is a 9,9-fluorenylidene group or a formula: —C ₆ H ₄ —, —O—C ₆ H _{4. -CO-C 6 H 4 -O -} , - O -, - S -, - CO -, - C (CF 3) 2 -, - C (CH 3) 2 -, - CH 2 -, - O-C _{6 H 4 -C (CH 3)} 2 -C 6 H 4 -O -, - O-C 6 H 4 -C (CF 3) 2 -C 6 H 4 -O -, - C (CH 3) 2 - _{C 6 H 4 -C (CH 3} ) 2 -, - from _{O-C 6 H 4 -C 6} H 4 -O-, and _{-O-C 6} H 4 -O- consisting groups represented by the group Showing the one member-option.)
In the description of the definitions of formulas (8) to (11), the group represented by —C ₆ H ₄ — may be an o-phenylene group, an m-phenylene group, or a p-phenylene group, or an m-phenylene group. And a p-phenylene group are preferred, and a p-phenylene group is more preferred.

R ¹¹ in the formulas (8) to (11) is preferably a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, from the viewpoint of heat resistance of the resulting polyimide resin. Is more preferable.

Q ′ in the formula (11) is a 9,9-fluorenylidene group, —C ₆ H ₄ —, —O—C from the viewpoint of the balance between the heat resistance of the resulting polyimide resin and the solubility in a solvent. ₆ H ₄ —O—, —O—, —C (CH ₃ ) ₂ —, —CH ₂ —, or —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— is preferred. , —O—C ₆ H ₄ —O— or —O— is particularly preferable.

  Preferred examples of the compound represented by the formula (7) include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 3,3′-diaminodiphenylethane. 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-aminophenoxy) benzene, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methyl) Ruphenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, p-diaminobenzene, m-diaminobenzene, o-diamino Benzene, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 3,4′-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1, 5-diaminonaphthalene, 4,4 ′-[1,3-phenylenebis (1-methyl-ethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisaniline, 2 , 2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, , 4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 1,3′-bis (4-aminophenoxy) -2, 2-dimethylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2-bis (4-aminophenyl) -hexafluoropropane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3 , 3 ′, 5,5′-tetramethylbenzidine, 1,5-bis (4-aminophenoxy) pentane, 4,4 ″ -diamino-p-terphe Nyl, bis [4- (4-aminophenoxy) phenyl] ketone, and the like.

  When the diamine component (BI) is a mixture of the diamine compound (B-Ia) described above and a diamine compound (B-Ic) other than the diamine compound (B-Ia), the diamine component (BI) The mass ratio of the diamine compound (B-Ic) to the mass of is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 50% by mass or more, and particularly preferably 70% by mass or more. The diamine compound (B-Ia) to be mixed with the diamine compound (B-Ic) is preferably a diamine compound represented by the formula (b1a) and / or a diamine compound represented by the formula (b1b). It is more preferable that it is a diamine compound represented by b1b). When the diamine component (B-I) is a mixture of the diamine compound represented by the formula (b1b) and the diamine compound (B-Ic), the mixing molar ratio ((b1b) :( B-Ic)) is 1: 99-99: 1 are preferable, 5: 95-80: 20 are more preferable, and 10: 90-70: 30 are further more preferable.

Content of the diamine component (BI) in a monomer component is not specifically limited in the range which does not inhibit the objective of this invention.
The content of the diamine component (BI) in the monomer component is such that the amount of the tetracarboxylic dianhydride component described later is 0.2 mol or more and 2 mol or less with respect to 1 mol of the diamine component (BI). The amount is preferable, and an amount that is 0.3 mol or more and 1.2 mol or less is more preferable.
The tetracarboxylic dianhydride component essentially contains tetracarboxylic dianhydrides (B-II), and other tetracarboxylic acids other than the tetracarboxylic dianhydrides (B-II) described below. An acid dianhydride is optionally included.

（式（ｂ２）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍは０以上１２以下の整数を示す。） (Tetracarboxylic dianhydride component)
The tetracarboxylic dianhydride component includes tetracarboxylic dianhydrides (B-II) described below. Tetracarboxylic dianhydrides (B-II) are represented by the following formula (b2): norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ′ ', 6,6''-tetracarboxylic dianhydrides.

(In the formula (b2), R ^b1 , R ^b2 , and R ^b3 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, m represents an integer of 0 or more and 12 or less.)

The alkyl group that can be selected as R ^b1 in formula (b2) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms of the alkyl group exceeds 10, the heat resistance of the resulting polyimide resin tends to decrease. When R ^b1 is an alkyl group, the number of carbon atoms is preferably 1 or more, 6 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 4 or less from the viewpoint of easily obtaining a polyimide resin excellent in heat resistance. 1 to 3 is particularly preferable.
When R ^b1 is an alkyl group, the alkyl group may be linear or branched.

As R ^b1 in formula (b2), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable independently from the viewpoint that the obtained polyimide resin is excellent in heat resistance. In view of easy availability and purification of tetracarboxylic dianhydrides (B-II), R ^b1 in formula (b2) is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group. Are more preferable, and a hydrogen atom or a methyl group is particularly preferable.
A plurality of R ^b1 in the formula (b2) are preferably the same group because the tetracarboxylic dianhydrides (B-II) can be easily purified.

M in the formula (b2) represents an integer of 0 or more and 12 or less. When the value of m is more than 12, it is difficult to purify tetracarboxylic dianhydride components (B-II).
In view of easy purification of the tetracarboxylic dianhydrides (B-II), the upper limit of m is preferably 5, and more preferably 3.
In view of the chemical stability of the tetracarboxylic dianhydrides (B-II), the lower limit of m is preferably 1, and more preferably 2.
M in the formula (b2) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^b2 and R ^b3 in the formula (b2) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^b1 .
R ^b2 and R ^b3 are each a hydrogen atom or 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably, from the viewpoint of easy purification of tetracarboxylic dianhydrides (B-II). Is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less), and particularly preferably a hydrogen atom or a methyl group.

  As tetracarboxylic dianhydrides (B-II) represented by the formula (b2), for example, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5, 5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ″ -norbornane-5,5 ″, 6 , 6 ″ -tetracarboxylic dianhydride ”), methylnorbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″-(methylnorbornane) -5,5 ″, 6,6 '' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride ( Also known as "Norbornane-2-spiro" 2′-cyclohexanone-6′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride ”), methylnorbornane-2-spiro-α-cyclohexanone-α ′ Spiro-2 ″-(methylnorbornane) -5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α′-spiro-2 ′ '-Norbornane-5,5' ', 6,6' '-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2' '-norbornane-5,5' ', 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic Acid dianhydride, norvo Nan-2-spiro-α-cyclooctanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α- Cyclononanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α′-spiro-2 ″ -Norbornane-5,5 ", 6,6" -tetracarboxylic dianhydride, norbornane-2-spiro- [alpha] -cycloundecanone- [alpha] '-spiro-2 "-norbornane-5,5" , 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetra Carboxylic dianhydride, norbornane 2-spiro-α-cyclotridecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclo Tetradecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α′- Spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α′-spiro-2 ″ Norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α′-spiro-2 ″ -norbornane-5,5 ′ ', 6,6 "-Tetracar Phosphate dianhydride, and the like.

（式（ｂ２−１）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍは、式（ｂ２）中のＲ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍと同義である。）
で表される化合物（Ｂ−ＩＩａ）及び下記式（ｂ２−２）：

（式（ｂ２−２）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍは、式（ｂ２）中のＲ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍと同義である。）
で表される化合物（Ｂ−ＩＩｂ）のうちの少なくとも１種を含有し、且つ、テトラカルボン酸二無水物の総モル数に対する化合物（Ｂ−ＩＩａ）及び化合物（Ｂ−ＩＩｂ）の総量が３０モル％以上であるのが好ましい。 Moreover, as a tetracarboxylic dianhydride represented by Formula (b2), from a viewpoint of adjustment of a film characteristic, a thermophysical property, a mechanical physical property, an optical characteristic, and an electrical property, following formula (b2-1):

(In the formula ^{(b2-1), R b1, R} b2, R b3, m have the same meanings as ^{R b1, R b2, R b3} , m in the formula (b2).)
Compound (B-IIa) represented by the following formula (b2-2):

(In the formula ^{(b2-2), R b1, R} b2, R b3, m have the same meanings as ^{R b1, R b2, R b3} , m in the formula (b2).)
And the total amount of compound (B-IIa) and compound (B-IIb) is 30 with respect to the total number of moles of tetracarboxylic dianhydride. It is preferably at least mol%.

(B-IIa) represented by the formula (b2-1) is a formula in which two norbornane groups are in a trans configuration, and the carbonyl group of a cycloalkanone has an endo configuration with respect to each of the two norbornane groups. It is an isomer of tetracarboxylic dianhydride represented by (b2) (trans-endo-endo).
In the compound (B-IIb) represented by the formula (b2-2), two norbornane groups are in cis configuration, and the carbonyl group of cycloalkanone is in the endo configuration with respect to each of the two norbornane groups. It is an isomer of tetracarboxylic dianhydride represented by the formula (b2) (cis-endo-endo).
In addition, the manufacturing method of the tetracarboxylic dianhydride containing such an isomer in the above ratio is not particularly limited, and a known method can be appropriately employed. For example, it is described in International Publication No. 2014/034760. These methods may be appropriately adopted.

As will be described later, the monomer component may contain other tetracarboxylic dianhydrides other than tetracarboxylic dianhydrides (B-II).
Tetracarboxylic dianhydrides (B-II) and tetracarboxylic dianhydrides relative to the total amount of tetracarboxylic dianhydride components, which is the sum of the amount of other tetracarboxylic dianhydrides ( The ratio of the amount of B-II) is typically 1% by weight or more, 5% by weight or more, 10% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, 90% by weight or more. The higher the ratio in this order, the better, and the most preferable is 100% by mass.
The quantitative relationship between the tetracarboxylic dianhydride component and the diamine component is as described above.

(Other tetracarboxylic dianhydrides)
The monomer component is a tetracarboxylic dianhydride (B-II) and other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydrides (B-II) as long as the object of the present invention is not impaired. May be included.

Preferable examples of other tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane. Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,3,3a, 4,5,9b-Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1 3,3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5 -(2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, bicyclo [2.2.1] -heptane-2,3,5,6-tetracarboxylic dianhydride, (4H, 8H) -decahydro-1,4: 5 , 8-dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, pentacyclo [9.2.1.1 ^{4, 7.} 0 ^2,10 . 0 ^3,8 ] -pentadecane-5,6,12,13-tetracarboxylic dianhydride and other aliphatic or alicyclic tetracarboxylic dianhydrides; pyromellitic dianhydride, 3,3 ′, 4 , 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxy) Phenoxy) diphenylsulf Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3, 3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 3,3 ', 4,4'- Biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) Anhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4 And aromatic tetracarboxylic dianhydrides such as 4,4'-diphenylmethane dianhydride.
In addition, when using aromatic tetracarboxylic dianhydride, in order to prevent coloring of the film | membrane formed, the usage-amount is a range in which the film | membrane formed can have sufficient transparency. It is preferable to change appropriately within.

［式（Ｓｉ−１）中、Ｒ^ｂ１１及びＲ^ｂ１２は、それぞれ独立に、単結合又はメチレン基、炭素原子数２以上２０以下のアルキレン基、炭素原子数３以上２０以下のシクロアルキレン基、又は炭素原子数６以上２０以下のアリーレン基等であり；
Ｒ^ｂ１３、Ｒ^ｂ１４及びＲ^ｂ１５は、それぞれ独立に、炭素原子数１以上２０以下の一価の炭化水素基、炭素原子数１以上２０以下のアミノ基、−Ｏ−Ｒ^ｂ１６で表される基（Ｒ^ｂ１６は炭素原子数１以上２０以下の炭化水素基）、炭素原子数２以上２０以下の１以上のエポキシ基を含む有機基であり；
Ｌ^ｂ１、Ｌ^ｂ２及びＬ^ｂ３は、それぞれ独立に、アミノ基、イソシアネート基、カルボキシル基、酸無水物基、カルボン酸エステル基、カルボン酸ハライド基、ヒドロキシ基、炭素原子数２以上２０以下の１以上のエポキシ基を含む有機基、又はメルカプト基であり；
ｊは、３以上２００以下の整数であり、ｋは、０以上１９７以下の整数である。］ As another resin precursor component, a compound represented by the following formula (Si-1) may be used. By adding the compound represented by the formula (Si-1), the total light transmittance and haze of the resulting polyimide film can be improved.

[In Formula (Si-1), R ^b11 and R ^b12 each independently represent a single bond or a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or An arylene group having 6 to 20 carbon atoms;
R ^b13 , R ^b14 and R ^b15 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or a group represented by —O—R ^b16. (R ^b16 is a hydrocarbon group having 1 to 20 carbon atoms), an organic group containing one or more epoxy groups having 2 to 20 carbon atoms;
L ^b1 , L ^b2 and L ^b3 are each independently an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid halide group, a hydroxy group, 1 having 2 to 20 carbon atoms. An organic group containing the above epoxy group, or a mercapto group;
j is an integer of 3 to 200, and k is an integer of 0 to 197. ]

In formula (Si-1), the alkylene group having 2 to 20 carbon atoms in R ^b11 and R ^b12 is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance and residual stress. Group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like.

  The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms from the above viewpoint, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group. . The arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms from the above viewpoint, and examples thereof include a phenylene group and a naphthylene group.

In formula (Si-1), the alkyl group having 1 to 20 carbon atoms in R ^b13 , R ^b14 and R ^b15 is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.
The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms from the above viewpoint, and specific examples include a cyclopentyl group and a cyclohexyl group.
The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms from the above viewpoint, and specific examples include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the amino group having 1 to 20 carbon atoms include an amino group and a substituted amino group (for example, a bis (trialkylsilyl) amino group).
^Examples of the group represented by —O—R ^b16 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a tolyloxy group, a naphthyloxy group, a propenyloxy group (for example, an allyloxy group), and Examples include a cyclohexyloxy group.
Among these, R ^b13 , R ^b14 and R ^b15 are preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

［式（Ｓｉ−２）中、Ｒ^ｂ１１〜Ｒ^ｂ１４は前記と同様である。ｌは３以上５０以下の整数である。］ In formula (Si-1), the amino group in L ^b1 , L ^b2 and L ^b3 may be substituted, and examples thereof include a bis (trialkylsilyl) amino group. When L ^b1 , L ^b2 and L ^b3 are amino groups, a compound represented by the following formula (Si-2) is preferable.

[In formula (Si-2), R ^{b11 to} R ^b14 are the same as described above. l is an integer of 3 to 50. ]

  Specific examples of the compound represented by the formula (Si-2) include both-terminal amino-modified methylphenyl silicone (for example, X-22-1660B-3 (number average molecular weight 4,400) and X-manufactured by Shin-Etsu Chemical Co., Ltd.) 22-9409 (number average molecular weight 1,300)), both-terminal amino-modified dimethyl silicone (for example, X-22-161A (number average molecular weight 1,600), X-22-161B (number average molecular weight, manufactured by Shin-Etsu Chemical Co., Ltd.)) 3,000) and KF8012 (number average molecular weight 4,400); BY16-835U (number average molecular weight 900) manufactured by Toray Dow Corning; and Silaplane FM3311 (number average molecular weight 1000) manufactured by Chisso Corporation). Among these, both terminal amine-modified methyl phenyl silicone oils are particularly preferable from the viewpoints of improving chemical resistance and Tg.

Specific examples of the compound in which L ^b1 , L ^b2 and L ^b3 are isocyanate groups include the above-mentioned isocyanate-modified silicones obtained by reacting both terminal amino-modified silicones with phosgene compounds.
Specific examples of the compound in which L ^b1 , L ^b2 and L ^b3 are carboxyl groups include, for example, Shin-Etsu Chemical Co., Ltd., X-22-162C (number average molecular weight 4,600), BY16-880 manufactured by Toray Dow Corning (several Average molecular weight 6,600) and the like.
When L ^b1 , L ^b2 and L ^b3 are acid anhydride groups, phthalic anhydride groups and maleic anhydride groups are preferred. As specific examples, X-22-168AS (manufactured by Shin-Etsu Chemical, number average molecular weight 1,000), X-22-168A (manufactured by Shin-Etsu Chemical, number average molecular weight 2,000), X-22-168B (manufactured by Shin-Etsu Chemical) , Number average molecular weight 3,200), X-22-168-P5-8 (manufactured by Shin-Etsu Chemical, number average molecular weight 4,200), DMS-Z21 (manufactured by Gerest, number average molecular weight 600 to 800). It is done.
As a specific example of the compound in the case where L ^b1 , L ^b2 and L ^b3 are carboxylic acid ester groups, the compound in which L ^b1 , L ^b2 and L ^b3 are carboxyl groups or acid anhydride groups is reacted with an alcohol. And the resulting compound.
Specific examples of the compound in which L ^b1 , L ^b2 and L ^b3 are carboxylic acid halide groups include carboxylic acid chlorides, carboxylic acid fluorides, carboxylic acid bromides, carboxylic acid iodides, and the like.
Specific examples of the compound in which L ^b1 , L ^b2, and L ^b3 are organic groups containing one or more epoxy groups having 2 to 20 carbon atoms include X-22-163 (Shin-Etsu Chemical) Manufactured, number average molecular weight 400), KF-105 (manufactured by Shin-Etsu Chemical, number average molecular weight 980), X-22-163A (manufactured by Shin-Etsu Chemical, number average molecular weight 2,000), X-22-163B (manufactured by Shin-Etsu Chemical, Number average molecular weight 3,500), X-22-163C (manufactured by Shin-Etsu Chemical, number average molecular weight 5,400); X-22-169AS (manufactured by Shin-Etsu Chemical, number average molecular weight 1) which is an alicyclic epoxy type at both ends , 000), X-22-169B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400); X-22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent 5,000 g / mol) ; Etc. The compound having an epoxy group is considered to react with diamine.
Specific examples of the compound in which L ^b1 , L ^b2 and L ^b3 are mercapto groups include X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400), X-22-167C (manufactured by Shin-Etsu Chemical Co., Ltd., number average) Molecular weight 4,600) and the like. A compound having a mercapto group is considered to react with a compound having a carboxyl group or an acid anhydride group.
Among these, from the viewpoint of improving the molecular weight of the resin precursor, or from the viewpoint of heat resistance of the resulting polyimide, it is preferable that L ^b1 , L ^b2 and L ^b3 are each independently an amino group or an acid anhydride group, Independently, it is more preferably an amino group. The same applies to suitable combinations of L ^b1 and L ^b2 when k = 0.

  In the formula (Si-1), j is an integer of 3 or more and 200 or less, preferably an integer of 10 or more and 200 or less, more preferably an integer of 20 or more and 150 or less, and further preferably an integer of 30 or more and 100 or less. Preferably it is an integer from 35 to 80. By setting it as the said range, the cloudiness of a polyimide precursor composition is suppressed and the mechanical strength of the polyimide film obtained is maintained.

  In formula (Si-1), k is an integer of 0 or more and 197 or less, preferably 0 or more and 100 or less, more preferably 0 or more and 50 or less, and particularly preferably 0 or more and 25 or less. By setting it as the said range, when k is 197 or less, when preparing the polyimide precursor composition containing a resin precursor and a solvent, the cloudiness of a polyimide precursor composition is suppressed. From the viewpoint of improving the molecular weight of the resin precursor or the heat resistance of the resulting polyimide, k = 0 is preferable. When k is 0, it is preferable that j is 3 or more and 200 or less from the viewpoint of improving the molecular weight of the resin precursor or the heat resistance of the resulting polyimide.

  What is necessary is just to prepare suitably content of the compound represented by a formula (Si-1) in the range of 0.1 mol or more and 5 mol or less with respect to 1 mol of tetracarboxylic dianhydride components, for example.

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。） [Polyamide acid (B-III)]
The polyimide precursor composition may contain polyamic acid (B-III) as the resin precursor component (B). The polyamic acid has a repeating unit represented by the following formula (b3). The repeating unit represented by the formula (b3) is a reaction between the diamine compound represented by the above formula (1) and the tetracarboxylic dianhydrides (B-II) represented by the above formula (b2). And generate by.

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )

（式（ｂ３−１）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、及びｍは、前述の式（ｂ３）と同様であり、Ｒ^Ｆ３は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を２つ以上有する２価の有機基である。）
で表される繰り返し単位を有するポリアミド酸（Ｂ−ＩＩＩａ）であるか、
前述の式（ｂ３）で表される繰り返し単位と、下記式（ｂ３−２）：

（式（ｂ３−２）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、及びｍは、前述の式（ｂ３）と同様であり、Ｒ^Ｆ２は、前述のＲ^Ｆ１以外の２価の有機基である。）
で表される繰り返し単位とを有するポリアミド酸（Ｂ−ＩＩＩｂ）であるのが好ましい。 The pre-lyamic acid (B-III) is represented by the following formula (b3-1):

(In Formula (b3-1), R ^b1 , R ^b2 , R ^b3 , and m are the same as those in Formula (b3) described above, and R ^F3 represents a sulfone bond, a carboxylic ester bond, and a carboxylic acid amide bond. A divalent organic group having two or more bonds selected from the group consisting of
Or polyamic acid (B-IIIa) having a repeating unit represented by:
The repeating unit represented by the above formula (b3) and the following formula (b3-2):

(In formula (b3-2), R ^b1 , R ^b2 , R ^b3 , and m are the same as those in the above-described formula (b3), and R ^F2 is a divalent organic group other than the above-described R ^F1. .)
It is preferable that it is a polyamic acid (B-IIIb) which has a repeating unit represented by these.

R ^F3 in formula (b3-1) represents at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond among the divalent organic groups corresponding to R ^F1 described above. It is a divalent organic group having two or more.
R ^F2 in formula (b3-2) is as described above.

（式（ｂ３−３）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、及びｍは、前述の式（ｂ３）と同様であり、Ｒ^Ｆ１０〜Ｒ^Ｆ１２は前述の式（ｂ１−１）と同様である。）
で表される繰り返し単位を含むか、
前述の式（ｂ３）で表される繰り返し単位として、下記式（ｂ３−４）：

（式（ｂ３−４）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、及びｍは、前述の式（ｂ３）と同様であり、Ｒ^Ｆ１３、及びＲ^Ｆ１４は置換基を有していてもよい２価の炭化水素基であり、Ｚ’は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合である。
で表される繰り返し単位を含むのが好ましい。
式（ｂ３−３）中のＲ^Ｆ１０〜Ｒ^Ｆ１２は前述の通りである。式（ｂ３−４）中のＲ^Ｆ１５及びＲ^Ｆ１６としては、前述のＲ^Ｆ１１及びＲ^Ｆ１２と同様の基が好ましい。 The polyamic acid (B-III) is represented by the following formula (b3-3) as a repeating unit represented by the above formula (b3) or a repeating unit represented by the above formula (b3-1):

(In the formula (b3-3), R ^b1 , R ^b2 , R ^b3 , and m are the same as the above-described formula (b3), and R ^{F10 to} R ^F12 are the same as the above-described formula (b1-1). is there.)
Or a repeating unit represented by
As a repeating unit represented by the above formula (b3), the following formula (b3-4):

(In formula (b3-4), R ^b1 , R ^b2 , R ^b3 , and m are the same as those in the above-described formula (b3), and R ^F13 and R ^F14 may have a substituent 2. And Z ′ is a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond.
It is preferable that the repeating unit represented by these is included.
R ^{F10 to} R ^F12 in formula (b3-3) are as described above. R ^F15 and R ^{F16 in} formula (b3-4) are preferably the same groups as R ^F11 and R ^F12 described above.

  The method for producing the polyamic acid is not particularly limited. The polyamic acid is typically produced by reacting the aforementioned diamine component (BI) with the tetracarboxylic dianhydride component in the aforementioned ratio.

  The ratio of the diamine component (BI) and the tetracarboxylic dianhydride component when synthesizing the polyamic acid is the ratio of the diamine component (BI) and the tetracarboxylic dianhydride component described for the monomer component. It is the same.

  The reaction of the tetracarboxylic dianhydride component and the diamine component (BI) is usually performed in an organic solvent. The organic solvent used for the reaction of the tetracarboxylic dianhydride component and the diamine component (BI) can dissolve the diamine component (BI) and the tetracarboxylic dianhydride component, and the diamine component The organic solvent is not particularly limited as long as it does not react with (BI) and the tetracarboxylic dianhydride component. An organic solvent can be used individually or in mixture of 2 or more types.

As the organic solvent used for the reaction between the tetracarboxylic dianhydride and the diamine component (BI), for example, a solvent (S) described later can be preferably used.
Among such organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, and N, N-dimethylformamide are derived from the solubility of the resulting polyamic acid in the solvent (S). N, N-diethylformamide, N-methylcaprolactam, and nitrogen-containing polar solvents such as N, N, N ′, N′-tetramethylurea are preferred.

  At the time of polyamic acid synthesis, for example, the organic solvent has a total mass of the tetracarboxylic dianhydride component and the diamine component (BI) of 0.1% by mass to 50% by mass in the reaction solution, preferably An amount that is 10% by mass or more and 30% by mass or less is used.

When reacting the tetracarboxylic dianhydride component and the diamine component (BI), a basic compound is further added to the organic solvent from the viewpoint of improving the reaction rate and obtaining a polyamic acid having a high degree of polymerization. Also good.
Such a basic compound is not particularly limited, and examples thereof include triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, α-picoline, 1 -Methyl piperidine and the like.
The amount of such a base compound used is preferably 0.001 equivalents or more and 10 equivalents or less, more preferably 0.01 equivalents or more and 0.1 equivalents or less, per 1 equivalent of the tetracarboxylic dianhydride component.

  The reaction temperature at the time of reacting the tetracarboxylic dianhydride component and the diamine component (BI) is not particularly limited as long as the reaction proceeds favorably, but is preferably 0 ° C. or higher and 100 ° C. or lower, preferably 15 ° C. or higher. 30 degrees C or less is still more preferable. The reaction is preferably performed in an inert gas atmosphere. The reaction time is not particularly limited, but is preferably 10 hours to 48 hours, for example.

<Solvent (S)>
The polyimide precursor composition according to the present invention contains a solvent (S). The polyimide precursor composition may be a paste containing a solid or may be a solution as long as a film can be formed. The polyimide precursor composition is preferably a solution from the viewpoint of easily forming a uniform and smooth film. A solvent can be used individually or in mixture of 2 or more types.

  The kind of solvent (S) is not specifically limited in the range which does not inhibit the objective of this invention. Examples of suitable solvents (S) include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylisobutyramide, N, N-diethylacetamide, N, N -Dimethylformamide (DMF), N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone (DMI), pyridine, and N, N, N ', N'-tetramethylurea (TMU) nitrogen-containing polar solvents; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and lactone polar solvents such as ε-caprolactone; dimethyl sulfoxide; hexamethyl Phosphoric triamide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, and ethyl cellosolve acetate, ethers such as glyme; benzene, toluene, aromatic solvents such as xylene.

（式（Ｓ１）中、Ｒ^Ｓ１及びＲ^Ｓ２は、それぞれ独立に炭素原子数１以上３以下のアルキル基であり、Ｒ^Ｓ３は下記式（Ｓ１−１）又は下記式（Ｓ１−２）：

で表される基である。式（Ｓ１−１）中、Ｒ^Ｓ４は、水素原子又は水酸基であり、Ｒ^Ｓ５及びＲ^Ｓ６は、それぞれ独立に炭素原子数１以上３以下のアルキル基である。式（Ｓ１−２）中、Ｒ^Ｓ７及びＲ^Ｓ８は、それぞれ独立に水素原子、又は炭素原子数１以上３以下のアルキル基である。） It is preferable that the solvent also contains a compound represented by the following formula (S1).

(In formula (S1), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is the following formula (S1-1) or the following formula (S1-2):

It is group represented by these. In Formula (S1-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (S1-2), R ^S7 and R ^S8 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. )

Specific examples of the compound represented by the formula (S1) when R ^S3 is a group represented by the formula (S1-1) include N, N, 2-trimethylpropionamide, N-ethyl, N , 2-dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, and N, N-diethyl-2-hydroxy-2-methylpropionamide and the like can be mentioned.

Specific examples of the compound represented by the formula (S1) when R ^S3 is a group represented by the formula (S1-2) include N, N, N ′, N′-tetramethylurea, N , N, N ′, N′-tetraethylurea and the like.

Among the examples of the compound represented by the formula (S1), particularly preferable compounds are N, N, 2-trimethylpropionamide and N, N, N ′, N′-tetramethylurea. N, N, 2-trimethylpropionamide has a boiling point of 175 ° C. under atmospheric pressure, and N, N, N ′, N′-tetramethylurea has a boiling point of 177 ° C. under atmospheric pressure. As described above, N, N, 2-trimethylpropionamide and N, N, N ′, N′-tetramethylurea have a relatively low boiling point among solvents capable of dissolving the monomer component and the polyamic acid.
Therefore, a polyimide precursor composition containing a solvent (S) containing at least one selected from N, N, 2-trimethylpropionamide and N, N, N ′, N′-tetramethylurea is used. In the heating at the time of forming the polyimide film, the solvent hardly remains in the polyimide film to be formed, and the resulting polyimide film is less likely to be lowered in tensile elongation.

  Furthermore, N, N, 2-trimethylpropionamide and N, N, N ′, N′-tetramethylurea are SVHC (substances that are feared to be harmful in the EU (European Union) REACH regulations. It is also useful in that it is a substance with low toxicity as not specified in “Substance of Very High Concern”.

  The content of the compound represented by the formula (S1) in the solvent (S) is not particularly limited as long as the object of the present invention is not impaired. The ratio of the compound represented by the formula (S1) to the mass of the solvent is typically preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. Is most preferred.

  Content of the solvent (S) in a polyimide precursor composition is not specifically limited in the range which does not inhibit the objective of this invention. The content of the solvent (S) in the polyimide precursor composition is appropriately adjusted according to the solid content in the polyimide precursor composition. Solid content in a polyimide precursor composition is 1 mass% or more and 80 mass% or less, for example, 5 mass% or more and 70 mass% or less are preferable, and 10 mass% or more and 60 mass% or less are more preferable.

<Other ingredients>
The polyimide precursor composition according to the present invention may contain other components in addition to the above components as long as the object of the present invention is not impaired. Examples of other components include base generator components, polymerizable components such as monomers, surfactants, plasticizers, viscosity modifiers, antifoaming agents, and colorants.

<Silicon-containing compound>
In addition to the components described above, the polyimide precursor composition according to the present invention includes one or more silicon-containing compounds selected from the group consisting of silicon-containing resins, silicon-containing resin precursors, and silane coupling agents. You may go out. Examples of the silicon-containing resin include siloxane resin and polysilane. Examples of the silicon-containing resin precursor include a silane compound that serves as a raw material monomer for a siloxane resin or polysilane.

  When the polyimide precursor composition contains a silicon-containing compound, the adhesion between the polyimide resin formed using the polyimide precursor composition or the polyimide precursor composition and the object to be coated is good. This effect is remarkable when the material of the coated body is glass. Since it can adhere to a to-be-coated body, the process margin of polyimide film formation improves. Further, when the polyimide precursor composition contains a silicon-containing compound, the UV laser exposure amount is increased in order to improve the releasability of the polyimide film from the coated body or the support during the UV laser peeling process described later. Even in this case, cloudiness and browning at the time of peeling are easily suppressed.

In addition, whether or not the silicon-containing compound is added to the polyimide precursor composition, and the amount of the silicon-containing compound used when adding the silicon-containing additive is determined by the polyimide film formed using the polyimide precursor composition. It is determined appropriately according to the application.
For example, when the laser peeling process described later is not provided, it is preferable that the polyimide film and the support such as a substrate have a lower adhesiveness so that the polyimide film can be easily peeled from the support. In this case, it is preferable that the silicon-containing compound is not added to the polyimide precursor composition, or the addition amount of the silicon-containing compound to the polyimide precursor composition is small.
On the other hand, when a laser peeling step is provided, it is desirable that the polyimide precursor composition film and the polyimide film do not peel from the support during the processing process. In this case, from the viewpoint of widening the process margin, a silicon-containing composition is positively added to the polyimide precursor composition to improve the adhesion of the polyimide precursor composition to the film or the support of the polyimide film. Is preferred.

  Hereinafter, the siloxane resin, polysilane, and silane coupling agent will be described in order.

[Siloxane resin]
The siloxane resin is not particularly limited as long as it is a resin that is soluble in the solvent (S).
The siloxane resin may be a siloxane resin obtained by hydrolysis and condensation of a silane compound composition containing at least one silane compound selected from silane compounds described below.

As the siloxane resin, for example, a siloxane resin obtained by hydrolytic condensation of at least one selected from silane compounds represented by the following formula (c1) is preferably used.
(R ^c1 ) _4-p Si (OR ^c2 ) _p (c1)

In the formula (c1), R ^c1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R ^c2 represents an alkyl group or a phenyl group, and p represents an integer of 2 or more and 4 or less. When multiple R ^c1 is bonded to Si, R ^c1 of the plurality may be different even in the same. The plurality of (OR ^c2 ) groups bonded to Si may be the same or different.

The alkyl group as R ^c1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. It is an alkyl group.
The alkenyl group as R ^c1 is preferably a linear or branched alkenyl group having 2 to 20 carbon atoms, more preferably a linear or branched alkenyl group having 2 to 4 carbon atoms. It is.

When R ^c1 is an aryl group or an aralkyl group, the aryl group contained in these groups is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the aryl group include groups represented by the following formulae.

Of the groups of the above formula, groups of the following formula are preferred.

In the above formula, R ^c3 is a hydrogen atom; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, or a propoxy group; a hydrocarbon group such as a methyl group, an ethyl group, a butyl group, or a propyl group. In the above formula, R ^c3 ′ is an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group.

Preferable specific examples when R ^c1 is an aryl group or an aralkyl group include benzyl group, phenethyl group, phenyl group, naphthyl group, anthracenyl group, phenanthryl group, biphenylyl group, fluorenyl group, pyrenyl group and the like.

  The number of benzene rings contained in the aryl group or aralkyl group is preferably 1 or more and 3 or less. When the number of benzene rings is 1 or more and 3 or less, the productivity of the siloxane resin is good, and the volatilization during firing is suppressed due to an increase in the degree of polymerization of the siloxane resin. For this reason, formation of a polyimide film is easy. The aryl group or aralkyl group may have a hydroxyl group as a substituent.

The alkyl group as R ^c2 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. The number of carbon atoms of the alkyl group as R ^c2 is particularly preferably 1 or 2 from the viewpoint of hydrolysis rate.
The silane compound (i) when p in the formula (c1) is 4 is represented by the following formula (c2).
Si ( ^ORc4 ) _a ( ^ORc5 ) _b ( ^ORc6 ) _c ( ^ORc7 ) _d ... (c2)

In formula (c2), R ^c4 , R ^c5 , R ^c6 and R ^c7 each independently represent the same alkyl group or phenyl group as R ^c2 above.

  a, b, c, and d are integers that satisfy 0 ≦ a ≦ 4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4, and satisfy the condition of a + b + c + d = 4.

The silane compound (ii) when n in the formula (c1) is 3 is represented by the following formula (c3).
R ^c8 Si (OR ^c9 ) _e (OR ^c10 ) _f (OR ^c11 ) _g (c3)

In formula (c3), R ^c8 represents a hydrogen atom, the same alkyl group, aryl group or aralkyl group as R ^c1 above. R ^c9 , R ^c10 , and R ^c11 each independently represent the same alkyl group or phenyl group as R ^c2 above.

  e, f, and g are integers that satisfy 0 ≦ e ≦ 3, 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, and satisfy the condition of e + f + g = 3.

The silane compound (iii) when n in the formula (c1) is 2 is represented by the following formula (c4).
R ^c12 R ^c13 Si (OR ^c14 ) _h (OR ^c15 ) _i (c4)

In formula (c4), R ^c12 and R ^c13 represent a hydrogen atom, the same alkyl group, aryl group or aralkyl group as R ^c1 above. R ^c14 and R ^c15 each independently represent the same alkyl group or phenyl group as R ^c2 .

  h and i are integers that satisfy 0 ≦ h ≦ 2, 0 ≦ i ≦ 2, and satisfy the condition of h + i = 2.

  Specific examples of the silane compound (i) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxy. Monomethoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxy Silane, triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutyl Xysilane, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane, Examples thereof include tetraalkoxysilanes such as dibutoxymonoethoxymonopropoxysilane and monomethoxymonoethoxymonopropoxymonobutoxysilane, among which tetramethoxysilane and tetraethoxysilane are preferable.

Specific examples of the silane compound (ii) include
Trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane, dipropoxymonoethoxysilane, dipentyloxylmonomethoxysilane , Dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxysilane, monopropoxydiethoxysilane, monobutoxydimethoxy Silane, monopentyloxydiethoxysilane, monophenyloxydiethoxysilane, etc. Hydrosilane compound;
Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltripentyloxysilane, methyltriphenyloxysilane, methylmonomethoxydiethoxysilane, methylmonomethoxydipropoxysilane, methylmonomethoxydipentyloxysilane, methylmono Methylsilane compounds such as methoxydiphenyloxysilane, methylmethoxyethoxypropoxysilane, and methylmonomethoxymonoethoxymonobutoxysilane;
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltripentyloxysilane, ethyltriphenyloxysilane, ethylmonomethoxydiethoxysilane, ethylmonomethoxydipropoxysilane, ethylmonomethoxydipentyloxysilane, ethylmono Ethylsilane compounds such as methoxydiphenyloxysilane, ethylmethoxyethoxypropoxysilane, and ethylmonomethoxymonoethoxymonobutoxysilane;
Propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltripentyloxysilane, and propyltriphenyloxysilane, propylmonomethoxydiethoxysilane, propylmonomethoxydipropoxysilane, propylmonomethoxydipentyloxysilane, propyl Propylsilane compounds such as monomethoxydiphenyloxysilane, propylmethoxyethoxypropoxysilane, and propylmonomethoxymonoethoxymonobutoxysilane;
Butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltripentyloxysilane, Butyltriphenyloxysilane, Butylmonomethoxydiethoxysilane, Butylmonomethoxydibromooxysilane, Butylmonomethoxydipentyloxysilane, Butyl Butylsilane compounds such as monomethoxydiphenyloxysilane, butylmethoxyethoxypropoxysilane, and butylmonomethoxymonoethoxymonobutoxysilane;
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltripentyloxysilane, phenyltriphenyloxysilane, phenylmonomethoxydiethoxysilane, phenylmonomethoxydipropoxysilane, phenylmonomethoxydipentyloxysilane, phenylmono Phenylsilane compounds such as methoxydiphenyloxysilane, phenylmethoxyethoxypropoxysilane, and phenylmonomethoxymonoethoxymonobutoxysilane;
Hydroxyphenyltrimethoxysilane, hydroxyphenyltriethoxysilane, hydroxyphenyltripropoxysilane, hydroxyphenyltripentyloxysilane, hydroxyphenyltriphenyloxysilane, hydroxyphenylmonomethoxydiethoxysilane, hydroxyphenylmonomethoxydipropoxysilane, hydroxyphenyl Hydroxyphenylsilane compounds such as monomethoxydipentyloxysilane, hydroxyphenylmonomethoxydiphenyloxysilane, hydroxyphenylmethoxyethoxypropoxysilane, and hydroxyphenylmonomethoxymonoethoxymonobutoxysilane;
Naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltripentyloxysilane, naphthyltriphenyloxysilane, naphthylmonomethoxydiethoxysilane, naphthylmonomethoxydipropoxysilane, naphthylmonomethoxydipentyloxysilane, naphthylmono Naphthylsilane compounds such as methoxydiphenyloxysilane, naphthylmethoxyethoxypropoxysilane, and naphthylmonomethoxymonoethoxymonobutoxysilane;
Benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltripentyloxysilane, benzyltriphenyloxysilane, benzylmonomethoxydiethoxysilane, benzylmonomethoxydipropoxysilane, benzylmonomethoxydipentyloxysilane, benzylmono Benzylsilane compounds such as methoxydiphenyloxysilane, benzylmethoxyethoxypropoxysilane, and benzylmonomethoxymonoethoxymonobutoxysilane;
Hydroxybenzyltrimethoxysilane, hydroxybenzyltriethoxysilane, hydroxybenzyltripropoxysilane, hydroxybenzyltripentyloxysilane, hydroxybenzyltriphenyloxysilane, hydroxybenzylmonomethoxydiethoxysilane, hydroxybenzylmonomethoxydipropoxysilane, hydroxybenzyl Hydroxybenzylsilane compounds such as monomethoxydipentyloxysilane, hydroxybenzylmonomethoxydiphenyloxysilane, hydroxybenzylmethoxyethoxypropoxysilane, and hydroxybenzylmonomethoxymonoethoxymonobutoxysilane;
Is mentioned.

Specific examples of the silane compound (iii) include
Dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxysilane, ethoxypentyloxysilane, and ethoxyphenyloxy Hydrosilane compounds such as silane;
Methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylethoxypropoxysilane, methyldipropoxysilane, methyldipentyloxysilane, methyldiphenyloxysilane, methylmethoxyphenyloxysilane Methyl hydrosilane compounds such as
Ethyldimethoxysilane, ethylmethoxyethoxysilane, ethyldiethoxysilane, ethylmethoxypropoxysilane, ethylmethoxypentyloxysilane, ethylethoxypropoxysilane, ethyldipropoxysilane, ethyldipentyloxysilane, ethyldiphenyloxysilane, ethylmethoxyphenyloxysilane Ethyl hydrosilane compounds such as
Propyldimethoxysilane, propylmethoxyethoxysilane, propyldiethoxysilane, propylmethoxypropoxysilane, propylmethoxypentyloxysilane, propylethoxypropoxysilane, propyldipropoxysilane, propyldipentyloxysilane, propyldiphenyloxysilane, propylmethoxyphenyloxysilane Propylhydrosilane compounds such as
Butyldimethoxysilane, butylmethoxyethoxysilane, butyldiethoxysilane, butylmethoxypropoxysilane, butylmethoxypentyloxysilane, butylethoxypropoxysilane, butyldipropoxysilane, butyldipentyloxysilane, butyldiphenyloxysilane, butylmethoxyphenyloxysilane Butyl hydrosilane compounds such as
Phenyldimethoxysilane, phenylmethoxyethoxysilane, phenyldiethoxysilane, phenylmethoxypropoxysilane, phenylmethoxypentyloxysilane, phenylethoxypropoxysilane, phenyldipropoxysilane, phenyldipentyloxysilane, phenyldiphenyloxysilane, phenylmethoxyphenyloxysilane Phenylhydrosilane compounds such as
Hydroxyphenyldimethoxysilane, hydroxyphenylmethoxyethoxysilane, hydroxyphenyldiethoxysilane, hydroxyphenylmethoxypropoxysilane, hydroxyphenylmethoxypentyloxysilane, hydroxyphenylethoxypropoxysilane, hydroxyphenyldipropoxysilane, hydroxyphenyldipentyloxysilane, hydroxyphenyl Hydroxyphenylhydrosilane compounds such as diphenyloxysilane and hydroxyphenylmethoxyphenyloxysilane;
Naphthyldimethoxysilane, naphthylmethoxyethoxysilane, naphthyldiethoxysilane, naphthylmethoxypropoxysilane, naphthylmethoxypentyloxysilane, naphthylethoxypropoxysilane, naphthyldipropoxysilane, naphthyldipentyloxysilane, naphthyldiphenyloxysilane, naphthylmethoxyphenyloxysilane Naphthylhydrosilane compounds such as
Benzyldimethoxysilane, benzylmethoxyethoxysilane, benzyldiethoxysilane, benzylmethoxypropoxysilane, benzylmethoxypentyloxysilane, benzylethoxypropoxysilane, benzyldipropoxysilane, benzyldipentyloxysilane, benzyldiphenyloxysilane, benzylmethoxyphenyloxysilane Benzylhydrosilane compounds such as;
Hydroxybenzyldimethoxysilane, hydroxybenzylmethoxyethoxysilane, hydroxybenzyldiethoxysilane, hydroxybenzylmethoxypropoxysilane, hydroxybenzylmethoxypentyloxysilane, hydroxybenzylethoxypropoxysilane, hydroxybenzyldipropoxysilane, hydroxybenzyldipentyloxysilane, hydroxybenzyl Hydroxybenzylhydrosilane compounds such as diphenyloxysilane and hydroxybenzylmethoxyphenyloxysilane;
Dimethylsilane compounds such as dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethylmethoxypropoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane;
Diethylsilane compounds such as diethyldimethoxysilane, diethylmethoxyethoxysilane, diethylmethoxypropoxysilane, diethyldiethoxysilane, diethyldipentyloxysilane, diethyldiphenyloxysilane, diethylethoxypropoxysilane, diethyldipropoxysilane;
Dipropoxy such as dipropyldimethoxysilane, dipropylmethoxyethoxysilane, dipropylmethoxypropoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dipropylethoxypropoxysilane, dipropyldipropoxysilane Silane compounds;
Dibutylsilane compounds such as dibutyldimethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutyldiethoxysilane, dibutyldipentyloxysilane, dibutyldiphenyloxysilane, dibutylethoxypropoxysilane, dibutyldipropoxysilane;
Diphenylsilane compounds such as diphenyldimethoxysilane, diphenylmethoxyethoxysilane, diphenylmethoxypropoxysilane, diphenyldiethoxysilane, diphenyldipentyloxysilane, diphenyldiphenyloxysilane, diphenylethoxypropoxysilane, diphenyldipropoxysilane;
Di (hydroxyphenyl) dimethoxysilane, di (hydroxyphenyl) methoxyethoxysilane, di (hydroxyphenyl) methoxypropoxysilane, di (hydroxyphenyl) diethoxysilane, di (hydroxyphenyl) dipentyloxysilane, di (hydroxyphenyl) diphenyl Di (hydroxyphenyl) silane compounds such as oxysilane, di (hydroxyphenyl) ethoxypropoxysilane, di (hydroxyphenyl) dipropoxysilane;
Dinaphthyl such as dinaphthyldimethoxysilane, dinaphthylmethoxyethoxysilane, dinaphthylmethoxypropoxysilane, dinaphthyldiethoxysilane, dinaphthyldipentyloxysilane, dinaphthyldiphenyloxysilane, dinaphthylethoxypropoxysilane, dinaphthyldipropoxysilane Silane compounds;
Dibenzyl such as dibenzyldimethoxysilane, dibenzylmethoxyethoxysilane, dibenzylmethoxypropoxysilane, dibenzyldiethoxysilane, dibenzyldipentyloxysilane, dibenzyldiphenyloxysilane, dibenzylethoxypropoxysilane, dibenzyldipropoxysilane Silane compounds;
Di (hydroxybenzyl) dimethoxysilane, di (hydroxybenzyl) methoxyethoxysilane, di (hydroxybenzyl) methoxypropoxysilane, di (hydroxybenzyl) diethoxysilane, di (hydroxybenzyl) dipentyloxysilane, di (hydroxybenzyl) diphenyl Di (hydroxybenzyl) silane compounds such as oxysilane, di (hydroxybenzyl) ethoxypropoxysilane, di (hydroxybenzyl) dipropoxysilane;
Methylethyl such as methylethyldimethoxysilane, methylethylmethoxyethoxysilane, methylethylmethoxypropoxysilane, methylethyldiethoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylethylethoxypropoxysilane, methylethyldipropoxysilane Silane compounds;
Methylpropyl such as methylpropyldimethoxysilane, methylpropylmethoxyethoxysilane, methylpropylmethoxypropoxysilane, methylpropyldiethoxysilane, methylpropyldipentyloxysilane, methylpropyldiphenyloxysilane, methylpropylethoxypropoxysilane, methylpropyldipropoxysilane Silane compounds;
Methylbutyl such as methylbutyldimethoxysilane, methylbutylmethoxyethoxysilane, methylbutylmethoxypropoxysilane, methylbutyldiethoxysilane, methylbutyldipentyloxysilane, methylbutyldiphenyloxysilane, methylbutylethoxypropoxysilane, methylbutyldipropoxysilane Silane compounds;
Methyl (phenyl) dimethoxysilane, methyl (phenyl) methoxyethoxysilane, methyl (phenyl) methoxypropoxysilane, methyl (phenyl) diethoxysilane, methyl (phenyl) dipentyloxysilane, methyl (phenyl) diphenyloxysilane, methyl (phenyl) ) Methyl (phenyl) silane compounds such as ethoxypropoxy silane, methyl (phenyl) dipropoxy silane;
Methyl (hydroxyphenyl) dimethoxysilane, methyl (hydroxyphenyl) methoxyethoxysilane, methyl (hydroxyphenyl) methoxypropoxysilane, methyl (hydroxyphenyl) diethoxysilane, methyl (hydroxyphenyl) dipentyloxysilane, methyl (hydroxyphenyl) diphenyl Methyl (hydroxyphenyl) silane compounds such as oxysilane, methyl (hydroxyphenyl) ethoxypropoxysilane, methyl (hydroxyphenyl) dipropoxysilane;
Methyl (naphthyl) dimethoxysilane, methyl (naphthyl) methoxyethoxysilane, methyl (naphthyl) methoxypropoxysilane, methyl (naphthyl) diethoxysilane, methyl (naphthyl) dipentyloxysilane, methyl (naphthyl) diphenyloxysilane, methyl (naphthyl) ) Methyl (naphthyl) silane compounds such as ethoxypropoxysilane, methyl (naphthyl) dipropoxysilane;
Methyl (benzyl) dimethoxysilane, methyl (benzyl) methoxyethoxysilane, methyl (benzyl) methoxypropoxysilane, methyl (benzyl) diethoxysilane, methyl (benzyl) dipentyloxysilane, methyl (benzyl) diphenyloxysilane, methyl (benzyl ) Methyl (benzyl) silane compounds such as ethoxypropoxy silane, methyl (benzyl) dipropoxy silane;
Methyl (hydroxybenzyl) dimethoxysilane, methyl (hydroxybenzyl) methoxyethoxysilane, methyl (hydroxybenzyl) methoxypropoxysilane, methyl (hydroxybenzyl) diethoxysilane, methyl (hydroxybenzyl) dipentyloxysilane, methyl (hydroxybenzyl) diphenyl Methyl (hydroxybenzyl) silane compounds such as oxysilane, methyl (hydroxybenzyl) ethoxypropoxysilane, methyl (hydroxybenzyl) dipropoxysilane;
Ethylpropyl such as ethylpropyldimethoxysilane, ethylpropylmethoxyethoxysilane, ethylpropylmethoxypropoxysilane, ethylpropyldiethoxysilane, ethylpropyldipentyloxysilane, ethylpropyldiphenyloxysilane, ethylpropylethoxypropoxysilane, ethylpropyldipropoxysilane Silane compounds;
Ethylbutyl such as ethylbutyldimethoxysilane, ethylbutylmethoxyethoxysilane, ethylbutylmethoxypropoxysilane, ethylbutyldiethoxysilane, ethylbutyldipentyloxysilane, ethylbutyldiphenyloxysilane, ethylbutylethoxypropoxysilane, ethylbutyldipropoxysilane Silane compounds;
Ethyl (phenyl) dimethoxysilane, ethyl (phenyl) methoxyethoxysilane, ethyl (phenyl) methoxypropoxysilane, ethyl (phenyl) diethoxysilane, ethyl (phenyl) dipentyloxysilane, ethyl (phenyl) diphenyloxysilane, ethyl (phenyl) ) Ethyl (phenyl) silane compounds such as ethoxypropoxy silane, ethyl (phenyl) dipropoxy silane;
Ethyl (hydroxyphenyl) dimethoxysilane, ethyl (hydroxyphenyl) methoxyethoxysilane, ethyl (hydroxyphenyl) methoxypropoxysilane, ethyl (hydroxyphenyl) diethoxysilane, ethyl (hydroxyphenyl) dipentyloxysilane, ethyl (hydroxyphenyl) diphenyl Ethyl (hydroxyphenyl) silane compounds such as oxysilane, ethyl (hydroxyphenyl) ethoxypropoxysilane, ethyl (hydroxyphenyl) dipropoxysilane;
Ethyl (naphthyl) dimethoxysilane, ethyl (naphthyl) methoxyethoxysilane, ethyl (naphthyl) methoxypropoxysilane, ethyl (naphthyl) diethoxysilane, ethyl (naphthyl) dipentyloxysilane, ethyl (naphthyl) diphenyloxysilane, ethyl (naphthyl) ) Ethyl (naphthyl) silane compounds such as ethoxypropoxysilane, ethyl (naphthyl) dipropoxysilane;
Ethyl (benzyl) dimethoxysilane, ethyl (benzyl) methoxyethoxysilane, ethyl (benzyl) methoxypropoxysilane, ethyl (benzyl) diethoxysilane, ethyl (benzyl) dipentyloxysilane, ethyl (benzyl) diphenyloxysilane, ethyl (benzyl ) Ethyl (benzyl) silane compounds such as ethoxypropoxy silane, ethyl (benzyl) dipropoxy silane;
Ethyl (hydroxybenzyl) dimethoxysilane, ethyl (hydroxybenzyl) methoxyethoxysilane, ethyl (hydroxybenzyl) methoxypropoxysilane, ethyl (hydroxybenzyl) diethoxysilane, ethyl (hydroxybenzyl) dipentyloxysilane, ethyl (hydroxybenzyl) diphenyl Ethyl (hydroxybenzyl) silane compounds such as oxysilane, ethyl (hydroxybenzyl) ethoxypropoxysilane, ethyl (hydroxybenzyl) dipropoxysilane;
Propylbutyl such as propylbutyldimethoxysilane, propylbutylmethoxyethoxysilane, propylbutylmethoxypropoxysilane, propylbutyldiethoxysilane, propylbutyldipentyloxysilane, propylbutyldiphenyloxysilane, propylbutylethoxypropoxysilane, propylbutyldipropoxysilane Silane compounds;
Propyl (phenyl) dimethoxysilane, propyl (phenyl) methoxyethoxysilane, propyl (phenyl) methoxypropoxysilane, propyl (phenyl) diethoxysilane, propyl (phenyl) dipentyloxysilane, propyl (phenyl) diphenyloxysilane, propyl (phenyl) ) Propyl (phenyl) silane compounds such as ethoxypropoxy silane, propyl (phenyl) dipropoxy silane;
Propyl (hydroxyphenyl) dimethoxysilane, propyl (hydroxyphenyl) methoxyethoxysilane, propyl (hydroxyphenyl) methoxypropoxysilane, propyl (hydroxyphenyl) diethoxysilane, propyl (hydroxyphenyl) dipentyloxysilane, propyl (hydroxyphenyl) diphenyl Propyl (hydroxyphenyl) silane compounds such as oxysilane, propyl (hydroxyphenyl) ethoxypropoxysilane, propyl (hydroxyphenyl) dipropoxysilane;
Propyl (naphthyl) dimethoxysilane, propyl (naphthyl) methoxyethoxysilane, propyl (naphthyl) methoxypropoxysilane, propyl (naphthyl) diethoxysilane, propyl (naphthyl) dipentyloxysilane, propyl (naphthyl) diphenyloxysilane, propyl (naphthyl) ) Propyl (naphthyl) silane compounds such as ethoxypropoxy silane, propyl (naphthyl) dipropoxy silane;
Propyl (benzyl) dimethoxysilane, propyl (benzyl) methoxyethoxysilane, propyl (benzyl) methoxypropoxysilane, propyl (benzyl) diethoxysilane, propyl (benzyl) dipentyloxysilane, propyl (benzyl) diphenyloxysilane, propyl (benzyl) ) Propyl (benzyl) silane compounds such as ethoxypropoxy silane, propyl (benzyl) dipropoxy silane;
Propyl (hydroxybenzyl) dimethoxysilane, propyl (hydroxybenzyl) methoxyethoxysilane, propyl (hydroxybenzyl) methoxypropoxysilane, propyl (hydroxybenzyl) diethoxysilane, propyl (hydroxybenzyl) dipentyloxysilane, propyl (hydroxybenzyl) diphenyl Propyl (hydroxybenzyl) silane compounds such as oxysilane, propyl (hydroxybenzyl) ethoxypropoxysilane, propyl (hydroxybenzyl) dipropoxysilane;
Is mentioned.

Moreover, as a silane compound, the silane compound represented, for example by a following formula (c5) may be sufficient.
^{_{(R c20 O) q R c18}} 3-q Si-R c17 -Si (OR c21) r R c19 3-r ··· (c5)
R ^c17 represents a divalent polycyclic aromatic group.
R ^c18 and R ^c19 are monovalent groups directly connected to a silicon atom, and represent a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, as in R ^c1 in the above formula (c1), and are the same or different. It may be.
R ^c20 and R ^c21 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
q and r are each independently an integer of 1 or more and 3 or less.

Even if a polycyclic aromatic group is a group in which two or more rings containing two or more aromatic rings are condensed, two or more rings containing two or more aromatic rings are a single bond or a divalent linking group. May be groups bonded to each other.
The partial structure in the polycyclic aromatic group may include a non-aromatic ring.
Specific examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, -CO-, -CS-, -O-, -S-, -NH-, -N = N-, -CO. -O-, -CO-NH-, -CO-S-, -CS-O-, -CS-S-, -CO-NH-CO-, -NH-CO-NH-, -SO-, and- SO ₂ — and the like can be mentioned.
The polycyclic aromatic group may be a hydrocarbon group and may contain one or more heteroatoms. Examples of heteroatoms include N, S, O, and P.
The number of rings contained in the polycyclic aromatic group is preferably an integer of 2 or more and 5 or less, and more preferably an integer of 2 or more and 4 or less.
The polycyclic aromatic group may have a substituent. Examples of the substituent include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, an amino group, a cyano group, and 2 to 6 carbon atoms. The following aliphatic acyl groups are exemplified.
Among these substituents, alkoxy groups such as methoxy group, ethoxy group, butoxy group and propoxy group, and alkyl groups such as methyl group, ethyl group, butyl group and propyl group are preferable.
When the polycyclic aromatic group has a substituent, the number of substituents is not particularly limited. The number of substituents is typically preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

  Specific examples of the divalent polycyclic aromatic group include naphthalene, biphenyl, terphenyl, anthracene, phenanthrene, anthraquinone, pyrene, carbazole, N-methylcarbazole, N-ethylcarbazole, Nn-propylcarbazole, N -N-butylcarbazole, dibenzofuran, dibenzothiophene, dibenzothiophene-5,5-dioxide, fluorene, 9,9-dimethylfluorene, 9,9-diethylfluorene, 9,9-di-n-propylfluorene, 9,9 -Groups obtained by removing two hydrogen atoms bonded to an aromatic ring from a polycyclic aromatic compound selected from the group consisting of di-n-butylfluorene and fluorenone.

Preferred specific examples of the silane compound represented by the formula (c5) are shown below.

A siloxane resin can be obtained by hydrolytic condensation of the silane compound described above according to a conventional method.
The mass average molecular weight of the siloxane resin is preferably 300 or more and 30000 or less, and more preferably 500 or more and 10,000 or less. When a siloxane resin having a mass average molecular weight within such a range is blended in the polyimide precursor composition, the film-forming property is excellent, and the peeling property of the polyimide film from the substrate is improved in the peeling step, and white turbidity is suppressed. In addition, when the polyimide film to be formed is laser peeled, the polyimide film is easily peeled off with lower energy.

（式（Ｃ−１）中、Ｒ^ｃ２２はアルキル基、アリール基、又はアラルキル基であり、Ｒ^ｃ２３は水素又はアルキル基、アリール基、又はアラルキル基であり、ｓは０又は１である。） Preferable examples of the siloxane resin obtained by hydrolytic condensation of the silane compound described above include a siloxane resin having a structural unit represented by the following formula (C-1). In the siloxane resin, the number of carbon atoms per one silicon atom is two or more.

(In Formula (C-1), R ^c22 is an alkyl group, an aryl group, or an aralkyl group, R ^c23 is hydrogen, an alkyl group, an aryl group, or an aralkyl group, and s is 0 or 1.)

The alkyl group, aryl group, or aralkyl group in R ^c22 and R ^c23 is the same as the alkyl group, aryl group, or aralkyl group in the aforementioned formula (c1).

The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a tert-butyl group.
Examples of the aryl group and aralkyl group include benzyl group, phenethyl group, phenyl group, naphthyl group, anthracenyl group, phenanthryl group, biphenyl group, fluorenyl group, and pyrenyl group.

As the aryl group and aralkyl group, specifically, a group having the following structure is preferable.

In the above formula, R ^c24 is a hydrogen atom; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, or a propoxy group; a hydrocarbon group such as a methyl group, an ethyl group, a butyl group, or a propyl group ^; Is an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group. In addition, the said aromatic hydrocarbon group should ^just have said ^Rc24 in the at least 1 aromatic ring in this aromatic hydrocarbon group, and may have multiple. In the case of having a plurality of R ^{c24 s} , these R ^c24s may be the same or different.

As particularly preferred R ^c22 , a group having a structure represented by the following formula (R ^c22 -a) or (R ^c22 -b) is preferred, and (R ²² -b) is particularly preferred.

  In the formula (C-1), s is preferably 0. In that case, the siloxane resin has a silsesquioxane skeleton. Furthermore, the siloxane resin is more preferably a ladder-type silsesquioxane.

  Furthermore, it is preferable that the structural unit (unit skeleton) represented by the formula (C-1) has an atomic ratio in which the number of carbon atoms is 2 or more and 15 or less with respect to one silicon atom.

The siloxane resin may have two or more types of structural units represented by the formula (C-1). Moreover, in the siloxane resin, the siloxane resin which consists of a different structural unit shown by Formula (C-1) may be mixed.
Specifically, the siloxane resin having two or more types of structural units represented by the formula (C-1) is represented by structural units represented by the following formulas (C-1-1) to (C-1-3). Siloxane resin.

[Polysilane]
The polysilane is not particularly limited as long as it is soluble in the solvent (S), and the structure of the polysilane is not particularly limited. The polysilane may be linear, branched, network, or cyclic, but a linear or branched chain structure is preferred.

  Suitable polysilanes include, for example, at least one of units represented by the following formulas (C-2) and (C-3), and the following formulas (C-4), (C-5) and (C And polysilanes optionally containing at least one unit selected from units represented by C-6). Such a polysilane essentially has a silanol group or an alkyl group bonded to a silicon atom.

式（Ｃ−２）、（Ｃ−４）、及び（Ｃ−５）中、Ｒ^ｃ２６及びＲ^ｃ２７は、水素原子、有機基又はシリル基を表す。Ｒ^ｃ２８は、水素原子又はアルキル基を表す。Ｒ^ｃ２８がアルキル基である場合、炭素原子数１以上４以下のアルキル基が好ましく、メチル基及びエチル基がより好ましい。

In formulas (C-2), (C-4), and (C-5), R ^c26 and R ^c27 represent a hydrogen atom, an organic group, or a silyl group. R ^c28 represents a hydrogen atom or an alkyl group. When R ^c28 is an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

Regarding R ^c26 and R ^c27 , the organic groups include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, alkoxy groups, alkenyloxy groups, cycloalkoxy groups, cyclo An alkenyloxy group, an aryloxy group, an aralkyloxy group, etc. are mentioned.
Among these groups, an alkyl group, an aryl group, and an aralkyl group are preferable. Suitable examples of the alkyl group, the aryl group, and the aralkyl group are the same as those in the case where R ^c1 in the above formula (c1) is an alkyl group, an aryl group, or an aralkyl group.

When R ^c26 and R ^c27 are silyl groups, ^examples of the silyl group include Si _1-10 silanyl groups (Si _1-6 silanyl group and the like) such as silyl group, disilanyl group, and trisilanyl group.

（（Ｃ−７）〜（Ｃ−１０）中、Ｒ^ｃ２６及びＲ^ｃ２７は、（Ｃ−２）、（Ｃ−４）、及び（Ｃ−５）中におけるＲ^ｃ２６及びＲ^ｃ２７と同様である。ａ、ｂ、及びｃは、それぞれ、２以上１０００以下の整数である）
ａ、ｂ、及びｃは、それぞれ、１０以上５００以下が好ましく、１０以上１００以下がより好ましい。各ユニット中の構成単位は、ユニット中に、ランダムに含まれていても、ブロック化された状態で含まれていてもよい。 The polysilane preferably contains the following units (C-7) to (C1-10).

((C-7) in ^{~ (C-10), R} c26 and ^{R c27} are the same as (C-2), (C -4), and (C-5) ^{R c26} and ^{R c27} in the A, b, and c are each an integer of 2 or more and 1000 or less)
a, b, and c are each preferably 10 or more and 500 or less, and more preferably 10 or more and 100 or less. The structural unit in each unit may be included randomly in the unit or may be included in a block state.

  Among the polysilanes described above, a polysilane containing a combination of a silanol group, an alkyl group, and an aryl group or an aralkyl group, each bonded to a silicon atom is preferable. More specifically, each is bonded to a silicon atom, a polysilane containing a combination of a silanol group, a methyl group, and a benzyl group, and each silanol group and a methyl group bonded to a silicon atom, A polysilane containing a combination with a phenyl group is preferably used.

  The mass average molecular weight of the polysilane is preferably from 100 to 100,000, more preferably from 500 to 50,000, particularly preferably from 1,000 to 30,000.

[Silane coupling agent]
The silane coupling agent binds or interacts with various components contained in the polyimide precursor composition via an alkoxy group and / or a reactive group bonded to a silicon atom, and a surface of a support such as a substrate. Or join. For this reason, the adhesiveness to the support bodies, such as a board | substrate of the polyimide film formed, is improved by mix | blending a silane coupling agent with a polyimide precursor composition.

  The silane coupling agent is not particularly limited. Preferable examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and n-butyltrimethoxy. Monoalkyltrialkoxysilanes such as silane and n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldimethoxy Diphenyl dialkoxysilanes such as silane and diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (Meth) acryloxyalkyl monoalkyl dialkoxysilanes such as xylpropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; (Meth) acryloxyalkyltrialkoxysilanes such as loxypropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiet Sisilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Amino group-containing tri (or di) alkoxysilanes such as N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; and amino groups thereof Non-alicyclic epoxyfluorenylidene group-containing alkyl such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Tori (or di) Alkoki Silane; non-alicyclic epoxy group-containing alkyl monoalkyl dialkoxysilane such as 3-glycidoxypropylmethyldiethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Alicyclic epoxy group-containing alkyltri (or di) such as epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane An alkoxysilane-containing alkylmonoalkyldialkoxysilane such as 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane; [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-Ethyl-3-oxeta Ol) methoxy] propyltriethoxysilane and other oxetanyl group-containing alkyltrialkoxysilanes; mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; Ureidoalkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; Isocyanatealkyltrialkoxysilanes such as 3-isocyanatopropyltriethoxysilane; Tris- (trimethoxysilylpropyl) isocyanurate, Tris- (triethoxysilylpropyl) isocyanate Isocyanurate-containing trialkoxysilanes such as nurate; 3-trimethoxysilylpropyl succinic anhydride, other acid anhydrides (For example, cyclohexanedicarboxylic acid anhydride group, 4-methyl-cyclohexanedicarboxylic acid anhydride group, 5-methyl-cyclohexanedicarboxylic acid anhydride group, bicycloheptanedicarboxylic acid anhydride group, 7-oxa-bicycloheptanedicarboxylic acid anhydride group Alkyl trialkoxysilanes containing acid anhydride groups such as trialkoxysilanes having a group, phthalic anhydride group, etc .; as carboxy groups, succinic acid groups, or half ester groups thereof, cyclohexanedicarboxylic acid groups, or half ester groups thereof 4-methyl-cyclohexanedicarboxylic acid group, or half ester group thereof, 5-methyl-cyclohexanedicarboxylic acid group, or half ester group thereof, bicycloheptane dicarboxylic acid group, or half ester group thereof, 7-oxa-bicycloheptane dica Carboxy group-containing alkyltrialkoxysilane having a rubonic acid group, or its half ester group, phthalic acid group, or its half ester group; N-tert-butyl-3- (3-trimethoxysilylpropyl) succinimide, etc. Imido group-containing alkyltrialkoxysilanes; Carbamate group-containing alkyltrialkoxysilanes such as (3-trimethoxysilylpropyl) -t-butylcarbamate and (3-triethoxysilylpropyl) -tert-butylcarbamate; Also suitable are amide group-containing trialkoxysilanes. Amide group-containing trialkoxysilane is a reaction of amino group-containing trialkoxysilane with carboxylic acid, acid chloride, dicarboxylic acid anhydride, or tetracarboxylic acid anhydride, or contains carboxyl group, acid chloride group, or acid anhydride group Obtained by reaction of trialkoxysilane and amine. Among these, an amide group-containing trialkoxy obtained by a reaction between an amino group-containing trialkoxysilane and a dicarboxylic acid anhydride or a tetracarboxylic acid anhydride, or obtained by a reaction between an acid anhydride group-containing trialkoxysilane and an amine. Alkoxysilane is preferred.

  In the case of reacting an amino group-containing trialkoxysilane and an acid anhydride, examples of the amino group-containing tri (or di) alkoxysilane include the same compounds as the amino group-containing tri (or di) alkoxysilane described above. Examples of the dicarboxylic acid anhydride include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid anhydride, 7-oxabicyclo Heptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinic anhydride, (3-tri And polybasic acid anhydrides such as ethoxysilylpropyl) succinic anhydride. Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 1,2,5,6-naphthalenetetracarboxylic acid And dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′-oxydiphthalic dianhydride, and 4,4′-oxydiphthalic dianhydride. These may be used alone or in combination of two or more.

  When the acid anhydride group-containing trialkoxysilane is reacted with an amine, examples of the acid anhydride group-containing trialkoxysilane include the same compounds as the acid anhydride group-containing trialkoxysilane described above. Examples of the amine include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, 2-ethylhexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine. Amine, tetradecylamine, hexadecylamine, 1-aminooctadecane, aniline, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, 2-aminotoluene, 3-aminotoluene 4-aminotoluene, 2,4-dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,5-trimethylaniline, 2,4,6-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3, 5,6-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2-ethyl-3-hexylaniline, 2-ethyl-4-hexylaniline, 2-ethyl-5-hexylaniline, 2-ethyl -6-hexylaniline, 3-ethyl-4-hexylaniline, 3-ethyl-5-hexylaniline, 3-ethyl-2-hexylaniline, 4-ethyl-2-hexylaniline, 5-ethyl-2-hexylaniline 6-ethyl-2-hexylaniline, 4-ethyl-3-hexylaniline, 5-ethyl-3-hexylaniline, 1,2-phenylenedia 1,3-phenylenediamine, 1,4-phenylenediamine, 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2- (4-aminophenyl) ethylamine, 2- (3-amino Phenyl) ethylamine, 2- (2-aminophenyl) ethylamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2 , 3-dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-dimethyl-m -Phenylenediamine, 2,6-dimethyl-m-phenylenediamine, 4,5-dimethyl-m-phen Nylenediamine, 3,4-dimethyl-o-phenylenediamine, 3,5-dimethyl-o-phenylenediamine, 3,6-dimethyl-o-phenylenediamine, 1,3-diamino-2,4,6-trimethylbenzene, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetramethyl-1,3-phenylenediamine, 3,4,5,6-tetramethyl-1,2, -Phenylenediamine, 2,4-diamino-3,5-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,4-diamino-4,6-diethyltoluene, 2,3-diamino-5 , 6-diethyltoluene, 2,4-diamino-3,6-diethyltoluene, 2,5-diamino-3,4-diethyltoluene, 2,5-diamino-3,6-diethyltoluene Ene, 2,5-diamino-4,6-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,3-diamino-4,6-diethyltoluene, 2,3-diamino-4,5 , 6-triethyltoluene, 2,4-diamino-3,5,6-triethyltoluene, 2,5-diamino-3,4,6-triethyltoluene, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline 2-methoxy-3-methylaniline, 2-methoxy-4-methylaniline, 2-methoxy-5-methylaniline, 2-methoxy-6-methylaniline, 3-methoxy-2-methylaniline, 3-methoxy- 4-methylaniline, 3-methoxy-5-methylaniline, 3-methoxy-6-methylaniline, 4-methoxy-2-methylaniline, 4- Toxi-3-methylaniline, 2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline, 4-methoxy-5-methylaniline, 4-methoxy-6-methylaniline, 2-methoxy-3-ethylaniline, 2 -Methoxy-4-ethylaniline, 2-methoxy-5-ethylaniline, 2-methoxy-6-ethylaniline, 3-methoxy-2-ethylaniline, 3-methoxy-4-ethylaniline, 3-methoxy-5- Ethylaniline, 3-methoxy-6-ethylaniline, 4-methoxy-2-ethylaniline, 4-methoxy-3-ethylaniline, 2-methoxy-3,4,5-trimethylaniline, 3-methoxy-2,4 , 5-trimethylaniline and 4-methoxy-2,3,5-trimethylaniline. These may be used alone or in combination of two or more.

［式中、Ｒ^１９は、単結合、酸素原子、硫黄原子、カルボニル基、又は炭素原子数１以上５以下のアルキレン基を示す。］ Further, the amide group-containing trialkoxysilane may be a compound obtained by reacting an acid dianhydride and an amino group-containing trialkoxysilane. As the acid dianhydride, an acid dianhydride represented by the following formula is preferable.

[Wherein, R ¹⁹ represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an alkylene group having 1 to 5 carbon atoms. ]

The amino group-containing trialkoxysilane to be reacted with the acid dianhydride represented by the above formula is the same as the compounds mentioned for the amino group-containing trialkoxysilane. Preferred specific examples of the reaction product are listed below.

As the amide group-containing trialkoxysilane, 2- (3-trimethoxysilylpropyl) succinic acid monophenylamide, 3- (3-trimethoxysilylpropyl) succinic acid monophenylamide, 2- (3-triethoxysilyl) is preferable. Propyl) succinic acid monophenylamide, 3- (3-triethoxysilylpropyl) succinic acid monophenylamide, 2- (3-methyldiethoxysilylpropyl) succinic acid monophenylamide, 3- (3-methyldiethoxysilyl) Propyl) succinic acid monophenylamide, the following formula (R ²⁰ O) ₃ Si—X ²⁰ —R ²¹ —Y ²⁰ —COOH [wherein R ²⁰ is an alkyl group having 1 to 12 carbon atoms, and X ²⁰ Is an alkylene group having 1 to 12 carbon atoms, carbon An atomic number of 6 to 12 of fluorenylidenemethane aryl ^{group, R 21} is -NHCO- or ^{-CONH-, Y 20} is a divalent aromatic hydrocarbon group or a divalent alicyclic hydrocarbon group is there. And the like, and compounds represented by the above formulas (Am-1) to (Am-3).

  Among these silane coupling agents, amino group-containing trialkoxysilanes and ketimine silanes or amide bond-containing trialkoxysilanes whose amino groups are protected with aldehydes are preferred. These silane coupling agents may be used alone or in combination of two or more.

A compound represented by the following formula (c6) is also preferably used as a silane coupling agent.
R ^c29 _d R ^c30 _(3-d) Si—R ^c31 —NH—C (O) —Y—R ^c32 —X (c6)
(In formula (c6), R ^c29 is an alkoxy group, R ^c30 is an alkyl group, d is an integer of 1 to 3, R ^c31 is an alkylene group, Y is —NH—, —O. ^-Or -S-, R ^c32 is a single bond or an alkylene group, X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, The ring bonded to —Y—R ^c32 — is a nitrogen-containing 6-membered aromatic ring, and —Y—R ^c32 — is bonded to the carbon atom in the nitrogen-containing 6-membered aromatic ring.

In formula (c6), R ^c29 represents an alkoxy group. Regarding R ^c29 , the number of carbon atoms of the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferred examples of R ^c29 include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, and n -A hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

The silanol group produced by hydrolysis of ^Rc29, which is an alkoxy group, reacts with the surface of the substrate, etc., so that the polyimide film formed using the polyimide precursor composition adheres to the surface of the support such as the substrate. Is easy to improve. For this reason, m is preferably 3 from the viewpoint of easily improving the adhesion of the polyimide film to the surface of a support such as a substrate.

In formula (c6), R ^c30 represents an alkyl group. For R ^c30 , the number of carbon atoms of the alkyl group is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferred examples of R ^c30 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (c6), R ^c31 represents an alkylene group. Regarding R ^c31 , the number of carbon atoms of the alkylene group is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and particularly preferably 2 or more and 4 or less. Preferable specific examples of R ^c31 include a methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1- Diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7- And diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. It is done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

  Y is —NH—, —O—, or —S—, and is preferably —NH—. Since the bond represented by —CO—NH— is less susceptible to hydrolysis than the bond represented by —CO—O— or —CO—S—, the compound in which Y is —NH— When the polyimide precursor composition contained as a ring agent is used, a polyimide film having excellent adhesion to a support such as a substrate can be formed.

R ^c32 is a single bond or an alkylene group, and preferably a single bond. A preferred example in the case where R ^c32 is an alkylene group is the same as R ^c31 .

X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, and the ring bonded to -Y-R ^c32 -in X is a nitrogen-containing 6-membered aromatic ring, —Y—R ^c32 — is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring. The reason is unknown, but when a polyimide precursor composition containing such a compound having X as a silane coupling agent is used, a polyimide film having excellent adhesion to a support such as a substrate can be formed.

  When X is a polycyclic heteroaryl group, the heteroaryl group may be a group in which a plurality of monocycles are condensed or a group in which a plurality of monocycles are bonded via a single bond. When X is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 or more and 3 or less. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing 6-membered aromatic ring in X may or may not contain a hetero atom, and may be an aromatic ring or an aromatic ring. It does not have to be a ring.

  Examples of the substituent that X which is a nitrogen-containing heteroaryl group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 2 to 6 carbon atoms. Alkenyl group, alkenyloxy group having 2 to 6 carbon atoms, aliphatic acyl group having 2 to 6 carbon atoms, benzoyl group, nitro group, nitroso group, amino group, hydroxy group, mercapto group, cyano group, sulfone An acid group, a carboxyl group, a halogen atom, etc. are mentioned. The number of substituents X has is not particularly limited as long as the object of the present invention is not impaired. The number of substituents X has is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

Preferable examples of X include groups represented by the following formula.

Among the above groups, a group of the following formula is more preferable as X.

Preferable specific examples of the compound represented by the formula (c6) described above include the following compounds 1 to 8.

The silicon-containing compounds described above may be used alone or in combination of two or more.
The content of the silicon-containing compound described above in the polyimide precursor composition is, for example, 0.01% by mass to 20% by mass, and 0.1% by mass to 20% by mass with respect to the solid content of the composition. The content is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less. By setting the content of the silicon-containing compound in the polyimide precursor composition within the above range, the effect expected by the addition of the silicon-containing compound can be sufficiently exhibited.

<Preparation of polyimide precursor composition>
The method for preparing the polyimide precursor composition is not particularly limited. For example, as the resin precursor component (B), at least one selected from the group consisting of the above-mentioned various monomer components and polyamic acid, a solvent (S), an imidazole compound (A), and the above-described other components as necessary. A polyimide resin precursor composition can be prepared by blending the components.

  As a resin precursor component (B), you may mix | blend both a monomer component and a polyamic acid. Usually, it is sufficient to blend only the monomer component or only the polyamic acid. It is possible to synthesize a ring-forming polymer after blending a monomer component as the component (B) in that the molecular weight of the polyamic acid can be increased in the presence of the imidazole compound (A) as described later. preferable. Moreover, it is preferable to mix | blend a precursor polymer as a (B) component at the point which can improve the ring closure efficiency of a ring-forming polymer in presence of an imidazole compound (A).

  In the polyimide precursor composition according to the present invention, after blending the monomer component as the resin precursor component (B) with the solvent (S), the polyamic acid is preferably formed in the presence of the imidazole compound (A). The resulting composition is also included.

  In the preparation of the polyimide precursor composition according to the present invention, the order of blending (adding) each component is not particularly limited. For example, blending of the imidazole compound (A) blends the resin precursor component (B). It may be before or after, or may be mixed at the same time.

≪Method for producing polyimide film≫
The manufacturing method of the polyimide film which is the 2nd aspect of this invention is the coating process by forming the coating process which consists of a polyimide precursor composition which is the 1st aspect of this invention, and a coating film. A cyclization step of cyclizing the polyamic acid derived from the resin precursor component (B) therein. Hereinafter, each step will be described.

<Formation process>
In the forming step, the above-described polyimide precursor composition is applied to the surface of the object to be coated to form a coating film made of the polyimide precursor composition. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, and a die coating. The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is, for example, from 0.1 μm to 1000 μm, preferably from 2 μm to 100 μm, and more preferably from 3 μm to 50 μm. The thickness of the coating film can be appropriately controlled by adjusting the coating method and the solid content concentration and viscosity of the polyimide precursor composition.

  You may heat a coating film in order to remove the solvent (S) in a coating film after forming a coating film and before moving to a ring-closing process. The heating temperature and the heating time are not particularly limited as long as the components contained in the polyimide precursor composition are not thermally deteriorated or decomposed. When the boiling point of the solvent (S) in the coating film is high, the coating film may be heated under reduced pressure.

（式（ｂ３）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種であり、Ｒ^Ｆ１は、スルホン結合、カルボン酸エステル結合、及びカルボン酸アミド結合から選択される少なくとも１種の結合を１つ以上有する２価の有機基であり、ｍは０以上１２以下の整数を示す。） <Ring-closing process>
In the ring-closing step, the polyamic acid derived from the resin precursor component (B) in the coating film is closed by heating the coating film formed in the forming step. Specifically, when a monomer component is blended as the resin precursor component (B), formation of a polyamic acid having a repeating unit represented by the following formula (b3) as a main component and an increase in the molecular weight proceed by heating. .

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )

  The polyamic acid formed from such monomer components is subsequently closed in a ring closing step to be changed to a polyimide resin. When a polyamic acid is blended as the resin precursor component (B), the ring is similarly closed and changed to a polyimide resin.

  As described above, in the ring closing step, the polyamic acid derived from the resin precursor component (B) is changed to a polyimide resin. As a result, a film containing polyimide resin is formed.

When heating the coating film, the heating temperature is set to, for example, 100 ° C. or more and 500 ° C. or less, preferably 120 ° C. or more and 350 ° C. or less, more preferably 150 ° C. or more and 350 ° C. or less. By heating the resin precursor component (B) at a temperature in such a range, it is possible to generate a polyimide film while suppressing thermal degradation and thermal decomposition of the resin precursor component (B) and the polyimide resin to be generated. it can.
When the coating film is heated, the atmosphere in the heated system may be an oxygen-containing atmosphere such as the air, or an inert atmosphere such as a nitrogen atmosphere, a reduced pressure, or a vacuum. An inert atmosphere is preferable in terms of the transparency of the film. In an inert atmosphere, the oxygen concentration is preferably low, for example, 1000 ppm or less, preferably 100 ppm or less, more preferably 10 ppm or less.

  In addition, when the resin precursor component (B) is heated at a high temperature, consumption of a large amount of energy and deterioration of the processing equipment over time at a high temperature may be promoted, so that the resin precursor component (B) is heated. Is preferably carried out at a lower temperature (sometimes referred to as “low temperature baking”). Specifically, the upper limit of the temperature at which the resin precursor component (B) is heated is, for example, 220 ° C. or less, preferably 200 ° C. or less, more preferably 180 ° C. or less, still more preferably 160 ° C. or less, and even more preferably 150 It can be made below ℃. Even in the case of heating at such a relatively low temperature, in the present invention, the polyimide resin can be sufficiently generated by heating in a relatively short time.

  The heating time depends on the composition, thickness, etc. of the coating film, but the lower limit is, for example, 0.5 hours, preferably 1 hour, more preferably 1.5 hours, and the upper limit is, for example, 4 hours, preferably The heating time can be 3 hours, more preferably 2.5 hours, and the heating time can also be applied to heating at 130 ° C. to 150 ° C., typically 140 ° C., for example.

  By low-temperature baking, it is possible to increase the molecular weight of the polyamic acid, and it is possible to increase the molecular weight preferably without widening the molecular weight distribution. The high molecular weight of the polyamic acid by low-temperature baking is suitable in that the high molecular weight of the formed polyamic acid is promoted particularly when a monomer component is blended as the resin precursor component (B). When performing low-temperature baking, the imidazole compound (A) usually remains. For this reason, the high molecular weight of polyamic acid advances by the effect | action of an imidazole compound (A), and the tensile strength and breaking elongation of the polyimide film obtained improve.

  Even by heating at such a relatively low temperature, since the polyimide precursor composition of the present invention contains the imidazole compound (A), the polyimide film is superior in tensile strength and elongation at break than conventional polyimide films. Can be obtained. The imidazole compound (A) is considered to act as a catalyst. The resulting polyimide film is considered to be excellent in mechanical properties because of excellent tensile elongation.

The heating of the coating film is also referred to as stepwise heating (“step baking”) in which heating at a temperature higher than the heating temperature in low temperature baking (sometimes referred to as “high temperature baking”) is performed after low temperature baking. ) May be performed.
The high temperature baking can be set to, for example, 500 ° C. or less, preferably 450 ° C. or less, more preferably 420 ° C. or less, and further preferably 400 ° C. or less as the upper limit of the heating temperature. , Preferably 250 ° C. or higher, more preferably 300 ° C. or higher, further preferably 350 ° C. or higher, and even more preferably 380 ° C. or higher.
The heating time in the high-temperature baking depends on the composition and thickness of the coating film, but the lower limit is, for example, 10 minutes or longer, preferably about 20 minutes or longer, and may be 1 hour or longer as necessary. The heating time can be, for example, 4 hours, preferably 3 hours, more preferably 2.5 hours, and the heating time is also applied when heating at, for example, 390 ° C. to 410 ° C., typically 400 ° C. be able to.

（式（１’−１）及び（１’−２）中、Ｒ^１〜Ｒ^４は前記Ｒ^１〜Ｒ^４と同様であり、ｎは０以上３以下の整数である。） When the polyimide film is formed by performing the above-mentioned low temperature baking but not high temperature baking, the imidazole compound (A) may remain. On the other hand, when the polyimide film is formed by high-temperature baking, the imidazole compound (A) may be decomposed and further sublimated by the high-temperature baking, so that the imidazole compound (A) does not substantially remain.
Even in a polyimide film formed by high-temperature baking, a decomposition product from the component (A) (for example, the following formula (1′-2) reacts with the component (B) and the polyamic acid is closed. It may be contained in the permanent film by bonding with a part of the polyimide resin, the polyimide film produced by the second aspect, the permanent film of the third aspect, and the polyimide of the fourth or fifth aspect When a film | membrane contains (A) component, the case where it couple | bonds with a part of said imide ring and / or oxazole ring containing polymer shall also be included.

(In the formulas (1′-1) and (1′-2), R ^{1 to} R ⁴ are the same as the above R ^{1 to} R ⁴ , and n is an integer of 0 or more and 3 or less.)

  When performing stepwise heating, low temperature baking may be omitted. In particular, when a monomer component is blended as the resin precursor component (B), the high molecular weight of the polyamic acid can be advanced in the presence of the imidazole compound (A), so that it is sufficiently high without performing low-temperature baking. A molecular weight polyimide resin can be obtained.

  The conversion to the polyimide resin can be performed to a degree sufficient to solve the problems of the present invention even by low-temperature baking. For example, the ring-closing reaction can be substantially completed by substantially eliminating the unclosed structure. However, a part of the unclosed ring structure may remain after low-temperature baking. By carrying out high temperature baking, the ring closure reaction can be substantially completed.

<Peeling process>
When a glass substrate is used as a substrate to be coated or a ring closing step, a polyimide film obtained using the polyimide precursor composition according to the present invention may be peeled off using a UV laser or the like.

The polyimide film obtained using the polyimide precursor composition according to the present invention is a film containing a polyimide resin excellent in transparency and mechanical properties such as tensile strength.
Therefore, such a polyimide film is suitable for applications that require excellent tensile strength, for example. Such applications include, for example, electronic circuit board members, semiconductor devices, lithium ion battery members, solar cell members, fuel cell members, gas separation membrane members, motor windings, engine peripheral members, paints, optical components, heat dissipation bases and Examples include electromagnetic shielding base materials, adhesives and sealants in surge parts, insulating materials, substrate materials, protective materials, etc., and can be used as an alternative to glass used in display materials, for example, In addition to automobile reflectors, it is also suitable for flexible films for displays, low moisture permeable membranes, and the like.

≪Permanent film≫
The permanent film of the third aspect of the present invention contains the above-mentioned imidazole compound (A) and a polyimide resin in which a polyamic acid mainly composed of the repeating unit represented by the above formula (b3) is closed. .
The permanent film is a film formed on or between parts constituting a product, and is a generic name for films that remain even after the product is completed.
The permanent film can be suitably obtained by the method for producing a polyimide film according to the second aspect of the present invention described above.

  The permanent film of the present invention contains an imidazole compound (A), and even if it is a film formed at a relatively low temperature, it is superior in tensile strength and elongation at break than conventional polyimide films.

  Therefore, the permanent film of the present invention can be used as a permanent film for a liquid crystal element or an organic EL element, for example, and is suitable as a permanent film for an organic EL element. As the permanent film, an insulating film, a planarizing film, or the like is preferable.

≪Polyimide film≫
A fourth aspect of the present invention relates to a polyimide film obtained using the polyimide precursor composition of the first aspect. The polyimide film of the fourth aspect is not limited to a film used as a permanent film.
The method for producing the polyimide film of the fourth aspect is not particularly limited as long as it is a method using the polyimide precursor composition of the first aspect. The polyimide film of the fourth aspect is preferably produced by the method for producing a polyimide film according to the second aspect.

  When the polyimide film of the fourth aspect is used in a display device, the effect of suppressing the decrease in contrast and improving the viewing angle can be obtained. Therefore, the thickness direction retardation (Rth) measured at a wavelength of 590 nm has a thickness of 10 μm. It is preferably a polyimide film (polyimide film) of −1000 nm to 1000 nm (more preferably −500 nm to 500 nm, more preferably −250 nm to 250 nm). The “retardation in the thickness direction (Rth)” of the polyimide film of the fourth aspect is the refractive index (589 nm) of each polyimide film measured as described below, using the product name “AxoScan” manufactured by AXOMETRICS as a measuring device. ) Is input to the measuring device, and the retardation in the thickness direction of the polyimide film is measured using light with a wavelength of 590 nm under the conditions of temperature: 25 ° C. and humidity: 40%. Based on the measured value of retardation (measured value by automatic measurement (automatic calculation) of the measuring device), it can be obtained by converting into a retardation value per 10 μm of film thickness. Note that the size of the polyimide film of the measurement sample is not particularly limited as long as it is larger than the photometric part (φ diameter: about 1 cm) of the stage of the measuring instrument. However, the length is 76 mm, the width is 52 mm, and the thickness is 13 μm. It is preferable.

  In addition, the value of “refractive index of the polyimide film (589 nm)” used for the measurement of retardation (Rth) in the thickness direction is an unstretched film made of the same type of polyimide as the polyimide forming the polyimide film to be measured for retardation. After the film is formed, the unstretched film is used as a measurement sample (in the case where the film to be measured is an unstretched film, the film can be used as it is as a measurement sample). , Using a refractive index measuring device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.) as a measuring device, using a light source of 589 nm, at a temperature condition of 23 ° C., in the in-plane direction (thickness direction and thickness direction) Can be obtained by measuring the refractive index for light of 589 nm in the vertical direction. Since the measurement sample is unstretched, the refractive index in the in-plane direction of the film is constant in any direction in the plane, and by measuring the refractive index, the intrinsic refractive index of the polyimide can be measured. (Nx = Ny when the refractive index in the in-plane delay axis direction is Nx and the in-plane refractive index perpendicular to the delay axis direction is Ny because the measurement sample is not stretched). Thus, the intrinsic refractive index (589 nm) of polyimide is measured using an unstretched film, and the obtained measurement value is used for the measurement of retardation (Rth) in the thickness direction described above. Here, the size of the polyimide film of the measurement sample is not particularly limited as long as it is a size that can be used in the refractive index measurement device, and may be 1 cm square (1 cm in length and width) and 13 μm in thickness.

A fifth aspect of the present invention is a polyimide film containing the above-described imidazole compound (A) and a polyimide resin in which a polyamic acid composed of a repeating unit represented by the above formula (b2) is closed. The polyimide film of the fifth aspect is not limited to a film used as a permanent film.
The method for producing the polyimide film of the fifth aspect is not particularly limited as long as the polyimide film contains a predetermined component. The polyimide film of the fifth aspect typically includes a polyamic acid composed of a repeating unit represented by the above-described formula (b2), or a resin precursor component selected so that the polyamic acid is generated ( Using the polyimide precursor composition of the first aspect containing B), it is produced by the method for producing a polyimide film according to the second aspect.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Synthesis Example 1]
In Synthesis Example 1, an imidazole compound (A1) having the following structure was synthesized.

First, 30 g of cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40 ° C. Methanol was distilled off and the residue was suspended in 200 g of water. To the obtained suspension, 200 g of tetrahydrofuran was mixed and stirred, and the aqueous phase was separated. Under ice cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After allowing the mixture to stand, the oil phase was collected. The target product was crystallized from the oil phase, and the precipitate was collected to obtain an imidazole compound (A1) having the above structure.

The measurement result of ¹ H-NMR of the imidazole compound (A1) having the above structure is as follows.
¹ H-NMR (DMSO): 11.724 (s, 1H), 7.838 (s, 1H), 7.340 (d, 2H, J = 4.3 Hz), 7.321 (d, 1H, J = 7.2 Hz), 6.893 (d, 2H, J = 4.3 Hz), 6.876 (d, 1H, J = 6.1 Hz), 5.695 (dd, 1H, J = 4.3 Hz) 3.2 Hz), 3.720 (s, 3H), 3.250 (m, 2H)

[Example 1]
<Preparation of tetracarboxylic dianhydride>
In accordance with the method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, tetracarboxylic dianhydride (CpODA: norbornane-2-spiro-α-cyclo) represented by the following formula: Pentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride) was prepared.

<Preparation of polyamic acid>
First, a 30 ml three-necked flask was heated with a heat gun and sufficiently dried. Next, the atmosphere gas in the three-necked flask was replaced with nitrogen, and the inside of the three-necked flask was changed to a nitrogen atmosphere. After adding 0.2045 g (0.90 mmol: Nippon Pure Chemicals Co., Ltd .: DABAN) of 4,4′-diaminobenzanilide into the three-necked flask, N, N, N ′, N′-tetramethylurea (TMU ) Was added. The contents of the three-necked flask were stirred to obtain a slurry liquid in which aromatic diamine (DABAN) was dispersed in TMU.
Next, after adding 0.3459 g (0.90 mmol) of tetracarboxylic dianhydride (CpODA) of the above formula into a three-necked flask, the contents of the flask were stirred at room temperature (25 ° C.) for 12 hours under a nitrogen atmosphere. To obtain a reaction solution. In this way, a reaction solution in which the polyamic acid was 15% by mass (TMU solvent: 85 parts by mass) was formed in the reaction solution.

<Imidazole compound (A) addition step>
To the reaction solution obtained as described above, imidazole compound A1 obtained in Synthesis Example 1 (0.206 g, 5.6 parts by mass with respect to 100 parts by mass of reaction solution) was added under a nitrogen atmosphere. It was. Next, the reaction solution was stirred at 25 ° C. for 12 hours to obtain a liquid polyimide precursor composition containing the imidazole compound (A) and the polyamic acid.

<Preparation of polyimide film>
A polyimide precursor composition obtained as described above on a glass substrate (large slide glass, trade name “S9213” manufactured by Matsunami Glass Industry Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm), The coating film was formed by spin coating so that the thickness of the coating film after heat curing was 13 μm. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ° C. and allowed to stand for 2 hours, and the solvent was removed from the coating film by evaporation.
After removing the solvent, the glass substrate on which the coating film was formed was put into an inert oven in which nitrogen was flowing at a flow rate of 3 L / min. After standing in an inert oven for 0.5 hours under a temperature condition of 25 ° C. in a nitrogen atmosphere, it is heated for 0.5 hours under a temperature condition of 135 ° C., and further 1 under a temperature condition of 300 ° C. (final heating temperature). The coating film was cured by heating for a time to obtain a polyimide-coated glass in which a thin film (polyimide film) made of polyimide was coated on the glass substrate.

  The obtained polyimide-coated glass was immersed in hot water at 90 ° C., and the polyimide film was peeled from the glass substrate to obtain a polyimide film (a film having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm).

In order to identify the molecular structure of the resin that is the material of the obtained polyimide film, the IR spectrum of the sample of the polyimide film was measured using an IR measuring machine (trade name: FT / IR-4100, manufactured by JASCO Corporation). did.
As a result of the measurement, it was found that the C═O stretching vibration of imidecarbonyl was observed at 1696.2 cm ⁻¹ in the IR spectrum of the resin that is the material of the polyimide film. From the molecular structure identified based on such results, it was confirmed that the obtained polyimide film was indeed made of a polyimide resin.

  About the obtained polyimide film, according to the following method, measurement of thermal expansion coefficient (CTE), measurement of tensile strength and breaking elongation, glass transition temperature of polyimide resin, total light transmittance, and haze (turbidity) And yellowness (YI) was measured. These evaluation results are shown in Table 2.

<Measurement of thermal expansion coefficient>
The thermal expansion coefficient of the polyimide film is desirably 20 ppm / K or less. When such a thermal expansion coefficient exceeds the upper limit, peeling is likely to occur due to thermal history when combined with a metal or an inorganic material having a thermal expansion coefficient range of 5 ppm / K or more and 20 ppm / K or less. Further, such a polyimide film has a thermal expansion coefficient of −20 ppm / from the viewpoint of sufficiently suppressing the occurrence of peeling due to the thermal history and further improving the dimensional stability. It is more preferably K or more and 20 ppm / K or less, and further preferably 0 ppm / K or more and 15 ppm / K or less. In addition, when such a thermal expansion coefficient is less than the lower limit, peeling or curling tends to occur easily. Moreover, the following values are employ | adopted as a value of the thermal expansion coefficient of such a polyimide film.
That is, first, regarding a polyimide film as a measurement object, a film having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm, which is made of the same material as that of the polyimide film (polyimide), is formed. Thereafter, the film is vacuum-dried (120 ° C. for 1 hour) and heat-treated at 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a dry film. The dry film thus obtained was used as a sample, and a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) was used as a measuring device, under a nitrogen atmosphere, in a tensile mode (49 mN), ascending. By adopting a temperature rate of 5 ° C./min, the change in the length of the sample in the vertical direction at 50 ° C. or higher and 450 ° C. or lower is measured, and 1 ° C. (1K) in the temperature range of 100 ° C. or higher and 300 ° C. or lower. Find the average value of the change in per-length. And the said average value calculated | required in this way is employ | adopted as a value of the thermal expansion coefficient of the polyimide film of this invention (The value of the thermal expansion coefficient of a polyimide film in case thickness is 13 micrometers is used for the polyimide of this invention. Adopted as the value of the coefficient of thermal expansion of the film.)

<Measurement of tensile strength>
The tensile strength (unit: MPa) and elongation at break (unit:%) of the polyimide film (thickness: 13 μm) were measured according to the following method.
First, the product name “Super Dumbbell Cutter (Model: SDMK-1000-D, JIS K7139 (2009) manufactured by Dumbbell Co., Ltd.” is used for the SD lever type sample cutter (Dubell Co., Ltd. (Model SDL-200)). The size of the polyimide film is 75 mm long, the distance between tabs is 57 mm, the length of the parallel part is 30 mm, the radius of the shoulder is 30 mm, Width: 10 mm, width of central parallel part: 5 mm, thickness: 13 μm, dumbbell-shaped test piece (except for the thickness of 13 μm, in accordance with the standard of JIS K7139 type A22 (scale test piece)) Were prepared as measurement samples.
Next, using a Tensilon type universal testing machine (model number “UCT-10T” manufactured by A & D Co., Ltd.), the width between the gripping tools is 57 mm and the width of the gripping portion is 10 mm (the total width of the end portion). ), And then a tensile test is performed by pulling the measurement sample under the conditions of load full scale: 0.05 kN, test speed: 1 mm / min to 300 mm / min, and the value of tensile strength is obtained. It was.
The above test is a test based on JIS K7162 (issued in 1994).
The case where the value of the tensile strength was 100 MPa or more was judged as ◯, and the case where it was less than 100 MPa was judged as x.

<Measurement of glass transition temperature (Tg)>
Using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku), the glass transition temperature (Tg) value of the polyimide resin, which is the material of the polyimide film, was raised in a nitrogen atmosphere. It was measured by inserting a transparent quartz pin (tip diameter: 0.5 mm) into the film with a pressure of 500 mN at a speed of 5 ° C./min and a temperature range of 30 ° C. to 550 ° C. (scanning temperature) (so-called Measurement by penetration method).

<Measurement of total light transmittance, haze (turbidity) and yellowness (YI)>
The value of total light transmittance (unit:%) and haze (turbidity: HAZE) are JIS K7361 using a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device. 1 (issued in 1997).
The value of yellowness (YI) is obtained by performing measurement in accordance with ASTM E313-05 (issued in 2005) using a product name “Spectral Color Meter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device. Asked.

<Measurement of retardation (Rth) in thickness direction>
Using a trade name “AxoScan” manufactured by AXOMETRICS as a measuring device, the refractive index (589 nm) of each polyimide film measured as described below was input to the measuring device, and then temperature: 25 ° C., humidity: Under the condition of 40%, the retardation in the thickness direction of the polyimide film is measured using light with a wavelength of 590 nm, and the measured value of the retardation in the thickness direction (measured value by automatic measurement (automatic calculation) of the measuring device) is obtained. Based on this, it was determined by converting into a retardation value per 10 μm of film thickness.
In addition, the refractive index (refractive index with respect to light of 589 nm) of the polyimide film is 1 cm square (vertical and horizontal 1 cm) from the polyimide film (unstretched film) produced in the same manner as the method employed in each example and each comparative example. A film having a thickness of 13 μm was cut out and used as a measurement sample, a refractive index measurement device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.) was used as a measurement device, a light source of 589 nm, and a temperature condition of 23 ° C. The refractive index (inherent refractive index of polyimide) in the in-plane direction (direction perpendicular to the thickness direction) with respect to 589 nm light was measured.

[Examples 2 to 11 and Comparative Example 1]
In Examples 2-9, the diamine component (B-1) containing the diamine compound of the type and molar ratio (mol%) shown in Table 1 which is equimolar to DABAN used in Example 1 is used. Otherwise, a polyimide precursor composition was obtained in the same manner as in Example 1. That is, the mass of imidazole compound A1 described in Table 2 with respect to a total of 100 parts by mass of the solution of the polyamic acid obtained by the same method as described in “Preparation of polyamic acid” and the solvent described in Table 2. Part was added.

  In Example 10 and Example 11, the tetracarboxylic dianhydride containing tetracarboxylic dianhydride having the type and molar ratio (mol%) shown in Table 1 is equimolar to CpODA used in Example 1. Use an anhydride component and use a diamine component (B-1) that is equimolar to DABAN used in Example 1 and contains a diamine compound of the type and molar ratio (mol%) shown in Table 1. Otherwise, a polyimide precursor composition was obtained in the same manner as in Example 1. That is, the mass of imidazole compound A1 described in Table 2 with respect to a total of 100 parts by mass of the solution of the polyamic acid obtained by the same method as described in “Preparation of polyamic acid” and the solvent described in Table 2. Part was added.

  In Comparative Example 1, a polyimide precursor composition was obtained in the same manner as in Example 1 except that the imidazole compound as the component (A) was not used.

A polyimide film was formed in the same manner as in Example 1 using the polyimide precursor composition of each Example and Comparative Example.
About the obtained polyimide film, like Example 1, thermal expansion coefficient, tensile strength, glass transition temperature of polyimide resin, total light transmittance, haze (turbidity), yellowness (YI), Thickness direction retardation (Rth) was measured. These evaluation results are shown in Table 2.

In addition, the abbreviation of tetracarboxylic dianhydride in Table 1 is as follows.
CpODA: norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride 6FDA: 4,4′- (2,2-hexafluoroisopropylidene) diphthalic anhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride PMDA: pyromellitic anhydride BPDA: 3,3 ′, 4 4'-biphenyltetracarboxylic dianhydride Abbreviations of diamine compounds in Table 1 are as follows.
3ATFMB: N, N′-di (3-aminophenylcarbonyl) -2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl FDA: 9,9-bis (4-aminophenyl) fluorene 4,4 ′ -DDS: 4,4'-diaminodiphenyl sulfone 3,3'-DDS: 3,3'-diaminodiphenyl sulfone TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

According to Table 2, the imidazole compound having a predetermined structure represented by the formula (1) is included as the component (A), and at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond A diamine component (BI) containing at least one diamine compound (B-Ia) in the same molecule, and an alicyclic tetracarboxylic dianhydride (B-II) having a predetermined structure. When the polyimide precursor composition of the example containing the polyamic acid generated from the monomer component as the resin precursor component (B) is used, a polyimide film having high total light transmittance (transparency) and good tensile strength is formed. I understand that I can do it.
On the other hand, according to the comparative example, when the polyimide precursor composition does not contain the imidazole compound having the predetermined structure represented by the formula (1) as the component (A), a polyimide film excellent in transparency and tensile strength is formed. It is difficult to do.

Claims (9)

Containing an imidazole compound (A), a resin precursor component (B), and a solvent (S);
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
The resin precursor component (B) includes a diamine compound (B-Ia) having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond in the same molecule. Diamine component (BI) and the following formula (b2):

(In the formula (b2), R ^b1 , R ^b2 , and R ^b3 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, m represents an integer of 0 or more and 12 or less.)
Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydrides (B-II) And a monomer component containing the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
The polyimide precursor composition which is at least 1 selected from the group which consists of the polyamic acid (B-III) which has a repeating unit represented by these. Only from the diamine compound (B-Ib) in which the diamine component (BI) has at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond in the same molecule. Or a mixture of the diamine compound (B-Ia) and a diamine compound (B-Ic) other than the diamine compound (B-Ia),
The polyamic acid (B-III) is represented by the following formula (b3-1):

(In Formula (b3-1), R ^b1 , R ^b2 , R ^b3 , and m are the same as those in Formula (b3) described above, and R ^F3 represents a sulfone bond, a carboxylic ester bond, and a carboxylic acid amide bond. A divalent organic group having two or more bonds selected from the group consisting of
Or polyamic acid (B-IIIa) having a repeating unit represented by:
The repeating unit represented by the above formula (b3) and the following formula (b3-2):

(In Formula (b3-2), R ^b1 , R ^b2 , R ^b3 , and m are the same as those in Formula (b3), and R ^F2 is a divalent organic group other than R ^F1 .)
A polyamic acid (B-IIIb) having a repeating unit represented by:
The polyimide precursor composition according to claim 1. The diamine component (BI) is represented by the following formula (b1-1) as the diamine compound (b-Ia) or the diamine compound (b-Ib):

(In Formula (b1-1), R ^{F10 to} R ^F12 are divalent hydrocarbon groups which may have a substituent, and Z is independently an oxygen atom or NH.)
Or a diamine compound (b-Ia) represented by the following formula (b1-2):

(In Formula (b1-2), R ^F13 and R ^F14 are divalent hydrocarbon groups which may have a substituent, and Z is an oxygen atom or NH.)
The polyimide precursor composition of Claim 1 or 2 containing the compound represented by these. The polyamic acid (B-III) is represented by the following formula (b3-3) as a repeating unit represented by the formula (b3) or a repeating unit represented by the formula (b3-1):

(In Formula (b3-3), R ^b1 , R ^b2 , R ^b3 , and m are the same as in Formula (b3), and R ^{F10 to} R ^F12 are the same as in Formula (b1-1). )
Or a repeating unit represented by
As a repeating unit represented by the formula (b3), the following formula (b3-4):

(In the formula (b3-4), R ^b1 , R ^b2 , R ^b3 , and m are the same as in the formula (b3), and R ^F13 and R ^F14 may have a substituent. Z ′ is a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond.
The polyimide precursor composition of any one of Claims 1-3 containing the repeating unit represented by these.   The polyimide precursor composition according to claim 1, further comprising one or more silicon-containing compounds selected from the group consisting of a silicon-containing resin, a silicon-containing resin precursor, and a silane coupling agent. A forming step of forming a coating film comprising the polyimide precursor composition according to any one of claims 1 to 5,
And a ring-closing step of ring-closing the polyamic acid derived from the resin precursor component (B) in the coating film by heating the coating film. Including an imidazole compound (A) and a polyimide resin,
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
The polyimide resin has the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
A permanent film, which is a resin in which a polyamic acid (B-III) whose main component is a repeating unit represented by   The polyimide film obtained using the polyimide precursor composition of any one of Claims 1-5. Including an imidazole compound (A) and a polyimide resin,
The imidazole compound (A) is represented by the following formula (0):

(In formula (0), R ² is an aromatic group which may have a substituent, R ³⁰ is a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms, and R ⁴ is A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is an integer of 0 to 3. is there.)
A compound represented by
The polyimide resin has the following formula (b3):

(In formula (b3), R ^b1 , R ^b2 , and R ^b3 are each independently one type selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, R ^F1 is a divalent organic group having at least one bond selected from a sulfone bond, a carboxylic acid ester bond, and a carboxylic acid amide bond, and m represents an integer of 0 or more and 12 or less. )
A polyimide film, which is a resin in which a polyamic acid (B-III) whose main component is a repeating unit represented by