TWI811316B - Polyimide precursor composition, polyamide acid, polyimide resin, polyimide film and optical device - Google Patents

Abstract

The present invention provides a polyimide precursor composition that can provide a polyimide film with high refractive index and low retardation, and a preferred polyimide acid as a precursor component in the polyimide precursor composition. , a polyimide resin produced using the aforementioned polyimide precursor composition, a polyimide film produced using the aforementioned polyimide precursor composition, and an optical device provided with the aforementioned polyimide film By. The present invention is an aromatic diamine compound in which two amine group-containing aromatic groups of a specific structure are bonded to the same carbon atom in a polycyclic skeleton such as a fluorene skeleton, and is contained in a resin as a diamine component (B1). In the precursor component (B), or polyamide (B3) containing a structural unit having a structure derived from the aromatic diamine compound with the above-mentioned specific structure is used as the resin precursor component (B) to form a polyamide. Amine resin or polyimide membrane.

Description

Polyimide precursor composition, polyimide acid, polyimide resin, polyimide film and optical device

The present invention relates to a polyimide precursor composition containing a precursor component of a polyimide resin, a preferred polyamide acid as a precursor component in the polyimide precursor composition, and the use of the aforementioned polyamide A polyimide resin produced from a polyimide precursor composition, a polyimide film produced using the polyimide precursor composition, and an optical device provided with the polyimide film.

Polyimide resin has excellent heat resistance, mechanical strength, insulation or low dielectric properties. Therefore, polyimide resin can be widely used as an insulating material or protective material for various components or electrical and electronic parts of electronic substrates such as multilayer wiring boards.

As the polyimide resin, for example, fully aromatic polyimide (for example, the trade name "Kapton") has been used for advanced industries such as space and aviation applications since it has excellent mechanical properties or heat resistance. Such fully aromatic polyimide is synthesized by the reaction of aromatic tetracarboxylic dianhydride and aromatic diamine. The aforementioned Kapton is known to exhibit the highest level of heat resistance (glass transition temperature (Tg): 410° C.) among heat-resistant polymers (see Non-Patent Document 1).

In addition, from the viewpoint of improving the transparency of the polyimide resin, research on polyimide resins containing an alicyclic skeleton is being conducted (see Non-Patent Document 2). Examples of such alicyclic polyimides include resins obtained by the reaction of alicyclic tetracarboxylic dianhydride and alicyclic diamines, resins obtained by the reaction of alicyclic tetracarboxylic dianhydride and aromatic diamines, and Resins obtained by the reaction of amines, and three types of resins obtained by the reaction of aromatic tetracarboxylic dianhydrides and alicyclic diamines. [Prior technical literature] [Non-patent literature]

[Non-patent document 1] Engineering Plastics, Kyoritsu Publishing, issued in 1987, p88 [Non-patent document 2] Macromolecules, volume 27, issued in 1994, p1117

[Problem solved by the invention]

For films used in OLED lighting devices and the like, a high refractive index is required from the viewpoint of light extraction efficiency. However, there is still room for improvement in making the refractive index of the polyimide resin known in the past as high as mentioned above.

The present invention was made in view of the above problems, and aims to provide a polyimide precursor composition that provides a polyimide film with a high refractive index, and a precursor in the polyimide precursor composition. The material components are preferably polyamide acid, a polyimide resin manufactured using the aforementioned polyimide precursor composition, a polyimide film manufactured using the aforementioned polyimide precursor composition, and An optical device equipped with the aforementioned polyimide film. [Means to solve the problem]

The present inventors discovered that an aromatic diamine compound containing two amine group-containing aromatic groups of a specific structure bonded to the same carbon atom in a polycyclic skeleton such as a fluorene skeleton contains it as the diamine component (B1). In the resin precursor component (B), or polyamide (B3) containing a structural unit having a structure derived from the aromatic diamine compound with the above-mentioned specific structure is used as the resin precursor component (B) to form a polyamide. The present invention can be accomplished by solving the above-mentioned problems using an amide resin or a polyimide film. Specifically, the present invention provides the following.

The 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) contains a diamine component (B1) and a tetracarboxylic acid The monomer component composed of the acid dianhydride component (B2) and/or the polyamic acid (B3); the diamine component (B1) contains an aromatic diamine compound represented by the following formula (b1); (In 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g and the group represented by -N(R ^4h ) ₂ are substituted by one or more groups of the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently a -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, a methyl methylene group that may have a substituent, a methyl group that may have a substituent, and a heteroatom between two carbon atoms. Ethylene group, -O- group, -NH- group, or -S- group; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5 an integer; n5 and n6 are each independently an integer from 0 to 4); Polyamic acid (B3) contains: a polyamic acid having a structural unit 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 formula (b1); Z ¹ is a tetravalent organic group).

The second aspect of the present invention is a polyamide having a structural unit 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, Substituted with one or more groups consisting of a cyano group, a group represented by -NHR ^4g and a group represented by -N(R ^4h ) ₂ ; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently is -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, a methyl group that may have a substituent, may have a substituent, and may contain heteroatoms between two carbon atoms. ethylidene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5 an integer; n5 and n6 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic radical).

The third aspect of the present invention is a polyimide resin having a structural unit 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, Substituted with one or more groups consisting of a cyano group, a group represented by -NHR ^4g and a group represented by -N(R ^4h ) ₂ ; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently is -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, a methyl group that may have a substituent, may have a substituent, and may contain heteroatoms between two carbon atoms. ethylidene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5 an integer; n5 and n6 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic radical).

A fourth aspect of the present invention includes forming a coating film composed of the polyimide precursor composition of the first aspect, and heating the coating film to remove the resin precursor component from the coating film ( B) A method for manufacturing a polyimide film in which the polyamide is ring-closed.

A fifth aspect of the present invention is a polyimide film formed by hardening a coating film composed of the polyimide precursor composition of the first aspect.

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

A seventh aspect of the present invention is an optical device having the polyimide film of the fifth aspect or the sixth aspect. [Effects of the invention]

According to the present invention, it is possible to provide a polyimide precursor composition for imparting a high refractive index to a polyimide film, a preferred polyimide acid as a precursor component in the polyimide precursor composition, and use of A polyimide resin produced from the polyimide precursor composition, a polyimide film produced from the polyimide precursor composition, and an optical device provided with the polyimide film.

[Types of carrying out the invention]

≪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). The necessary or optional components contained in the polyimide precursor composition are described in sequence below.

＜Accelerator (A)＞ The polyimide precursor composition may contain an accelerator (A) as a component that accelerates the imidization of the resin precursor component (B). Examples of such accelerators include imidazole compounds, pyridine compounds, tertiary amine compounds such as triethylamine, amino acid compounds, etc.), with imidazole compounds being preferred. The imidazole compound (A1) is a compound that can directly promote the imidization of the resin precursor component (B) in this form, or can be a compound that promotes the resin precursor component by the action of energy such as heat or light. The compound of the imidized imidazole compound of (B). Since the polyimide precursor composition has good stability over time, the imidazole compound (A1) is an imidazole compound (A1) that can generate an imide that can promote the resin precursor component (B) by the action of energy such as heat or light. Aminated imidazole compounds are preferred. As such an imidazole compound (A1), a known thermal imidazole generator or photoimidazole generator can be used without particular limitation.

Preferable examples of the imidazole compound (A1) include compounds represented by the following formula (1). The compound represented by the following formula (1) corresponds to a thermal imidazole generating agent that can generate an imidazole compound by heating.

(In formula (1), R ¹ is a hydrogen atom or an alkyl group; R ² is an aromatic group which may have a substituent; R ³ is an alkylene group which may have a substituent; R ⁴ is a halogen atom, a hydroxyl group, a mercapto group, thioether group, silicon group, silanol group, nitro group, nitroso group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, or organic group; n is an integer from 0 to 3).

In formula (1), R ¹ 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 of the alkyl group is not particularly limited, it is preferably from 1 to 20 and preferably from 1 to 10, and more preferably from 1 to 5.

Specific examples of preferred alkyl groups for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecan Alkyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecyl and n-eicosanyl.

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

The type of aromatic hydrocarbon group is not particularly limited as long as it does not hinder the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, a group formed by condensation of two or more aromatic hydrocarbon groups, or a group formed by a single bond bonding of two or more aromatic hydrocarbon groups. As the aromatic hydrocarbon group, phenyl, naphthyl, biphenyl, anthracenyl and phenanthracenyl are preferred.

The type of aromatic heterocyclic group is not particularly limited as long as it does not hinder the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl and benzimidazole group are preferred.

Examples of substituents that the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, and a nitroso group. Sulfenyl group, sulfonic acid group, sulfonate group, phosphine group, phosphine oxide group, phosphonyl group, phosphonic acid group, amine group, quaternary ammonium group and organic group. When the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has a plurality of substituents, the plurality of 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. The organic group may contain a bond or substituent other than the hydrocarbon group such as a hetero atom. In addition, the structure of the organic group may be linear, branched, or cyclic. This organic group is usually a monovalent organic group. When the organic group forms a cyclic structure, the organic group may be a divalent or higher organic group.

When there is a substituent on the carbon atom adjacent to the aromatic group, the two substituents bonded to the adjacent carbon atom are bonded to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring or an aliphatic ring containing hetero atoms.

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 effect of the present invention is not impaired. The organic group may contain: oxygen atoms, nitrogen atoms, silicon atoms and other impurities. The bonder of atoms. Specific examples of the bond containing a heteroatom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imine bond (-N =C(-R)-, -C(=NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonium bond, sulfenyl bond, azo bond, etc.

From the viewpoint of the heat resistance of the imidazole compound represented by the formula (1), the bond containing the heteroatom that the organic group may have is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, Amide bond, amine bond (-NR-: R represents a hydrogen atom or a monovalent organic group) urethane bond, imine bond (-N=C(-R)-, -C(=NR)- : R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond and a sulfenyl 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 the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyanate group, a cyanooxy group, an isocyanate group, a thiocyanateoxy group, and an isothiocyanooxy group. , Silica group, silanol group, alkoxy group, alkoxycarbonyl group, amine group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamine group, aminoformyl group, Thiaminoformyl group, nitro group, nitroso group, carboxylic acid ester group, acyl group, acyloxy group, sulfinyl group, sulfonic acid group, phosphine group, phosphinyl group, phosphonic acid group, alkyl ether group , alkenyl ether group, alkyl thio ether group, alkenyl thio ether group, aryl ether group and aryl thio ether group, etc. The hydrogen atoms contained in the above substituents may also be substituted by hydrocarbon groups. In addition, the hydrocarbon group contained in the above-mentioned substituent may be linear, branched, or cyclic.

The substituents of the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group include an alkyl group with 1 to 12 carbon atoms, an aryl group with 1 to 12 carbon atoms, and an aryl group with 1 to 12 carbon atoms. The following alkoxy groups, aryloxy groups having 1 to 12 carbon atoms, arylamine groups having 1 to 12 carbon atoms, and halogen atoms are preferred.

As R ² , the imidazole compound represented by the formula (1) can be synthesized cheaply and easily. Since the imidazole compound has good solubility in water or organic solvents, a phenyl group, a furyl group, or a thienyl group which may have various substituents is used. good.

In formula (1), R ³ is an alkylene group which may have a substituent. The substituent that the alkylene group may have is not particularly limited as long as it does not hinder the object of the present invention. 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 straight-chain alkylene group or a branched-chain alkylene group, with a straight-chain alkylene group being preferred. The number of carbon atoms in the alkylene group is not particularly limited, but it is preferably from 1 to 20 and preferably from 1 to 10, and particularly preferably from 1 to 5. Furthermore, the number of carbon atoms of the alkylene group does not include the carbon atom of the substituent bonded to the alkylene group.

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

The amine group as the substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or dialkylamino group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamino group is not particularly limited, but is preferably from 1 to 10, preferably from 1 to 6, and particularly from 1 to 3. good.

Specific examples of preferred alkylene groups for R ³ include methyl, ethane-1,2-diyl, n-propane-1,3-diyl, and n-propane-2,2-diyl. , n-butane-1,4-diyl, n-pentane-1,5-diyl, n-hexane-1,6-diyl, n-heptane-1,7-diyl, n -Octane-1,8-diyl, n-nonane-1,9-diyl, n-decane-1,10-diyl, n-undecane-1,11-diyl, n- Dodecane-1,12-diyl, n-tridecane-1,13-diyl, n-tetradecane-1,14-diyl, n-pentadecan-1,15-diyl, n-Hexadecane-1,16-diyl, n-heptadecan-1,17-diyl, n-octadecane-1,18-diyl, n-nonadecane-1,19-diyl base and n-eicosane-1,20-diyl.

R ⁴ is a halogen atom, hydroxyl group, mercapto group, thioether group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, or organic group. n is an integer from 0 to 3. When n is an integer from 2 to 3, the plural R ⁴ 's may each 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 in R ² may have as a substituent.

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 chain alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group and an isopropyl group are preferred. As the aromatic hydrocarbon group, phenyl, naphthyl, biphenyl, anthracenyl and phenanthracenyl are preferred, phenyl and naphthyl are more preferred, and phenyl is particularly preferred. As the aromatic heterocyclic group, pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl and benzimidazolyl groups are preferred, and furyl and thienyl groups are preferred.

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

Among the imidazole compounds represented by the above formula (1), the compound represented by the following formula (1-1) is a compound that can be synthesized at low cost and easily and has excellent solubility in water or organic solvents. Preferably, the compound in which R ³ represented by formula (1-1) is a methylene group is preferred.

(In formula (1-1), R ¹ , R ³ , R ⁴ and n are the same as formula (1), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom or a hydroxyl group. , mercapto group, thioether group, silyl group, silanol group, nitro group, nitroso group, sulfinyl group, sulfonate group, sulfonate group, phosphine group, phosphinyl group, phosphonyl group, phosphonate group, amine group , quaternary ammonium group, or organic group, but 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, it is also preferable that at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is the substituent below, and it is particularly preferable that R ⁹ is the substituent below. When R ⁹ is the following substituent, R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms. -OR ¹⁰ (R ¹⁰ is a hydrogen atom or an organic group).

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

Among the compounds represented by the above formula (1-1), the compound represented by the following formula (1-1-1) is preferred. (In formula (1-1-1), R ¹ , R ⁴ and n are the same as formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a hydroxyl group, a thiol group, a sulfur group. Ether group, silyl group, silanol group, nitro group, nitroso group, sulfinyl group, sulfonate group, sulfonate group, phosphine group, phosphinyl group, phosphonate group, phosphonate group, amine group, quaternary ammonium group, or Organic group, but 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), it is also preferred that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is the group represented by -OR ¹⁰ , and R ¹⁵ is - Those with the base shown in OR ¹⁰ are particularly good. 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 compounds.

In the polyimide precursor composition, the content of the accelerator (A) or the imidazole compound (A1) is not particularly limited as long as it does not hinder the object of the present invention. The content of the accelerator (A) or the imidazole compound (A1) is, for example, 1 part by mass or more based on 100 parts by mass of the resin precursor component (B) described below. The upper limit of the content is not particularly limited, but is, for example, 60 parts by mass or less for 100 parts by mass of the resin precursor component (B) described below. The content of the accelerator (A) or the imidazole compound (A1) is preferably 5 to 50 parts by mass based on 100 parts by mass of the resin precursor component (B) described below, and is preferably 10 to 40 parts by mass. Excellent. By using the accelerator (A) or the imidazole compound (A1) in this range, it is easy to form a polyimide film with excellent tensile strength and elongation at break, as well as excellent heat resistance.

<Resin precursor component (B)> The resin precursor component (B) contains a monomer component composed of a diamine component (B1) and a tetracarboxylic dianhydride component (B2) and/or polyamic acid (B3). The following describes the monomer components and polyamide (B3).

[Single component] The monomer component is as described above and consists of a diamine component (B1) and a tetracarboxylic dianhydride component (B2). The diamine component (B1) and the tetracarboxylic dianhydride component (B2) will be described below.

(Diamine component (B1)) The diamine component contains an aromatic diamine compound represented by the following formula (b1); (In 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ , monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g and the group represented by -N(R ^4h ) ₂ are substituted by one or more groups of the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently a -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, a methyl methylene group that may have a substituent, a methyl group that may have a substituent, and a heteroatom between two carbon atoms. Ethylene group, -O- group, -NH- group, or -S- group; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5 Integers; n5 and n6 are each independently an integer from 0 to 4).

By introducing the structure derived from the aromatic diamine compound represented by formula (b1) into the polyimide resin, the polyimide resin formed using the resin precursor component (B) exhibits high refractive index and low retardation.

Regarding the above formula (b1), examples of ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (such as naphthalene Rings such as C _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (such as anthracene rings, phenanthrene rings, etc.), etc. Condensation 2 to 4 cyclic aromatic hydrocarbon ring] etc. Ring Y ¹ , ring Y ² , ring Y ³ and ring Y ⁴ are each preferably a benzene ring or a naphthalene ring, with a benzene ring being more preferred. Ring Y ³ and ring Y ⁴ may be the same or different, and the one in which either ring is a benzene ring is particularly preferred. Ring Y ¹ and ring Y ² may be the same or different, and the one in which either ring is a benzene ring is particularly preferred.

For 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-, even if there is a carbonyl group (-CO-) on the ring Y ³ side, an amine group (-NH-) may also be present on the ring Y ³ side.

For formula (b1), as R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b , for example, alkyl groups (such as methyl, ethyl, propyl, isopropyl, butyl, etc. C _1-12 Alkyl group, preferably C _1-8 alkyl group, preferably C _1-6 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group) , preferably C _5-6 cycloalkyl, etc.), aryl groups (such as phenyl, tolyl, xylyl, naphthyl, etc. C _6-14 aryl groups, preferably C _6-10 aryl groups, preferably 1-valent hydrocarbon groups such as C _6-8 aryl, etc.), aralkyl (benzyl, phenethyl, etc. C _6-10 aryl-C _1-4 alkyl, etc.); alkoxy (methoxy, C _1-12 alkoxy groups such as ethoxy, propoxy and butoxy, preferably C _1-8 alkoxy, preferably C _1-6 alkoxy, etc.), cycloalkoxy (cycloalkoxy) Hexyloxy and other C _5-10 cycloalkoxy groups, etc.), aryloxy groups (such as phenoxy and other C _6-10 aryloxy groups), aralkyloxy groups (such as benzyloxy and other C _{6- 10} Aryl-C _1-4 alkyloxy), etc. -OR ^4a group; Alkylthio (methylthio, ethylthio, propylthio, butylthio, etc. C _1-12 Alkylthio group, preferably C _1-8 alkylthio group, preferably C _1-6 alkylthio group, etc.), cycloalkylthio group (C _5-10 cycloalkylthio group such as cyclohexylthio group) group, etc.), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (such as C _6-10 aryl-C _1-4 alkyl group such as phenylthio group) Thiol), etc. - the group shown in SR ^4b ; Carboxyl group (acetyl group, etc. C _1-6 carboxyl group, etc.); Alkoxycarbonyl group (methoxycarbonyl group, etc. C _1-4 alkoxy-carbonyl group, etc.); Halogen Atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); cyano group; alkylamine group (methylamino group, ethylamino group, propylamino group, butylamino group, etc. C _1-12 alkyl group Amino group, preferably C _1-8 alkylamino group, preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (such as cyclohexylamino group, C _5-10 cycloalkylamino group, etc.) ), arylamine group (C _6-10 arylamine group such as phenylamine group), aralkylamine group (such as C _6-10 aryl-C _1-4 alkylamino group such as benzylamine group) ) and other groups shown in -NHR ^4c ; dialkylamino group (dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other two (C _1-12 alkyl) amino groups , preferably di(C _1-8 alkyl)amine group, preferably di(C _1-6 alkyl)amine group, etc.), bicycloalkylamino group (dicyclohexylamine group, etc. di(C _{5 -10} cycloalkyl)amine group, etc.), diarylamine group (di(C _6-10 aryl)amine group such as diphenylamine group), diaralkylamine group (such as diphenylmethylamine group) Non-reactive substituents such as di(C _6-10 aryl-C _1-4 alkyl)amine group) and other -N(R ^4d ) ₂ groups are preferred.

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

Preferable examples of these substituents include the group represented by -OR ^4a , the group represented by -SR ^4b , a hydroxyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a group represented by -NHR ^4c and -N(R ^4d ) ₂ Preferred examples of the bases shown are the same.

When R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b each exist in plural form, the plural bases 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.

Regarding formula (b1), n1 and n2 are each independently an integer from 0 to 4, with 0 or 1 being preferred, and 0 being preferred. n3 and n4 are each independently an integer from 0 to 5, with 0 or 1 being preferred, and 0 being preferred. n5 and n6 are each independently an integer from 0 to 5, with 0 or 1 being preferred, and 0 being preferred.

For formula (b1), R is a single bond, an optionally substituted methyl group, an optionally substituted ethyl group and a heteroatom between two carbon atoms, a group represented by -O-, -NH- The group shown, or the group shown by -S-, is generally a single bond. Examples of the substituent include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and other C _1-6 alkyl groups) and aryl groups (phenyl and other C _6-10 aryl groups), etc.] etc. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like.

As the aromatic diamine compound represented by formula (b1) described above, an aromatic diamine compound represented by the following formula (b1-1) is preferred; (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 Same as formula (b1); n7 and n8 are each independently an integer from 0 to 4); For formula (b1-1), as n7 and n8, each is preferably 0 or 1, and 0 is more preferably.

As the aromatic diamine compound represented by the above formula (b1-1), an aromatic diamine compound represented by the following formula (b1-2) is preferred; (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4). Regarding the formula (b1-2), 0 or 1 is preferred for each of n7 and n8, and 0 is preferred.

As the aromatic diamine compound represented by the above formula (b1-2), an aromatic diamine compound represented by the following formula (b1-3) is preferred; (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4); for formula (b1-3), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

Furthermore, as the aromatic diamine compound represented by the above formula (b1-2), an aromatic diamine compound represented by the following formula (b1-4) is also preferable. (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4); for formula (b1-4), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

As the aromatic diamine compound represented by the above formula (b1-3), an aromatic diamine compound represented by the following formula (b1-5) is preferred; (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4); for formula (b1-5), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

Regarding the formula (b1) explained above, as with the formulas (b1-1) to (b1-5), each of ring Y ¹ and ring Y ² is a benzene ring, and R is preferably a single bond. In other words, the aromatic diamine compound represented by formula (b1) is preferably one containing a fluorene ring.

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

Also, replace the amide bond (-CO-NH-) in the above compound with -CO-O-, -NH-CO-NH-, -CO-NH-CO-, -O-CO-NH-, or Compounds substituted with -CO-NH-CO-NH- can also be cited as preferred examples of the compounds represented by the formula (b1).

The method for producing the aromatic diamine compound represented by the aforementioned formula (b1) is not particularly limited. The aromatic diamine compound represented by the aforementioned formula (b1), for example, can be converted into an amine _group ( -NH ₂ ).

(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～n6 are the same as formula (b1)).

As the compound represented by the above formula (b1-I), a compound represented by the following formula (b1-I-1) is preferred; (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～n6 are consistent with the formula (b1) Same).

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) can be produced by reacting an aromatic compound represented by the following formula (b1-Ia). -I) The compound shown; (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 the formula (b1); the group X ^1a is a group that forms the group X ¹ in the formula (b1-I) by reaction with the group X ^1b ; the group X ^{2a It} is a group that forms group X 2 in formula (b1-1) by reaction with group X ^2b ). Wherein, when X ^{1a and} Better. Furthermore, the reaction between the compound represented by formula (b1-Ia), the compound represented by formula (b1-Ib) and the compound represented by formula (b1-Ic) can be carried out by mixing the three compounds simultaneously, or it can be carried out. The compound represented by formula (bI-Ia) is performed by adding either one of the compound represented by formula (b1-Ib) and the compound represented by formula (b1-Ic), and then adding the other compound.

The reaction between group X ^1a and group X ^1b produces group X ¹ . The reaction between group X ^2a and group X ^2b produces group X ² . ^{The combination of radicals X 1a} _and ^radicals COOH) or the combination of halocarbonyl (-COHal) and hydroxyl; the combination of amine (-NH ₂ ) and isocyanate group; the combination of carboxyl (-COOH) or halocarbonyl (-COHal) and aminomethyl (-CO The combination of -NH ₂ ); the combination of hydroxyl group and isocyanate group; or the combination of aminoformyl group (-CO-NH ₂ ) and isocyanate group. For these combinations, for example, when the combination of groups X ^1a and X ^1b is a combination of a carboxyl group and an amine group, X ^1a can be a carboxyl group and X ^1b can be an amine group; X ^1a can be an amine group and X ^1b can be a carboxyl group.

The combination of carboxyl group (-COOH) or halocarbonyl group (-COOHal) and amine group (-NH ₂ ) is a combination that generates -CO-NH-. The combination of carboxyl group (-COOH) or halocarbonyl group (-COOHal) and hydroxyl group generates -CO-O-. The combination of amine group (-NH ₂ ) and isocyanate group is a combination that generates -NH-CO-NH-. The combination of carboxyl (-COOH) or halocarbonyl (-COHal) and aminoformyl group (-CO-NH ₂ ) is a combination that generates -CO-NH-CO-. The combination of hydroxyl and isocyanate groups creates -O-CO-NH-. The combination of aminoformyl group (-CO-NH ₂ ) and isocyanate group is a combination that generates -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 not particularly limited. The reaction method can be appropriately selected from known methods in consideration of the combination of group X ^1a and group X ^1b and the combination of group X ^2a and group X ^2b .

When the aromatic compound represented by the formula (b1-Ia), the compound represented by the following formula (b1-Ib) and the compound represented by the following formula (b1-Ic) are reacted, these usage amounts can produce the desired amount of It is not particularly limited as long as it is a compound represented by formula (b1-I). The usage amount of the compound represented by formula (b1-Ib) and the usage amount of the compound represented by formula (b1-Ic), for each independently 1 mole of the compound represented by formula (b1-Ia), should be 0.5 mole or more. 2 moles or less is preferred, 0.7 moles or more and 1.5 moles or less is more preferred, and 0.9 moles or more and 1.1 moles or less is particularly preferred.

The method for converting the nitro group (-NO ₂ ) of the aromatic dinitro compound represented by formula (b1-1) into the amino group (-NH ₂ ) by hydrogenation is not particularly limited, and can be appropriately selected from known methods. Hydrogenation method of nitro. A general method is to bring the aromatic dinitro compound represented by the formula (b1-I) into contact with hydrogen in the presence of a palladium catalyst.

The aromatic diamine compound can be, for example, deprotected by deprotecting the protected amino group represented by Z ¹ -NH- or Z ² -NH- in the aromatic compound represented by the following formula (b1-II), It is produced by converting it into an amine group (-NH ₂ ).

(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 formula (b1); Z ¹ and Z ² are protective groups that protect each amine group and can be deprotected).

As the compound represented by the above formula (b1-II), a compound represented by the following formula (b1-II-1) is preferred; (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～n6 are consistent with the formula (b1) is the same; Z ¹ and Z ² are protective groups that protect each amine group and can be deprotected).

The so-called protecting group for Z ¹ and Z ² means a functional group that converts an amine group into a different chemical group that is essentially inert to specific chemical reaction conditions. Protecting groups can be removed simply and selectively with good yields. Examples of protective groups include formyl, acetyl, benzyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tert-butyloxycarbonyl (Boc), p-methoxybenzyl, methoxymethyl, tosyl, trifluoroacetyl, trimethylsilyl (TMS), fluorenylmethyloxycarbonyl (Fmoc), 2-trimethyl Silylethoxycarbonyl, 1-methyl-1-(4-biphenyl)ethoxycarbonyl, allyloxycarbonyl, benzyloxycarbonyl (CBZ), 2-trimethylsilyl- Ethane sulfonyl (SES), trityl and substituted trityl, 9-fluorenylmethyloxycarbonyl (FMOC), nitro-veratryloxycarbonyl (NVOC), etc., but are not limited to And so on.

The method for producing the compound represented by formula (b1-II) is not particularly limited. For example, by reacting 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), the formula (b1- II) The compound shown; (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 the formula (b1); Z ¹ and Z ² are the same as the formula (b1-II); the group X ^1a is formed by the reaction with the group X ^1b to form the formula (b1) The radical X ¹ in -II); the radical X ^2a is the radical X 2 ⁱⁿ the formula (b1-II) formed by reaction with the radical X ^2b ).

For the combination ^of the group X ^1a and ^{the group} Ic) Description of the reaction of the compound shown.

When the aromatic compound represented by the formula (b1-Ia), the compound represented by the following formula (b1-IIb) and the compound represented by the following formula (b1-IIc) are reacted, these usage amounts can produce the desired amount of The compound represented by formula (b1-II) suffices and is not particularly limited. The usage amount of the compound represented by formula (b1-IIb) and the usage amount of the compound represented by formula (b1-IIc), for each mole of the compound represented by formula (b1-Ia) independently, should be 0.5 mol or more. 2 moles or less is preferred, 0.7 moles or more and 1.5 moles or less is more preferred, and 0.9 moles or more and 1.1 moles or less is particularly preferred.

The method for deprotecting the protected amine group represented by Z ¹ -NH- or Z ² -NH- and converting it into an amino group (-NH ₂ ) is not particularly limited as long as it is a conventionally known method. Deprotection can be performed by known means according to the type of protecting group.

Furthermore, the aromatic diamine compound represented by the formula (b1) can be obtained by combining a compound represented by the following formula (b1-IIIb), a compound represented by the following formula (b1-IIIc), and an aromatic compound represented by the following formula (b1-Ia). Manufactured by reacting family compounds; (Formula (b1-Ia), formula (b1-IIIb) and formula (b1-IIIc) and among them, 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 the formula (b1); the group X ^1a is a group that forms the group X ¹ in the formula (b1) by reaction with the group X ^1b ; the group X ^2a is The radical of radical X ² in formula (b1) is formed by reaction with radical X ^2b ). According to this method, side reactions are likely to occur, and steps such as hydrogenation of the nitro group or deprotection of the protected amine group are not required, so the synthesis of the aromatic amine compound represented by formula (b1) is easy.

For the combination ^of the group X ^1a and ^{the group} Ic) Description of the reaction of the compound shown. 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 combination of X ^1a and the group X ^1b and the group X ^2a The combination with _the ^group , or a combination of carboxyl (-COOH) or halocarbonyl (-COHal) and aminomethyl (-CO-NH ₂ ).

The diamine component (B1) may contain both the aromatic diamine compound represented by the formula (b1) and other diamine compounds that are not equivalent to the aromatic diamine compound represented by the formula (b1), as long as the purpose of the present invention is not hindered. Preferable examples of the other diamine compounds include diamine compounds represented by the following formula (2). One type of other diamine compounds may be used alone, or two or more types may be used in combination. H ₂ NR ^b10 -NH ₂ ･･･(2) (In the formula, R ^b10 is an aryl group with a carbon number of 6 to 40. However, the diamine compound represented by the formula (2) does not correspond to the formula (b1) Aromatic diamine compounds shown).

The aryl group selected as R ^b10 in formula (2) is an aryl group with a carbon number of 6 to 40, preferably 6 to 30, and preferably 12 to 20. When the number of carbon atoms in the aryl group exceeds 40, the heat resistance of the resulting polyimide resin tends to decrease. If the number of carbon atoms in the aryl group is less than 6, the solubility of the obtained polyimide resin in the solvent tends to decrease.

R ^b10 in the formula (2) is represented by the following formulas (3) to (9) from the viewpoint of the balance between the high refractive index, heat resistance, and solubility of the polyimide resin obtained. It is better to show at least one of the bases.

(In formulas (5) to (7) and formula (9), R ¹¹ represents one species 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. Formula In (6), Q ¹ represents one selected from -C ₆ H ₄ -, -CONH-C ₆ H ₄ -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -OCO-C ₆ H ₄ -COO-, -OCO-C ₆ H ₄ -C ₆ H ₄ -COO-, -OCO-, -O-, -S-, -CO-, -CONH -, -SO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -CH=CH-, -C≡C-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -C(CF ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -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 -, -OC ₆ H ₄ -C ₆ H ₄ -O-, -OC ₆ H ₄ -O-, -OC ₁₀ H ₆ -O- and -OC ₆ Br ₂ H ₂ -C(CH ₃ ) ₂ -C ₆ Br ₂ H ₂ -O- and one of the groups represented by the following formula (10); 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 benzene diyl (phenylene group), preferably benzene-1,4-diyl (p-phenylene group). -C ₁₀ H ₆ - represents naphthalenediyl, and naphthalene-1,6-diyl, naphthalene-1,5-diyl and naphthalene-1,4-diyl are preferred. -C ₆ Br ₂ H ₂ - represents dibromophenylene group, preferably 3,5-dibromobenzene-1,4-diyl)

R ¹¹ in the formulas (5) to (7) and (9) is 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 obtained polyimide resin. Preferably, hydrogen atom is particularly preferred.

Q ¹ in the formula (6) is -OC ₆ H ₄ -O-, -O-, -C from the viewpoint of the balance between the heat resistance of the polyimide resin and the solubility in the solvent. (CH ₃ ) ₂ -, -CH ₂ -, or -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -CONH- is preferred, with -OC ₆ H ₄ -O-, Or -O- is particularly good. In addition, from the viewpoint of easily obtaining a polyimide resin with a high refractive index, as Q ¹ in the formula (6), -S-, -SO-, -SO ₂ -, -OC ₆ H ₄ -SC ₆ H ₄ -O-, -OC ₆ H ₄ -SO-C ₆ H ₄ -O-, or -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O- is preferred.

Among the groups represented by formulas (3) to (9), from the viewpoint of easily achieving a balance between the refractive index and other characteristics other than the refractive index of the polyamide resin obtained, the groups represented by formulas (5) to (9) are The groups represented by the formulas (6) to (9) are particularly preferred.

Preferable 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-diamino-2,8-dimethyl Diamino sulfides such as dibenzothiophene and 2,2-bis(3-amino-4-hydroxyphenyl) sulfide; 4,4'-diaminodiphenyl terine, 3,3'-diaminodiphenyl terine, bis{4-(4-aminophenoxy)phenyl}terine, bis{4 -(3-Aminophenoxy)phenyl}terine, 3,7-diamino-2,8-dimethyldibenzothiophene-5-oxide and 2,2-bis(3-amine Diamine-based sterines such as hydroxyphenyl-4-hydroxyphenyl)terosine; 4,4'-Diaminodiphenylsine, 3,3'-Diaminodiphenylsine, bis{4-(4-aminophenoxy)phenyl}sine, bis{4-(3 -Aminophenoxy)phenyl}terine, 2,2-bis(3-amino-4-hydroxyphenyl)terine and 3,7-diamino-2,8-dimethyldibenzothiophene -Diamine trioxides such as 5,5-dioxide; Bromine-substituted diamines such as 2,2-bis{4-(4-aminophenoxy)-3,5-dibromophenyl}propane; Carbon-carbon double bonds such as 4,4’-diaminostilbene, 3,3’-diaminostilbene and 3,4’-diaminostilbene contain diamines; 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 2,4-diamino-4 '-Phenylethynyl diphenyl ether and other carbon-carbon bonds contain diamines; 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 1,5-bis(4-aminophenoxy)naphthalene, 1,4-bis(4-aminophenoxy)naphthalene ) naphthalene and other polycyclic aromatic diamines.

The amount of the aromatic diamine compound represented by formula (b1) in the diamine component (B1) is not particularly limited as long as it does not hinder the object of the present invention. Regarding the mass of the diamine component (B1), the mass ratio of the aromatic diamine compound represented by the formula (b1) is, for example, preferably 50 mass% or more, more preferably 70 mass% or more, and 90 mass% or more. More preferably, 95% by mass or more is particularly preferred. 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 it does not hinder the object of the present invention. The content of the diamine component (B1) in the monomer component and the amount of the tetracarboxylic dianhydride component (B2) described below are 0.2 mol or more and 2 mol or less per 1 mol of the diamine component (B1). Preferably, the amount is 0.3 mol or more and 1.2 mol or less.

(Tetracarboxylic dianhydride component (B2)) The tetracarboxylic dianhydride component (B2) is not particularly limited as long as it is a tetracarboxylic dianhydride used in the production of conventional polyimide resins. The tetracarboxylic dianhydride component (B2) can be contained in combination with two or more kinds of tetracarboxylic dianhydride.

From the viewpoint of balancing the excellent transparency and excellent mechanical properties of the obtained polyimide resin, the tetracarboxylic dianhydride component (B2) preferably contains a tetracarboxylic dianhydride having an alicyclic group. Contains norbornane-2-spiro-α-cycloalkanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride represented by the following formula (b2) Those of the same type are better. (In formula (b2), R ^b1 , R ^b2 and R ^b3 each independently represent one type selected from the group consisting of a hydrogen atom, an alkyl group with a carbon number of 1 to 10 and a fluorine atom, and m represents 0 to 12 integer).

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

R ^b1 in the formula (b2) are preferably each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint that the obtained polyimide resin has excellent heat resistance. From the viewpoint of easy acquisition or purification of the tetracarboxylic dianhydride represented by the formula (b2), R ^b1 in the formula (b2) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group. The best ones are hydrogen atoms or methyl groups. From the viewpoint of easy purification of the tetracarboxylic dianhydride represented by the formula (b2), the plural R ^b1 in the formula (b2) are preferably the same group.

m in formula (b2) represents an integer from 0 to 12. When the value of m exceeds 12, purification of the tetracarboxylic dianhydride represented by formula (b2) becomes difficult. From the perspective of the ease of purification of the tetracarboxylic dianhydride represented by formula (b2), the upper limit of m is preferably 5, and 3 is more preferred. From the viewpoint of the chemical stability of the tetracarboxylic dianhydride represented by formula (b2), the lower limit of m is preferably 1, and the lower limit of m is 2. The m in formula (b1) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^b2 and R ^b3 in formula (b2) is the same as the alkyl group with 1 to 10 carbon atoms that can be selected as R ^b1 . From the viewpoint of easy purification of the tetracarboxylic dianhydride represented by formula (b2), R ^b2 and R ^b3 contain a hydrogen atom or a carbon number of 1 to 10 (preferably 1 to 6), preferably 1 or more. 5 or less, more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less) alkyl group, particularly preferably an alkyl group containing 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 (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic acid 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 (alias "Norbornan Alkane-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, norbornane-2-spiro-α-cyclotridecanone-α’-spiro-2” -Norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanoe-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 acid Dianhydride and norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2”-norbornane-5,5”, 6,6”-tetracarboxylic dianhydride, etc.

Moreover, the tetracarboxylic dianhydride represented by formula (b2) contains the following formula (b2-1) from the viewpoint of adjustment of film properties, thermal properties, mechanical properties, optical properties, and electrical properties: (In formula (b2-1), R ^b1 , R ^b2 , R ^b3 , m are synonymous with R ^b1 , R ^b2 , R ^b3 , m in formula (b2)) Compound (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)). At least one of the compounds (B2-2) represented by Whichever is better. At this time, with respect to the amount of the tetracarboxylic dianhydride represented by the formula (b2), the total ratio of the compound (B2-1) and the compound (B2-2) is preferably 30 mol% or more.

The compound (B2-1) represented by the formula (b2-1) becomes the following isomer. The isomer is: the two norbornyl groups are in the trans configuration, and for each of the two norbornyl groups The isomer of the tetracarboxylic dianhydride represented by the formula (b2) in which the carbonyl group of the cycloalkanone is the terminal stereoconfiguration. The compound (B2-2) represented by the formula (b2-2) becomes the following isomer. The isomer is: the two norbornyl groups are in the cis configuration, and for each of the two norbornyl groups , an isomer of tetracarboxylic dianhydride represented by formula (b2) in which the carbonyl group of the cycloalkanone is the terminal stereoconfiguration. Moreover, the method for producing the tetracarboxylic dianhydride containing such an isomer at the above ratio is not particularly limited, and a known method can be suitably used. For example, the method described in International Publication No. 2014/034760 can also be suitably used. Methods etc.

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

Preferable examples of other tetracarboxylic dianhydrides include butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 1,2,3,4-cyclobutane tetracarboxylic dianhydride. Pentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran Tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo -3-Furyl)-naphthalene[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran)-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-dimethylnaphthalene-2,3,6,7-tetracarboxylic dianhydride, pentacyclic [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ]-Pentadecan-5,6,12,13-tetracarboxylic dianhydride and other aliphatic or alicyclic tetracarboxylic dianhydride; benzene Tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,4,5 ,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic acid Dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenyl-bis(triphenylphthalic acid) dianhydride, m-phenylene Phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)- 4,4'-diphenylmethane dianhydride and other aromatic tetracarboxylic dianhydrides. Furthermore, when aromatic tetracarboxylic dianhydride is used, coloring may easily occur in the formed film. At this time, it is preferable to appropriately change the usage amount in consideration of the coloring degree of the film to be formed.

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

[Polyamide (B3)] When the resin precursor component (B) contains polyamide (B3), the polyamide (B3) contains: a polyamide having a structural unit represented by the following formula (b3) Amino acids; (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 formula (b1); Z ¹ is a tetravalent organic group).

The structural unit represented by the formula (b3) is the same as the aromatic diamine compound represented by the aforementioned formula (b1). By having the structure of the structural unit represented by the formula (b3), the polyester is formed using the resin precursor component (B). Imine resin shows high refractive index and low retardation.

If Z ¹ in formula (b3) is a tetravalent organic group, it is not particularly limited as long as it does not hinder the object of the present invention. Z ¹ is generally a tetravalent residue obtained by removing two acid anhydride groups from the compound exemplified for the tetracarboxylic dianhydride component (B2). As Z ¹ , from the viewpoint of easily obtaining a highly transparent polyimide resin with less coloring, a tetravalent organic group containing an alicyclic group is preferred. In order to exclude the tetracarboxylic dianhydride represented by the formula (b2) The 4-valent residue of the 2 acid anhydride groups is preferred. In other words, as Z ¹ , the following formula (b2-1) (In the formula (b2-1), R ^b1 , R ^b2 , R ^b3 and m are the same as those in the formula (b2)), a tetravalent organic group is preferred.

As the structural unit represented by formula (b3), the following formula (b3-1) is used: (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 It is the same as formula (b1); n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group) and the structural unit shown is preferably. In formula (b3-1), as n7 and n8, each is preferably 0 or 1, and 0 is more preferably.

As the structural unit represented by formula (b3-1), the following formula (b3-2) is used: (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group) and the structural unit shown is preferably. Regarding formula (b3-2), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

As the structural unit represented by formula (b3-2), the following formula (b3-3) is used: (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group) and the structural unit shown is preferably. Regarding formula (b3-3), as n7 and n8, 0 or 1 is each preferred, and 0 is preferred.

As the structural unit represented by formula (b3-2), the following formula (b3-4) is used: (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group) and the structural unit shown is also preferred. Regarding formula (b3-4), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

As the structural unit represented by formula (b3-4), the following formula (b3-5) is used: (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 the same as formula (b1) ; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group) and the structural unit shown is preferably. Regarding formula (b3-5), as n7 and n8, 0 or 1 is preferred, and 0 is preferred.

The manufacturing method of polyamide (B3) is not specifically limited. Polyamide (B3) is generally produced by reaction of the aforementioned diamine component (B1) and tetracarboxylic dianhydride component (B2). The polyamide preferably contains a structural unit derived from the tetracarboxylic dianhydride represented by the aforementioned formula (b2) and the diamine component (B1), so that the aforementioned compound (B2-1) and the diamine component (B1) are ) and the structural units derived from the aforementioned compound (B2-2) and the diamine component (B1) are contained in the same molar ratio as the compound (B2-1) and the compound (B2-2). Which is better.

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

The reaction between 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 between the diamine component (B1) and the tetracarboxylic dianhydride component (B2) can dissolve the diamine component (B1) and the tetracarboxylic dianhydride component (B2) with the diamine component (B1 ) and the tetracarboxylic dianhydride component (B2) may be any organic solvent that does not react, and is not particularly limited. The organic solvent can be used alone, or two or more types can be mixed and used.

As an organic solvent used for the reaction of the diamine component (B1) and the tetracarboxylic dianhydride component (B2), it is preferable to use, for example, the solvent (S) described below. Among the organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylethyl, and Amide, N,N-diethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactamide and N,N,N Nitrogen-containing polar solvents such as ',N'-tetramethylurea are preferred.

When synthesizing polyamide (B3), the amount of organic solvent used is, for example, 0.1 mass in the reaction solution based on the total mass of the diamine component (B1) and the tetracarboxylic dianhydride component (B2). % or more and not more than 50 mass%, preferably the usage amount is not less than 10 mass% and not more than 30 mass%.

When the diamine component (B1) and the tetracarboxylic dianhydride component (B2) are reacted, a base may be further added to the organic solvent from the viewpoint of obtaining a polyamide with an increased reaction rate and a high degree of polymerization. compound. Such a basic compound is not particularly limited, and examples thereof include triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo[5.4.0]-undecene-7, Pyridine, isoquinoline, α-methylpyridine, etc. The usage amount of such a base compound is preferably from 0.001 to 10 equivalents per 1 equivalent of the tetracarboxylic dianhydride component, and is preferably from 0.01 to 0.1 equivalents.

The reaction temperature when reacting the diamine component (B1) and the tetracarboxylic dianhydride component (B2) is not particularly limited as long as the reaction proceeds satisfactorily. The reaction temperature is preferably between 15°C and 30°C. The reaction is preferably carried out under an inert gas environment. The reaction time is not particularly limited, but for example, it is preferably not less than 10 hours and not more than 48 hours.

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

The resin precursor component (B) contains: a monomer component composed of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-1) and a tetracarboxylic dianhydride component (B2) , and/or polyamide (B3) having a structural unit represented by the above formula (b3-1) is preferred.

The resin precursor component (B) contains: a monomer component composed of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-2) and a tetracarboxylic dianhydride component (B2) , and/or polyamide (B3) having a structural unit represented by the above formula (b3-2) is preferred.

The resin precursor component (B) contains: a monomer component composed of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-3) and a tetracarboxylic dianhydride component (B2) , and/or polyamide (B3) having a structural unit represented by the above formula (b3-3) is preferred.

The resin precursor component (B) contains: a monomer component composed of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-4) and a tetracarboxylic dianhydride component (B2) , and/or polyamide (B3) having a structural unit represented by the above formula (b3-4) is preferred.

The resin precursor component (B) contains: a monomer component composed of a diamine component (B1) containing an aromatic diamine compound represented by the above formula (b1-5) and a tetracarboxylic dianhydride component (B2) , and/or polyamide (B3) having a structural unit represented by the above formula (b3-5) is preferred.

＜Solvent(S)＞ The 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. From the viewpoint of easily forming a homogeneous and smooth film, the polyimide precursor composition is preferably a solution. The solvent can be used alone or in a mixture of two or more types.

The type of solvent (S) is not particularly limited as long as it does not hinder the object of the present invention. Examples of preferred solvents (S) include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylisobutyl N,N-diethylformamide, N,N-diethylformamide, N,N-dimethylformamide (DMF), N,N-diethylformamide, N-methylcaprolactamide, 1 , Nitrogen-containing polar solvents such as 3-dimethyl-2-imidazolinone (DMI), pyridine and N,N,N',N'-tetramethylurea (TMU); β-propiolactone, γ-butylene Lactone series polar solvents such as lactone, γ-valerolactone, δ-valerolactone, γ-caprolactone and ε-caprolactone; dimethyl styrene; hexamethylphosphotriamine; acetonitrile; lactic acid Fatty acid esters such as ethyl ester and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate and ethyl cellosolve B Ethers such as acid esters and glycol dimethyl ether (Glyme); ketones such as cyclopentanone and cyclohexanone; aromatic solvents such as benzene, toluene, and xylene.

The solvent preferably 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): The base shown. In the formula (S1-1), ^RS4 is a hydrogen atom or a hydroxyl group, and ^RS5 and ^RS6 are each independently an alkyl group having 1 to 3 carbon atoms. In the formula (S1-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

In the compound represented by formula (S1), specific examples of R ^S3 being a group represented by formula (S1-1) include N,N,2-trimethylpropylamine, N-ethyl, N ,2-dimethylpropionamide, N,N-diethyl-2-methylpropionamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-Dimethyl-2-hydroxypropylpropamide and N,N-diethyl-2-hydroxy-2-methylpropamide, etc.

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, etc.

Among the examples of the compound represented by the formula (S1), N,N,2-trimethylpropamide and N,N,N',N'-tetramethylurea are particularly preferred. The boiling point of N,N,2-trimethylpropylamine at atmospheric pressure is 175°C, and the boiling point of N,N,N’,N’-tetramethylurea at atmospheric pressure is 177°C. In this way, N,N,2-trimethylpropamide and N,N,N',N'-tetramethylurea have relatively low boiling points in solvents that can dissolve monomer components and polyamide acid. . Therefore, a polyimide precursor containing at least one solvent (S) selected from N,N,2-trimethylpropamide and N,N,N',N'-tetramethylurea is used. When forming the composition, the heating during the formation of the polyimide film will make it difficult for the solvent to remain in the polyimide film produced, and will not easily lead to a decrease in the degree of stretch of the polyimide film obtained.

In addition, N,N,2-trimethylpropylamide and N,N,N',N'-tetramethylurea are designated as substances with harmful concerns in the REACH regulations of the EU (European Consortium). SVHC (Substance of Very High Concern) is useful from the perspective of less harmful substances.

The content of the compound represented by the formula (S1) in the solvent (S) is not particularly limited as long as it does not hinder the object of the present invention. The ratio of the compound represented by the formula (S1) based on the mass of the solvent is generally 70 mass % or more, more preferably 80 mass % or more, particularly 90 mass % or more, and 100 mass % or more.

The content of the solvent (S) in the polyimide precursor composition is not particularly limited as long as it does not hinder the purpose of the present invention. The content of the solvent (S) in the polyimide precursor composition can be appropriately adjusted in accordance with the solid content in the polyimide precursor composition. The solid content in the polyimide precursor composition is, for example, 1 mass % or more and 80 mass % or less, preferably 5 mass % or more and 70 mass % or less, preferably 10 mass % or more and 60 mass % or less. .

＜Other ingredients＞ The polyimide precursor composition may also contain other components in addition to the above-mentioned components within the scope that does not hinder the object of the present invention. Examples of other components include base generator components, polymerizable components such as monomers, surfactants, plasticizers, viscosity adjusters, defoaming agents, colorants, and the like. Furthermore, the polyimide precursor composition may contain one or more silicon-containing compounds selected from the group consisting of silicon-containing resin, silicon-containing resin precursor, and silane coupling agent. Examples of the silicon-containing resin include siloxane resin and polysilane. Examples of the silicon-containing resin precursor include silane compounds that serve as raw material monomers for siloxane resin or polysilane. When the polyimide precursor composition contains a silicon-containing compound, use the polyimide precursor composition or the polyimide resin formed from the polyimide precursor composition to ensure close adhesion with the object to be coated Sex is good. This effect is remarkable when the material of the object to be coated is glass. It can adhere closely to the object to be coated, so it can improve the process range of polyimide film formation. In addition, if the polyimide precursor composition contains a silicon-containing compound, in the peeling step by UV laser described below, it is necessary to improve the peelability of the polyimide film from the coated body or the support, even if When the UV laser exposure is increased, white turbidity during peeling can be easily suppressed.

＜Preparation of polyimide precursor composition＞ The method of preparing the polyimide precursor composition is not particularly limited. For example, it is by adding as the resin precursor component (B) a component selected from the group consisting of the above-mentioned various monomer components and polyamide (B3). It can be prepared by mixing at least one type, the solvent (S) and the other required above-mentioned ingredients.

As the resin precursor component (B), both the monomer component and the polyamide (B3) can be added. It is usually sufficient to add only the monomer component or only the polyamide (B3). The polyamide precursor composition also includes a composition in which the monomer component as the resin precursor component (B) is added to the solvent (S) to generate polyamide acid. Regarding the preparation of the polyimide precursor composition, the order in which the components are added is not particularly limited.

≪Polyimide resin≫ The resin precursor component (B) contained in the polyimide precursor composition described above is condensed and imidized, or imidized to obtain polyimide. Amine resin. The polyimide resin is a polyimide resin having a structural unit 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g and the group represented by -N(R ^4h ) ₂ are substituted by one or more groups of the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently is -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, a methyl group that may have a substituent, may have a substituent, and may contain heteroatoms between two carbon atoms. ethylidene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5 an integer; n5 and n6 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic radical). Each abbreviation in the above formula (4) is as explained for the resin precursor component (B) related to each polyimide precursor composition. The polyimide resin exhibits a high refractive index and low retardation by having the structural unit represented by the above formula (B4).

≪Manufacturing method of polyimide film≫ The manufacturing method of the polyimide film includes: forming a coating film composed of the aforementioned polyimide precursor composition, and heating the coating film to cause the resin precursor component (B) in the coating film to Polyamide undergoes ring closure. Hereinafter, the process of forming a coating film is also referred to as a "forming step", and the process of closing the loop of polyamide acid is also referred to as a "loop-closing step". Each step is explained below.

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

After the coating film is formed and before moving to the loop closing step, the coating film can also be heated for the purpose of removing the solvent (S) in the coating film. The heating temperature or heating time is not particularly limited as long as the components contained in the polyimide precursor composition do not undergo thermal degradation or thermal decomposition. When the boiling point of the solvent (S) in the coating film is high, the coating film can also be heated under reduced pressure.

＜Closed loop step＞ In the ring closing step, by heating the coating film formed in the above forming step, the polyamide derived from the resin precursor component (B) in the coating film is cycle closed. By closing the ring, polyamide acid is converted into polyimide resin. As a result, a film containing polyimide resin is formed.

When the coating film is heated, the heating temperature is, for example, 100°C or more and 500°C or less, preferably 120°C or more and 350°C or less, and more preferably 150°C or more and 350°C or less. By heating the resin precursor component (B) at such a temperature range, not only can thermal deterioration or thermal decomposition of the resin precursor component (B) or the generated polyimide resin be suppressed, but polyimide can also be generated. amine film.

In addition, when the resin precursor component (B) is heated at a high temperature, a large amount of energy is consumed, or the time-dependent deterioration of the processing equipment is accelerated at a high temperature. Therefore, the resin precursor component (B) is It is better to heat at a lower temperature (sometimes called "low temperature grilling"). Specifically, the upper limit of the heating temperature for the resin precursor component (B) is, for example, set to 220°C or lower, preferably 200°C or lower, more preferably 180°C or lower, more preferably 160°C or lower, more preferably Below 150℃. Even when heating is performed at such a relatively low temperature, according to the present invention, the polyimide resin can be fully produced in a relatively short heating time.

Although the heating time also depends on the composition, thickness, etc. of the coating film, the lower limit is, for example, 0.5 hours, preferably 1 hour, and more preferably 1.5 hours, and the upper limit is, for example, 4 hours, preferably 3 hours. , preferably 2.5 hours. The heating time can be, for example, 130°C or more and 150°C or less. It is also applicable when heating is generally performed at 140°C.

By low-temperature grilling, the polyamide acid can be polymerized, preferably without excessively expanding the molecular weight distribution. In order to increase the molecular weight of polyamic acid by low-temperature grilling, it is preferable to add a monomer component as the resin precursor component (B) in order to increase the molecular weight of the polyamide acid formed. . When the polyimide precursor composition contains an imidazole compound (A1), the imidazole compound (A1) usually remains in the coating film during low-temperature baking. When polyamide is polymerized by the action of the imidazole compound (A1), the tensile strength and elongation at break of the resulting polyimide film can be improved.

In this way, when the polyimide precursor composition contains the imidazole compound (A1), by heating at a relatively low temperature, a polyimide film with better tensile strength and elongation at break can be easily obtained than conventional polyimide films. Imide membrane. The imidazole compound (A1) is considered to function as a catalyst. Since the obtained polyimide film has excellent stretchability, it is also considered to have excellent mechanical properties.

After low-temperature grilling is performed to heat the coating film, step-by-step heating (also called "staged grilling") to a higher temperature than the heating temperature in low-temperature grilling (sometimes called "high-temperature grilling") can be performed. ). In high-temperature barbecue, the upper limit of the heating temperature can be set to, for example, 500°C or lower, preferably 450°C or lower, preferably 420°C or lower, more preferably 400°C or lower. The lower limit of the heating temperature can be, for example, 220°C. Above, 250°C or above is preferred, 300°C or above is more preferred, 350°C or above is more preferred, and 380°C or above is more preferred. Although the heating time in high-temperature grilling depends on the composition and thickness of the coating film, the lower limit is, for example, 10 minutes or more, preferably about 20 minutes or more. If necessary, it can be set to 1 hour or more as the upper limit. , for example, 4 hours, preferably 3 hours, preferably 2.5 hours. The heating time is, for example, above 390°C and below 410°C. Generally, heating is performed at 400°C.

When performing staged heating, low-temperature grilling can be omitted. Especially when a monomer component is added as the resin precursor component (B), a sufficiently high molecular weight polyimide resin can be obtained without performing low-temperature baking.

The conversion of polyimide resin can also be carried out by low-temperature barbecue to the extent that the problem of the present invention can be fully solved. For example, the ring-closing reaction can be substantially completed without substantially no unclosed ring structure, but it can also be performed by low-temperature barbecue. A part of the unclosed loop structure remains. By performing high-temperature grilling, the closed-loop reaction can be substantially completed.

＜Peel-off step＞ When a glass substrate is used as the coated object or the support in the ring closing step, the polyimide film obtained by using the polyimide precursor composition can be peeled off using UV laser or the like.

≪Polyimide membrane≫ As described above, a polyimide film is formed by curing the coating film composed of the polyimide precursor composition. The polyimide film formed by this can also be called a polyimide film containing a polyimide resin having a structural unit represented by the aforementioned formula (b4). The polyimide film exhibits a high refractive index and low retardation derived from the skeleton of the aromatic diamine represented by the aforementioned formula (b1). Therefore, this polyimide film has been well known in the past and can be applied to optical devices having high refractive index films. Among them, the so-called optical devices are not only devices of a certain size such as lighting devices and display devices, but may also include micro-elements represented by light-emitting elements, photoelectric conversion elements, lens elements, etc.

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

In addition, in addition to the high refractive index derived from the skeleton of the aromatic diamine represented by formula (b1), the retardation is also low. Therefore, the above-mentioned polyimide film can be preferably used as a film material for OLED lighting devices, liquid crystal displays, organic EL displays, etc. As an example, by using the above-mentioned polyimide film in an OLED lighting device, not only the light extraction efficiency can be improved, but also a simple-structured, lightweight and thin-layered lighting device can be produced. [Example]

The following examples illustrate the present invention in further detail. The scope of the present invention is not limited to these examples.

[Synthesis Example 1: Synthesis of aromatic diamine compound (9,9'-bis(4-(4-aminobenzylamine)phenyl)fluorene)] In a laboratory equipped with a thermometer, a titration funnel and a stirring wing In a four-necked flask, 2 mL of thionite chloride was added to the pyridine solution of 4-aminobenzoic acid (2.74 g, 0.02 mol). After adding thionite chloride, the contents of the flask were stirred at room temperature for 3 hours to obtain 4-aminobenzoyl chloride. To the obtained 4-aminobenzoyl chloride, 9,9'-bis(4-aminophenyl)fluorene (3.48g, 0.01) dissolved in N-methyl-2-pyrrolidone (NMP) was added mol) and stirred for 5 hours. The obtained reaction liquid was slowly poured into 0-5°C ice water stirred at a certain speed in small amounts, and solid-liquid separation was performed. In order to remove unreacted 4-aminobenzoic acid, the separated wet body was washed four times with a sodium bicarbonate aqueous solution having a concentration of 10% by mass. Next, the wet body was washed with anhydrous methanol and dried at 80°C to obtain 9,9'-bis(4-(4-aminobenzoylamino)phenyl)fluorene with a yield of 58%. . The ¹ H-NMR measurement results of 9,9'-bis(4-(4-aminobenzoylamino)phenyl)fluorene are as follows. ¹ H-NMR (400MHz, 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 method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, tetracarboxylic dianhydride represented by the following formula was prepared. Anhydride (norbornane-2-spiro-α-cyclopentanone-α'-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride).

＜Preparation of polyamide＞ First, a 30 ml three-necked flask was heated with a heat gun and then dried sufficiently. Secondly, the ambient gas in the three-necked flask was replaced with nitrogen, and the inside of the three-necked flask was used as a nitrogen environment. In a three-necked flask, 0.5280 g (0.90 mmol) of the aromatic diamine obtained in Synthesis Example 1 was added, and then 3.50 g of N,N,N',N'-tetramethylurea (TMU) was added. The contents of the three-necked flask are stirred to obtain a liquid in which the aromatic diamine is dispersed in TMU. Next, 0.3459g (0.90mmol) of the tetracarboxylic dianhydride of the above formula was added to a three-necked flask, and then the contents of the flask were stirred at room temperature (25° C.) for 24 hours under a nitrogen environment to obtain a reaction solution. . In this way, polyamide is formed in the reaction liquid to become a reaction liquid of 20% by mass (TMU solvent: 80% by mass).

＜Steps for adding imidazole compounds＞ To the reaction liquid obtained above, an imidazole compound (0.262 g, 6.0 parts by mass based on 100 parts by mass of the reaction liquid) was added under a nitrogen atmosphere. Next, the reaction liquid was stirred at 25° C. for 24 hours to obtain a liquid polyimide precursor composition containing an imidazole compound and polyamide acid.

＜Preparation of polyimide film＞ The polyimide precursor composition obtained above was placed on a glass substrate (large sliding glass, trade name "S9213" manufactured by Shonami Glass Industry Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm). Spin coating until the thickness of the coating film after heating and hardening becomes 10 μm to form a coating film. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 70° C. and left to stand for 0.5 hours. Then, the solvent was evaporated from the coating film and removed. After the solvent was removed, the glass substrate on which the coating film was formed was put into an inert atmosphere furnace with nitrogen flowing at a flow rate of 5 L/min. In an inert atmosphere furnace, under a nitrogen environment, let it stand for 0.5 hours at a temperature of 25°C, then heat at a temperature of 80°C for 0.5 hours, and further heat at a temperature of 300°C for 30 minutes, and then heat at 360 After heating for 30 minutes under temperature conditions of ℃ (final heating temperature), the coating film is hardened, and a polyimide coating is obtained in which a film made of polyimide (polyimide film) is coated on the glass substrate. layer of glass.

The obtained polyimide-coated glass was immersed in water at 90° C., and the polyimide film was peeled off from the glass substrate to obtain a polyimide film (length: 76 mm, width: 52 mm, thickness: 10 μm).

In order to identify the molecular structure of the resin that is the material of the obtained polyimide film, an IR measuring machine (trade name: FT/IR-4100 manufactured by JASCO Corporation) was used to measure the IR spectrum of the polyimide film sample. . The measurement results revealed that in the IR spectrum of the resin that is the material of the polyimide film, the C=O stretching vibration of the imine carbonyl group was observed to be 1704.4 cm ^-1 . From the molecular structure identified based on the above results, it was confirmed that the obtained polyimide film was definitely made of polyimide resin.

[Comparative example 1] A transparent polyimide film (Neoprim (registered trademark) L-3430 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), thickness 100 μm) was used as a standard product. Furthermore, the structure of the polyimide resin contained in the polyimide film of Comparative Example 1 does not include a structural unit represented by the aforementioned formula (b4).

[Comparative example 2] The same procedure as Example 1 was performed except that 0.5280 g (0.90 mmol) of the aromatic diamine obtained in Synthesis Example 1 was replaced with 0.2045 g (0.90 mmol: DABAN) of commercially available 4,4'-diaminobenzoaniline. , to obtain a polyimide precursor composition and a polyimide film.

For the polyimide films of Example 1 and Comparative Example 1, the thermal decomposition temperature, glass transition temperature, thermal expansion rate, tensile strength, elongation at break, total light transmittance, haze value (turbidity ), evaluation of yellowness (YI) and refractive index. The results of these evaluations are shown in Table 1.

＜Thermal decomposition temperature (Td5%: 5% weight loss temperature)＞ The 5% weight loss temperature is obtained as follows. From the thin films obtained in each of the Examples and Comparative Examples, 2 to 4 mg of each sample was prepared, placed in an aluminum sample pan, and a thermogravimetric analyzer (manufactured by II Nanotechnology Co., Ltd.) was used as a measuring device. Named "TG/DTA7200"), in a nitrogen environment, set the scanning temperature between 30°C and 550°C, heat at a temperature rise rate of 10°C/min, and measure the temperature at which the weight of the sample used is reduced by 5%. .

<Measurement of glass transition temperature (Tg)> The value (unit: °C) of the glass transition temperature (Tg) of the resin constituting the film was measured as follows. That is, a sample with a length of 20 mm and a width of 5 mm cut out from each polyimide film was used, and a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku) was used as a measuring device, and the tensile mode was tested in a nitrogen environment. (49mN), the TMA curve was obtained by measuring at a temperature rise rate of 5°C/min. For the inflection point of the TMA curve caused by glass transfer, the composition of the polyimide was obtained by extrapolating the front and rear curves. The value of the glass transition temperature (Tg) of the film's resin (unit: ℃). The results obtained are shown in Table 1.

＜Measurement of thermal expansion rate (CTE)＞ The CTE (unit: ppm/K) of the film is obtained 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 measurement film was vacuum dried (120° C., 1 hour), and then heat-treated at 200° C. for 1 hour in a nitrogen atmosphere to prepare a measurement sample (dry film). Here, the obtained measurement sample (dried film) was used, and a thermomechanical analysis device (trade name "TMA8311" manufactured by Rigaku) was used as a measurement device in a nitrogen environment, using a tensile mode (49mN) and a temperature rise rate of 5°C. /min conditions, measure the change in length of the sample in the temperature range of 50°C to 200°C, and determine by finding the average length change per 1°C in the temperature range of 100°C to 200°C. The results obtained are shown in Table 1.

＜Measurement of tensile strength and elongation at break＞ The tensile strength (unit: MPa) and elongation at break (unit: %) of the film are measured as follows. That is, each resin film is first prepared as follows: An SD-type lever-type sample cutter (cutter (type SDL-200) manufactured by Dumbbell Co., Ltd.) is mounted with a "Super dumbbell cutter" manufactured by Dumbbell Co., Ltd. with a trade name. (Type: SDMK-1000-D, JIS K7139 (issued in 2009) based on the A22 specification)", cut each resin film to the size of the total length: 75mm, distance between label parts: 57mm, parallel part length: 30mm, shoulder Radius: 30mm, end width: 10mm, central parallel part width: 5mm, dumbbell-shaped test pieces (JIS K7139 type A22 (scaled test piece) specifications are used as the basis) were prepared as measurement samples. Here, an electromechanical universal material testing machine (model "5943" manufactured by INSTRON) is used, and the measurement sample is arranged so that the width between the gripping tools is 57mm and the width of the gripping part is 10mm (full width of the end) , under the conditions of load cell: 1.0kN, test speed: 5mm/min, stretch the measurement sample for a tensile test, and obtain the values of tensile strength and elongation at break. This test is based on the test of JIS K7162 (issued in 1994). Furthermore, the value (%) of the elongation at break is the distance between the label portions of the sample (= width between gripping tools: 57 mm) until it breaks (grasping tool at the time of rupture) as L0 When the width between spaces: 57mm+α) is taken as L, it is obtained by calculating the following formula; [Elongation at break (%)]={(L-L0)/L0}×100 The results obtained are shown in Table 1.

<Measurement of total light transmittance, haze value (turbidity) and yellowness (YI)> For the measurement of total light transmittance and haze value (turbidity), a measuring device "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. was used. For the measurement of yellowness (YI), a The measuring device is a product name "Spectrophotometer SD6000" manufactured by Nippon Denshoku Industries Co., Ltd. In addition, the total light transmittance is measured based on JIS K7361-1 (issued in 1997), the haze value (turbidity) is measured based on JIS K7136 (issued in 2000), and the yellowness (YI) is based on Obtained by measuring ASTM E313-05 (issued in 2005).

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

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

<Measurement of retardation (Rth) in thickness direction> The retardation (Rth) in the thickness direction is that the polyimide film (length: 76 mm, width: 52 mm) produced in each example and each comparative example was directly used as a measurement sample, and a brand name manufactured by AXOMETRICS Co., Ltd. was used as the measurement device. "AxoScan", after inputting the value of the refractive index of each polyimide film (the refractive index of the film for light at 589nm determined by the above refractive index measurement), set the temperature to 25°C and humidity to 40%. Under the conditions, use light with a wavelength of 589 nm to measure the retardation in the thickness direction, and use the measured value of the obtained retardation in the thickness direction (measured value obtained by automatic measurement of the measuring device) to convert it into a film thickness of 10 μm. Obtained from the delay value. When the retardation is 200 nm or less, it is judged as ○, and when it exceeds 200 nm, it is judged as ×.

According to Table 1 and Table 2, the polyimide film containing the polyimide resin having the structural unit represented by the aforementioned formula (b4) has a high refractive index, low retardation and high total light transmittance, and has good mechanical properties or Thermal characteristics are not inferior to those of commercially available products.

Claims (19)

A polyimide precursor composition, which is a polyimide precursor composition containing a resin precursor component (B) and a solvent (S), and is characterized by: the aforementioned resin precursor component (B) contains: A monomer component composed of a diamine component (B1) and a tetracarboxylic dianhydride component (B2), and/or a polyamide (B3); the diamine component (B1) contains the following formula (b1) Represents aromatic diamine compounds;

(In 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g is substituted with one or more groups in the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently -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, a methyl group that may have a substituent, an ethyl group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, The group represented by -NH-, or the group represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5; n5 and n6 are each independently an integer from 0 to 4 The following integers); the aforementioned polyamic acid (B3) contains: a polyamic acid having a structural unit 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 the aforementioned formula (b1), Z ¹ is a tetravalent organic group). In the polyimide precursor composition of claim 1, the diamine component (B1) contains an aromatic diamine compound represented by 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 Same as the aforementioned formula (b1), n7 and n8 are each independently an integer from 0 to 4); the aforementioned polyamide (B3) contains: a polyamide having a structural unit represented by 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 Same as the aforementioned formula (b1); n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group). The polyimide precursor composition of claim 2, wherein the aforementioned diamine component (B1) contains an aromatic diamine compound represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4); the aforementioned polyamide (B3) contains: a polyamide having a structural unit represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group). The polyimide precursor composition of claim 3, wherein the aforementioned diamine component (B1) contains an aromatic diamine compound represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4); the aforementioned polyamide (B3) contains: a polyamide having a structural unit represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group). The polyimide precursor composition of claim 3, wherein the diamine component (B1) contains an aromatic diamine compound represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4); the aforementioned polyamide (B3) contains: a polyamide having a structural unit represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group). The polyimide precursor composition of claim 4, wherein the aforementioned diamine component (B1) contains an aromatic diamine compound represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4); the aforementioned polyamide (B3) contains: a polyamide having a structural unit represented by 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 consistent with the aforementioned formula (b1) The same; n7 and n8 are each independently an integer from 0 to 4; Z ¹ is a tetravalent organic group). For example, the polyimide precursor composition of claim 1 or 2, wherein each of the aforementioned ring Y ¹ and the aforementioned ring Y ² is a benzene ring; the aforementioned R is a single bond. The polyimide precursor composition of claim 1 or 2, wherein the aforementioned tetracarboxylic dianhydride component (B2) contains a tetracarboxylic dianhydride having an alicyclic group, and the aforementioned Z ¹ is a component containing an alicyclic group. 4-valent organic base. The polyimide precursor composition of claim 8, wherein the tetracarboxylic dianhydride component (B2) contains norbornane-2-spiro-α-cycloalkanone-α represented by the following formula (b2) '-Spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydrides;

(In formula (b2), R ^b1 , R ^b2 and R ^b3 each independently represent one type selected from the group consisting of a hydrogen atom, an alkyl group with a carbon number of 1 to 10 and a fluorine atom; m represents 0 to 12 integer); the aforementioned Z ¹ is a tetravalent organic group represented by the following formula (b2-1);

(In the formula (b2-1), R ^b1 , R ^b2 , R ^b3 and m are the same as in the aforementioned formula (b2)). A polyamide, characterized by having a structural unit 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g is substituted with one or more groups in the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently -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, a methyl group that may have a substituent, an ethyl group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, The base represented by -NH-, or the base represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5; n5 and n6 are each independently an integer from 0 to 4 The following integers; Z ¹ is a 4-valent organic group). Such as the polyamide of claim 10, wherein the aforementioned Z ¹ is a tetravalent organic group containing an alicyclic group. The polyamide of claim 11, wherein the aforementioned Z ¹ is a tetravalent organic group represented by the following formula (b2-1);

(In the formula (b2-1), R ^b1 , R ^b2 and R ^b3 each independently represent one type selected from the group consisting of a hydrogen atom, an alkyl group with a carbon number of 1 to 10 and a fluorine atom; m represents 0 to 12 the following integers). A polyimide resin characterized by having a structural unit 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 , a group represented by -SR ^4b , a hydroxyl group, an alkoxy group Carbonyl group, halogen atom, cyano group, group represented by -NHR ^4c , or group represented by -N(R ^4d ) ₂ ; monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkyl The oxycarbonyl group, the group represented by -NHR ^4c and the group represented by -N(R ^4d ) ₂ can be selected from the group represented by -OR ^4e , the group represented by -SR ^4f , acyl group, alkoxycarbonyl group, halogen atom, cyanide The group represented by -NHR ^4g is substituted with one or more groups in the group; R ^4a ~ R ^4g are each independently a monovalent hydrocarbon group; X ¹ and X ² are each independently -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, a methyl group that may have a substituent, an ethyl group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, The group represented by -NH-, or the group represented by -S-; n1 and n2 are each independently an integer from 0 to 4; n3 and n4 are each independently an integer from 0 to 5; n5 and n6 are each independently an integer from 0 to 4 The following integers; Z ¹ is a 4-valent organic group). A method for manufacturing a polyimide film, characterized by comprising: forming a coating film composed of the polyimide precursor composition of any one of claims 1 to 9, and by causing the aforementioned coating film to undergo The polyamide derived from the resin precursor component (B) in the coating film is cycle-closed by heating. A polyimide film characterized by hardening a coating film formed of the polyimide precursor composition of any one of claims 1 to 9. A polyimide film, characterized by containing the polyimide resin of claim 13. For example, the polyimide film of claim 15 or 16 has a refractive index of 1.61 or above. An optical device, characterized by having a polyimide film according to any one of claims 15 to 17. Such as the optical device of claim 18, which is an OLED lighting device.