KR102502596B1 - Compositions, composites prepared therefrom, and films and electronic devices including the same - Google Patents

Abstract

A composition including a polyamic acid modified with an alkoxysilane group and an oligo silica compound, a polyimide composite prepared therefrom, and an electronic device including the composite are provided. The polyamic acid modified with the alkoxysilane group includes a reaction product between a condensation polymerization product of an acid dianhydride and diamine and a reactive organic silane compound. The oligo silica compound includes a condensation reaction product of an organosilane diol and an alkoxysilane compound. The Si atom content in the composition is 15% or less by weight based on the total weight of solids in the composition.

Description

Compositions, composites prepared therefrom, and films and electronic devices including the same

It relates to a composition, a composite prepared therefrom, and a film and electronic device comprising the same.

Polyimide is a type of high-performance polymer, and includes a cyclic imide and an aromatic ring in its main chain. Polyimide is gaining considerable importance in advanced technology fields such as microelectronics, aerospace and separation technology because it has relatively good thermal stability, mechanical properties and optical properties. For example, polyimide is finding utility as a transparent substrate (eg, flexible substrate) or a flexible transparent protective film in electronic devices such as various display devices and light emitting diodes or complementary metal oxide semiconductor sensors. Accordingly, there is a demand for the development of polyimide-based materials with improved optical properties such as yellow index, light transmittance, and haze.

Such polyimide-based materials may be exposed to high temperatures during processing for final products such as displays or electronic devices. For example, organic LED manufacturing includes a process of treating a substrate at a high temperature of about 350° C. or higher for a certain period of time in order to maintain the main characteristic quality of the panel. However, when the transparent polyimide substrate is heat treated at a high temperature equal to or higher than the glass transition temperature, optical properties (light transmittance, haze, yellow index) of the material may be significantly deteriorated. For example, high-temperature heat treatment may cause inter-chain or intra-chain packing due to movement of polymer chains. As a result, a charge transfer complex (hereinafter referred to as CTC) may be formed, which dominantly absorbs visible light in a low wavelength region and is considered as a cause of yellowing. Also, after heat treatment, the polyimide substrate may exhibit degraded mechanical properties. Accordingly, there is a demand for development of a polyimide-based material capable of maintaining original physical properties (eg, optical and mechanical properties such as transmittance and yellow index) even after a high-temperature process.

One embodiment relates to a composition for preparing a polyimide composite that exhibits improved optical properties and can maintain original properties even after high-temperature treatment.

Another embodiment is for a polyimide composite film prepared from the composition.

Another embodiment relates to an electronic device including the polyimide composite film.

In one embodiment, the composition includes a polyamic acid modified with an alkoxysilane group and an oligo silica compound, and the Si atom content in the composition is 15% by weight or less based on the total solid weight of the composition. The polyamic acid modified with the alkoxysilane group includes a reaction product between a condensation polymerization product of an acid dianhydride and diamine and a reactive organic silane compound. The oligo silica compound includes a condensation reaction product of an organosilane diol and an alkoxysilane compound.

The water content in the composition may be 100 ppm or less. For example, the composition is substantially free of water.

The condensation polymerization product of the acid dianhydride and diamine may include a condensation polymerization product of an acid dianhydride represented by the following Chemical Formula 1 and a diamine represented by the following Chemical Formula 2, wherein the polycondensation product has the reactive organosilane compound at least one end thereof. may have a moiety that can react with:

[Formula 1]

Here, A ₁ is selected from a substituted or unsubstituted tetravalent C5 to C24 aliphatic ring group, a substituted or unsubstituted tetravalent C6 to C24 aromatic ring group, and a substituted or unsubstituted tetravalent C4 to C24 heteroaromatic ring group. is a moiety, wherein the aliphatic or (hetero) aromatic ring group is present alone; or two or more are bonded to each other to form a polycyclic ring; Or two or more of the aliphatic rings or two or more of the (hetero) aromatic rings have a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ , -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), straight chain of C1 to C10 Or a C1 to C10 alkylene group having at least one substituent selected from a branched aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group, and a C6 to C20 alicyclic hydrocarbon group, C ( ═O)NH, or a combination thereof;

[Formula 2]

NH ₂ -A ₂ -NH ₂

Here, A ₂ is a substituted or unsubstituted divalent C5 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group, a substituted or unsubstituted divalent C4 to C24 heteroaromatic ring group, and -L-SiR ₂ -O-SiR ₂ -L (where L is a single bond or a C1 to C10 alkylene group), wherein the aliphatic or aromatic ring group exists alone; or two or more are bonded to each other to form a polycyclic ring; Or two or more of the aliphatic rings or two or more of the aromatic rings are single bonds, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ , - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), C1 to C10 linear or branched chain A C1 to C10 divalent alkylene group having at least one substituent selected from an aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group, and a C6 to C20 alicyclic hydrocarbon group, -C(= O) NH-, or a combination thereof.

In Formula 1, A ₁ may be any one of the following:

here,

X ¹ to X ⁸ are the same or different and are each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, - C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-;

Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C1 to C5 alkyl group;

Z ² and Z ³ are the same or different, and each independently -N= or -C(R ³⁰¹ )= wherein R ³⁰¹ is hydrogen or a C1 to C5 alkyl group, but Z ² and Z ³ are simultaneously -C (R ³⁰¹ )= not,

R ³⁰ to R ⁵⁰ and R ⁵⁴ to R ⁶⁰ are the same or different, and each independently represents a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

R ⁵¹ to R ⁵³ are the same or different, and each independently represents hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

k30, k31, and k32 are independently integers from 0 to 2;

k33, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently integers from 0 to 3;

k34 is 0 or 1;

k38, k45, k50, k55, and k56 are independently integers from 0 to 4;

k40, k41, k47, k48, and k49 are independently integers from 0 to 5, and

k58, k59, and k60 are independently integers from 0 to 8.

In Formula 2, A ₂ may be represented by any one of the following:

here,

X ¹⁰ to X ¹⁶ are the same or different, and each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,

R ⁷⁰ to R ⁸⁶ and R ⁸⁹ to R ⁹⁰ are the same or different, and each independently represents a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

R ⁸⁷ and R ⁸⁸ are the same or different, and are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82, and k83 are independently integers from 0 to 4;

k71, k72, k85, and k86 are independently integers from 0 to 3, and

k84, k89, and k90 are independently integers from 0 to 10.

The condensation polymerization product of the acid dianhydride and the diamine is 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicycle Rho[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroiso propylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic Pyromellitic dianhydride (PMDA), 4-((2,5-dioxotedrahydrofuran-3-yl)-1,2,3,4-tetranaphthalene-1,2-dicarboxylic acid Hydride (4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzene tetracarboxylic acid dianhydride; 1,2,3,4-benzene tetracarboxylic acid dianhydride; 1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis(3,4-dicarboxy phenoxy) benzene dianhydride; 1,2,4,5-naphthalene tetracarboxylic dianhydride; 1,2,5,6-naphthalene tetracarboxylic dianhydride; 1,4,5,8-naphthalene tetracarboxylic 2,3,6,7-naphthalene tetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,7-dichloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride;2,3,6,7-tetrachloronaphthalene-1,4 ,5,8-tetracarboxylic dianhydride; 2,2',3,3'-diphenyl tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride; bis(2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylether dianhydride; bis(3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; bis(3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride; 2,2',3,3'-benzophenone tetracarboxylic dianhydride; 2,3,3',4'-benzophenone tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride; bis(2,3-dicarboxyphenyl) methane dianhydride; bis(3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride; 1,2-bis(3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride; [4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy) diphenyl]propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiophene tetracarboxylic dianhydride; 2,3,5,6-pyrazine tetracarboxylic dianhydride; 1,8,9,10-phenanthrene tetracarboxylic dianhydride; 3,4,9,10-perylene tetracarboxylic dianhydride; 1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 1,1-bis(3,4-dicarboxyphenyl)-1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethanedianhydride; an acid dianhydride selected from 4,4′-bis[2-(3,4-dicarboxyphenyl)hexafluoroisopropyl]diphenyl etherdianhydride, or mixtures thereof; and

2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, m-phenylene diamine; p-phenylene diamine; 1,3-bis(4-aminophenyl) propane; 2,2-bis(4-aminophenyl) propane; 4,4'-diamino-diphenyl methane; 1,2-bis(4-aminophenyl) ethane; 1,1-bis(4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; bis(4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; bis(3-aminophenyl) sulfone; bis(4-aminophenyl) sulfone; 4,4'-diamino-dibenzyl sulfoxide; bis(4-aminophenyl) ether; bis(3-aminophenyl) ether; bis(4-aminophenyl)diethyl silane; bis(4-aminophenyl) diphenyl silane; bis(4-aminophenyl) ethyl phosphine oxide; bis(4-aminophenyl) phenyl phosphine oxide; bis(4-aminophenyl)-N-phenyl amine; bis(4-aminophenyl)-N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl; 3,3'-diamino-biphenyl; 3,3'-dichloro-4,4'-diamino-biphenyl; 3,3'-dimethyl-4,4'-diamino-biphenyl; 2,2'-dimethyl-4,4'-diamino-biphenyl; 3,3'-dimethoxy-4,4'-diamino-biphenyl; 4,4'-bis(4-aminophenoxy)-biphenyl; 2,4-diamino-toluene; 2,5-diamino-toluene; 2,6-diamino-toluene; 3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene; 1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene; 1,4-diamino-2-methoxy-5-methyl-benzene; 1,4-diamino-2,3,5,6-tetramethyl-benzene; 1,4-bis(2-methyl-4-amino-pentyl)-benzene; 1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene; 1,4-bis(4-aminophenoxy)-benzene; o-xylylene diamine; m-xylylene diamine; p-xylylene diamine; 3,3'-diamino-benzophenone; 4,4'-diamino-benzophenone; 2,6-diamino-pyridine; 3,5-diamino-pyridine; 1,3-diamino-adamantane; bis[2-(3-aminophenyl)hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1, 1'-diadamantane; N-(3-aminophenyl)-4-aminobenzamide; 4-aminophenyl 3-aminobenzoate; 2,2-bis(4-aminophenyl) hexafluoropropane; 2,2-bis(3-aminophenyl) hexafluoropropane; 2-(3-aminophenyl)-2-(4-aminophenyl)hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane; 2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl]hexafluoropropane; 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane; 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane; 1,4-bis(3-aminophenyl)buta-1-en-3-yne; 1,3-bis(3-aminophenyl) hexafluoropropane; 1,5-bis(3-aminophenyl) decafluoropentane; and 4,4'-bis[2-(4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine: TFDB), and diaminofluorene, 1,1-bis(4-aminophenyl)cyclohexane (BACH) , 4,4'-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline) (4,4'-(hexafluoroisopropylidene) bis(4-phenoxyaniline, 6FIDDA), 9,9-bis(4 -aminophenyl)fluorene (BAPF), and a condensation polymerization product of a diamine selected from mixtures thereof and may have an anhydride moiety, an amine moiety, or both at one or both ends.

The polycondensation product of the acid dianhydride and the diamine is an acid dianhydride selected from biphenyldianhydride (BPDA), bis(3,4-dicarboxyphenyl)hexafluoropropanedianhydride (6FDA), or mixtures thereof and bistrifluoromethyldiaminophenyl (TFDB), and may have an anhydride residue, an amine residue, or both of them at one or both ends.

The reactive organosilane compound may be a compound represented by Formula 3 below:

[Formula 3]

Here, L is a single bond, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof, and A Is -NH ₂ or an acid anhydride group,

R ₁ to R ₃ are each independently a C1 to C6 alkyl group or a C1 to C6 alkoxy group, but at least one of R ₁ to R ₃ is a C1 to C6 alkoxy group.

The reactive organic silane compound may be gammaaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(triethoxysilyl)propyl succinylanhydride, or a combination thereof.

The amount of the reactive organic silane compound may be 0.01 mol or more and 10 mol or less per 1 mol of the alkoxysilane compound.

The organosilane diol may be represented by Formula 4 below:

[Formula 4]

Here, n is an integer of 1 to 10, and R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms substituted with a cycloalkyl group having 1 to 20 carbon atoms. An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The alkoxysilane compound may be tetramethoxysilane, tetraethoxysilane, or a mixture thereof.

The condensation reaction between the organic silane diol and the alkoxysilane compound may be a non-hydrogenated condensation reaction performed in the presence of an alkaline earth metal hydroxide.

The content of the alkoxysilane compound may be 2 to 10 moles per 1 mole of the organic silane diol.

The content of the oligo silica compound may be 1 to 10 parts by weight per 100 parts by weight of the polyamic acid modified with the alkoxysilane group.

In another embodiment, the polyimide composite includes a cured product of the aforementioned composition. In the polyimide composite, the Si atom content may be 15% by weight or less based on the total weight of the polyimide composite. The Si atomic content may be determined by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX).

The cured product does not contain isolated silica particles having a size of 200 nm or more when observed with a transmission electron microscope.

The polyimide composite may have a Si atom content of 4% to 14% based on the total weight of the composite.

The polyimide composite may have a transmittance of 65% or more for light having a wavelength of 430 nm and a haze of 1% or less.

The polyimide composite may have a coefficient of thermal expansion (CTE) of 150 ppm/ºC or less obtained by heating a specimen of the composite from 30ºC to 400ºC at a rate of 10ºC/min under a load of 0.05N.

In another embodiment, the film includes the polyimide composite.

In another embodiment, an electronic device includes the film.

The electronic device may be a flat panel display, a touch panel, a solar cell, an e-window, a heat mirror, a transparent transistor, a flexible display, a complementary metal oxide semiconductor sensor, or a light emitting diode light.

In another embodiment, a method for producing a polyimide composite includes preparing a polyamic acid by reacting an acid dianhydride with diamine,

preparing a polyamic acid modified with an alkoxysilane group by reacting the polyamic acid with a reactive organosilane compound;

Preparing an oligo silica compound by a non-hydrogenated condensation reaction of an organosilane diol and an alkoxysilane compound;

Mixing the polyamic acid modified with the alkoxysilane group and the oligo silica compound, and

hardening step

includes

The polyimide composite prepared from the composition according to one embodiment may exhibit improved optical properties (eg, light transmittance, yellow index, and haze value), and may suppress or prevent deterioration in physical properties that may occur due to a high-temperature process. there is.

1 schematically shows a reaction scheme for producing a polyimide composite according to a non-limiting embodiment.
2 is a graph showing the results of a thermomechanical analysis test of the polyimide of Comparative Example 1 and the polyimide composites of Examples 1 to 3.
3 shows a transmission electron microscope image of the polyimide composite prepared in Example.
4 shows a transmission electron microscope image of the polyimide composite prepared in Comparative Example.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "substitution" means that one or more hydrogen atoms included in a given functional group or compound is a halogen atom (-F, -Cl, -Br or -I), a hydroxyl group, a nitro group, A cyano group, an amino group (NH ₂ , NH(R ¹⁰⁰ ) or N(R ¹⁰¹ )(R ¹⁰² ), where R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² are the same or different from each other, and are each independently a C1 to C10 alkyl group) , Amidino group, hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group (eg, cycloalkyl group, etc.), substituted or unsubstituted aryl groups (e.g., benzyl group, naphthyl group, fluorenyl group, etc.) as a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group means substituted with one or more substituents selected from the group consisting of, and the substituents may be linked to each other to form a ring.

In this specification, unless otherwise specified, "alkyl group" means a C1 to C30 alkyl group, specifically means a C1 to C15 alkyl group, and "cycloalkyl group" means a C3 to C30 cycloalkyl group, specifically C3 to C18 cycloalkyl group, "alkoxy group" means a C1 to C30 alkoxy group, specifically means a C1 to C18 alkoxy group, "ester group" means a C2 to C30 ester group, and specifically means a C2 to C18 alkoxy group. Means a C18 ester group, "ketone group" means a C2 to C30 ketone group, specifically means a C2 to C18 ketone group, "aryl group" means a C6 to C30 aryl group, specifically C6 to C18 aryl group, and "alkenyl group" means a C2 to C30 alkenyl group, specifically a C2 to C18 alkenyl group.

Here, “alkylene” is a straight-chain or branched-chain, saturated, aliphatic hydrocarbon group, having a valence of at least 2, optionally substituted with one or more substituents within a range not exceeding the valence of the alkylene group. there is.

Here, "arylene" is a divalent radical formed by removing two hydrogen atoms from one or more rings of an aromatic hydrocarbon, and the hydrogens may be removed from the same or different rings, and each ring may be aromatic or non-aromatic.

Here, "heteroalkylene" refers to an alkylene group containing one or more heteroatoms linked to one or more carbon atoms of the alkylene group. Heteroatoms can be independently selected from nitrogen, oxygen, sulfur, and phosphorus.

In the present specification, the term "reactive organosilane compound" refers to an organosilane compound having a functional group capable of reacting with a reactive functional group (eg, an anhydride group or an amine group) included in the condensation reaction product of acid dianhydride and diamine. say

In the present specification, "polyamic acid modified with an alkoxysilane group" refers to a polyamic acid modified to have an alkoxysilane group.

In this specification, the term "alkoxysilane group" refers to a group (e.g., alkoxysilyl, etc.) derived from a silane having one or more alkoxy groups (eg, 1, 2, 3, 4, etc.).

Here, the term “silica” is not limited to SiO ₂ , and refers to materials based on Si—O linkages, and depending on the context, silica refers to SiO _x (x is 1.5 to 2.5), siloxane, and/or or organic materials such as silica or siloxane having an organic substituent (hydrogen, aryl, alkyl, etc.).

The composition according to one embodiment includes a polyamic acid modified with an alkoxysilane group and an oligosilica compound, but the content of Si atoms in the composition is 15% by weight or less based on the total solid weight of the composition. The composition is substantially free of water. For example, the water content in the composition is 100 ppm or less. The moisture content in the composition may be attributable to an amount of moisture unavoidably included in the preparation of the composition (eg, a trace amount of moisture included in a reactant or solvent). Solid content is related to the content of the polymer, and here refers to the content of diamine and dianhydride included in the composition. The Si content can be calculated from the contents of components (or reaction raw materials) constituting the solid content in the composition.

The polyamic acid modified with an alkoxysilane group is a condensation polymerization product of an acid dianhydride and diamine having a reactive functional group such as an anhydride group and/or an amine group at at least one end (e.g., an anhydride group and at least one end) / or a polyamic acid having an amine group) and a reactive organic silane compound.

The acid dianhydride may be represented by Formula 1 below:

[Formula 1]

Here, A ₁ is selected from a substituted or unsubstituted tetravalent C5 to C24 aliphatic ring group, a substituted or unsubstituted tetravalent C6 to C24 aromatic ring group, and a substituted or unsubstituted tetravalent C4 to C24 heteroaromatic ring group. is a moiety, wherein the aliphatic or (hetero) aromatic ring group is present alone; or two or more are bonded together to form a polycyclic (aromatic) ring; Or two or more of the aliphatic rings or two or more of the (hetero) aromatic rings have a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ , -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), straight chain of C1 to C10 Or a C1 to C10 alkylene group having at least one substituent selected from a branched aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group, and a C6 to C20 alicyclic hydrocarbon group (eg For example, as CR ₂ -, R is independently hydrogen, a C1 to C10 aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group, wherein R is not simultaneously hydrogen) C(=O) are linked by NH, or a combination thereof.

In Formula 1, A ₁ may be any one of the following:

here,

X ¹ to X ⁸ are the same or different and are each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, - C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,

Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C1 to C5 alkyl group;

Z ² and Z ³ are the same or different, and are each independently -N= or -C(R ³⁰¹ )= wherein R ³⁰¹ is hydrogen or a C1 to C5 alkyl group, but Z ² and Z ³ are simultaneously -C(R ³⁰¹ )= not,

R ³⁰ to R ⁵⁰ and R ⁵⁴ to R ⁶⁰ are the same or different, and are each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

R ⁵¹ to R ⁵³ are the same or different, and each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

k30, k31, and k32 are independently integers from 0 to 2;

k33, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently integers from 0 to 3;

k34 is 0 or 1;

k38, k45, k50, k55, and k56 are independently integers from 0 to 4;

k40, k41, k47, k48, and k49 are independently integers from 0 to 5, and

k58, k59, and k60 are independently integers from 0 to 8.

In Formula 2, A ₂ may be represented by any one of the following:

here,

X ¹⁰ to X ¹⁶ are the same or different, and each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,

R ⁷⁰ to R ⁸⁶ and R ⁸⁹ to R ⁹⁰ are the same or different, and each independently represents a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

R ⁸⁷ and R ⁸⁸ are the same or different, and are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82, and k83 are independently integers from 0 to 4;

k71, k72, k85, and k86 are independently integers from 0 to 3, and

k84, k89, and k90 are independently integers from 0 to 10.

In Formula 1 above, A ₁ may be selected from:

Each L is the same or different, and each independently, a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si (CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where, 1≤p≤10), -(CF ₂ ) _q - (Where, 1≤q≤10), -CR ₂ - (Wherein, R is the same or different and each independently hydrogen, a C1 to C10 straight or branched aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group, but two R not all simultaneously hydrogen), -C(CF ₃ ) ₂ -, -C(CF ₃ )(C ₆ H ₅ )-, or -C(=O)NH-;

The aromatic ring is unsubstituted, or at least one hydrogen is a C1 to C15 alkyl group, -F, -Cl, -Br, -I, a C1 to C15 haloalkyl group, a C1 to C15 alkoxy group, a C6 to C12 substituted with an aryl group, a C6 to C12 aryloxy group, a nitro group, a hydroxy group, or a combination thereof, and * is a portion connected to the carbon of the carbonyl group.

For example, A ₁ can be selected from, but is not limited to:

A non-limiting example of the acid dianhydride represented by Formula 1 is 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) , bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, DSDA), 4,4'-(hexafluoro Leuisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4'-oxydiphthalic anhydride (ODPA), pyro Pyromellitic dianhydride (PMDA), 4-((2,5-dioxotedrahydrofuran-3-yl)-1,2,3,4-tetranaphthalene-1,2-dicarboxyl Rick anhydride (4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzene tetracar carboxylic acid dianhydride; 1,2,3,4-benzene tetracarboxylic acid dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 1,3-bis(3,4- dicarboxyphenoxy) benzene dianhydride; 1,2,4,5-naphthalene tetracarboxylic dianhydride; 1,2,5,6-naphthalene tetracarboxylic dianhydride; 1,4,5,8-naphthalene Tetracarboxylic dianhydride; 2,3,6,7-naphthalene tetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,7-dichloro Naphthalene-1,4,5,8-tetracarboxylic dianhydride;2,3,6,7-tetrachloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride; 2,2',3,3'-diphenyl tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride; bis(2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylether dianhydride; bis(3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; bis(3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride; 2,2',3,3'-benzophenone tetracarboxylic dianhydride; 2,3,3',4'-benzophenone tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride; bis(2,3-dicarboxyphenyl) methane dianhydride; bis(3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride; 1,2-bis(3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiophene tetracarboxylic dianhydride; 2,3,5,6-pyrazine tetracarboxylic dianhydride; 1,8,9,10-phenanthrene tetracarboxylic dianhydride; 3,4,9,10-perylene tetracarboxylic dianhydride; 1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 1,1-bis(3,4-dicarboxyphenyl)-1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethanedianhydride; and 4,4'-bis[2-(3,4-dicarboxyphenyl)hexafluoroisopropyl] diphenyl etherdianhydride. These acid dianhydride monomers can be synthesized by known methods or are commercially available. Acid dianhydride can be used individually or in mixture of 2 or more types as needed.

The diamine may be represented by Formula 2 below.

[Formula 2]

NH ₂ -A ₂ -NH ₂

Here, A ₂ is a substituted or unsubstituted divalent C5 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group, a substituted or unsubstituted divalent C4 to C24 heteroaromatic ring group, and -L-SiR ₂ -O-SiR ₂ -L (where L is a single bond or a C1 to C10 alkylene group), wherein the aliphatic or aromatic ring group exists alone; or two or more are bonded together to form a polycyclic (aromatic) ring; Or two or more of the aliphatic rings or two or more of the aromatic rings are single bonds, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ , - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), C1 to C10 linear or branched chain A C1 to C10 divalent alkylene group having at least one substituent selected from an aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group, and a C6 to C20 alicyclic hydrocarbon group, -C(= O) NH-, or a combination thereof.

In Formula 2, A ₂ can be one of:

here,

X ¹⁰ to X ¹⁶ Same or different and each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,

R ⁷⁰ to R ⁸⁶ and R ⁸⁹ to R ⁹⁰ are the same or different and are each independently halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

R ⁸⁷ and R ⁸⁸ are the same or different and each independently represents hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;

k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82, and k83 are independently integers from 0 to 4;

k71, k72, k85, and k86 are independently integers from 0 to 3, and

k84, k89, and k90 are independently integers from 0 to 10.

In Formula 2, A ₂ may be selected from:

In the above formulas, L is the same or different, a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where, 1≤p≤10), -(CF ₂ ) _q - (Where, 1≤q≤10), -CR ₂ - (Wherein, R is the same or different and each independently hydrogen, a C1 to C10 straight or branched aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group, but two R not all simultaneously hydrogen), -C(CF ₃ ) ₂ -, -C(CF ₃ )(C ₆ H ₅ )-, or -C(=O)NH-;

X is the same or different, and each independently represents a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C4 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

The aromatic or alicyclic ring is unsubstituted, or at least one hydrogen is a C1 to C15 alkyl group, -F, -Cl, -Br, -I, a C1 to C15 haloalkyl group, a C1 to C15 alkoxy group, a C6 to C12 aryl group, C6 to C12 aryloxy group, nitro group, hydroxy group, or a combination thereof, and * is a moiety connected to nitrogen.

The A ₂ may be selected from the following, but is not limited thereto.

In one embodiment, the diamine may be one or more selected from the following compounds:

Here, R ³² to R ⁵² are the same or different from each other, and each independently hydrogen, halogen, nitro group, substituted or unsubstituted C1 to C15 alkyl group, substituted or unsubstituted C1 to C15 alkoxy group, substituted or unsubstituted substituted or unsubstituted C3 to C15 fluoroalkyl group, a substituted or unsubstituted C3 to C15 cycloalkyl group, a substituted or unsubstituted C3 to C15 heterocycloalkyl group, a substituted or unsubstituted C3 to C15 oxycycloalkyl group, a substituted or unsubstituted C6 to C15 oxycycloalkyl group, A C15 aryl group, a substituted or unsubstituted C6 to C15 oxyaryl group, or a substituted or unsubstituted C2 to C15 heteroaryl group,

X ² to X ¹² are the same or different from each other, and are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 An arylene group, SO ₂ , O, CO, or a combination thereof;

n35 to n37 and n40 to n49 are integers from 0 to 4;

n38 and n39 are integers from 0 to 3;

In a non-limiting example, the diamine can have the formula:

Specific examples of usable diamine monomers include m-phenylene diamine; p-phenylene diamine; 1,3-bis(4-aminophenyl) propane; 2,2-bis(4-aminophenyl) propane; 4,4'-diamino-diphenyl methane; 1,2-bis(4-aminophenyl) ethane; 1,1-bis(4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; bis(4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; bis(3-aminophenyl) sulfone; bis(4-aminophenyl) sulfone; 4,4'-diamino-dibenzyl sulfoxide; bis(4-aminophenyl) ether; bis(3-aminophenyl) ether; bis(4-aminophenyl)diethyl silane; bis(4-aminophenyl) diphenyl silane; bis(4-aminophenyl) ethyl phosphine oxide; bis(4-aminophenyl) phenyl phosphine oxide; bis(4-aminophenyl)-N-phenyl amine; bis(4-aminophenyl)-N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl; 3,3'-diamino-biphenyl; 3,3'-dichloro-4,4'-diamino-biphenyl; 3,3'-dimethyl-4,4'-diamino-biphenyl; 2,2'-dimethyl-4,4'-diamino-biphenyl; 3,3'-dimethoxy-4,4'-diamino-biphenyl; 4,4'-bis(4-aminophenoxy)-biphenyl; 2,4-diamino-toluene; 2,5-diamino-toluene; 2,6-diamino-toluene; 3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene; 1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene; 1,4-diamino-2-methoxy-5-methyl-benzene; 1,4-diamino-2,3,5,6-tetramethyl-benzene; 1,4-bis(2-methyl-4-amino-pentyl)-benzene; 1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene; 1,4-bis(4-aminophenoxy)-benzene; o-xylylene diamine; m-xylylene diamine; p-xylylene diamine; 3,3'-diamino-benzophenone; 4,4'-diamino-benzophenone; 2,6-diamino-pyridine; 3,5-diamino-pyridine; 1,3-diamino-adamantane; bis[2-(3-aminophenyl)hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1, 1'-diadamantane; N-(3-aminophenyl)-4-aminobenzamide; 4-aminophenyl-3-aminobenzoate; 2,2-bis(4-aminophenyl) hexafluoropropane; 2,2-bis(3-aminophenyl) hexafluoropropane; 2-(3-aminophenyl)-2-(4-aminophenyl)hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane; 2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl hexafluoropropane; 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane; 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane; 1,4-bis(3-aminophenyl)buta-1-en-3-yne; 1,3-bis(3-aminophenyl) hexafluoropropane; 1,5-bis(3-aminophenyl) decafluoropentane; and 4,4'-bis[2-(4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, 2 ,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine: TFDB), and diaminofluorene, 1,1-bis(4-aminophenyl)cyclohexane (BACH), 4,4'-(hexafluoroisopropylidene) bis(4-phenoxyaniline) (4,4'-(hexafluoroisopropylidene) bis(4-phenoxyaniline, 6FIDDA), and 9,9-bis(4-aminophenyl ) Fluorene (BAPF), but is not limited thereto.

In one embodiment, the polycondensation product of the acid dianhydride and diamine is biphenyldianhydride (BPDA), bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6FDA), or a mixture thereof It includes polycondensation products of an acid dianhydride selected from bistrifluoromethyldiaminophenyl (TFDB).

Condensation polymerization can be carried out by stirring acid dianhydride and diamine at a predetermined temperature (eg, 50 degrees C or lower) under an air atmosphere or an inert gas atmosphere. The conditions and general mechanism of such condensation polymerization are known. The polymerization method is not particularly limited and can be selected appropriately.

For example, the polycondensation may be carried out in a solution, optionally including a polycondensation catalyst. In the case of solution polymerization, any solvent known for producing polyamic acid may be used as the polymerization solvent. Examples of the solvent include dipolar aprotic solvents such as N-methyl pyrrolidone, dimethylacetamide, dimethyl formamide, and dimethyl sulfoxide, gamma butyrolactone, monochlorobenzene, and the like. Not limited to this. Examples of the condensation polymerization catalyst include, but are not limited to, p-toluenesulfonic acid and the like. Addition of a given acid dianhydride monomer, optionally in the presence of a given catalyst, to a given diamine monomer at a given temperature in a polymerization solvent as described above, such as a dipolar aprotic solvent, yields the amino group to the carbonyl carbon of the anhydride group. The condensation reaction proceeds by nucleophilic attack. The polymerization time and temperature can also be appropriately selected depending on the type of monomer used. For example, the polymerization may be carried out at a temperature of 50 degrees C or less, eg -20 degrees C to 30 degrees C, for 30 minutes or more, eg 1 hour or more. The monomer concentration in the solution can also be appropriately selected and is not particularly limited. Acid dianhydride and diamine monomers can be easily prepared by known synthetic methods or are commercially available. By adjusting the molar ratio of acid dianhydride to diamine (acid dianhydride/diamine), the polycondensation product has anhydride residues at one or both ends. For example, the content of acid dianhydride may be in the range of 0.8 to 0.99, for example, 0.9 to 0.97, based on 1 mole of diamine.

The condensation polymerization product (eg, polyamic acid) having a reactive functional group (eg, anhydride and/or amine moiety) at one or both ends reacts with a reactive organosilane compound to obtain a polyamic acid modified with an alkoxysilane group. In a non-limiting example, referring to FIG. 1 , a reactive functional group (eg, amino group) of a reactive organosilane compound may react with an anhydride group of the polycondensation product to obtain a polyamic acid having an alkoxysilane group at a chain terminal.

The reactive organosilane compound may be a compound represented by Formula 3 below:

[Formula 3]

Here, L is a single bond, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof, and A Is -NH ₂ or an acid anhydride group, R ₁ to R ₃ are each independently a C1 to C6 alkyl group or a C1 to C6 alkoxy group, but at least one of R ₁ to R ₃ is a C1 to C6 alkoxy group.

Examples of the reactive organosilane compound include, but are not limited to, gamma-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, and 3-(triethoxysilyl)propylsuccinylanhydride.

Reaction conditions between the reactive organosilane compound and the polycondensation product are not particularly limited. For example, by stirring an aminoalkoxy silane and a polyamic acid in an optional solvent (eg, dimethylacetamide (DMAc), etc.) at a temperature of 100 degrees C or less, such as 50 degrees C or less, or 30 degrees C or less, the alkoxysilane group is formed. A modified polyamic acid can be obtained.

The content of the reactive organic silane compound is determined by considering the content of polyamic acid having a reactive functional group (e.g., an anhydride group or an amine group) at one or both terminals and the content of an alkoxysilane compound included in an oligo silica compound described later. can be selected appropriately. For example, the content of the reactive organosilane compound may be in the range of 1 to 1.5 moles per mole of the reactive functional group (anhydride or amine residue) of the polyamic acid, but is not limited thereto. For example, the content of the reactive organic silane compound (e.g., aminoalkoxysilane) is 0.01 to 10 moles, for example, 0.1 to 3 moles, or 0.5 to 2 moles per mole of the alkoxysilane compound included in the oligo silica compound. , or may be in the range of 0.8 mole to 1.5 mole, but is not limited thereto.

The polyamic acid modified with an alkoxysilane group can react with a hydroxy group or alkoxy group of an oligo silica compound.

The oligo silica compound includes a condensation reaction product of an organosilane diol and an alkoxysilane compound. The alkoxysilane compound includes monoalkoxysilane, dialkoxysilane, trialkoxysilane, tetraalkoxysilane, or a combination thereof. In one embodiment, an oligosilica compound is prepared through a non-hydrogenated condensation reaction, and a composition is obtained by mixing the prepared oligosilica compound with the aforementioned polycondensation product.

The organosilane diol may be represented by Formula 4 below:

[Formula 4]

Here, n is an integer of 1 to 10, and R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms substituted with a cycloalkyl group having 1 to 20 carbon atoms. They are an alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, and a C6-C20 aryl group.

For example, the silane diol is diphenylsilanediol, diisobutylsilanediol, silanol-terminated polydimethylsiloxane, silanol-terminated polydimethylsiloxane, silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer, silanol terminal polydiphenylsiloxane, silanol-terminated polydiphenylsiloxane, silanol-terminated polytrifluoropropylmethylsiloxane, or mixtures thereof. When diphenylsilanediol is used as the silane diol, an optically transparent oligo-silica compound solution can be obtained.

The alkoxysilane compound may be tetramethoxysilane, tetraethoxysilane, or a mixture thereof.

For transparency of the oligo-silica compound or for improved optical properties of the prepared composite, the content of the alkoxysilane compound per 1 mole of the organosilane diol may be 1 to 10 moles. A non-hydrogenated condensation reaction using only an alkoxysilane compound gives an opaque oligo silica compound, whereas using an alkoxysilane compound and a silane diol in the above-mentioned amounts, for example, by controlling the rate of the non-hydrogenated sol-gel reaction , a clear viscous solution containing an oligo-silica compound can be obtained.

The condensation reaction between the organosilane diol and the alkoxysilane compound may be a non-hydrogenated condensation reaction in the presence of an alkaline earth metal hydroxide, for example, a non-hydrogenated sol-gel reaction. That is, in this embodiment, the composition for producing a polyimide composite does not contain water.

A composition containing an oligo-silica compound prepared by a hydrolytic condensation reaction requires a large amount of silica to improve optical properties (eg, transmittance). When such a large amount of silica is included, deterioration of mechanical properties of the final composite is inevitable, and, for example, brittleness of the final composite is remarkably increased.

In contrast, a composition comprising an organo-silica precursor obtained by a non-hydrogenated sol-gel reaction has improved optical properties (e.g., increased light transmittance and reduced yellowness index), even when the composite is prepared with a smaller content of silica. can indicate In the composition according to one embodiment, the content of the oligo silica compound is 1 part by weight or more, for example, 2 parts by weight or more, 3 parts by weight or more, or 4 parts by weight or more, based on 100 parts by weight of the polyamic acid modified with the alkoxysilane group. It may be more than one part by weight. For example, the content of the oligo silica compound may be 15 parts by weight or less, for example, 14.5 parts by weight or less, 14 parts by weight or less, based on 100 parts by weight of the polyamic acid modified with the alkoxysilane group. Since optical properties can be improved even by adding a small amount of the oligo-silica compound, a composite of improved quality can be provided while minimizing the effect of silica particles on mechanical properties such as brittleness of the composite.

On the other hand, in the case of a hydrosol-gel reaction, a reaction time of 24 hours or more is usually required. It was confirmed that this non-aqueous sol-gel reaction can significantly shorten the time required for preparing the composition for preparing the composite and for preparing the composite. When the oligo-silica compound is prepared by a non-hydrogenated sol-gel reaction, the composition including the oligo-silica compound does not include water and a solvent for the sol-gel reaction. Therefore, the decrease in the viscosity of the composition due to water and the solvent does not occur, and thus productivity can be improved in the composite manufacturing process and handling of the composition becomes easy.

In contrast, when the oligo-silica compound prepared by the hydrogel reaction is included, the final composition inevitably contains water. Polyamic acid, a precursor of polyimide, is sensitive to the presence of moisture. In particular, when polyamic acid is heated in the presence of moisture, the main chain is decomposed and the molecular weight of polyimide in the final polymer composite is lowered, which may lead to deterioration of physical properties of a molded article (eg, film) including the prepared polymer composite. In addition, when the content of the organo-silica precursor prepared by the hydrogel reaction increases, the final composition contains an increased amount of water. This increased amount of water causes a decrease in the viscosity of the polyamic acid solution, thereby reducing the processability. And it is disadvantageous in terms of handleability.

In a non-limiting example, referring to FIG. 1 , a non-hydrogenated condensation reaction between a hydroxyl group of a silanediol and an alkoxy group of an alkoxysilane may form a crosslinked silica precursor (eg, alcohol is removed). The non-hydrogenated condensation reaction may be carried out in the presence of a metal hydroxide catalyst. Non-limiting examples of the metal hydroxide catalyst include barium hydroxide, strontium hydroxide, and the like. The amount of the catalyst may be 0.0001 to 10 mol%, but is not limited thereto. The non-hydrogenated condensation reaction may be performed for 10 minutes or more, for example, 30 minutes to 5 hours, but is not limited thereto. The reaction temperature may be 0 degrees Celsius or higher and 200 degrees Celsius or lower, but is not limited thereto. For example, the reaction can be carried out at room temperature. Alcohol produced by the condensation reaction may be removed by an appropriate method (eg, vacuum evaporation, etc.) before mixing with the modified polyamic acid.

A composition is obtained by mixing a modified polyamic acid and an oligo silica compound (formed by a non-hydrogenated condensation reaction). The obtained composition may optionally be made into a film or the like and dried. Drying temperature may be carried out at 50 ° C to 200 ° C, but is not limited thereto. Drying may be performed in a nitrogen atmosphere, but is not limited thereto. The composition is optionally dried and cured to provide a polyimide composite in which organosilica (eg, nanoparticles thereof) is dispersed. During optional drying and curing, the polyamic acid is converted to polyimide and the oligosilica compound can form a silica network, in particular, the reactive group (e.g., alkoxy group or hydroxyl group) of the organo-silica precursor can form an alkoxy group at the end of the polyamic acid. It can react with silane to form cross-links.

Accordingly, another embodiment of the present invention relates to a polyimide composite comprising a cured product of the above-described composition.

Curing of the composition may be performed by heating the composition to a temperature sufficient to cause imidization of the polyamic acid. The temperature may be in the range of 50 degrees C or higher, for example, 80 degrees C to 400 degrees C, but is not limited thereto. Curing may be performed in a nitrogen atmosphere, but is not limited thereto. The composition can solve the problem of lowering transmittance during high-temperature curing, and the composite obtained by curing can exhibit improved transparency, reduced thermal expansion coefficient, and improved heat resistance, even compared to a composition containing an oligo-silica compound that is a product of a hydrosol-gel reaction. there is. In particular, the aforementioned effect can be obtained even when the silica content in the composite is low.

In one embodiment, the cured product does not contain silica particles having a size of 200 nm or more (even, 150 nm or more) when observed with a transmission electron microscope (TEM). In one embodiment, the cured product does not include oligo silica domains separated from the polyimide matrix when observed with a transmission electron microscope. In the polyimide composite, the Si content may be in the range of, for example, 4 wt% to 14 wt% based on the total weight of the composite. When Si is included within this range, the composite may exhibit improved optical properties in terms of transmittance, yellow index, and haze. The polyimide composite may have a transmittance of 65% or more, for example, 68% or more, and a haze of 1% or less, for example, 0.5% or less, for light having a wavelength of 430 nm. For example, the polyimide composite may simultaneously satisfy light transmittance of 70% or more, YI of 12 or less, and haze of 5% or less.

In addition, the composite may exhibit remarkably improved heat resistance at a high temperature of more than 300 degrees Celsius, for example, about 400 degrees Celsius. Therefore, the composite can solve the problem of deterioration of optical properties and physical properties of the polyimide film in a subsequent high-temperature process. For example, the polyimide composite has a coefficient of thermal expansion (CTE) obtained by heating a specimen from 30 ° C to 400 ° C at a rate of 10 ° C / min under a load of 0.05 N is 150 ppm / ° C or less, for example, 130 ppm / may be below degrees Celsius.

In another embodiment, the film includes the polyimide composite.

In another embodiment, an electronic device includes the film. The film may be used for a substrate of an electronic device, an insulating film, a dielectric film, a flat film, a protective film, and the like.

The electronic device may be a flat panel display, a touch panel, a solar cell, an e-window, a heat mirror, a transparent transistor, a flexible display, a complementary metal oxide semiconductor sensor, or a light emitting diode light.

Hereinafter, embodiments of the invention will be described in detail with reference to examples. However, the following examples are merely illustrative of embodiments of the invention by way of example, and the scope of the invention is not limited thereto.

[Example]

I. Preparation of Compositions and Composites

Example 1;

[1] Production of poly(amic acid):

Under a nitrogen atmosphere, N-Methyl-2-pyrrolidone (NMP) was introduced into the reactor. 2,2'-bistrifluoromethyl-4,4'-biphenyldiamine (TFDB) is added to the reactor and dissolved to prepare a TFDB solution. 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added to the TFDB solution so that the molar ratio (TFDB/BPDA) with TFDB was between 0.9 and 0.99, and at 25 degrees Celsius. The reaction is performed for 48 hours to obtain polyamic acid.

[2] End capping treatment with aminoalkyl siloxane:

Add gammaaminopropyltrimethoxysilane to the solution containing the polyamic acid prepared in item [1] and stir at 25°C to cap the anhydride end of the polyamic acid with an alkoxysilane. The content of gamma aminopropyltrimethoxysilane is 2.0 to 2.3 times the difference between diamine and dianhydride molar content.

[3] Preparation of reactive oligo silica compounds (through non-hydrogenated condensation reaction)

10 grams (0.066 mol) of tetramethoxysilane and 3.57 grams (0.0165 mol) of diphenylsilanediol were placed in a flask, to which barium hydroxide was again added in an amount of 0.2 mol% based on 1 mol of tetramethoxysilane, and then 80 Stir for 5 hours at ° C. Methanol is removed from the obtained reaction mixture using a vacuum evaporator to obtain a reactive oligo silica compound.

[4] Preparation of a composition and preparation of a composite by curing the composition

A predetermined amount of the aminosiloxane end-capped polyamic acid prepared in item [2] and a predetermined amount of the reactive oligosilica compound obtained in item [3] are mixed and stirred to obtain a composition. The Si content in the composition is 4.3% by weight.

The obtained composition is coated on a glass substrate to form a film, and the obtained film is heat-treated at 300° C. for 60 minutes in a nitrogen atmosphere to obtain a polyimide composite containing oligo-silica.

Examples 2 to 5:

A composition and a polyimide composite were prepared in the same manner as in Example 1, except that a predetermined amount of the aminosiloxane end-capped polyamic acid and a predetermined amount of the reactive oligosilica compound were mixed to obtain a composition in which the Si content in the composition was shown in Table 1, respectively. manufacture

Comparative Example 1

A polyimide was prepared in the same manner as in Example 1 except for using the composition composed of the aminosiloxane end-capped polyamic acid without adding a reactive oligo silica compound.

Comparative Examples 2 to 3

A composition and a polyimide composite were prepared in the same manner as in Example 1, except that a predetermined amount of the aminosiloxane end-capped polyamic acid and a predetermined amount of the reactive oligosilica compound were mixed to obtain a composition in which the Si content in the composition was shown in Table 1, respectively. manufacture

Comparative Example 4:

A composition and a polyimide composite were prepared in the same manner as in Example 1, except that a predetermined amount of non-endcapped polyamic acid and a predetermined amount of a reactive oligosilica compound were mixed to obtain a composition having Si content in the composition as shown in Table 1, respectively. do.

Comparative Example 5 and Comparative Example 6:

Except for using a silica precursor prepared by a hydrous sol-gel reaction instead of the oligo silica compound prepared through a non-hydrous sol-gel reaction, and the silica content of the composition as shown in Table 1, respectively, Example 1 and A composition was prepared in the same way, and a silica-containing polyimide composite was obtained therefrom.

II. Characterization and physical property evaluation of the prepared composite

1. Measurement of light transmittance of the composite

For the composites obtained from Examples 1 to 5 and Comparative Examples 1 to 6, the transmittance (%) of the full wave for 300 to 800 nm light and the transmittance (%) for light with a wavelength of 430 nm were measured in the following manner:

A part of the sample was cut into a width of 50mm x length of 50mm and the transmittance was measured using Minolta Spectrophotometer CM-3600d.

The results are summarized in Table 1.

2. Measurement of yellowness index of composites

The yellow index (YI) of the composites obtained from Examples 1 to 5 and Comparative Examples 1 to 6 was measured in the following manner:

A part of the sample was cut into a width of 50mm x length of 50mm and the yellowness index was measured using a Minolta Spectrophotometer CM-3600d.

The results are summarized in Table 1.

3. Haze measurement of the composite

The haze of the composites obtained from Examples 1 to 5 and Comparative Examples 1 to 6 was measured in the following manner:

A part of the sample was cut into a width of 50 mm x a length of 50 mm and haze was measured using a Minolta Spectrophotometer CM-3600d.

The results are summarized in Table 1.

4. Measurement of the thermal expansion coefficient of the composite

The coefficient of thermal expansion (CTE) of the composites obtained from Examples 1 to 3 and Comparative Example 1 was measured in the following manner:

A portion of the sample is cut into a width of 5 mm x a length of 30 mm, and a coefficient of thermal expansion (CTE) is measured using TA's thermal mechanical analysis apparatus Q400. After hanging the sample on a quartz hook and applying a force of 0.050 N, it is heated from 30 to 400 at a rate of 10/min in a nitrogen atmosphere. The value of the coefficient of thermal expansion is found within the range of 50 to 400.

The results are shown in Fig. 2 and Table 2.

5. Transmission electron microscopy analysis of the complex

The composite of Example 4 and the composite of Comparative Example 4 were subjected to transmission electron microscopy analysis using a Tecnai G2 device from FEI, and the results are shown in FIGS. 3 and 4 , respectively.

Si content*
(wt%) Transmittance (%) YI haze Total @430 nm Comparative Example 1 0 84 63 17.3 0.5 Example 1 4.3 86 72 11.4 0.3 Example 2 8.3 86 72 11.3 0.3 Example 3 11.9 87 78 7.2 0.2 Example 4 13.9 88 80 6.9 0.3 Example 5 14.9 86 75 8.9 2.5 Comparative Example 2 15.3 73 56 15.5 43.1 Comparative Example 3 18.4 58 45 18.9 98.5 Comparative Example 4 13.9 86 71 14.1 0.9 Comparative Example 5 20 86 66 14.7 0.4 Comparative Example 6 25 86 72 10.3 0.6

Note *: The Si content in Table 1 is the Si atom content derived from oligosilica compounds.

The results of Table 1 confirm that the composites of Examples 1 to 4 exhibit improved optical properties compared to the composites of Comparative Examples. For example, the composites of Example 1 and Example 4, although having Si contents of 4.3% and 13.9%, respectively, can exhibit approximately 14% and 27% improved transmittance (at 430 nm) compared to Comparative Example 1, whereas , the composite of Comparative Example 6 has a Si content of as much as 25% by weight, but exhibits only 10% higher transmittance (at 430 nm) compared to Comparative Example 1. That is, the composites of Examples 1 to 5 can exhibit improved optical properties such as higher transmittance (even in the short wavelength region) even when the composites of Examples 1 to 5 include a reduced amount of silica, and thus do not affect other mechanical properties such as brittleness. It is possible to improve the optical properties of the composite without

From the results of Comparative Example 6, it is confirmed that the silica content to be added must be much larger (e.g., eg, 3 times) in order to realize optical properties such as non-hydrolysis through hydrolysis.

Si content
(wt%) CTE (ppm/)
50 to 400 Comparative Example 1 0 314.7 Example 1 4.3 107.7 Example 2 8.3 91.1 Example 3 11.9 84.0

From the results of Table 2 and FIG. 2, it was confirmed that the composites of Examples 1 to 3 can exhibit a significantly lower coefficient of thermal expansion CTE (especially, when heat treated at a high temperature of 400 ° C) compared to the polyimide of Comparative Example 1. do. Therefore, it can be advantageously applied to an optical element (eg, a transparent substrate or a light-transmitting film) in a process including a subsequent heat treatment at a high temperature, such as an organic LED manufacturing process.

Although the embodiments of the invention have been described in detail through examples, the invention is not limited to these examples, and those skilled in the art will, the spirit of the invention and the invention and It will be appreciated that all modifications or variations to the invention embodiments readily made therefrom are within the scope of the invention.

Claims (22)

A composition comprising a polyamic acid modified with an alkoxysilane group and an oligo silica compound,
The Si atom content in the composition is 15% by weight or less based on the total solid weight of the composition,
The polyamic acid modified with an alkoxysilane group includes a reaction product between a condensation polymerization product of an acid dianhydride and a diamine and a reactive organosilane compound, and the oligosilica compound is a non-hydrogenated condensation reaction product of an organosilane diol and an alkoxysilane compound. A composition comprising According to claim 1,
A composition in which the content of water in the composition is 100 ppm or less. According to claim 1,
The condensation polymerization product of the acid dianhydride and diamine includes a condensation polymerization product of an acid dianhydride represented by the following formula (1) and a diamine represented by the following formula (2), and has a functional group capable of reacting with the reactive organosilane compound at at least one end thereof. Composition:
[Formula 1]

Here, A ₁ is the same or different, and each independently a substituted or unsubstituted tetravalent C6 to C24 aliphatic ring group, a substituted or unsubstituted tetravalent C6 to C24 aromatic ring group, or a substituted or unsubstituted 4 It is a valent C4 to C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group exists alone, or two or more rings are fused together to form a condensed ring; Two or more rings are directly bonded, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, ( CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), a C1 to C10 linear or branched aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, A C1 to C10 alkylene group having at least one substituent selected from a C6 to C20 aromatic hydrocarbon group and a C6 to C20 alicyclic hydrocarbon group, -C(CF ₃ ) ₂ -, -C(CF ₃ ) (C ₆ H ₅ )-, or -C(=0)NH-;
[Formula 2]
NH ₂ -A ₂ -NH ₂
Here, A ₂ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group, or a substituted or unsubstituted divalent C4 to C24 heteroaromatic ring group, The aliphatic ring group, aromatic ring group, or heteroaromatic ring group exists alone, or two or more rings are fused together to form a condensed ring; Two or more rings are directly bonded, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, ( CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), a C1 to C10 linear or branched aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, A C1 to C10 alkylene group having at least one substituent selected from a C6 to C20 aromatic hydrocarbon group and a C6 to C20 alicyclic hydrocarbon group, -C(CF ₃ ) ₂ -, -C(CF ₃ ) (C ₆ H ₅ )-, or connected by -C(=O)NH-. According to claim 3,
A composition in Formula 1 wherein A ₁ is any one of the following:

here,
X ¹ to X ⁸ are the same or different and are each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, - C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-;
Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C1 to C5 alkyl group;
Z ² and Z ³ are the same or different, and are each independently -N= or -C(R ³⁰¹ )= (where R ³⁰¹ is hydrogen or a C1 to C5 alkyl group), but Z ² and Z ³ are simultaneously -C(R ³⁰¹ )= not,
R ³⁰ to R ⁵⁰ and R ⁵⁴ to R ⁶⁰ are the same or different, and are each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;
R ⁵¹ to R ⁵³ are the same or different, and each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;
k30, k31, and k32 are independently integers from 0 to 2;
k33, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently integers from 0 to 3;
k34 is 0 or 1;
k38, k45, k50, k55, and k56 are independently integers from 0 to 4;
k40, k41, k47, k48, and k49 are independently integers from 0 to 5, and
k58, k59, and k60 are independently integers from 0 to 8;
* is the part connected to the carbon of the carbonyl group. According to claim 3,
In Formula 2, A ₂ is any one of the following compositions:

here,
X ¹⁰ to X ¹⁶ are the same or different, and each independently a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - where 1≤p≤10, -(CF ₂ ) _q - where 1≤q≤10, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,
R ⁷⁰ to R ⁸⁶ and R ⁸⁹ to R ⁹⁰ are the same or different, and are each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;
R ⁸⁷ and R ⁸⁸ are the same or different, and are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group;
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82, and k83 are independently integers from 0 to 4;
k71, k72, k85, and k86 are independently integers from 0 to 3, and
k84, k89, and k90 are independently integers from 0 to 10;
* is the part connected to nitrogen. According to claim 1,
The condensation polymerization product of the acid dianhydride and the diamine is 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicycle Rho[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroiso propylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic Pyromellitic dianhydride (PMDA), 4-((2,5-dioxotedrahydrofuran-3-yl)-1,2,3,4-tetranaphthalene-1,2-dicarboxylic acid Hydride (4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzene tetracarboxylic acid dianhydride; 1,2,3,4-benzene tetracarboxylic acid dianhydride; 1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis(3,4-dicarboxy phenoxy) benzene dianhydride; 1,2,4,5-naphthalene tetracarboxylic dianhydride; 1,2,5,6-naphthalene tetracarboxylic dianhydride; 1,4,5,8-naphthalene tetracarboxylic 2,3,6,7-naphthalene tetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,7-dichloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride;2,3,6,7-tetrachloronaphthalene-1,4 ,5,8-tetracarboxylic dianhydride; 2,2',3,3'-biphenyl tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride; bis(2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylether dianhydride; bis(3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfide dianhydride; bis(3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride; 2,2',3,3'-benzophenone tetracarboxylic dianhydride; 2,3,3'4'-benzophenone tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride; bis(2,3-dicarboxyphenyl) methane dianhydride; bis(3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride; 1,2-bis(3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiophene tetracarboxylic dianhydride; 2,3,5,6-pyrazine tetracarboxylic dianhydride; 1,8,9,10-phenanthrene tetracarboxylic dianhydride; 3,4,9,10-perylene tetracarboxylic dianhydride; 1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 1,1-bis(3,4-dicarboxyphenyl)-1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethanedianhydride; an acid dianhydride selected from 4,4′-bis[2-(3,4-dicarboxyphenyl)hexafluoroisopropyl]diphenyl etherdianhydride, or mixtures thereof; and
bistrifluoromethyldiaminophenyl (TFDB), m-phenylene diamine; p-phenylene diamine; 1,3-bis(4-aminophenyl) propane; 2,2-bis(4-aminophenyl) propane; 4,4'-diamino-diphenyl methane; 1,2-bis(4-aminophenyl) ethane; 1,1-bis(4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; bis(4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; bis(3-aminophenyl) sulfone; bis(4-aminophenyl) sulfone; 4,4'-diamino-dibenzyl sulfoxide; bis(4-aminophenyl) ether; bis(3-aminophenyl) ether; bis(4-aminophenyl)diethyl silane; bis(4-aminophenyl) diphenyl silane; bis(4-aminophenyl) ethyl phosphine oxide; bis(4-aminophenyl) phenyl phosphine oxide; bis(4-aminophenyl)-N-phenyl amine; bis(4-aminophenyl)-N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl;3,3'-diamino-biphenyl;3,3'-dichloro-4,4'-diamino-biphenyl;3,3'-dimethyl-4,4'-diamino-biphenyl;3,4'-dimethyl-4,4'-diamino-biphenyl;3,3'-dimethoxy-4,4'-diamino-biphenyl;4,4'-bis(4-aminophenoxy)-biphenyl;2,4-diamino-toluene;2,5-diamino-toluene;2,6-diamino-toluene;3,5-diamino-toluene;1,3-diamino-2,5-dichloro-benzene;1,4-diamino-2,5-dichloro-benzene;1-methoxy-2,4-diamino-benzene;1,4-diamino-2-methoxy-5-methyl-benzene;1,4-diamino-2,3,5,6-tetramethyl-benzene;1,4-bis(2-methyl-4-amino-pentyl)-benzene;1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene;1,4-bis(4-aminophenoxy)-benzene; o-xylylene diamine; m-xylylene diamine; p-xylylene diamine; 3,3'-diamino-benzophenone;4,4'-diamino-benzophenone;2,6-diamino-pyridine;3,5-diamino-pyridine;1,3-diamino-adamantane; bis[2-(3-aminophenyl)hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1,1'-diadamantane;N-(3-aminophenyl)-4-aminobenzamide;4-aminophenyl-3-aminobenzoate; 2,2-bis(4-aminophenyl) hexafluoropropane; 2,2-bis(3-aminophenyl) hexafluoropropane; 2-(3-aminophenyl)-2-(4-aminophenyl)hexafluoropropane; 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane; 2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl hexafluoropropane; 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane; 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane; 1,4-bis(3-aminophenyl)buta-1-en-3-yne; 1,3-bis(3-aminophenyl) hexafluoropropane; 1,5-bis(3-aminophenyl) decafluoropentane; and 4,4'-bis[2-(4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, 2 ,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine: TFDB), and diaminofluorene, 1,1-bis(4-aminophenyl)cyclohexane (BACH), 4,4'-(hexafluoroisopropylidene) bis(p-phenyleneoxy)dianiline (4,4'-(hexafluoroisopropylidene) bis(4-phenoxyaniline, 6FIDDA), 9,9-bis(4-amino phenyl)fluorene (BAPF), and polycondensation products of diamines selected from mixtures thereof;
A composition having functional groups capable of reacting with the reactive organosilane compound at one or both terminals.
According to claim 1,
The reactive organosilane compound is a composition represented by Formula 3 below:
[Formula 3]

Here, L is a single bond, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof, and A Is -NH ₂ or an acid anhydride group, R ₁ to R ₃ are each independently a C1 to C6 alkyl group or a C1 to C6 alkoxy group, but at least one of R ₁ to R ₃ is a C1 to C6 alkoxy group. According to claim 1,
The reactive organic silane compound is gamma aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propyl succinyl anhydride, or a combination thereof. According to claim 1,
The amount of the reactive organosilane compound is 0.01 mol to 10 mol per 1 mol of the alkoxysilane compound composition. According to claim 1,
The organosilane diol is represented by Formula 4 below;
[Formula 4]

Here, n is an integer of 1 to 10, and R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms substituted with a cycloalkyl group having 1 to 20 carbon atoms. An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
Wherein the alkoxysilane compound is tetramethoxysilane, tetraethoxysilane, or a mixture thereof. According to claim 1,
The non-hydrogenated condensation reaction of the organosilane diol and the alkoxysilane compound is a non-hydrogenated condensation reaction in the presence of an alkaline earth metal hydroxide. According to claim 1,
A composition in which the content of the alkoxysilane compound is 2 to 10 moles per mole of the organic silane diol. According to claim 1,
The content of the oligo silica compound is 1 to 10 parts by weight per 100 parts by weight of the polyamic acid modified with the alkoxysilane group. A composite comprising a cured product of the composition of claim 1. According to claim 14,
The cured product has a size of 200 nm or more when observed with a transmission electron microscope and does not contain silica domains separated from the polyimide matrix. According to claim 14,
The cured product, when observed with a transmission electron microscope, does not contain silica domains separated from the polyimide matrix. According to claim 14,
The composite has a Si content of 4% to 14% based on the total weight of the composite. According to claim 14,
The composite has a transmittance of 65% or more for light having a wavelength of 430 nm and a haze of 1% or less. According to claim 14,
The composite has a coefficient of thermal expansion (CTE) of 150 ppm / ° C or less obtained by heating the specimen from 30 ° C to 400 ° C under a load of 0.05 N at a rate of 10 ° C / min. A film comprising the complex of claim 14 . An electronic device comprising the film of claim 20. A method for producing a polyimide composite comprising the following steps:
Preparing a polyamic acid by the reaction of acid dianhydride and diamine;
preparing a polyamic acid modified with an alkoxysilane group by reacting the polyamic acid with a reactive organosilane compound;
Preparing an oligo silica compound by a non-hydrogenated condensation reaction of an organosilane diol and an alkoxysilane compound;
Mixing the polyamic acid modified with the alkoxysilane group and the oligo silica compound, and curing.

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