JP7150465B2 - Polyimide precursor composition, polyamic acid, polyimide resin, polyimide film, and optical device - Google Patents

Description

The present invention can be produced using a polyimide precursor composition containing a polyimide resin precursor component, a polyamic acid suitable as a precursor component in the polyimide precursor composition, and the above-described polyimide precursor composition. The present invention relates to a polyimide resin, a polyimide film that can be produced using the aforementioned polyimide precursor composition, and an optical device comprising the aforementioned polyimide film.

Polyimide resin has properties such as excellent heat resistance, mechanical strength, insulation, and low dielectric constant. It is widely used as a material and protective material.

As a polyimide resin, for example, a wholly aromatic polyimide (for example, the product name "Kapton") has been used in advanced industries such as space and aviation applications because it has excellent mechanical properties and heat resistance. . Such a wholly aromatic polyimide is synthesized by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine. Kapton described above is known to exhibit the highest class of heat resistance (glass transition temperature (Tg): 410° C.) among heat-resistant polymers (see Non-Patent Document 1).

In addition, from the viewpoint of increasing the transparency of polyimide resins, research has been conducted on polyimide resins containing an alicyclic skeleton (see Non-Patent Document 2).
Examples of such alicyclic polyimides include reactions between alicyclic tetracarboxylic dianhydrides and alicyclic diamines, reactions between alicyclic tetracarboxylic dianhydrides and aromatic diamines, and aromatic tetracarboxylic dianhydrides. There are three types of resins obtained by reacting acid dianhydrides with alicyclic diamines.

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

A film used in an OLED lighting device or the like is required to have a high refractive index in terms of light extraction efficiency. However, conventionally known polyimide resins such as those described above have room for improvement in increasing the refractive index.

The present invention has been made in view of the above problems, a polyimide precursor composition that provides a polyimide film having a high refractive index, a suitable polyamic acid as a precursor component in the polyimide precursor composition, An object of the present invention is to provide a polyimide resin that can be produced using the polyimide precursor composition, a polyimide film that can be produced using the polyimide precursor composition, and an optical device comprising the polyimide film.

The present inventors have used an aromatic diamine compound in which two amino group-containing aromatic groups having a specific structure are bonded to the same carbon atom in a polycyclic skeleton such as a fluorene skeleton as a diamine component (B1). Contained in the precursor component, polyamic acid (B3) containing a structural unit having a structure derived from the aromatic diamine compound having the specific structure described above is used as the resin precursor component (B) to produce a polyimide resin or polyimide film. The present inventors have found that the above problems can be solved by forming Specifically, the present invention provides the following.

（式（ｂ１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、及びＲ^３ｂは、それぞれ独立に、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｃで表される基、又は－Ｎ（Ｒ^４ｄ）_２で表される基であり、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、－ＮＨＲ^４ｃで表される基、及び－Ｎ（Ｒ^４ｄ）_２で表される基は、－ＯＲ^４ｅで表される基、－ＳＲ^４ｆで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｇで表される基、及び－Ｎ（Ｒ^４ｈ）_２で表される基からなる群より選択される１以上の基で置換されていてもよく、
Ｒ^４ａ～Ｒ^４ｇは、それぞれ独立に１価の炭化水素基であり、
Ｘ^１、及びＸ^２は、それぞれ独立に、－ＣＯ－ＮＨ－、－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＯ－ＮＨ－ＣＯ－、－Ｏ－ＣＯ－ＮＨ－、又は－ＣＯ－ＮＨ－ＣＯ－ＮＨ－であり、
環Ｙ^１、環Ｙ^２、環Ｙ^３及び環Ｙ^４は、それぞれ独立に芳香族炭化水素環であり、
Ｒは、単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、－Ｏ－で表される基、－ＮＨ－で表される基、又は－Ｓ－で表される基であり、
ｎ１及びｎ２は、それぞれ独立に０以上４以下の整数であり、
ｎ３及びｎ４は、それぞれ独立に０以上５以下の整数であり、
ｎ５及びｎ６は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物を含み、
ポリアミド酸（Ｂ３）が、下記式（ｂ３）：

（式（ｂ３）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、ｎ１、ｎ２、ｎ３、ｎ４、ｎ５、及びｎ６は式（ｂ１）と同様であり、Ｚ^１は４価の有機基である。）
で表される構成単位を有するポリアミド酸を含む、ポリイミド前駆体組成物である。 A first aspect of the present invention is a polyimide precursor composition containing a resin precursor component (B) and a solvent (S), wherein the resin precursor component (B) is a diamine component (B1) A monomer component consisting of a tetracarboxylic dianhydride component (B2) and / or a polyamic acid (B3),
The diamine component (B1) has the following formula (b1):

(In the formula (b1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are A group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4g , and a group represented by -N(R ^4h ) ₂ optionally substituted with one or more groups selected from the group consisting of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - CO-NH-CO-NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 or more and 4 or less. )
containing an aromatic diamine compound represented by
Polyamic acid (B3) is represented by the following formula (b3):

(In formula (b3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R, n1 , n2, n3, n4, n5, and n6 are the same as in formula (b1), and Z1 is ^a tetravalent organic group.)
It is a polyimide precursor composition containing a polyamic acid having a structural unit represented by.

（式（ｂ３）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、及びＲ^３ｂは、それぞれ独立に、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｃで表される基、又は－Ｎ（Ｒ^４ｄ）_２で表される基であり、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、－ＮＨＲ^４ｃで表される基、及び－Ｎ（Ｒ^４ｄ）_２で表される基は、－ＯＲ^４ｅで表される基、－ＳＲ^４ｆで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｇで表される基、及び－Ｎ（Ｒ^４ｈ）_２で表される基からなる群より選択される１以上の基で置換されていてもよく、
Ｒ^４ａ～Ｒ^４ｇは、それぞれ独立に１価の炭化水素基であり、
Ｘ^１、及びＸ^２は、それぞれ独立に、－ＣＯ－ＮＨ－、－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＯ－ＮＨ－ＣＯ－、－Ｏ－ＣＯ－ＮＨ－、又は－ＣＯ－ＮＨ－ＣＯ－ＮＨ－であり、
環Ｙ^１、環Ｙ^２、環Ｙ^３及び環Ｙ^４は、それぞれ独立に芳香族炭化水素環であり、
Ｒは、単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、－Ｏ－で表される基、－ＮＨ－で表される基、又は－Ｓ－で表される基であり、
ｎ１及びｎ２は、それぞれ独立に０以上４以下の整数であり、
ｎ３及びｎ４は、それぞれ独立に０以上５以下の整数であり、
ｎ５及びｎ６は、それぞれ独立に０以上４以下の整数であり、
Ｚ^１は、４価の有機基である。）
で表される構成単位を有するポリアミド酸である。 A second aspect of the present invention is represented by the following formula (b3):

(In the formula (b3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are a group represented by —OR ^4e , a group represented by —SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by —NHR ^4g , and a group represented by —N(R ^4h ) ₂ optionally substituted with one or more groups selected from the group consisting of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - CO-NH-CO-NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 to 4,
Z ¹ is a tetravalent organic group. )
is a polyamic acid having a structural unit represented by

（式（ｂ４）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、及びＲ^３ｂは、それぞれ独立に、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｃで表される基、又は－Ｎ（Ｒ^４ｄ）_２で表される基であり、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、－ＮＨＲ^４ｃで表される基、及び－Ｎ（Ｒ^４ｄ）_２で表される基は、－ＯＲ^４ｅで表される基、－ＳＲ^４ｆで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｇで表される基、及び－Ｎ（Ｒ^４ｈ）_２で表される基からなる群より選択される１以上の基で置換されていてもよく、
Ｒ^４ａ～Ｒ^４ｇは、それぞれ独立に１価の炭化水素基であり、
Ｘ^１、及びＸ^２は、それぞれ独立に、－ＣＯ－ＮＨ－、－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＯ－ＮＨ－ＣＯ－、－Ｏ－ＣＯ－ＮＨ－、又は－ＣＯ－ＮＨ－ＣＯ－ＮＨ－であり、
環Ｙ^１、環Ｙ^２、環Ｙ^３及び環Ｙ^４は、それぞれ独立に芳香族炭化水素環であり、
Ｒは、単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、－Ｏ－で表される基、－ＮＨ－で表される基、又は－Ｓ－で表される基であり、
ｎ１及びｎ２は、それぞれ独立に０以上４以下の整数であり、
ｎ３及びｎ４は、それぞれ独立に０以上５以下の整数であり、
ｎ５及びｎ６は、それぞれ独立に０以上４以下の整数であり、
Ｚ^１は、４価の有機基である。）
で表される構成単位を有するポリイミド樹脂である。 A third aspect of the present invention is represented by the following formula (b4):

(In formula (b4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are a group represented by —OR ^4e , a group represented by —SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by —NHR ^4g , and a group represented by —N(R ^4h ) ₂ optionally substituted with one or more groups selected from the group consisting of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - CO-NH-CO-NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 to 4,
Z ¹ is a tetravalent organic group. )
is a polyimide resin having a structural unit represented by

A fourth aspect of the present invention is to form a coating film made of the polyimide precursor composition according to the first aspect;
A method for producing a polyimide film, comprising heating the coating film to ring-close polyamic acid derived from the resin precursor component (B) in the coating film.

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

A sixth aspect of the present invention is a polyimide film containing the polyimide resin according to the third aspect.

A seventh aspect of the present invention is an optical device comprising the polyimide film according to the fifth or sixth aspect.

According to the present invention, a polyimide precursor composition that provides a polyimide film with a high refractive index, a polyamic acid suitable as a precursor component in the polyimide precursor composition, and the polyimide precursor composition described above. It is possible to provide a polyimide resin obtained, a polyimide film that can be produced using the polyimide precursor composition described above, and an optical device comprising the polyimide film described above.

<<Polyimide Precursor Composition>>
The polyimide precursor composition contains a resin precursor component (B) and a solvent (S). Moreover, the polyimide precursor composition may contain an accelerator (A).
Essential or optional components contained in the polyimide precursor composition are described below in order.

<Accelerator (A)>
The polyimide precursor composition may contain an accelerator (A) as a component that promotes imidization of the resin precursor component (B). Examples of such accelerators include imidazole-based compounds, pyridine-based compounds, tertiary amine-based compounds such as triethylamine, amino acid-based compounds, etc.), and imidazole-based compounds are preferred.
The imidazole-based compound (A1) may be a compound that promotes imidization of the resin precursor component (B) as it is. It may be a compound that generates an imidazole compound that promotes the imidization of .
Since the polyimide precursor composition has good stability over time, the imidazole compound (A1) is an imidazole compound that promotes imidization of the resin precursor component (B) by the action of energy such as heat and light. are preferred. As such an imidazole compound (A1), known thermal imidazole generators and photoimidazole generators can be used without particular limitation.

Suitable examples of the imidazole compound (A1) include compounds represented by the following formula (1). A compound represented by the following formula (1) corresponds to a thermal imidazole generator that generates an imidazole compound by heating.

（式（１）中、Ｒ^１は水素原子又はアルキル基であり、Ｒ^２は置換基を有してもよい芳香族基であり、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。）

(In formula (1), R ¹ is a hydrogen atom or an alkyl group, R ² is an optionally substituted aromatic group, and R ³ is an optionally substituted alkylene group. , ^R4 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 sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n is 0 or more. It is an integer of 3 or less.)

In formula (1), ^R1 is a hydrogen atom or an alkyl group. When R ¹ is an alkyl group, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

Specific examples of alkyl groups suitable for 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 n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups.

In formula (1), R ² is an aromatic group which may have a substituent. The aromatic group optionally having substituents may be an aromatic hydrocarbon group optionally having substituents or an aromatic heterocyclic group optionally having substituents.

The type of 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 formed by condensation of two or more aromatic hydrocarbon groups. may be formed by combining with a single bond. Preferred aromatic hydrocarbon groups are phenyl, naphthyl, biphenylyl, anthryl and phenanthrenyl groups.

The type of 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. Preferred aromatic heterocyclic groups are pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl groups.

Substituents that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, and nitroso groups. , sulfino groups, sulfo groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonato groups, amino groups, ammonio groups, and organic groups. When the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has multiple substituents, the multiple substituents may be the same or different.

When the substituent of the aromatic group 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, an aralkyl group, and the like. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. Moreover, this organic group may be linear, branched, or cyclic. This organic group is usually monovalent, but may be a divalent or higher organic group when forming a cyclic structure.

When an aromatic group has substituents on adjacent carbon atoms, two substituents attached on adjacent carbon atoms may be joined together to form a cyclic structure. Cyclic structures include aliphatic hydrocarbon rings and heteroatom-containing aliphatic rings.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effects of the present invention are not impaired, and the organic group may be an oxygen atom, a nitrogen atom, a silicon atom, or the like. may contain a bond containing a heteroatom of Specific examples of bonds containing heteroatoms include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-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.

From the viewpoint of heat resistance of the imidazole compound represented by formula (1), the heteroatom-containing bond that the organic group may have includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, and an amide bond. bond, amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (-N=C(-R)-, -C(=NR)-: R is a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, and sulfinyl bond are preferred.

When the organic group is a substituent other than a hydrocarbon group, the type of the 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, and 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, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl ether group, alkylthioether group, alkenylthioether group, arylether group, arylthioether group and the like. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents possessed by a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 carbon atom. An alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom are preferred.

As R ² , the imidazole compound represented by the formula (1) can be synthesized inexpensively and easily, and the imidazole compound has good solubility in water and organic solvents. groups, furyl groups and thienyl groups are preferred.

In formula (1), R ³ is an optionally substituted alkylene group. The substituents that the alkylene group may have are not particularly limited as long as the objects of the present invention are 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, a halogen atom, and the like. The alkylene group may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably from 1 to 20, preferably from 1 to 10, and more preferably from 1 to 5. The number of carbon atoms in the alkylene group does not include the carbon atoms of the substituents bonded to the alkylene group.

An alkoxy group as a substituent bonded to an alkylene group may be a straight-chain alkoxy group or a branched-chain alkoxy group. Although the number of carbon atoms in the alkoxy group as a substituent is not particularly limited, it 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.

An amino group as a substituent bonded to an 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 straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms in 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 alkylene groups suitable for R ³ include methylene, ethane-1,2-diyl, n-propane-1,3-diyl, n-propane-2,2-diyl, 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 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.

^R4 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 sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n is 0 to 3 It is an integer below. When n is an integer of 2 or more and 3 or less, a plurality of R ⁴ may be the same or different.

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, phenyl group, naphthyl group, biphenylyl group, anthryl group and phenanthrenyl group are preferred, phenyl group and naphthyl group are more preferred, and phenyl group is particularly preferred. Preferred aromatic heterocyclic groups are pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl groups. A furyl group and a thienyl group are more preferred.

When R ⁴ is an alkyl group, the binding position of the alkyl group on the imidazole ring is preferably 2-position, 4-position or 5-position, more preferably 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 2-position.

Among the imidazole compounds represented by the above formula (1), compounds represented by the following formula (1-1) are preferred because they can be synthesized inexpensively and easily and have excellent solubility in water and organic solvents. , wherein R ³ is a methylene group is more preferred.

（式（１－１）中、Ｒ^１、Ｒ^３、Ｒ^４、及びｎは、式（１）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、又は有機基であり、ただし、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９のうち少なくとも１つは水素原子以外の基である。）

(In formula (1-1), R ¹ , R ³ , R ⁴ and n are the same as in formula (1), 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, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, provided that at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a group other than a hydrogen atom.)

When R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are organic groups, the organic groups are the same as the organic groups that R ² in Formula (1) has as a substituent. R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms from the viewpoint of the solubility of the imidazole compound in the solvent (S).

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.
- OR ¹⁰
( ^R10 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 (1) 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（１－１－１）において、Ｒ^１、Ｒ^４、及びｎは、式（１）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、又は有機基であり、ただし、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５のうち少なくとも１つは水素原子以外の基である。） Among the compounds represented by the above formula (1-1), compounds represented by the following formula (1-1-1) are preferred.

(In formula (1-1-1), R ¹ , R ⁴ and n are the same as in formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently , hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group , or an organic group, provided that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a group other than a hydrogen atom.)

Among the compounds represented by formula (1-1-1), at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by —OR ¹⁰ described above. is preferred, and it is particularly preferred that R ¹⁵ is a group represented by —OR ¹⁰ . When R ¹⁵ is a group represented by —OR ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms.

Preferable specific examples of the imidazole compound represented by formula (1) include the following.

The content of the accelerator (A) or the imidazole compound (A1) in the polyimide precursor composition is not particularly limited as long as the object of the present invention is not impaired. The content of the accelerator (A) or the imidazole compound (A1) is, for example, 1 part by mass or more with respect to 100 parts by mass of the resin precursor component (B) described later, and the upper limit is not particularly limited, but for example 60 Part by mass or less. 5 parts by mass or more and 50 parts by mass or less is more preferable, and 10 parts by mass or more and 40 parts by mass or less is particularly preferable. By using the promoter (A) or the imidazole compound (A1) in such an amount, it is easy to form a polyimide film having excellent tensile strength and elongation at break and excellent heat resistance.

<Resin precursor component (B)>
The resin precursor component (B) contains a monomer component consisting of a diamine component (B1) and a tetracarboxylic dianhydride component (B2) and/or polyamic acid (B3). The monomer component and the polyamic acid (B3) are described below.

[Monomer component]
The monomer component consists of a diamine component (B1) and a tetracarboxylic dianhydride component (B2), as described above. The diamine component (B1) and the tetracarboxylic dianhydride component (B2) are described below.

（式（ｂ１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、及びＲ^３ｂは、それぞれ独立に、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｃで表される基、又は－Ｎ（Ｒ^４ｄ）_２で表される基であり、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、－ＮＨＲ^４ｃで表される基、及び－Ｎ（Ｒ^４ｄ）_２で表される基は、－ＯＲ^４ｅで表される基、－ＳＲ^４ｆで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｇで表される基、及び－Ｎ（Ｒ^４ｈ）_２で表される基からなる群より選択される１以上の基で置換されていてもよく、
Ｒ^４ａ～Ｒ^４ｇは、それぞれ独立に１価の炭化水素基であり、
Ｘ^１、及びＸ^２は、それぞれ独立に、－ＣＯ－ＮＨ－、－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＯ－ＮＨ－ＣＯ－、－Ｏ－ＣＯ－ＮＨ－、又は－ＣＯ－ＮＨ－ＣＯ－ＮＨ－であり、
環Ｙ^１、環Ｙ^２、環Ｙ^３及び環Ｙ^４は、それぞれ独立に芳香族炭化水素環であり、
Ｒは、単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、－Ｏ－で表される基、－ＮＨ－で表される基、又は－Ｓ－で表される基であり、
ｎ１及びｎ２は、それぞれ独立に０以上４以下の整数であり、
ｎ３及びｎ４は、それぞれ独立に０以上５以下の整数であり、
ｎ５及びｎ６は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物を含む。 (Diamine component (B1))
The diamine component has the following formula (b1):

(In the formula (b1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are A group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4g , and a group represented by -N(R ^4h ) ₂ optionally substituted with one or more groups selected from the group consisting of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - CO-NH-CO-NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 or more and 4 or less. )
Including the aromatic diamine compound represented by.

The structure derived from the aromatic diamine compound represented by the formula (b1) is introduced into the polyimide resin, whereby the polyimide resin formed using the resin precursor component (B) has a high refractive index and a low retardation. show.

In the above formula (b1), ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ include, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [e.g., a condensed bicyclic hydrocarbon ring (e.g. C _8-20 condensed bicyclic hydrocarbon ring such as naphthalene ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (e.g. anthracene ring, phenanthrene) condensed 2- to 4-ring aromatic hydrocarbon ring] and the like. Each of ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. Ring Y ³ and ring Y ⁴ may be the same or different, and both rings are particularly preferably benzene rings. Ring Y ¹ and ring Y ² may be the same or different, and both rings are particularly preferably benzene rings.

In formula (b1), X ¹ and X ² are —CO—NH—, —CO—O—, —NH—CO—NH—, —CO—NH—CO—, —O—CO—NH—, or -CO-NH-CO-NH-. The direction of these bonds is not particularly limited. For example, when X ¹ is -CO-NH-, a carbonyl group (-CO-) may be present on the ring Y ³ side, or an amino group (-NH-) may be present on the ring Y ³ side. .

In formula (b1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , and R ^3b are non-reactive substituents such as; C _1-12 alkyl groups such as isopropyl group and butyl group, preferably C _1-8 alkyl groups, more preferably C _1-6 alkyl groups, etc.), cycloalkyl groups (C _5-10 cycloalkyl groups such as cyclohexyl group , preferably C _5-8 cycloalkyl groups, more preferably C _5-6 cycloalkyl groups, etc.), aryl groups (e.g., C _6-14 aryl groups such as phenyl, tolyl, xylyl, naphthyl groups, etc., preferably is a C _6-10 aryl group, more preferably a C _6-8 aryl group, etc.), an aralkyl group (a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group, a phenethyl group, etc.), etc. hydrogen group;
Alkoxy group (C _1-12 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (cyclohexyloxy C _5-10 cycloalkoxy groups such as groups), aryloxy groups (C _6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (for example, C _6-10 aryl-C _1- a group represented by —OR ^4a such as ₄ alkyloxy group);
Alkylthio group (C _1-12 alkylthio group such as methylthio group, ethylthio group, propylthio group, butylthio group, preferably C _1-8 alkylthio group, more preferably C _1-6 alkylthio group, etc.), cycloalkylthio group (cyclohexylthio C _5-10 cycloalkylthio groups such as groups), arylthio groups (C _6-10 arylthio groups such as phenylthio groups), aralkylthio groups (e.g. C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio groups ) group represented by —SR ^4b ;
acyl group (such as a C _1-6 acyl group such as an acetyl group);
alkoxycarbonyl group (such as C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group);
halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.);
cyano group;
Alkylamino group (C _1-12 alkylamino group such as methylamino group, ethylamino group, propylamino group, butylamino group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc. ), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (e.g., benzylamino group a group represented by —NHR ^4c such as a C _6-10 aryl-C _1-4 alkylamino group such as
Dialkylamino group (di(C _1-12 alkyl)amino group such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, preferably di(C _1-8 alkyl)amino group, more preferably di( C _1-6 alkyl)amino group, etc.), dicycloalkylamino group (di(C _5-10 cycloalkyl)amino group such as dicyclohexylamino group, etc.), diarylamino group (di(C _{6- 10} aryl)amino group), dialkylamino group (e.g., di(C _6-10 aryl-C _1-4 alkyl)amino group such as dibenzylamino group), etc. -N(R ^4d ) ₂ group , is preferred.

R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are monovalent hydrocarbon groups, groups represented by —OR ^4a , groups represented by —SR ^4b , acyl groups, alkoxycarbonyl groups , a group represented by —NHR ^4c , and a group represented by —N(R ^4d ) ₂ , these groups are a group represented by —OR ^4e , a group represented by —SR ^4f , substituted with one or more groups selected from the group consisting of an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by —NHR ^4g , and a group represented by —N(R ^4h ) ₂ may

Preferred examples of these substituents include a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , and The same as the preferred examples of the group represented by —N(R ^4d ) ₂ .

When a plurality of each of R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are present, the plurality of groups may be the same or different. The substitution positions of R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are not particularly limited.

In formula (b1), n1 and n2 are each independently an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0. n3 and n4 are each independently an integer of 0 or more and 5 or less, preferably 0 or 1, more preferably 0. n5 and n6 are each independently an integer of 0 or more and 5 or less, preferably 0 or 1, more preferably 0.

In formula (b1), R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, —O— is a group represented by -NH- or a group represented by -S-, and is typically a single bond. Examples of substituents include cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), monovalent hydrocarbon group [e.g., alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group , C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group), etc.] and the like. Heteroatoms include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms and the like.

（式（ｂ１－１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物が好ましい。式（ｂ１－１）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the aromatic diamine compound represented by the formula (b1) described above, the following formula (b1-1):

(In formula (b1-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 is the same as in formula (b1), and n7 and n8 are each independently an integer of 0 or more and 4 or less.)
An aromatic diamine compound represented by is preferred. In formula (b1-1), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ１－２）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物が好ましい。式（ｂ１－２）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the aromatic diamine compound represented by the above formula (b1-1), the following formula (b1-2):

(In formula (b1-2), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 to 4.)
An aromatic diamine compound represented by is preferred. In formula (b1-2), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ１－３）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物が好ましい。式（ｂ１－３）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the aromatic diamine compound represented by the above formula (b1-2), the following formula (b1-3):

(In formula (b1-3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 to 4.)
An aromatic diamine compound represented by is preferred. In formula (b1-3), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ１－４）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物も好ましい。式（ｂ１－４）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 Further, as the aromatic diamine compound represented by the above formula (b1-2), the following formula (b1-4):

(In formula (b1-4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 to 4.)
An aromatic diamine compound represented by is also preferred. In formula (b1-4), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ１－５）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数である。）
で表される芳香族ジアミン化合物が好ましい。式（ｂ１－５）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the aromatic diamine compound represented by the above formula (b1-3), the following formula (b1-5):

(In formula (b1-5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 to 4.)
An aromatic diamine compound represented by is preferred. In formula (b1-5), each of n7 and n8 is preferably 0 or 1, more preferably 0.

In formula (b1) and formulas (b1-1) to (b1-5) described above, ring Y ¹ and ring Y ² are each preferably a benzene ring, and R is preferably a single bond. . That is, the aromatic diamine compound represented by formula (b1) preferably contains a fluorene ring.

Preferred specific examples of the aromatic amine compound represented by formula (b1) described above include fluorene compounds having two identical substituents at the 9-position of the following formula.

In addition, the amide bond (-CO-NH-) in the above compounds, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - A compound substituted with CO--NH--CO--NH-- is also mentioned as a suitable example of the compound represented by the formula (b1).

The method for producing the aromatic diamine compound represented by the above formula (b1) is not particularly limited.
_The aromatic diamine compound represented by the above formula (b1) is, for example, an amino group (- NH ₂ ).

（式（ｂ１－Ｉ）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様である。）

(In formula (b1-I), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R , and n1 to n6 are the same as in formula (b1).)

（式（ｂ１－Ｉ－１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様である。）
で表される化合物が好ましい。 As the compound represented by the above formula (b1-I), the following formula (b1-I-1):

(In formula (b1-I-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, and n1 to n6 are , which is similar to formula (b1).)
A compound represented by is preferred.

（式（ｂ１－Ｉａ）、式（ｂ１－Ｉｂ）、及び式（ｂ１－Ｉｃ）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様であり、
基Ｘ^１ａは、基Ｘ^１ｂとの反応により、式（ｂ１－Ｉ）中の基Ｘ^１を形成させる基であり、
基Ｘ^２ａは、基Ｘ^２ｂとの反応により、式（ｂ１－１）中の基Ｘ^２を形成させる基である。）
を反応させて、式（ｂ１－Ｉ）で表される化合物を製造することができる。
ここで、Ｘ^１ａ及びＸ^２ａが同一の基である場合、式（ｂ１－Ｉｂ）で表される化合物と、式（ｂ１－Ｉｃ）で表される化合物とは、同一の化合物であっても、異なる化合物であってもよく、同一の化合物であるのが好ましい。
また、式（ｂ１－Ｉａ）で表される化合物と、式（ｂ１－Ｉｂ）で表される化合物、及び式（ｂ１－Ｉｃ）で表される化合物との反応は、３つの化合物を同時に混合して行われてもよく、式（ｂＩ－Ｉａ）で表される化合物に対して、式（ｂ１－Ｉｂ）で表される化合物、及び式（ｂ１－Ｉｃ）で表される化合物のいずれか一方の化合物を加えた後に、他方の化合物を加えて行われてもよい。 The method for producing the compound represented by formula (b1-I) is not particularly limited. For example, an aromatic compound represented by the following formula (b1-Ia), a compound represented by the following formula (b1-Ib), and a compound represented by the following formula (b1-Ic):

(In formula (b1-Ia), formula (b1-Ib), and formula (b1-Ic), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R, and n1 to n6 are the same as in formula (b1);
The group X ^1a is a group which, upon reaction with the group X ^1b , forms the group X ¹ in formula (b1-I),
Group X ^2a is a group that forms group X ² in formula (b1-1) by reaction with group X ^2b . )
can be reacted to produce a compound represented by formula (b1-I).
Here, when X ^1a and X ^2a are the same group, the compound represented by formula (b1-Ib) and the compound represented by formula (b1-Ic) may be the same compound. , may be different compounds, preferably the same compound.
Further, the reaction of the compound represented by formula (b1-Ia), the compound represented by formula (b1-Ib), and the compound represented by formula (b1-Ic) is performed by mixing three compounds at the same time Either a compound represented by formula (b1-Ib) or a compound represented by formula (b1-Ic) for a compound represented by formula (bI-Ia) The addition of one compound may be followed by the addition of the other compound.

Reaction of group X ^1a with group X ^1b yields group X ¹ and reaction of group X ^2a with group X ^2b yields group X ² .
The combination of groups X ^1a and X ^1b and the combination of groups X ^2a and X ^2b are each independently
a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and an amino group (--NH ₂ );
a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a hydroxyl group;
a combination of an amino group (—NH ₂ ) and an isocyanate group;
a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a carbamoyl group (--CO--NH ₂ );
a combination of a hydroxyl group and an isocyanate group, or
It is a combination of a carbamoyl group (--CO--NH ₂ ) and an isocyanate group.
For these combinations, for example, when the combination of groups X ^1a and X ^1b is a combination of a carboxy group and an amino group, X ^1a may be a carboxy group and X ^1b may be an amino group; ^1a may be an amino group and X ^1b may be a carboxy group.

A combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and an amino group (--NH ₂ ) is a combination that produces --CO--NH--.
A combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a hydroxyl group is a combination that produces --CO--O--.
A combination of an amino group (--NH ₂ ) and an isocyanate group is a combination that produces --NH--CO--NH--.
A combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a carbamoyl group (--CO--NH ₂ ) is a combination that produces --CO--NH--CO--.
A combination of a hydroxyl group and an isocyanate group is a combination that produces --O--CO--NH--.
A combination of a carbamoyl group (--CO--NH ₂ ) and an isocyanate group is a combination that produces --CO--NH--CO--NH--.

The method of reacting the aromatic compound represented by the above formula (b1-Ia), the compound represented by the following formula (b1-Ib), and the compound represented by the following formula (b1-Ic) is particularly limited. not. The reaction method is appropriately selected from known methods in consideration of the combination of the groups ^X1a and ^X1b and the combination of the groups ^X2a and ^X2b .

Use thereof in reacting an aromatic compound represented by formula (b1-Ia), a compound represented by formula (b1-Ib) below, and a compound represented by formula (b1-Ic) below The amount is not particularly limited as long as the desired amount of the compound represented by formula (b1-I) can be produced. The amount of the compound represented by formula (b1-Ib) used and the sample amount of the compound represented by formula (b1-Ic) are each independently 1 mol of the compound represented by formula (b1-Ia) is preferably 0.5 mol or more and 2 mol or less, more preferably 0.7 mol or more and 1.5 mol or less, and particularly preferably 0.9 mol or more and 1.1 mol or less.

The method for hydrogenating the nitro group (--NO ₂ ) of the aromatic dinitro compound represented by formula (b1-1) to convert it to an amino group (--NH ₂ ) is not particularly limited. selected as appropriate from the conversion method. A typical method includes contacting the aromatic dinitro compound represented by formula (b1-I) with hydrogen in the presence of a palladium catalyst.

The aromatic diamine compound is obtained, for example, by deprotecting the protected amino group represented by Z ¹ -NH- or Z ² -NH- of the aromatic compound represented by the following formula (b1-II). , to an amino group (—NH ₂ ).

（式（ｂ１－ＩＩ）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様であり、Ｚ^１、及びＺ^２はそれぞれアミノ基を保護し、且つ脱保護可能な保護基である。）

(In formula (b1-II), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R , and n1 to n6 are the same as in formula (b1), and Z ¹ and Z ² are protecting groups that protect and deprotect the amino group, respectively.)

（式（ｂ１－ＩＩ－１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様であり、Ｚ^１、及びＺ^２はそれぞれアミノ基を保護し、且つ脱保護可能な保護基である。）
で表される化合物が好ましい。 As the compound represented by the above formula (b1-II), the following formula (b1-II-1):

(In formula (b1-II-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, and n1 to n6 are , is the same as formula (b1), and Z ¹ and Z ² are protecting groups capable of protecting and deprotecting the amino group, respectively.)
A compound represented by is preferred.

Protecting groups as Z ¹ and Z ² refer to functional groups that convert an amino group into a different chemical group that is substantially inert to certain chemical reaction conditions. Protecting groups can be easily and selectively removed with good yields. Examples of protecting groups include formyl, acetyl, benzyl, tert-butyldimethylsilyl, tert-butidyldiphenylsilyl, tert-butyloxycarbonyl (Boc), p-methoxybenzyl, methoxymethyl. , tosyl group, trifluoroacetyl group, trimethylsilyl (TMS) group, fluorenylmethyloxycarbonyl group (Fmoc), 2-trimethylsilylethoxycarbonyl group, 1-methyl-1-(4-biphenylyl)ethoxycarbonyl group, allyl oxycarbonyl group, benzyloxycarbonyl group (CBZ), 2-trimethylsilyl-ethanesulfonyl (SES), trityl and substituted trityl groups, 9-fluorenylmethyloxycarbonyl (FMOC), nitro-veratryloxycarbonyl (NVOC), etc. including but not limited to.

（式（ｂ１－Ｉａ）、式（ｂ１－ＩＩｂ）、及び式（ｂ１－ＩＩｃ）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様であり、Ｚ^１、及びＺ^２は式（ｂ１－ＩＩ）と同様であり、
基Ｘ^１ａは、基Ｘ^１ｂとの反応により、式（ｂ１－ＩＩ）中の基Ｘ^１を形成させる基であり、
基Ｘ^２ａは、基Ｘ^２ｂとの反応により、式（ｂ１－ＩＩ）中の基Ｘ^２を形成させる基である。）
を反応させて、式（ｂ１－ＩＩ）で表される化合物を製造することができる。 The method for producing the compound represented by formula (b1-II) is not particularly limited. For example, an aromatic compound represented by the following formula (b1-Ia), a compound represented by the following formula (b1-IIb), and a compound represented by the following formula (b1-IIc):

(In formula (b1-Ia), formula (b1-IIb), and formula (b1-IIc), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R, and n1 to n6 are the same as in formula (b1), Z ¹ and Z ² are the same as in formula (b1-II),
The group X ^1a is a group which, upon reaction with the group X ^1b , forms the group X ¹ in formula (b1-II),
The group X ^2a is a group which, upon reaction with the group X ^2b , forms the group X ² in formula (b1-II). )
can be reacted to produce a compound represented by formula (b1-II).

As for the combination of the group X ^1a and the group X ^1b and the combination of the group X ^2a and the group X ^2b , the aromatic compound represented by the formula (b1-Ia) and the aromatic compound represented by the formula (b1-Ib) and the compound represented by formula (b1-Ic) are as described above.

Use thereof in reacting an aromatic compound represented by formula (b1-Ia), a compound represented by formula (b1-IIb) below, and a compound represented by formula (b1-IIc) below The amount is not particularly limited as long as the desired amount of the compound represented by formula (b1-II) can be produced. The amount of the compound represented by the formula (b1-IIb) and the amount of the compound represented by the formula (b1-IIc) used are each independently 1 mol of the compound represented by the formula (b1-Ia). is preferably 0.5 mol or more and 2 mol or less, more preferably 0.7 mol or more and 1.5 mol or less, and particularly preferably 0.9 mol or more and 1.1 mol or less.

The method for deprotecting the protected amino group represented by Z ¹ -NH- or Z ² -NH- to convert it to an amino group (-NH ₂ ) is not particularly limited as long as it is a conventionally known method. not. Deprotection is carried out by known means depending on the type of protecting group.

（式（ｂ１－Ｉａ）、式（ｂ１－ＩＩＩｂ）、及び式（ｂ１－ＩＩＩｃ）、及び中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、及びｎ１～ｎ６は、式（ｂ１）と同様であり
基Ｘ^１ａは、基Ｘ^１ｂとの反応により、式（ｂ１）中の基Ｘ^１を形成させる基であり、
基Ｘ^２ａは、基Ｘ^２ｂとの反応により、式（ｂ１）中の基Ｘ^２を形成させる基である。）
を反応させて製造できる。
この方法によれば、副反応が生じやすい場合がある、ニトロ基の水素化や、保護されたアミノ基の脱保護等の工程が不要であることから、式（ｂ１）で表される芳香族アミン化合物の合成が容易である。 Further, the aromatic diamine compound represented by the formula (b1) includes a compound represented by the following formula (b1-IIIb), a compound represented by the following formula (b1-IIIc), and a compound represented by the following formula (b1-Ia ) and an aromatic compound represented by:

(Formula (b1-Ia), Formula (b1-IIIb), and Formula (b1-IIIc), and R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , Ring Y ¹ , Ring Y ² , ring Y ³ , ring Y ⁴ , R, and n1 to n6 are the same as in formula (b1) and group X ^1a reacts with group X ^1b to form group X ¹ in formula (b1) is the basis for
The group X ^2a is a group which, upon reaction with the group X ^2b , forms the group X ² in formula (b1). )
can be produced by reacting
According to this method, there is no need for steps such as hydrogenation of the nitro group and deprotection of the protected amino group, which may easily cause side reactions. Synthesis of amine compounds is easy.

As for the combination of the group X ^1a and the group X ^1b and the combination of the group X ^2a and the group X ^2b , the aromatic compound represented by the formula (b1-Ia) and the aromatic compound represented by the formula (b1-Ib) and the compound represented by formula (b1-Ic) are as described above.
However, when the aromatic compound represented by the formula (a1-Ia), the compound represented by the formula (a1-IIIb) and the compound represented by the formula (a1-IIIc) are reacted, the group X ^1a and the group X ^1b , and the combination of the group X ^2a and the group X ^2b ,
a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and an amino group (--NH ₂ );
a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a hydroxyl group, or a combination of a carboxy group (--COOH) or a halocarbonyl group (--COHal) and a carbamoyl group (--CO--NH ₂ ) is limited to

The diamine component (B1), together with the aromatic diamine compound represented by formula (b1), other diamine compounds that do not correspond to the aromatic diamine compounds represented by formula (b1), as long as the object of the present invention is not hindered. may contain
Preferred examples of such other diamine compounds include diamine compounds represented by the following formula (2). Another diamine compound may be used individually by 1 type, and may be used in combination of 2 or more type.
H ₂ N—R ^b10 —NH ₂ (2)
(In the formula, R ^b10 is an aryl group having 6 to 40 carbon atoms. However, the diamine compound represented by formula (2) does not correspond to the aromatic diamine compound represented by formula (b1). .)

The aryl group that can be selected as R ^b10 in formula (2) is an aryl group having 6 to 40 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 12 to 20 carbon atoms.
When the number of carbon atoms in the aryl group exceeds 40, the heat resistance of the obtained polyimide resin tends to be lowered. If the number of carbon atoms in the aryl group is less than 6, the resulting polyimide resin tends to be less soluble in solvents.

R ^b10 in formula (2) is represented by the following formulas (3) to (9) from the viewpoint of the balance between the high refractive index of the resulting polyimide resin, heat resistance, and solubility in a solvent. preferably at least one of the groups.

（式（５）～（７）、及び式（９）中、Ｒ^１１は、水素原子、臭素原子、フッ素原子、水酸基、メチル基、エチル基、及びトリフルオロメチル基よりなる群から選択される１種を示す。
式（６）中、Ｑ^１は、－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－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－、－ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－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－Ｓ－Ｃ_６Ｈ_４－Ｏ－、－Ｏ－Ｃ_６Ｈ_４－ＳＯ－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－、－Ｏ－Ｃ_６Ｈ_４－Ｏ－、－Ｏ－Ｃ_１０Ｈ_６－Ｏ－、及び－Ｏ－Ｃ_６Ｂｒ_２Ｈ_２－Ｃ（ＣＨ_３）_２－Ｃ_６Ｂｒ_２Ｈ_２－Ｏ－、下記式（１０）：

で表される基よりなる群から選択される１種を示す。
式（７）中、Ａは、－Ｓ－、－ＳＯ－、又は－ＳＯ_２－を示す。
式（１０）中、Ｑ^２は、単結合、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－、又は－ＣＨ_２－を示す。
－Ｃ_６Ｈ_４－はベンゼンジイル基（フェニレン基）を示し、ベンゼン－１，４－ジイル基（ｐ－フェニレン基）が好ましい。
－Ｃ_１０Ｈ_６－はナフタレンジイル基を示し、ナフタレン－１，６－ジイル基、ナフタレン－１，５－ジイル基、及びナフタレン－１，４－ジイル基が好ましい。
－Ｃ_６Ｂｒ_２Ｈ_２－は、ジブロモフェニレン基を示し、３，５－ジブロモベンゼン－１，４－ジイル基が好ましい。）

(In formulas (5) to (7) and formula (9), R ¹¹ is selected from the group consisting of a hydrogen atom, a bromine atom, a fluorine atom, a hydroxyl group, a methyl group, an ethyl group, and a trifluoromethyl group. 1 type is shown.
In formula (6), Q ¹ is -C ₆ H ₄ -, -CONH-C ₆ H ₄ -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -OC ₆ H 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-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -CH=CH-, -C≡C-, -O -C6H4-C( _CH3 ) _{2 - C6H4 -} O-, _{-OC6H4 -} C( _CF3 ) _{2 - C6H4 -} O-, _{-OC6H 4} -SC ₆ H ₄ -O-, -OC ₆ H ₄ -SO-C ₆ H ₄ -O-, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-,- C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -, -O-C ₆ H ₄ -C ₆ H ₄ -O-, -O-C ₆ H ₄ -O-, -O- C ₁₀ H ₆ —O— and —O—C ₆ Br ₂ H ₂ —C(CH ₃ ) ₂ —C ₆ Br ₂ H ₂ —O—, the following formula (10):

One selected from the group consisting of groups represented by
In formula (7), A represents -S-, -SO- or -SO ₂ -.
In formula (10), Q ² represents a single bond, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, or -CH ₂ -.
—C ₆ H ₄ — represents a benzenediyl group (phenylene group), preferably a benzene-1,4-diyl group (p-phenylene group).
—C ₁₀ H ₆ — represents a naphthalene diyl group, preferably a naphthalene-1,6-diyl group, a naphthalene-1,5-diyl group and a naphthalene-1,4-diyl group.
—C ₆ Br ₂ H ₂ — represents a dibromophenylene group, preferably a 3,5-dibromobenzene-1,4-diyl group. )

R ¹¹ in formulas (5) to (7) and formula (9) is more preferably a hydrogen atom, a bromine atom, a fluorine atom, a methyl group or an ethyl group, from the viewpoint of the heat resistance of the resulting polyimide resin. Hydrogen atoms are particularly preferred.

Q ¹ in formula (6) is -O-C ₆ H ₄ -O-, -O-, -C( CH ₃ ) ₂ -, -CH ₂ -, or -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -CONH- is preferred, and -OC ₆ H ₄ - O- or -O- is particularly preferred.
In addition, from the point of easily obtaining a polyimide resin with a high refractive index, Q ¹ in the formula (6) may be -S-, -SO-, -SO ₂ -, -OC ₆ H ₄ -SC ₆ H ₄ -O-, -O-C ₆ H ₄ -SO-C ₆ H ₄ -O-, or -O-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O- are preferred.

Among the groups represented by the formulas (3) to (9), the refractive index of the resulting polyamide resin and the other properties other than the refractive index are easily balanced, so the groups represented by the formulas (5) to (9) Groups represented by formulas (6) to (9) are particularly preferred.

Suitable specific examples of the diamine compound represented by formula (2) include:
4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, bis{4-(4-aminophenoxy)phenyl}sulfide, bis{4-(3-aminophenoxy)phenyl}sulfide, 3,7- Diaminosulfides such as diamino-2,8-dimethyldibenzothiophene and 2,2-bis(3-amino-4-hydroxyphenyl)sulfide;
4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfoxide, bis{4-(4-aminophenoxy)phenyl}sulfoxide, bis{4-(3-aminophenoxy)phenyl}sulfoxide, 3,7- Diaminosulfoxides such as diamino-2,8-dimethyldibenzothiophene-5-oxide and 2,2-bis(3-amino-4-hydroxyphenyl)sulfoxide;
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, bis{4-(4-aminophenoxy)phenyl}sulfone, bis{4-(3-aminophenoxy)phenyl}sulfone, 2,2- Diaminosulfones such as bis(3-amino-4-hydroxyphenyl)sulfone and 3,7-diamino-2,8-dimethyldibenzothiophene-5,5-dioxide;
Bromo-substituted diamines such as 2,2-bis{4-(4-aminophenoxy)-3,5-dibromophenyl}propane;
carbon-carbon double bond-containing diamines such as 4,4′-diaminostilbene, 3,3′-diaminostilbene, and 3,4′-diaminostilbene;
4,4'-diaminodiphenylacetylene, 3.3'-diaminodiphenylacetylene, 3,4'-diaminodiphenylacetylene, 1,3-bis(3-aminophenoxy)-5-(2-phenylethynyl)benzene, 1 , 3-bis(4-aminophenoxy)-5-(2-phenylethynyl)benzene, and carbon-carbon triple bond-containing diamines such as 2,4-diamino-4′-phenylethynyldiphenyl ether;
3,3′-diphenyl-4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis{3-phenyl-4-(4-aminophenoxy)phenyl}propane, 1,6-bis(4 -aminophenoxy)naphthalene, and polycyclic aromatic diamines such as 1,5-bis(4-aminophenoxy)naphthalene and 1,4-bis(4-aminophenoxy)naphthalene.

The amount of the aromatic diamine compound represented by formula (b1) in the diamine component (B1) is not particularly limited as long as the object of the present invention is not impaired. The ratio of the mass of the aromatic diamine compound represented by the formula (b1) to the mass of the diamine component (B1) is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. Preferably, 95% by mass or more is particularly preferable. The diamine component (B1) may contain only the aromatic diamine compound represented by formula (b1).

The content of the diamine component (B1) in the monomer component is not particularly limited as long as the object of the present invention is not impaired.
The content of the diamine component (B1) in the monomer component is such that the amount of the tetracarboxylic dianhydride component (B2) described later is 0.2 mol or more and 2 mol or less per 1 mol of the diamine component (B1). is preferred, and an amount of 0.3 mol or more and 1.2 mol or less is more preferred.

(Tetracarboxylic dianhydride component (B2))
The tetracarboxylic dianhydride component (B2) is not particularly limited as long as it is a tetracarboxylic dianhydride conventionally used in the production of polyimide resins. The tetracarboxylic dianhydride component (B2) may contain a combination of two or more tetracarboxylic dianhydrides.

（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。） From the viewpoint of achieving both excellent transparency and excellent mechanical properties of the resulting polyimide resin, the tetracarboxylic dianhydride component (B2) contains a tetracarboxylic dianhydride containing an alicyclic group. Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic represented by the following formula (b2) More preferably, it contains dianhydrides.

(in 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 Rb1 in formula ( ^b2 ) is an alkyl group having 1 or more and 10 or less carbon atoms. When the number of carbon atoms in the alkyl group exceeds 10, the heat resistance of the obtained polyimide resin tends to decrease. When R ^b1 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a polyimide resin having excellent heat resistance. 1 or more and 3 or less are particularly preferable.
When R ^b1 is an alkyl group, the alkyl group may be linear or branched.

R ^b1 in the formula (b2) is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms independently from the viewpoint that the resulting polyimide resin has excellent heat resistance. Since the tetracarboxylic dianhydride represented by the formula (b2) is easily available and purified, R ^b1 in the formula (b2) is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or isopropyl is more preferred, and a hydrogen atom or a methyl group is particularly preferred.
A plurality of R ^b1 in the formula (b2) are preferably the same group because the tetracarboxylic dianhydride represented by the formula (b2) 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 exceeds 12, it is difficult to purify the tetracarboxylic dianhydride represented by formula (b2).
The upper limit of m is preferably 5, more preferably 3, from the viewpoint of facilitating purification of the tetracarboxylic dianhydride represented by formula (b2).
From the viewpoint of chemical stability of the tetracarboxylic dianhydride represented by the formula (b2), the lower limit of m is preferably 1, more preferably 2.
As for m in Formula (b1), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^b2 and R ^b3 in 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 hydrogen atoms, or have 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 or more and 5 or less, still more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less), and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by formula (b2) include 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″-tetra carboxylic acid dianhydride”), methylnorbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-(methylnorbornane)-5,5″,6,6″-tetracarboxylic acid 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 dianhydride, norbornane-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-α-cycloundecanone-α'-spiro-2''- norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α′-spiro-2″-norbornane-5,5″, 6,6''-tetracarboxylic dianhydride, norborna n-2-spiro-α-cyclotridecanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α- Cyclotetradecanone-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''-tetracarboxylic 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（Ｂ２－１）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（Ｂ２－２）のうちの少なくとも１種を含有し、且つ、化合物（Ｂ２－１）及び化合物（Ｂ２－２）の総量が３０モル％以上であるものが好ましい。 Further, the tetracarboxylic dianhydride represented by the formula (b2) is represented by the following formula (b2-1) from the viewpoint of adjustment of film properties, thermophysical properties, mechanical properties, optical properties, and electrical properties:

(In formula (b2-1), R ^b1 , R ^b2 , R ^b3 and m are synonymous with R ^b1 , R ^b2 , R ^b3 and m in formula (b2).)
A compound represented by (B2-1) and the following formula (b2-2):

(In formula (b2-2), R ^b1 , R ^b2 , R ^b3 and m are synonymous with R ^b1 , R ^b2 , R ^b3 and m in formula (b2).)
It preferably contains at least one compound (B2-2) represented by and the total amount of compound (B2-1) and compound (B2-2) is 30 mol % or more.

In the compound (B2-1) represented by the formula (b2-1), two norbornane groups are in a trans configuration and the carbonyl group of the cycloalkanone is in an endo configuration with respect to each of the two norbornane groups. It is an isomer of the tetracarboxylic dianhydride represented by the formula (b2).
In the compound (B2-2) represented by the formula (b2-2), two norbornane groups are cis-configured and the carbonyl group of the cycloalkanone is endo-configured with respect to each of the two norbornane groups. It is an isomer of the tetracarboxylic dianhydride represented by the formula (b2).
In addition, the method for producing a tetracarboxylic dianhydride containing such isomers in the above ratio is not particularly limited, and a known method can be appropriately employed. method, etc. may be adopted as appropriate.

The tetracarboxylic dianhydride component (B2) may contain a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by formula (b2).

Suitable examples of other tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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-dimethanonaphthalene-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, such as aliphatic or alicyclic tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3′,4 ,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3 ,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride product, 3,3′,4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis(3,4-di Carboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride , 3,3′,4,4′-perfluoroisopropylidene diphthalic 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) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 aromatic tetracarboxylic acid dianhydrides such as '-diphenylmethane dianhydride;
When using an aromatic tetracarboxylic dianhydride, the formed film may be colored. In this case, it is preferable to appropriately change the amount used, taking into consideration the degree of coloring of the film to be formed.

The ratio of the amount of the tetracarboxylic dianhydride represented by the formula (b2) to the total amount of the tetracarboxylic dianhydride component (B2) is typically 50% by mass or more, and 70% by mass or more is It is preferably 90% by mass or more, and particularly preferably 100% by mass.
The quantitative relationship between the tetracarboxylic dianhydride component (B2) and the diamine component (B1) is as described above.

（式（ｂ３）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、環Ｙ^３、環Ｙ^４、Ｒ、ｎ１、ｎ２、ｎ３、ｎ４、ｎ５、及びｎ６は式（ｂ１）と同様であり、Ｚ^１は４価の有機基である。）
で表される構成単位を有するポリアミド酸を含む。 [Polyamic acid (B3)]
When the resin precursor component (B) contains a polyamic acid (B3), the polyamic acid (B3) has the following formula (b3):

(In formula (b3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R, n1 , n2, n3, n4, n5, and n6 are the same as in formula (b1), and Z1 is ^a tetravalent organic group.)
Contains a polyamic acid having a structural unit represented by.

The structural unit represented by the formula (b3), like the aromatic diamine compound represented by the formula (b1), has the structure of the structural unit represented by the formula (b3), whereby the resin precursor component A polyimide resin formed using (B) exhibits a high refractive index and a low retardation.

（式（ｂ２－１）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、及びｍは、式（ｂ２）と同様である。）
で表される４価の有機基が好ましい。 Z ¹ in formula (b3) is not particularly limited as long as it is a tetravalent organic group as long as it does not impair the object of the present invention.
Z ¹ is typically a tetravalent residue obtained by removing two acid anhydride groups from the compounds exemplified for the tetracarboxylic dianhydride component (B2) described above.
Z ¹ is preferably a tetravalent organic group containing an alicyclic group, since it is easy to obtain a highly transparent polyimide resin with little coloration, and the tetracarboxylic dianhydride represented by the formula (b2). Tetravalent residues excluding anhydride groups are preferred.
That is, as Z ¹ , the following formula (b2-1)

(In formula (b2-1), R ^b1 , R ^b2 , R ^b3 and m are the same as in formula (b2).)
A tetravalent organic group represented by is preferred.

（式（ｂ３－１）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、Ｘ^１、Ｘ^２、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数であり、Ｚ^１は４価の有機基である。）
で表される構成単位が好ましい。式（ｂ３－１）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the structural unit represented by formula (b3), the following formula (b3-1):

(In formula (b3-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 is the same as in formula (b1), n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z1 is ^a tetravalent organic group.)
Structural units represented by are preferred. In formula (b3-1), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ３－２）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数であり、Ｚ^１は４価の有機基である。）
で表される構成単位が好ましい。式（ｂ３－２）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 Examples of structural units represented by formula (b3-1) include the following formula (b3-2):

(In formula (b3-2), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z ¹ is a tetravalent organic group.)
Structural units represented by are preferred. In formula (b3-2), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ３－３）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数であり、Ｚ^１は４価の有機基である。）
で表される構成単位が好ましい。式（ｂ３－３）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the structural unit represented by formula (b3-2), the following formula (b3-3):

(In formula (b3-3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z ¹ is a tetravalent organic group.)
Structural units represented by are preferred. In formula (b3-3), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ３－４）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数であり、Ｚ^１は４価の有機基である。）
で表される構成単位も好ましい。式（ｂ３－４）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 As the structural unit represented by formula (b3-2), the following formula (b3-4):

(In formula (b3-4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z ¹ is a tetravalent organic group.)
Structural units represented by are also preferred. In formula (b3-4), each of n7 and n8 is preferably 0 or 1, more preferably 0.

（式（ｂ３－５）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、環Ｙ^１、環Ｙ^２、Ｒ、ｎ１、ｎ２、ｎ５、及びｎ６は式（ｂ１）と同様であり、ｎ７及びｎ８は、それぞれ独立に０以上４以下の整数であり、Ｚ^１は４価の有機基である。）
で表される構成単位が好ましい。式（ｂ３－５）において、ｎ７及びｎ８としては、それぞれ、０又は１が好ましく、０がより好ましい。 The structural unit represented by formula (b3-4) includes the following formula (b3-5):

(In formula (b3-5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are represented by formula (b1) and n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z ¹ is a tetravalent organic group.)
Structural units represented by are preferred. In formula (b3-5), each of n7 and n8 is preferably 0 or 1, more preferably 0.

The method for producing polyamic acid (B3) is not particularly limited. Polyamic acid (B3) is typically produced by reacting the aforementioned diamine component (B1) with tetracarboxylic dianhydride component (B2).
The polyamic acid preferably contains a structural unit derived from the tetracarboxylic dianhydride represented by the above formula (b2) and the diamine component (B1), and the above compound (B2-1) and the diamine component. The structural unit derived from (B1) and the structural unit derived from the aforementioned compound (B2-2) and the diamine component (B1) are combined into compound (B2-1) and compound (B2-2). It is more preferable to contain them in a similar molar ratio.

The ratio of the diamine component (B1) and the tetracarboxylic dianhydride component (B2) when synthesizing the polyamic acid is the ratio of the diamine component (B1) and the tetracarboxylic dianhydride component (B2) described for the monomer component. Similar to ratio.

The reaction of the diamine component (B1) and the tetracarboxylic dianhydride component (B2) is usually carried out in an organic solvent. The organic solvent used for the reaction of the diamine component (B1) and the tetracarboxylic dianhydride component (B2) can dissolve the diamine component (B1) and the tetracarboxylic dianhydride component (B2), The organic solvent is not particularly limited as long as it does not react with the diamine component (B1) and the tetracarboxylic dianhydride component (B2). An organic solvent can be used individually or in mixture of 2 or more types.

As the organic solvent used for the reaction of the diamine component (B1) and the tetracarboxylic dianhydride component (B2), for example, the solvent (S) described later can be preferably used.
Among such organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N Nitrogen-containing polar solvents such as -dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.

When synthesizing the polyamic acid (B3), the organic solvent is, for example, the total weight of the diamine component (B1) and the tetracarboxylic dianhydride component (B2) is 0.1% by mass or more and 50% by mass in the reaction solution. Hereinafter, it is preferably used in an amount of 10% by mass or more and 30% by mass or less.

When reacting the diamine component (B1) and the tetracarboxylic dianhydride component (B2), a basic compound is further added to the organic solvent from the viewpoint of improving the reaction rate and obtaining polyamic acid with a high degree of polymerization. may
Such basic compounds are not particularly limited, and examples thereof include triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo[5.4.0]-undecene-7, pyridine, isoquinoline, α-picoline and the like. mentioned.
The amount of such a basic compound to be used is preferably 0.001 to 10 equivalents, more preferably 0.01 to 0.1 equivalents, relative to 1 equivalent of the tetracarboxylic dianhydride component.

The reaction temperature for reacting the diamine component (B1) and the tetracarboxylic dianhydride component (B2) is not particularly limited as long as the reaction proceeds well. The reaction temperature is preferably 15°C or higher and 30°C or lower. The reaction is preferably carried out under an inert gas atmosphere. Although the reaction time is not particularly limited, it is preferably, for example, 10 hours or more and 48 hours or less.

As described above, the resin precursor component (B) is a monomer composed of a diamine component (B1) containing an aromatic diamine compound represented by the formula (b1) and a tetracarboxylic dianhydride component (B2). component and/or a polyamic acid (B3) having a structural unit represented by the above formula (b3).

The resin precursor component (B) is a monomer component consisting of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-1) and a tetracarboxylic dianhydride component (B2), and/ Alternatively, it preferably contains a polyamic acid (B3) having a structural unit represented by the above formula (b3-1).

The resin precursor component (B) is a monomer component consisting of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-2) and a tetracarboxylic dianhydride component (B2), and/ Alternatively, it preferably contains a polyamic acid (B3) having a structural unit represented by the above formula (b3-2).

The resin precursor component (B) is a monomer component consisting of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-3) and a tetracarboxylic dianhydride component (B2), and/ Alternatively, it preferably contains a polyamic acid (B3) having a structural unit represented by the above formula (b3-3).

The resin precursor component (B) is a monomer component consisting of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-4) and a tetracarboxylic dianhydride component (B2), and/ Alternatively, it preferably contains a polyamic acid (B3) having a structural unit represented by the above formula (b3-4).

The resin precursor component (B) is a monomer component consisting of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-5) and a tetracarboxylic dianhydride component (B2), and/ Alternatively, it preferably contains a polyamic acid (B3) having a structural unit represented by the above formula (b3-5).

<Solvent (S)>
A polyimide precursor composition contains a solvent (S). The polyimide precursor composition may be a paste containing solids or a solution as long as it can form a film. The polyimide precursor composition is preferably a solution in terms of easy formation of a homogeneous and smooth film. A solvent can be used individually or in mixture of 2 or more types.

The type of solvent (S) is not particularly limited as long as the object of the present invention is not impaired. 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 nitrogen-containing polar solvents such as (TMU); lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; hexamethyl Phosphoric triamide; Acetonitrile; Fatty acid esters such as ethyl lactate and butyl lactate; , cyclohexanone and other ketones; and benzene, toluene, xylene and other aromatic solvents.

（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。） The solvent preferably also contains a compound represented by the following formula (S1).

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

Among the compounds represented by formula (S1), specific examples in which R 1 ^S3 is a group represented by 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 and N,N-diethyl-2-hydroxy-2-methylpropionamide.

Among the compounds represented by formula (S1), specific examples in which R ^S3 is a group represented by formula (S1-2) include N,N,N',N'-tetramethylurea, N , N,N',N'-tetraethylurea and the like.

Among examples of the compound represented by formula (S1), particularly preferred are N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea. The boiling point of N,N,2-trimethylpropionamide under atmospheric pressure is 175°C, and the boiling point of N,N,N',N'-tetramethylurea under atmospheric pressure is 177°C. Thus, N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea have relatively low boiling points among solvents capable of dissolving the monomer component and 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. When the polyimide film is heated during the formation of the polyimide film, the solvent is less likely to remain in the resulting polyimide film, and the tensile elongation of the obtained polyimide film is less likely to be lowered.

Furthermore, N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are SVHC ( It is also useful in that it is a substance with low toxicity, as it is not designated as a Substance of Very High Concern.

The content of the compound represented by 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.

The content of the solvent (S) in the polyimide precursor composition is not particularly limited as long as the object of the present invention is not impaired. The content of the solvent (S) in the polyimide precursor composition is appropriately adjusted according to the solid content in the polyimide precursor composition. The solid content in the polyimide precursor composition is, for example, 1% by mass or more and 80% by mass or less, preferably 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 60% by mass or less.

<Other ingredients>
The polyimide precursor composition may contain other components in addition to the components described above, 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.
The polyimide precursor composition may also contain one or more silicon-containing compounds selected from the group consisting of silicon-containing resins, silicon-containing resin precursors, and silane coupling agents. Examples of silicon-containing resins include siloxane resins and polysilanes. Silicon-containing resin precursors include, for example, siloxane resins and silane compounds that are raw material monomers for polysilane.
When the polyimide precursor composition contains a silicon-containing compound, the adhesion between the polyimide precursor composition or the polyimide resin formed using the polyimide precursor composition and the object to be coated is good. This effect is remarkable when the material of the object to be coated is glass. Since it can be brought into close contact with the object to be coated, the process margin for polyimide film formation is improved. Further, when the polyimide precursor composition contains a silicon-containing compound, the exposure dose of the UV laser is increased in order to improve the peelability of the polyimide film from the substrate or support during the peeling step using a UV laser, which will be described later. Even in the case where the coating is applied, white turbidity at the time of peeling is likely to be suppressed.

<Preparation of polyimide precursor composition>
The method for preparing the polyimide precursor composition is not particularly limited, for example, at least one selected from the group consisting of the various monomer components described above as the resin precursor component (B), and polyamic acid (B3), It can be prepared by blending the solvent (S) and, if necessary, the other components described above.

Both the monomer component and the polyamic acid (B3) may be blended as the resin precursor component (B). It is usually sufficient to mix only the monomer component or only the polyamic acid (B3).
The polyimide precursor composition also includes a composition obtained by blending a solvent (S) with a monomer component as a resin precursor component (B) and then generating a polyamic acid.
In the preparation of the polyimide precursor composition, the order of blending (adding) each component is not particularly limited.

（式（ｂ４）中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、及びＲ^３ｂは、それぞれ独立に、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｃで表される基、又は－Ｎ（Ｒ^４ｄ）_２で表される基であり、１価の炭化水素基、－ＯＲ^４ａで表される基、－ＳＲ^４ｂで表される基、アシル基、アルコキシカルボニル基、－ＮＨＲ^４ｃで表される基、及び－Ｎ（Ｒ^４ｄ）_２で表される基は、－ＯＲ^４ｅで表される基、－ＳＲ^４ｆで表される基、アシル基、アルコキシカルボニル基、ハロゲン原子、シアノ基、－ＮＨＲ^４ｇで表される基、及び－Ｎ（Ｒ^４ｈ）_２で表される基からなる群より選択される１以上の基で置換されていてもよく、
Ｒ^４ａ～Ｒ^４ｇは、それぞれ独立に１価の炭化水素基であり、
Ｘ^１、及びＸ^２は、それぞれ独立に、－ＣＯ－ＮＨ－、－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＯ－ＮＨ－ＣＯ－、－Ｏ－ＣＯ－ＮＨ－、又は－ＣＯ－ＮＨ－ＣＯ－ＮＨ－であり、
環Ｙ^１、環Ｙ^２、環Ｙ^３及び環Ｙ^４は、それぞれ独立に芳香族炭化水素環であり、
Ｒは、単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、－Ｏ－で表される基、－ＮＨ－で表される基、又は－Ｓ－で表される基であり、
ｎ１及びｎ２は、それぞれ独立に０以上４以下の整数であり、
ｎ３及びｎ４は、それぞれ独立に０以上５以下の整数であり、
ｎ５及びｎ６は、それぞれ独立に０以上４以下の整数であり、
Ｚ^１は、４価の有機基である。）
で表される構成単位を有するポリイミド樹脂である。
上記式（４）中の、各略号は、それぞれポリイミド前駆体組成物に関して樹脂前駆体成分（Ｂ）について説明した通りである。
ポリイミド樹脂は上記式（Ｂ４）で表される構成単位を備えることにより高い屈折率と低リタデーションを示す。 ≪Polyimide Resin≫
A polyimide resin is obtained by condensation and imidization, or imidization of the resin precursor component (B) contained in the polyimide precursor composition described above.
The polyimide resin has the following formula (b4):

(In formula (b4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are A group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4g , and a group represented by -N(R ^4h ) ₂ optionally substituted with one or more groups selected from the group consisting of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or - CO-NH-CO-NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 to 4,
Z ¹ is a tetravalent organic group. )
is a polyimide resin having a structural unit represented by
Each abbreviation in the above formula (4) is as described for the resin precursor component (B) with respect to the polyimide precursor composition.
The polyimide resin exhibits a high refractive index and a low retardation due to the constitutional unit represented by the above formula (B4).

<<Method for producing polyimide film>>
The method for producing a polyimide film is
Forming a coating film made of the polyimide precursor composition described above;
Ring-closing polyamic acid derived from the resin precursor component (B) in the coating film by heating the coating film;
including.
Hereinafter, the formation of the coating film is also referred to as the “formation step”, and the ring closure of the polyamic acid is also referred to as the “ring closure step”. Each step will be described below.

<Formation process>
In the forming step, the polyimide precursor composition described above is applied to the surface of the object to be coated to form a coating film made of the polyimide precursor composition. Examples of coating methods include dipping, spraying, bar coating, roll coating, spin coating, curtain coating, and die coating. The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is, for example, 0.1 μm or more and 1000 μm or less, preferably 2 μm or more and 100 μm or less, and more preferably 3 μm or more and 50 μm or less. 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.

After forming the coating film, the coating film may be heated for the purpose of removing the solvent (S) in the coating film before proceeding to the ring-closing step. The heating temperature and heating time are not particularly limited as long as the components contained in the polyimide precursor composition are not thermally degraded or thermally decomposed. When the boiling point of the solvent (S) in the coating film is high, the coating film may be heated under reduced pressure.

<Ring closure step>
In the ring-closing step, the polyamic acid derived from the resin precursor component (B) in the coating film is ring-closed by heating the coating film formed in the forming step. The ring closure converts the polyamic acid into a polyimide resin. As a result, a film containing polyimide resin is formed.

When the coating film is heated, the heating temperature is set to, for example, 100° C. or higher and 500° C. or lower, preferably 120° C. or higher and 350° C. or lower, more preferably 150° C. or higher and 350° C. or lower. By heating the resin precursor component (B) at a temperature within such a range, it is possible to form a polyimide film while suppressing thermal deterioration and thermal decomposition of the resin precursor component (B) and the resulting polyimide resin. can.

In addition, when the resin precursor component (B) is heated at a high temperature, a large amount of energy is consumed and the aging of the processing equipment at high temperatures may be accelerated. is preferably performed at a lower temperature (sometimes referred to as "low temperature bake"). Specifically, the upper limit of the temperature for heating the resin precursor component (B) 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, still more preferably 150° C. °C or less. Even in the case of heating at such a relatively low temperature, in the present invention, a polyimide resin can be sufficiently produced by heating for 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 It can be 3 hours, more preferably 2.5 hours, and this heating time can also be applied to heating at, for example, 130°C or higher and 150°C or lower, typically 140°C.

The low-temperature baking can promote the increase in the molecular weight of the polyamic acid, preferably without widening the molecular weight distribution too much. Increasing the molecular weight of the polyamic acid by low-temperature baking is suitable, particularly in the case of blending a monomer component as the resin precursor component (B), in terms of increasing the molecular weight of the formed polyamic acid.
When the polyimide precursor composition contains the imidazole compound (A1), the imidazole compound (A1) usually remains in the coating film after low-temperature baking. With respect to polyamic acid, the imidazole compound (A1) increases the molecular weight of the polyamic acid, and the obtained polyimide film can have excellent tensile strength and elongation at break.

Thus, when the polyimide precursor composition contains the imidazole compound (A1), even by heating at a relatively low temperature, tensile strength than conventional polyimide films, and excellent elongation at break easily obtain a polyimide film. . The imidazole compound (A1) is believed to act as a catalyst. The obtained polyimide film is considered to have excellent mechanical properties due to its excellent tensile elongation.

As the heating of the coating film, after performing low temperature baking, stepwise heating (sometimes referred to as "high temperature baking") is performed at a higher temperature than the heating temperature in low temperature baking (also referred to as "step baking". ) may be performed.
In high-temperature baking, the upper limit of the heating temperature is, for example, 500° C. or lower, preferably 450° C. or lower, more preferably 420° C. or lower, and even more preferably 400° C. or lower, and the lower limit of the heating temperature is, for example, 220° C. or higher. , preferably 250° C. or higher, more preferably 300° C. or higher, still more preferably 350° C. or higher, and even more preferably 380° C. or higher.
The heating time in high-temperature baking depends on the composition, thickness, etc. of the coating film, but the lower limit may be, for example, 10 minutes or longer, preferably about 20 minutes or longer, and if necessary, 1 hour or longer. , For example, 4 hours, preferably 3 hours, more preferably 2.5 hours, and such a heating time is, for example, 390 ° C. or higher and 410 ° C. or lower, typically 400 ° C. be able to.

If staged heating is used, the low temperature bake may be omitted. In particular, when a monomer component is blended as the resin precursor component (B), a sufficiently high-molecular-weight polyimide resin can be obtained without low-temperature baking.

Conversion to a polyimide resin can be carried out to a sufficient degree to solve the problems of the present invention even by low-temperature baking. For example, it is also possible to substantially eliminate unclosed ring structures and substantially complete ring closure reactions However, some unclosed ring structures may remain after low-temperature baking. By performing high temperature baking, the ring closure reaction can be substantially completed.

<Peeling process>
When a glass substrate is used as an object to be coated or a support during the ring-closing step, a UV laser or the like may be used to peel off the polyimide film obtained using the polyimide precursor composition.

≪Polyimide film≫
As described above, a polyimide film is formed by curing a coating film composed of the above polyimide precursor composition. The polyimide film formed in this manner can also be rephrased as a polyimide film containing a polyimide resin having a structural unit represented by the above formula (b4).
Such a polyimide film exhibits a high refractive index and a low retardation due to the skeleton derived from the aromatic diamine represented by the above formula (b1). For this reason, such a polyimide film can be preferably applied to conventionally widely known optical devices having a high refractive index film.
Here, the optical device includes not only devices having a relatively large size such as a lighting device and a display device, but also minute elements such as a light emitting element, a photoelectric conversion element, and a lens element.

The refractive index of the polyimide film is preferably 1.61 or more, more preferably 1.63 or more, and particularly preferably 1.65 or more, as measured with light having a wavelength of 589 nm.

In addition to the high refractive index, the retardation is also low due to the skeleton derived from the aromatic diamine represented by the formula (b1). Therefore, the above polyimide film is suitably used as a film material for OLED lighting devices, liquid crystal displays, organic EL displays, and the like. As an example, by using the above-described polyimide film in an OLED lighting device, it is possible to manufacture a lighting device that has a simple structure, is lightweight, and can be made thin while increasing the light extraction efficiency.

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

[Synthesis Example 1: Synthesis of aromatic diamine compound (9,9′-bis(4-(4-aminobenzoylamino)phenyl)fluorene)]
To a solution of 4-aminobenzoic acid (2.74 g, 0.02 mol) in pyridine was added 2 mL of thionyl chloride in a four-necked flask equipped with a thermometer, dropping funnel, and stirrer. After adding thionyl chloride, the contents of the flask were stirred at room temperature for 3 hours to give 4-aminobenzoyl chloride. 9,9′-bis(4-aminophenyl)fluorene (3.48 g, 0.01 mol) dissolved in N-methyl-2-pyrrolidone (NMP) was added to the obtained 4-aminobenzoyl chloride, and the mixture was stirred for 5 hours. Stirred. The obtained reaction solution was gradually poured into ice water of 0 to 5° C. which was stirred at a constant rate, and then solid-liquid separation was performed. In order to remove unreacted 4-aminobenzoic acid, the separated wet body was washed four times with a sodium hydrogen carbonate aqueous solution having a concentration of 10% by mass. The wet product was then washed with anhydrous methanol and dried at 80° C. to obtain 9,9′-bis(4-(4-aminobenzoylamino)phenyl)fluorene with a yield of 58%.
¹ H-NMR measurement results of 9,9′-bis(4-(4-aminobenzoylamino)phenyl)fluorene are as follows.
¹ H-NMR (400 MHz, DMSO-d6) δ = 9.72 (2H, s), 7.94 (2H, d), 7.70 (4H, d), 7.65 (4H, d), 7 .3-7.5 (6H, m)

[Example 1]
<Preparation of tetracarboxylic dianhydride>
According to the methods described in Synthesis Example 1, Example 1 and Example 2 of WO 2011/099518, a tetracarboxylic dianhydride (norbornane-2-spiro-α-cyclopentanone -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 to dry it sufficiently. Next, the atmospheric gas in the three-necked flask was replaced with nitrogen to create a nitrogen atmosphere in the three-necked flask. After adding 0.5280 g (0.90 mmol) of the aromatic diamine obtained in Synthesis Example 1 into a three-necked flask, 3.50 g of N,N,N',N'-tetramethylurea (TMU) was added. The contents of the three-necked flask were stirred to obtain a liquid in which the aromatic diamine was dispersed in TMU.
Next, 0.3459 g (0.90 mmol) of the tetracarboxylic dianhydride of the above formula is added to the three-necked flask, and the contents of the flask are stirred at room temperature (25° C.) for 24 hours under a nitrogen atmosphere to react. I got the liquid. In this manner, a reaction liquid containing 20% by mass of polyamic acid (TMU solvent: 80% by mass) was formed.

<Step of adding imidazole compound>
An imidazole compound (0.262 g, 6.0 parts by mass with respect to 100 parts by mass of the reaction liquid) was added to the reaction solution obtained as described above under a nitrogen atmosphere. Then, the reaction solution was stirred at 25° C. for 24 hours to obtain a liquid polyimide precursor composition containing an imidazole compound and polyamic acid.

<Preparation of polyimide film>
The polyimide precursor composition obtained as described above is placed 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). A coating film was formed by spin coating so that the thickness of the coating film after heat curing was 10 μm. Then, the glass substrate with the coating film formed thereon was placed on a hot plate at 70° C. and allowed to stand still for 0.5 hour to evaporate and remove the solvent from the coating film.
After removing the solvent, the glass substrate with the coating film formed thereon was put into an inert oven in which nitrogen was flowing at a flow rate of 5 L/min. After standing for 0.5 hour under a nitrogen atmosphere in an inert oven at a temperature of 25° C., heating at a temperature of 80° C. for 0.5 hour, further heating at a temperature of 300° C. for 30 minutes, and heating to 360° C. C. (final heating temperature) for 30 minutes to cure the coating film to obtain polyimide-coated glass in which a thin film of polyimide (polyimide film) is coated on a glass substrate.

The resulting polyimide-coated glass was immersed in hot water at 90° C. to separate the polyimide film from the glass substrate to obtain a polyimide film (76 mm long, 52 mm wide, and 10 μm thick). .

In order to identify the molecular structure of the resin that is the material of the resulting polyimide film, an IR spectrometer (manufactured by JASCO Corporation, trade name: FT/IR-4100) was used to measure the IR spectrum of the polyimide film sample. did.
As a result of the measurement, it was found that C═O stretching vibration of imidecarbonyl was observed at 1704.4 cm ⁻¹ in the IR spectrum of the resin that was 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 polyimide resin.

[Comparative Example 1]
A transparent polyimide film (Neoplim (registered trademark) L-3430 (manufactured by Mitsubishi Gas Chemical Company, Inc.) with a thickness of 100 μm) was used as a sample.
The structure of the polyimide resin contained in the polyimide film of Comparative Example 1 does not include the structural unit represented by the above formula (b4).

[Comparative Example 2]
Example 1 except that 0.5280 g (0.90 mmol) of the aromatic diamine obtained in Synthesis Example 1 was changed to 0.2045 g (0.90 mmol: DABAN) of commercially available 4,4'-diaminobenzanilide. In the same manner as above, a polyimide precursor composition and a polyimide film were obtained.

For the polyimide films of Example 1 and Comparative Example 1, according to the following methods, thermal decomposition temperature, glass transition temperature, coefficient of thermal expansion, tensile strength, elongation at break, total light transmittance, haze (turbidity), yellowness (YI ), and the refractive index were evaluated. These evaluation results are shown in Table 1.

<Thermal decomposition temperature (Td5%: 5% weight loss temperature)>
For the 5% weight loss temperature, prepare 2 to 4 mg samples from the films obtained in each example and each comparative example, put them in an aluminum sample pan, and use a thermogravimetric analyzer (SII) as a measuring device.・ Using a product name "TG/DTA7200" manufactured by Nano Technology Co., Ltd.), set the scanning temperature from 30 ° C to 550 ° C in a nitrogen gas atmosphere, and heat at a temperature increase rate of 10 ° C / min. , was obtained by measuring the temperature at which the weight of the sample used decreased by 5%.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) value (unit: °C) of the resin constituting the film was measured as follows. That is, using a sample with a size of 20 mm in length and 5 mm in width cut from each polyimide film, and using a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku) as a measuring device, under a nitrogen atmosphere, tensile Mode (49 mN), temperature rise rate of 5 ° C./min to determine the TMA curve, by extrapolating the curves before and after the inflection point of the TMA curve due to the glass transition, polyimide The glass transition temperature (Tg) value (unit: °C) of the resin constituting the film was determined. Table 1 shows the results obtained.

<Measurement of coefficient of thermal expansion (CTE)>
The CTE (unit: ppm/K) of the film was determined as follows. That is, first, from each resin film, a measurement film having a length of 20 mm and a width of 5 mm was formed. Next, the obtained film for measurement was vacuum-dried (120° C., 1 hour) and then heat-treated at 200° C. for 1 hour in a nitrogen atmosphere to prepare a measurement sample (dried film). Next, using the obtained measurement sample (dried film), using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) as a measuring device, under a nitrogen atmosphere, tensile mode (49 mN), heating rate Adopt the condition of 5 ° C./min, measure the change in length of the sample at 50 ° C. to 200 ° C., and obtain the average value of the change in length per 1 ° C. in the temperature range of 100 ° C. to 200 ° C. It was measured by Table 1 shows the results obtained.

<Measurement of tensile strength and elongation at break>
The tensile strength (unit: MPa) and breaking elongation (unit: %) of the film were measured as follows. That is, first, each resin film is placed in an SD-type lever-type sample cutter (cutter (model SDL-200) manufactured by Dumbbell Co., Ltd.), a product name “Super Dumbbell Cutter (model: SDMK) manufactured by Dumbbell Co., Ltd. -1000-D, compliant with A22 standard of JIS K7139 (issued in 2009)”, the size of each resin film is total length: 75 mm, distance between tabs: 57 mm, length of parallel part: 30 mm, Shoulder radius: 30 mm, end width: 10 mm, central parallel part width: 5 mm, dumbbell-shaped test piece (JIS K7139 Type A22 (scale test piece) standard ) were prepared as measurement samples. Next, using an electromechanical universal material testing machine (manufactured by INSTRON, model number "5943"), the measurement sample was measured so that the width between the grips was 57 mm and the width of the gripped portion was 10 mm (entire width of the end). After placement, a tensile test was performed by pulling the measurement sample under the conditions of load cell: 1.0 kN, test speed: 5 mm/min, and values of tensile strength and elongation at break were obtained. In addition, such a test was made into the test based on JISK7162 (issued in 1994). In addition, the value (%) of the elongation at break is defined by the distance between the tabs of the sample (= the width between the grips: 57 mm), L0, the distance between the tabs of the sample until breaking (the width between the grips when broken : 57 mm + α), the following formula:
[Breaking elongation (%)] = {(L-L0) / L0} x 100
was calculated and obtained. Table 1 shows the results obtained.

<Measurement of total light transmittance, haze (turbidity) and yellowness index (YI)>
For the measurement of total light transmittance and haze (turbidity), a product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measurement device, and for the measurement of yellowness (YI), the measurement device was A trade name “spectral colorimeter SD6000” manufactured by Nippon Denshoku Industries Co., Ltd. was used. Incidentally, the total light transmittance is determined by performing a measurement in accordance with JIS K7361-1 (issued in 1997), the haze (turbidity) is measured in accordance with JIS K7136 (issued in 2000), the yellowness (YI ) was determined by performing measurements in accordance with ASTM E313-05 (published in 2005).

<Measurement of refractive index (589 nm)>
The refractive index of the films obtained in each example and each comparative example was measured at 589 nm using a refractive index measuring device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.).
was measured under a light source at 23°C.

Further, the polyimide film of Example 1 and the polyimide film of Comparative Example 2 were compared in terms of refractive index (589 nm), retardation (589 nm), and total light transmittance. Retardation (589 nm) was measured by the following method.

<Measurement of thickness direction retardation (Rth)>
The retardation (Rth) in the thickness direction is measured using the polyimide film (length: 76 mm, width: 52 mm) produced in each example and each comparative example as it is, and using the product name "AxoScan" manufactured by AXOMETRICS as a measuring device. , After inputting the value of the refractive index of each polyimide film (refractive index for light of 589 nm of the film obtained by the above refractive index measurement), temperature: 25 ° C., humidity: 40%, wavelength 589 nm After measuring the retardation in the thickness direction using the light of , using the measured value of the obtained retardation in the thickness direction (measured by automatic measurement of the measuring device), convert to the retardation value per 10 μm of film thickness. I asked for it. When the retardation was 200 nm or less, it was determined as ◯, and when it was more than 200 nm, it was determined as x.

According to Tables 1 and 2, the polyimide film containing the polyimide resin containing the structural unit represented by the above formula (b4) has a high refractive index, low retardation, high total light transmittance, and It can be seen that the mechanical properties and thermal properties are comparable to or superior to the commercial products.

Claims (19)

A polyimide precursor composition containing a resin precursor component (B) and a solvent (S), wherein the resin precursor component (B) comprises a diamine component (B1) and a tetracarboxylic dianhydride component ( B2) and / or polyamic acid (B3),
The diamine component (B1) has the following formula (b1):

(In the formula (b1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are One or more selected from the group consisting of a group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, and a group represented by -NHR ^4g may be substituted with a group of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or -CO-NH-CO- NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 or more and 4 or less. )
containing an aromatic diamine compound represented by
The polyamic acid (B3) is represented by the following formula (b3):

(In formula (b3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , ring Y ³ , ring Y ⁴ , R, n1 , n2, n3, n4, n5, and n6 are the same as in formula (b1) above, and Z1 is ^a tetravalent organic group.)
A polyimide precursor composition comprising a polyamic acid having a structural unit represented by The diamine component (B1) has the following formula (b1-1):

(In formula (b1-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 is the same as in formula (b1) above, and n7 and n8 are each independently an integer of 0 or more and 4 or less.)
containing an aromatic diamine compound represented by
The polyamic acid (B3) has the following formula (b3-1):

(In formula (b3-1), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , X ¹ , X ² , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 is the same as in formula (b1) above, n7 and n8 are each independently an integer of 0 or more and 4 or less, and Z1 is ^a tetravalent organic group.)
The polyimide precursor composition according to claim 1, comprising a polyamic acid having a constitutional unit represented by. The diamine component (B1) has the following formula (b1-2):

(In formula (b1-2), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), and n7 and n8 are each independently an integer of 0 to 4.)
containing an aromatic diamine compound represented by
The polyamic acid (B3) has the following formula (b3-2):

(In formula (b3-2), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), n7 and n8 are each independently an integer of 0 to 4, and Z ¹ is a tetravalent organic group.)
3. The polyimide precursor composition according to claim 2, comprising a polyamic acid having a constitutional unit represented by. The diamine component (B1) has the following formula (b1-3):

(In formula (b1-3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), and n7 and n8 are each independently an integer of 0 to 4.)
containing an aromatic diamine compound represented by
The polyamic acid (B3) has the following formula (b3-3):

(In formula (b3-3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), n7 and n8 are each independently an integer of 0 to 4, and Z ¹ is a tetravalent organic group.)
The polyimide precursor composition according to claim 3, comprising a polyamic acid having a constitutional unit represented by. The diamine component (B1) has the following formula (b1-4):

(In formula (b1-4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), and n7 and n8 are each independently an integer of 0 to 4.)
containing an aromatic diamine compound represented by
The polyamic acid (B3) has the following formula (b3-4):

(In formula (b3-4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), n7 and n8 are each independently an integer of 0 to 4, and Z ¹ is a tetravalent organic group.)
The polyimide precursor composition according to claim 3, comprising a polyamic acid having a constitutional unit represented by. The diamine component (B1) has the following formula (b1-5):

(In formula (b1-5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), and n7 and n8 are each independently an integer of 0 to 4.)
containing an aromatic diamine compound represented by
The polyamic acid (B3) has the following formula (b3-5):

(In formula (b3-5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , ring Y ¹ , ring Y ² , R, n1, n2, n5, and n6 are ), n7 and n8 are each independently an integer of 0 to 4, and Z ¹ is a tetravalent organic group.)
The polyimide precursor composition according to claim 4, comprising a polyamic acid having a constitutional unit represented by. The polyimide precursor composition according to any one of claims 1 to 6, wherein said ring Y ¹ and said ring Y ² are each a benzene ring, and said R is a single bond. Claim 1, wherein the tetracarboxylic dianhydride component (B2) comprises a tetracarboxylic dianhydride containing an alicyclic group, and Z ¹ is a tetravalent organic group containing an alicyclic group. 8. The polyimide precursor composition according to any one of items 1 to 7. The tetracarboxylic dianhydride component (B2) has the following formula (b2):

(in 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 acid dianhydrides represented by
The Z ¹ is represented by the following formula (b2-1)

(In formula (b2-1), R ^b1 , R ^b2 , R ^b3 and m are the same as in formula (b2).)
The polyimide precursor composition according to claim 8, which is a tetravalent organic group represented by. The following formula (b3):

(In formula (b3), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are One or more selected from the group consisting of a group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, and a group represented by -NHR ^4g may be substituted with a group of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or -CO-NH-CO- NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 to 4,
Z ¹ is a tetravalent organic group. )
Polyamic acid having a structural unit represented by. 11. The polyamic acid according to claim 10, wherein Z1 is ^a tetravalent organic group containing an alicyclic group. The Z ¹ is represented by the following formula (b2-1)

(In formula (b2-1), R ^b1 , R ^b2 , and R ^b3 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. and m is an integer from 0 to 12. )
Polyamic acid according to claim 11, which is a tetravalent organic group represented by The following formula (b4):

(In formula (b4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are each independently a monovalent hydrocarbon group, a group represented by —OR ^4a , —SR ^4b a group represented by , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ , which is a monovalent hydrocarbon group , a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c and a group represented by -N(R ^4d ) ₂ are One or more selected from the group consisting of a group represented by -OR ^4e , a group represented by -SR ^4f , an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, and a group represented by -NHR ^4g may be substituted with a group of
R ^4a to R ^4g are each independently a monovalent hydrocarbon group,
X ¹ and X ² each independently represent -CO-NH-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or -CO-NH-CO- NH-,
ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each independently an aromatic hydrocarbon ring,
R is a single bond, an optionally substituted methylene group, an optionally substituted ethylene group which may contain a heteroatom between two carbon atoms, a group represented by -O- , a group represented by -NH-, or a group represented by -S-,
n1 and n2 are each independently an integer of 0 to 4,
n3 and n4 are each independently an integer of 0 to 5,
n5 and n6 are each independently an integer of 0 to 4,
Z ¹ is a tetravalent organic group. )
Polyimide resin having a structural unit represented by. Forming a coating film made of the polyimide precursor composition according to any one of claims 1 to 9;
A method for producing a polyimide film, comprising heating the coating film to ring-close polyamic acid derived from the resin precursor component (B) in the coating film. A polyimide film obtained by curing a coating film comprising the polyimide precursor composition according to any one of claims 1 to 9. A polyimide film comprising the polyimide resin according to claim 13 . 17. The polyimide film according to claim 15 or 16, which has a refractive index of 1.61 or more. An optical device comprising the polyimide film according to any one of claims 15-17. 19. An optical device according to claim 18, which is an OLED lighting device.