KR20160115770A - Compositions, composites prepared therefrom, and films and electronic devices including the same - Google Patents

Abstract

Provided are a composition, a polyimide composite manufactured therefrom, and an electronic element comprising the composite. The composition comprises polyamic acid modified with an alkoxysilane group, and an oligo silica compound. The polyamic acid modified with an alkoxysilane group includes a reaction product between a reactive organic silane compound and a product of condensation polymerization of acid anhydride and diamine. The oligo silica compound includes a product of condensation reaction of organic silanediol and alkoxysilane compound. The Si element content in the composition is less than or equal to 15 wt%, based on the total weight of solids in the composition.

Description

FIELD OF THE INVENTION [0001] The present invention relates to compositions, composites prepared therefrom, and films and electronic devices comprising the same. BACKGROUND OF THE INVENTION < RTI ID =

Compositions, composites prepared therefrom, and films and electronic devices comprising them.

Polyimide is a kind of high performance polymer, and includes a cyclic imide and an aromatic ring in the main chain. Polyimides have gained considerable importance in advanced technology fields such as microelectronics, aviation and separation technology because they have relatively good thermal stability, mechanical properties and optical properties. For example, polyimide finds its usefulness as a transparent substrate (for example, a 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, development of a polyimide-based material having improved optical properties such as yellow index, light transmittance and haze has been demanded.

Such a polyimide-based material can be exposed to high temperatures during the process for a final product such as a display or an electronic device. For example, organic LED manufacturing involves processing the substrate at a high temperature of about 350 or greater for a period of time to maintain the key characteristic quality of the panel. However, when the transparent polyimide substrate is heat-treated at a temperature higher than the glass transition temperature, the optical properties (light transmittance, haze, yellow index) of the material may be significantly deteriorated. For example, high temperature heat treatment can cause interchain or chain packing phenomena due to the movement of the polymer chain. As a result, a charge transfer complex (CTC) can be formed, which is considered to be a cause of yellowing by dominantly absorbing visible light in a low wavelength region. Further, after the heat treatment, the polyimide substrate may exhibit degraded mechanical properties. Accordingly, development of a polyimide-based material capable of maintaining the original physical properties (e.g., optical properties such as transmittance, yellow index, and mechanical properties) after high-temperature processing is required.

One embodiment is directed to a composition for producing a polyimide composite that exhibits improved optical properties and is capable of maintaining original properties even after high temperature processing.

Another embodiment is directed to a polyimide composite film made from the composition.

Another embodiment is directed to an electronic device comprising the polyimide composite film.

In one embodiment, the composition comprises a polyamic acid modified with an alkoxysilane group and a oligo silica compound, wherein the Si atomic content in the composition is 15 wt% or less based on the total weight of solids of the composition. The polyamic acid modified with the alkoxysilane group includes a reaction product between a polycondensation product of an acid dianhydride and a diamine and a reactive organosilane compound. The oligosilica compound includes a condensation reaction product of an organosilane diol and an alkoxysilane compound.

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

The polycondensation product of the acid dianhydride and the diamine may include an acid dianhydride represented by the following formula (1) and a condensation product of a diamine of the following formula (2), and the condensation product of the condensation product may contain at least one reactive organosilane compound Lt; RTI ID = 0.0 > and / or < / RTI >

[Chemical Formula 1]

Wherein A ₁ is selected from substituted or unsubstituted quadrivalent C5 to C24 aliphatic cyclic groups, substituted or unsubstituted quadrivalent C6 to C24 aromatic ring groups, and substituted or unsubstituted quadrivalent C4 to C24 heteroaromatic cyclic groups. And the aliphatic or (hetero) aromatic ring group is present alone; Or two or more of them are bonded to each other to form a polycyclic ring; Or two or more of said aliphatic rings or two or more said (hetero) aromatic rings are single bonds, -O-, -S-, -C (= O) -, -CH (OH) ₂ , -Si (CH ₃ ) ₂ -, - (CH ₂ ) _p - wherein ₁ ? _P ? 10, - (CF ₂ ) _q - A C1 to C10 alkylene group having at least one substituent selected from a C1 to C10 aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group and a C6 to C20 alicyclic hydrocarbon group, a C = O) NH, or a combination thereof;

(2)

NH ₂ -A ₂ -NH ₂

Wherein 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 is a residue selected from (where, L is a single bond or a C1 to C10 alkylene group), the aliphatic or aromatic group is present singularly; Or two or more of them are bonded to each other to form a polycyclic ring; Or two or more of the aliphatic ring, or two or more of the aromatic ring is a single 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), C1 to C10 straight- or branched-chain A C1 to C10 divalent alkylene group having at least one substituent selected from an aliphatic hydrocarbon group of C1 to C10, a fluoroalkyl group of C1 to C10, an aromatic hydrocarbon group of C6 to C20 and an alicyclic hydrocarbon group of C6 to C20, O) NH-, or a combination thereof.

In formula (1), A ₁ can be any of the following:

here,

X ¹ to X ⁸ 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-,

Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different, each independently represent -N = or -C (R ³⁰¹⁾ =, where R ³⁰¹ is hydrogen or a C1 to C5 being alkilgiyi, Z ² and Z ³ together -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 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,

k30, k31, and k32 are independently an integer of 0 to 2,

k33, k35, k35, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently an integer of 0 to 3,

k34 is 0 or 1,

k38, k45, k50, k55, and k56 are independently an integer of 0 to 4,

k40, k41, k47, k48, and k49 are independently an integer of 0 to 5, and

k58, k59, and k60 are independently an integer of 0 to 8;

In Formula 2 A ₂ can be represented by any of the following:

here,

X ¹⁰ to X ¹⁶ are the same or different and each is 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 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 an integer of 0 to 4,

k71, k72, k85, and k86 are independently an integer of 0 to 3, and

k84, k89, and k90 are independently an integer of 0 to 10.

The polycondensation product of the acid dianhydride and the diamine is preferably selected from the group consisting of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicyclic tetracarboxylic dianhydride (2.2.2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo [2.2.2] oct- BTDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4' - (hexafluorois Hexafluoroisopropylidene diphthalic anhydride, 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic anhydride (4,4'- Pyromellitic dianhydride (PMDA), 4 - ((2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylic acid 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,4-bis (2,3-dicarboxyphenoxy Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalene Tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene- Tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5 , 8-tetracarboxylic acid dianhydride; 2,2 ', 3,3'-diphenyltetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide 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 acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid 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-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid 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-trifluoroethane dianhydride; Acid anhydride selected from 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride,

2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 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-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; 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-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 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) but-1-en-3-yl; 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 (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 -Aminophenyl) fluorene (BAPF), and mixtures thereof, and may have anhydride residues, amine residues, or both at one or both ends.

Wherein the condensation product of the acid dianhydride and the diamine is an acid anhydride selected from biphenyl dianhydride (BPDA), bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA) And bis-trifluoromethyldiaminophenyl (TFDB), and may have anhydride residues, amine residues, or both at one or both ends.

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

(3)

Wherein L is a single bond, a substituted or unsubstituted alkylene of 1 to 12 carbon atoms, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, is a group -NH ₂ or an acid anhydride,

R ₁ to R ₃ are each independently a C ₁ to C 6 alkyl group or a C ₁ to C 6 alkoxy group, and at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group.

The reactive organosilane compound may be gammaaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinianhyde, or a combination thereof.

The content of the reactive organosilane compound may be 0.01 mol or more and 10 mol or less per mol of the alkoxysilane compound.

The organosilane diol may be represented by the following formula (4): < EMI ID =

[Chemical Formula 4]

Wherein n is an integer of 1 to 10, and R ₁ and R ₂ are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group having 3 to 8 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 of the organosilane diol and the alkoxysilane compound may be a non-hydrocondensation reaction performed in the presence of an alkaline earth metal hydroxide.

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

The content of the oligosilica 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 comprises a cured product of the composition described above. In the polyimide composite, the Si atom content may be up to 15% by weight based on the total weight of the polyimide composite. The Si atom content can be determined by scanning electron microscopy (SEM) or energy dispersive X-ray spectroscopy (SEM / EDX).

The cured product does not include separated silica particles having a size of 200 nm or more when observed by 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 with respect to 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 / degree or less obtained by heating the specimen of the composite at a temperature of 30 ° C under a load of 0.05N at 400 ° C at a rate of 10 ° C / minute.

In another embodiment, the film comprises the polyimide complex.

In another embodiment, the electronic device comprises the film.

The electronic device can 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 illumination.

In another embodiment, a method of making a polyimide composite comprises the steps of preparing a polyamic acid by reaction of an acid dianhydride with an anhydride,

Reacting the polyamic acid with a reactive organosilane compound to prepare a polyamic acid modified with an alkoxysilane group,

Preparing an oligosilica compound by non-hydrolytic condensation reaction of an organosilane diol and an alkoxysilane compound,

Mixing the alkoxysilane group-modified polyamic acid with the oligosilica compound, and

Curing step

.

The polyimide composite prepared from the composition according to one embodiment can exhibit improved optical properties (e.g., light transmittance, yellow index, and haze value) and is capable of suppressing or preventing degradation of physical properties, have.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 schematically depicts a reaction scheme for preparing a polyimide complex according to one non-limiting embodiment.
2 is a graph showing the results of thermomechanical analysis of the polyimide of Comparative Example 1 and the polyimide composite of Examples 1 to 3.
3 shows a transmission electron microscope image of the polyimide composite prepared in the example.
Fig. 4 shows a transmission electron microscope image of the polyimide composite prepared in the comparative example.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom contained in a given functional group or compound is replaced by a halogen atom (-F, -Cl, -Br or -I), a hydroxy group, a cyano group, an amino group ^{_{(NH 2, NH (R 100}} ) , or ^{N (R 101) (R 102} ) , wherein R ^100, R ¹⁰¹ and R ¹⁰² are the same or different, being each independently selected from C1 to C10 alkyl group) , A substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group (e.g., a cycloalkyl group and the like), a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkyl group, 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 (for example, benzyl group, naphthyl group, fluorenyl group, One or more teeth selected from the group consisting of And the substituents may be connected to each other to form a ring.

Unless otherwise specified in the specification, "alkyl group" means C1 to C30 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C30 cycloalkyl group, specifically C3 Refers to a C1 to C30 alkoxy group, specifically a C1 to C18 alkoxy group, and an "ester group" means a C2 to C30 ester group, specifically, a C2 to C30 cycloalkyl group, Quot; means a C2 to C30 ketone group, specifically, a C2 to C18 ketone group, and the "aryl group" means a C6 to C30 aryl group, specifically, a C6 to C18 aryl Quot; alkenyl group "means a C2 to C30 alkenyl group, specifically, a C2 to C18 alkenyl group.

Means a straight or branched, saturated, aliphatic hydrocarbon group, having a valence of at least 2, optionally substituted with one or more substituents to the extent that the valency of the alkylene group is not exceeded have.

Herein, "arylene" is a bivalent radical formed by the removal of two hydrogen atoms from at least one ring of aromatic hydrocarbons, wherein hydrogen 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 at least one heteroatom linked to at least one carbon atom of the alkylene group. The heteroatom may be independently selected from nitrogen, oxygen, sulfur, and phosphorus.

As used herein, the term " reactive organosilane compound "means an organosilane compound having a functional group capable of reacting with a reactive functional group (for example, an hydride group or an amine group) included in the condensation reaction product of an acid dianhydride and a diamine It says.

The term " polyamic acid modified with an alkoxysilane group "as used herein refers to a polyamic acid modified to have an alkoxysilane group.

The term "alkoxysilane group" as used herein refers to a group derived from a silane (e.g., alkoxysilyl) having one or more (e.g., one, two, three, four or more) alkoxy groups.

Here, the term "silica" is not limited to SiO _{2 but} refers to a material based on Si-O bonds and, depending on the context, silica can be SiO _x (x is 1.5 to 2.5), siloxane, and / Or an organic material such as silica or siloxane having an organic substituent (hydrogen, aryl, alkyl, etc.).

The composition according to one embodiment comprises a polyamic acid modified with an alkoxysilane group and an oligosilica compound, wherein the Si atom content in the composition is no more than 15% by weight based on the total weight of solids 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 water (for example, a trace amount of water contained in the reactant or solvent) which is inevitably included in the preparation of the composition. The term " solid content " refers to the content of the polymer, and here, it refers to the content of diamine and dianhydride contained in the composition. The Si content can be calculated from the contents of the constituents (or reaction materials) constituting the solid content in the composition.

The polyamic acid modified with the alkoxysilane group may be a polycondensation product of an acid anhydride and a diamine (e.g., an anhydride group and / or an anhydride group at least at one terminal thereof) having at least one reactive functional group such as an anhydride group and / / Or a polyamic acid having an amine group) and a reactive organosilane compound.

The acid dianhydride may be represented by the following Formula 1:

[Chemical Formula 1]

Wherein A ₁ is selected from substituted or unsubstituted quadrivalent C5 to C24 aliphatic cyclic groups, substituted or unsubstituted quadrivalent C6 to C24 aromatic ring groups, and substituted or unsubstituted quadrivalent C4 to C24 heteroaromatic cyclic groups. And the aliphatic or (hetero) aromatic ring group is present alone; Or two or more of them are bonded to each other to form a polycyclic (aromatic) ring; Or two or more of said aliphatic rings or two or more said (hetero) aromatic rings are single bonds, -O-, -S-, -C (= O) -, -CH (OH) ₂ , -Si (CH ₃ ) ₂ -, - (CH ₂ ) _p - wherein ₁ ? _P ? 10, - (CF ₂ ) _q - Or a C1 to C10 alkylene group having at least one substituent selected from a branched chain aliphatic hydrocarbon group, a C1 to C10 fluoroalkyl group, a C6 to C20 aromatic hydrocarbon group, and a C6 to C20 alicyclic hydrocarbon group (e.g., g., CR ₂ - a, R is independently hydrogen, C1 to C10 aliphatic hydrocarbon groups, C6 to be C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon odd, R are not simultaneously hydrogen) C (= O) NH, or a combination thereof.

In formula (1), A ₁ can be any of the following:

here,

X ¹ to X ⁸ 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-,

Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different, each independently represent -N = or -C (R ³⁰¹⁾ =, where R ³⁰¹ is hydrogen or a C1 to C5 being alkilgiyi, Z ² and Z ³ together -C (R ³⁰¹⁾ = However,

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 an integer of 0 to 2,

k33, k35, k35, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently an integer of 0 to 3,

k34 is 0 or 1,

k38, k45, k50, k55, and k56 are each independently an integer of 0 to 4,

k40, k41, k47, k48, and k49 are independently an integer of 0 to 5, and

k58, k59, and k60 are independently an integer of 0 to 8;

In Formula 2 A ₂ can be represented by any of the following:

here,

X ¹⁰ to X ¹⁶ are the same or different and each is 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 each independently hydrogen, halogen, substituted or unsubstituted C 1 to C 10 aliphatic organic groups, or substituted or unsubstituted C 6 to C 20 aromatic organic groups,

k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are independently an integer of 0 to 4,

k71, k72, k85, and k86 are independently an integer of 0 to 3, and

k84, k89, and k90 are independently an integer of 0 to 10.

In the above formula (1), A ₁ can be selected from:

Each L is the same or different, 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 is hydrogen, a C1 to C10 linear or branched aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group, -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) - or -C (= O) NH-,

Wherein said aromatic ring is unsubstituted or substituted with one or more hydrogens selected from the group consisting of C1 to C15 alkyl groups, -F, -Cl, -Br, -I, C1 to C15 haloalkyl groups, C1 to C15 alkoxy groups, C6 to C12 An aryl group of C6 to C12, a nitro group, a hydroxy group, or a combination thereof, and * is a moiety connected to the carbon of the carbonyl group.

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

Non-limiting examples of the acid dianhydrides represented by the formula (1) include 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 (DSDA), 4,4' - (hexafluoro Hexafluoroisopropylidene diphthalic anhydride (6FDA), 4,4'-oxydiphthalic anhydride (ODPA), pyrochlore Pyromellitic dianhydride (PMDA), 4 - ((2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylate 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarb oxydic anhydride, DTDA), 1,2,4,5-benzenetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,4-bis (2,3- Naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-tetrahydrocarbamic acid dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, Naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4 , 5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene- 5,8-tetracarboxylic acid dianhydride; 2,2 ', 3,3'-diphenyltetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide 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 acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid 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-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid 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-trifluoroethane dianhydride; And 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride. Such acid dianhydride monomers can be synthesized by known methods or are commercially available. The acid dianhydrides can be used singly or as a mixture of two or more as necessary.

The diamine may be represented by the following general formula (2).

(2)

NH ₂ -A ₂ -NH ₂

Wherein 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 is a residue selected from (where, L is a single bond or a C1 to C10 alkylene group), the aliphatic or aromatic group is present singularly; Or two or more of them are bonded to each other to form a polycyclic (aromatic) ring; Or two or more of the aliphatic ring, or two or more of the aromatic ring is a single 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), C1 to C10 straight- or branched-chain A C1 to C10 divalent alkylene group having at least one substituent selected from an aliphatic hydrocarbon group of C1 to C10, a fluoroalkyl group of C1 to C10, an aromatic hydrocarbon group of C6 to C20 and an alicyclic hydrocarbon group of C6 to C20, O) NH-, or a combination thereof.

In formula _2, A 2 may be one of the following:

here,

X ¹⁰ to X ¹⁶ is the same or different and is a direct bond, each independently, -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 represent 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 each independently hydrogen, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups,

k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are independently an integer of 0 to 4,

k71, k72, k85, and k86 are independently an integer of 0 to 3, and

k84, k89, and k90 are independently an integer of 0 to 10;

In formula _2, A 2 may be selected from:

In the above formulas, L is the same or different and are 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 is hydrogen, a C1 to C10 linear or branched aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group, -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) - or -C (= O) NH-,

X is the same or different and is independently 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 may be unsubstituted or substituted with one or more hydrogen atoms selected from a C1 to C15 alkyl group, -F, -Cl, -Br, -I, a C1 to C15 haloalkyl group, a C1 to C15 alkoxy group, a C6 An aryl group of C12 to C12, an aryloxy group of C6 to C12, a nitro group, a hydroxyl 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:

Wherein R ³² to R ⁵² are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted C1 to C15 alkyl group, a substituted or unsubstituted C1 to C15 alkoxy 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 cycloalkyl group, 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 each independently represents 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 any of integers of 0 to 4,

and n38 and n39 are any of an integer of 0 to 3.

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

Specific examples of usable diamine monomers include m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 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-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; 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-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 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) but-1-en-3-yl; 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: TFDB), and diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (BACH) 4,4'- (hexafluoroisopropylidene) bis (4,4'- (hexafluoroisopropylidene) bis (4-phenoxyaniline, 6FIDDA), and 9,9-bis ) Fluorene (BAPF). The diamines may be used singly or as a mixture of two or more as necessary.

In one embodiment, the polycondensation product of the acid dianhydride and the diamine is selected from the group consisting of biphenyl dianhydride (BPDA), bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate (6FDA) , And polycondensation products of bis (trifluoromethyl) diaminophenyl (TFDB).

The condensation polymerization can be carried out by stirring the acid dianhydride and the diamine at a predetermined temperature (for example, 50 DEG C or less) in 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 appropriately selected.

For example, the condensation polymerization may be carried out in a solution containing a condensation polymerization catalyst, if desired. In the case of solution polymerization, the polymerization solvent may be any solvent known for the production of polyamic acid. Examples of the solvent include dipolar aprotic solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide and dimethylsulfoxide, gamma butyrolactone, monochlorobenzene and the like. But is not limited thereto. Examples of the condensation polymerization catalyst include, but are not limited to, paratoluenesulfonic acid and the like. In a polymerization solvent as described above, such as a dipolar aprotic solvent, the addition of a given acid dianhydride monomer, optionally in the presence of a predetermined catalyst, to a given diamine monomer at a given temperature will yield an amino group to the carbonyl carbon of the anhydride group Condensation proceeds by nucleophilic attack. The polymerization time and temperature can be appropriately selected depending on the type of the monomer used. For example, the polymerization may be carried out at a temperature of not more than 50 degrees Celsius, for example, a temperature of -20 degrees Celsius to 30 degrees Celsius, for not less than 30 minutes, for example, not less than 1 hour. The concentration of the monomer in the solution can also be appropriately selected and is not particularly limited. Acid dianhydrides and diamine monomers can be readily prepared by known synthetic methods or are commercially available. The molar ratio of acid dianhydride to acid diamine (acid dianhydride / diamine) is controlled so that the condensation product has anhydride residues at one or both ends. For example, the content of acid dianhydride may range from 0.8 to 0.99, for example, from 0.9 to 0.97, per mole of diamine.

The condensation polymerization product (for example, polyamic acid) having a reactive functional group (e.g., anhydride and / or amine residue) at one or both terminals is reacted with a reactive organosilane compound to obtain a polyamic acid modified with an alkoxysilane group. In a non-limiting example, referring to FIG. 1, the reactive functional group (e.g., amino group) of the reactive organosilane compound reacts with the anhydride group of the condensation product to obtain a polyamic acid having an alkoxysilane group at the chain end.

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

(3)

Wherein L is a single bond, a substituted or unsubstituted alkylene of 1 to 12 carbon atoms, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, Is an -NH ₂ or an acid anhydride group, R ₁ to R ₃ are each independently a C ₁ to C 6 alkyl group or a C ₁ to C 6 alkoxy group, and at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group.

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

The reaction conditions between the reactive organosilane compound and the condensation polymerization product are not particularly limited. For example, the aminoalkoxysilane and the polyamic acid are stirred in an optional solvent (e.g., dimethylacetamide (DMAc) or the like) at a temperature of not more than 100 degrees Celsius, such as not more than 50 degrees Celsius or not more than 30 degrees Celsius, A modified polyamic acid can be obtained.

The content of the reactive organosilane compound may be determined by considering the content of the polyamic acid having reactive functional groups (eg, anhydride group or amine group) at one or both terminals and the content of the alkoxysilane compound contained in the oligosilica compound It 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 organosilane compound (e.g., aminoalkoxysilane) is 0.01 to 10 moles, for example, 0.1 to 3 moles, 0.5 to 2 moles per mole of the alkoxysilane compound contained in the oligosilica compound , Or from 0.8 mole to 1.5 mole, but is not limited thereto.

The polyamic acid modified with the alkoxysilane group may react with the hydroxyl group or the alkoxy group of the oligosilica compound.

The oligosilica compound includes a condensation reaction product of an organosilane diol and an alkoxysilane compound. The alkoxysilane compound includes a monoalkoxysilane, a dialkoxysilane, a trialkoxysilane, a tetraalkoxysilane, or a combination thereof. In one embodiment, the oligosilica compound is prepared via non-hydroscopic condensation reaction, and the oligosilica compound thus prepared is mixed with the condensation product described above to obtain a composition.

The organosilane diol may be represented by the following formula (4): < EMI ID =

[Chemical Formula 4]

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

For example, the silanediol can be selected from the group consisting of 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 silanediol, an optically transparent oligosilica compound solution can be obtained.

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

For transparency of the oligosilica compound, or for improved optical properties of the resulting composite, the content of the alkoxysilane compound may be from 1 to 10 moles per mole of the organosilane diol. Non-hydroscopic condensation reactions using only an alkoxysilane compound provide an opaque oligosilica compound whereas the use of alkoxysilane compounds and silanediol in the abovementioned amounts can be achieved, for example, by controlling the rate of non- , A clear viscous solution containing an oligosilica compound can be obtained.

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

A composition comprising an oligosilica compound produced by a hydrolysis condensation reaction requires a large amount of silica in order to improve optical properties (for example, permeability). When such a large amount of silica is included, deterioration of the mechanical properties of the final composite is inevitable. For example, the final composite is remarkably increased in brittleness.

In contrast, compositions comprising organosilica precursors obtained by non-hydrophobic sol gel reactions show improved optical properties (e.g., increased light transmittance and reduced yellow index), even when containing less silica, . In the composition according to an embodiment, the content of the oligosilica 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 per 100 parts by weight of the polyamic acid modified with the alkoxysilane group Weight part or more. For example, the content of the oligosilica compound may be 15 parts by weight or less, for example, 14.5 parts by weight or less and 14 parts by weight or less, per 100 parts by weight of the polyamic acid modified with the alkoxysilane group. The optical properties can be improved by addition of a small amount of the oligosilica compound. Thus, it is possible to provide an improved quality composite while minimizing the influence of the silica particles on the mechanical properties such as brittleness of the composite.

On the other hand, in the case of the sorbent gas reaction, a reaction time of usually 24 hours or more is required. It has been confirmed that the non-hydrogel sol gel reaction can significantly shorten the time required for the preparation of the composite preparation composition and the preparation of the composite. When the oligosilica compound is prepared by a non-hydrosolvent reaction, the composition comprising the oligosilica compound does not include a solvent for water and sol-gel reaction. Therefore, the viscosity of the composition due to water and the solvent is not reduced, and thus the productivity can be improved in the process of producing the composite, and the handling of the composition is facilitated.

In contrast, if an oligosilica compound prepared by the hydrogel sol-gel reaction is included, the final composition will necessarily contain water. Polyamic acid, a precursor of polyimide, is sensitive to the presence of water. In particular, when the polyamic acid is heated in the presence of water, the main chain is decomposed to lower the molecular weight of the polyimide in the final polymer composite, which may lead to deterioration of physical properties of the molded article (e.g., film) containing the polymer composite. Also, as the content of the organosilica precursor produced by the hydrolysis of Solsol increases, the final composition will contain an increased amount of water, which increases the viscosity of the polyamic acid solution, And handling disadvantages.

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

The composition is obtained by mixing the modified polyamic acid and the oligosilica compound (formed by the non-hydration condensation reaction). The composition thus obtained may be optionally made into a film or the like and dried, for example. The drying temperature may be, but is not limited to, 50 ° C to 200 ° C. The 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 (e.g., nanoparticles thereof) is dispersed. During the optional drying and curing, the polyamic acid is converted to the polyimide and the oligosilica compound can form the silica network, and in particular, the reactants (e.g., alkoxy or hydroxy groups) of the organosilicon precursor react with the alkoxy Can react with the silane to form a crosslink.

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

Curing of the composition can 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 or more, for example, 80 degrees to 400 degrees, but is not limited thereto. The curing may be performed in a nitrogen atmosphere, but is not limited thereto. The composition can solve the problem of reduced permeability upon curing at high temperature and the composite obtained by curing can exhibit improved transparency, reduced thermal expansion coefficient, and improved heat resistance, compared to a composition comprising a oligosilica compound, have. In particular, even when the content of silica in the composite is low, the above-mentioned effect can be obtained.

In one embodiment, the cured product does not include silica particles having a size of 200 nm or more (even larger than 150 nm) when viewed with a transmission electron microscope (TEM). In one embodiment, the cured product does not include the domain of the oligosilica separated from the polyimide matrix when viewed by a transmission electron microscope. In the polyimide composite, the Si content may range, for example, from 4% by weight to 14% by weight, based on the total weight of the composite. When containing Si in 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 with respect to light having a wavelength of 430 nm, and a haze of 1% or less, for example, 0.5% or less. For example, the polyimide composite can simultaneously satisfy a light transmittance of 70% or more, a YI of 12 or less, and a haze of 5% or less.

In addition, the composite can exhibit significantly improved heat resistance at temperatures as high as 300 degrees Celsius, for example as high as 400 degrees Celsius. Therefore, the composite can solve the problem that the polyimide film shows deterioration of optical characteristics and physical properties in a subsequent high-temperature process. For example, the polyimide composite may have a coefficient of thermal expansion (CTE) of 150 ppm / degree or less, for example, 130 ppm or less, obtained by heating the specimen under a load of 0.05 N at a temperature of 30 degrees centigrade to 400 degrees centipoise at a rate of 10 degrees / / Can be less than.

In another embodiment, the film comprises the polyimide complex.

In another embodiment, the electronic device comprises the film. The film can be used as a substrate of an electronic device, an insulating film, a dielectric film, a flat film, a protective film or the like.

The electronic device can 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 illumination.

Hereinafter, embodiments of the present invention will be described in detail with reference to embodiments. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[Example]

I. Preparation of Compositions and Composites

Example 1;

[1] Poly (amic acid) Manufacture:

N-Methyl-2-pyrrolidone (NMP) is added to the reactor under a nitrogen atmosphere. 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 as to have a molar ratio (TFDB / BPDA) of 0.9 to 0.99 with TFDB, The reaction is carried out for 48 hours to obtain polyamic acid.

[2] End capping treatment with aminoalkylsiloxane:

Gamma aminopropyltrimethoxysilane is added to the solution containing the polyamic acid prepared in item [1] and stirred at 25 ° C to cap the anhydride terminal of the polyamic acid with the alkoxysilane. The content of gamma-aminopropyltrimethoxysilane is 2.0 to 2.3 times based on the difference between the content of diamine and the content of dianhydride.

[3] Production of reactive oligosilica compounds (via non-hydropolymerization)

Ten grams (0.066 mole) of tetramethoxysilane and 3.57 grams (0.0165 mole) of diphenylsilanediol were added to the flask, barium hydroxide was added thereto in an amount of 0.2 mol% based on 1 mole of tetramethoxysilane, and then 80 It is stirred for 5 hours in the city. Methanol is removed from the reaction mixture obtained using a reduced pressure evaporator to obtain a reactive oligosilica compound.

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

A predetermined amount of the amino siloxane endcapped 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 wt%.

The obtained composition is coated on a glass substrate to prepare a film, and the obtained film is heat-treated at a temperature of 300 DEG C for 60 minutes in a nitrogen atmosphere to obtain a polyimide composite containing an oligosilica.

Examples 2 to 5:

The composition and the polyimide composite were prepared in the same manner as in Example 1, except that the amounts of the amino siloxane end-capped polyamic acid and the reactive oligosilica compound were mixed to obtain a composition as shown in Table 1, respectively, .

Comparative Example 1

A polyimide is prepared in the same manner as in Example 1, except that the composition comprising the amino siloxane endcapped polyamic acid is used without addition of a reactive oligosilica compound.

Comparative Examples 2 to 3

The composition and the polyimide composite were prepared in the same manner as in Example 1, except that the amounts of the amino siloxane end-capped polyamic acid and the reactive oligosilica compound were mixed to obtain a composition as shown in Table 1, respectively, .

Comparative Example 4:

The composition and the polyimide composite were prepared in the same manner as in Example 1, except that the amounts of the non-endcapped polyamic acid and the reactive oligosilicate compound were mixed to obtain a composition as shown in Table 1, respectively, do.

Comparative Example 5 and Comparative Example 6:

The procedure of Example 1 was repeated except that a silica precursor prepared by a Suzuki gel reaction was used instead of the oligosilica compound prepared through the non-Suzanzel reaction and the silica content of the composition was changed as shown in Table 1 below. The composition is prepared in the same manner, from which a silica-containing polyimide complex is obtained.

II. Characterization and characterization of the prepared composites

1. Measurement of light transmittance of composite

The transmittance (%) of the composite obtained from Examples 1 to 5 and Comparative Examples 1 to 6 for the light of 300 to 800 nm wavelength and the light of 430 nm wavelength are measured in the following manner:

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

The results are summarized in Table 1.

2. Measurement of yellow index of composite

The yellow index (YI) is measured for the composite obtained from Examples 1 to 5 and Comparative Examples 1 to 6 by the following method:

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

The results are summarized in Table 1.

3. Measurement of composite haze

The haze of the complexes obtained in 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 and 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 thermal expansion coefficient of composite

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

A portion of the sample is cut to a width of 5 mm and a length of 30 mm, and the coefficient of thermal expansion (CTE) is measured using a TA mechanical thermal analysis apparatus Q400. The sample is placed on a quartz hook and subjected to a force of 0.050 N. The sample is then heated from 30 to 400 at a rate of 10 / min in a nitrogen atmosphere. The coefficient of thermal expansion is in the range of 50 to 400.

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

5. Transmission electron microscopy analysis of composite

The composite of Example 4 and the composite of Comparative Example 4 were subjected to a transmission electron microscopic analysis using an FEI Tecnai G2 apparatus, and the results are shown in Figs. 3 and 4, respectively.

Si content *
(wt%) Transmittance (%) YI Hayes 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: In Table 1, the Si content is the Si atom content derived from the oligosilica compound.

The results in Table 1 confirm that the composites of Examples 1 to 4 exhibit improved optical properties compared to the composites of the comparative examples. For example, the composites of Examples 1 and 4 have Si contents of 4.3% and 13.9%, respectively, but may exhibit an improved transmittance (at 430 nm) of approximately 14% and 27%, respectively, , The composite of Comparative Example 6 has a Si content of about 25 wt%, but shows a transmittance (at 430 nm) that is only 10% higher than that of Comparative Example 1. That is to say, the composites of Examples 1 to 5 can exhibit improved optical properties, including reduced transmittance (even in the short wavelength region), and thus have no effect on other mechanical properties such as brittleness The optical properties of the composite can be improved.

From the results of Comparative Example 6, it is confirmed that the silica content to be added should be much higher (e. G., 3 times) to achieve optical properties such as non-hydroscopic reactions in the hydrolysis reaction.

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 can be seen that the composites of Examples 1 to 3 showed a significantly lower coefficient of thermal expansion CTE (particularly at a high temperature of 400 ° C) than the polyimide of Comparative Example 1 do. Therefore, it can be advantageously applied to an optical element (for example, 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.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, It will be appreciated that modifications and variations of the inventive embodiments that may be easily made therein are all within the scope of the invention.

Claims (22)

An alkoxysilane group-modified polyamic acid and an oligosilica compound, wherein the Si atom content in the composition is 15% by weight or less based on the total weight of solids of the composition,
Wherein the alkoxysilane group-modified polyamic acid comprises a reaction product between a polycondensation product of an acid dianhydride and a diamine and a reactive organosilane compound, and the oligosilica compound comprises a condensation reaction product of an organosilane diol and an alkoxysilane compound Composition. The method according to claim 1,
Wherein the composition has a water content of 100 ppm or less. The method according to claim 1,
The polycondensation product of the acid dianhydride and the diamine includes a polycondensation product of an acid dianhydride represented by the following formula (1) and a diamine represented by the following formula (2) and having a functional group capable of reacting with at least one terminal of the reactive organosilane compound Composition:
[Chemical Formula 1]

Wherein A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted 4 And the aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q (where ₁ ? _Q ? 10), a straight or branched aliphatic hydrocarbon group of C1 to C10, a C1 to C10 fluoroalkyl group, A C 1 to C 10 alkylene group having at least one substituent selected from a C 6 to C 20 aromatic hydrocarbon group and a C 6 to C 20 alicyclic hydrocarbon group, -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= O) NH-;
(2)
NH ₂ -A ₂ -NH ₂
Wherein 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 hetero aromatic ring group, The aliphatic ring group, aromatic ring group or heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q (where ₁ ? _Q ? 10), a straight or branched aliphatic hydrocarbon group of C1 to C10, a C1 to C10 fluoroalkyl group, A C 1 to C 10 alkylene group having at least one substituent selected from a C 6 to C 20 aromatic hydrocarbon group and a C 6 to C 20 alicyclic hydrocarbon group, -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= O) NH-. The method of claim 3,
The composition of any one of the A ₁ in formula (1) are to:

here,
X ¹ to X ⁸ 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-,
Z ¹ is -O-, -S-, or -NR ³⁰⁰ -, wherein R ³⁰⁰ is hydrogen or a C 1 to C 5 alkyl group,
Z ² and Z ³ are the same or different, each independently represent -N = or -C (R ³⁰¹⁾ = (wherein R ³⁰¹ is hydrogen or C1 to C5 alkyl group), provided that, at the same time, Z ² and Z ³ -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 an integer of 0 to 2,
k33, k35, k35, k35, k36, k37, k39, k42, k43, k44, k46, k54, and k57 are independently an integer of 0 to 3,
k34 is 0 or 1,
k38, k45, k50, k55, and k56 are each independently an integer of 0 to 4,
k40, k41, k47, k48, and k49 are independently an integer of 0 to 5, and
k58, k59, and k60 are independently integers of from 0 to 8,
* Is the moiety attached to the carbon of the carbonyl group. The method of claim 3,
A ₂ of Formula 2 is any one of the following:

here,
X ¹⁰ to X ¹⁶ are the same or different and each is 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 each independently represents hydrogen, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups,
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are independently an integer of 0 to 4,
k71, k72, k85, and k86 are independently an integer of 0 to 3, and
k84, k89, and k90 are independently an integer of 0 to 10,
* Is the part connected to nitrogen. The method according to claim 1,
The polycondensation product of the acid dianhydride and the diamine is preferably selected from the group consisting of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicyclic tetracarboxylic dianhydride (2.2.2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo [2.2.2] oct- BTDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4' - (hexafluorois Hexafluoroisopropylidene diphthalic anhydride, 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic anhydride (4,4'- Pyromellitic dianhydride (PMDA), 4 - ((2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylic acid 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,4-bis (2,3-dicarboxyphenoxy Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalene Tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene- Tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5 , 8-tetracarboxylic acid dianhydride; 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide 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 acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid 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-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid 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-trifluoroethane dianhydride; Acid anhydride selected from 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride,
Bistrifluoromethyldiaminophenyl (TFDB), m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 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-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; 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-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 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) but-1-en-3-yl; 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: TFDB), and diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (BACH) 4,4'- (hexafluoroisopropylidene) bis (4-phenoxyaniline, 6FIDDA), 9,9-bis (4-amino Phenyl) fluorene (BAPF), and mixtures thereof.
And a functional group capable of reacting with the reactive organosilane compound at one or both ends thereof.
The method according to claim 1,
Wherein the reactive organosilane compound is a compound represented by the following formula (3):
(3)

Wherein L is a single bond, a substituted or unsubstituted alkylene of 1 to 12 carbon atoms, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, Is an -NH ₂ or an acid anhydride group, R ₁ to R ₃ are each independently a C ₁ to C 6 alkyl group or a C ₁ to C 6 alkoxy group, and at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group. The method according to claim 1,
Wherein the reactive organosilane compound is gammaaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinianhyde, or a combination thereof. The method according to claim 1,
Wherein the content of the reactive organosilane compound is 0.01 mol to 10 mol per 1 mol of the alkoxysilane compound. The method according to claim 1,
The organosilane diol is represented by the following general formula (4);
[Chemical Formula 4]

Wherein n is an integer of 1 to 10, and R ₁ and R ₂ are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group having 3 to 8 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. The method according to claim 1,
Wherein the condensation reaction of the organosilane diol and the alkoxysilane compound is a non-hydrocondensation reaction in the presence of an alkaline earth metal hydroxide. The method according to claim 1,
Wherein the content of the alkoxysilane compound per 1 mole of the organosilane diol is 2 to 10 moles. The method according to claim 1,
Wherein the content of the oligosilica compound per 100 parts by weight of the alkoxysilane-modified polyamic acid is 1 to 10 parts by weight. A composite comprising a cured product of the composition of claim 1. 15. The method of claim 14,
The cured product has a size of 200 nm or more when observed by a transmission electron microscope and does not include a silica domain separated from the polyimide matrix. 15. The method of claim 14,
The cured product does not include a silica domain separated from the polyimide matrix when observed by a transmission electron microscope. 15. The method of claim 14,
Wherein the composite has an Si content of 4% to 14% based on the total weight of the composite. 15. The method of claim 14,
Wherein the composite has a transmittance of 65% or more with respect to light having a wavelength of 430 nm and a haze of 1% or less. 15. The method of claim 14,
Wherein the composite has a coefficient of thermal expansion (CTE) of 150 ppm / degree C or less obtained by heating the specimen under a load of 0.05N at 30 degrees Celsius and at a rate of 10 degrees Celsius / minute. A film comprising the composite of claim 14. An electronic device comprising the film of claim 20. A method for producing a polyimide composite comprising the steps of:
Preparing a polyamic acid by reaction of an acid dianhydride with a diamine,
Reacting the polyamic acid with a reactive organosilane compound to prepare a polyamic acid modified with an alkoxysilane group,
Preparing an oligosilica compound by non-hydrolytic condensation reaction of an organosilane diol and an alkoxysilane compound,
Mixing the alkoxysilane group-modified polyamic acid with the oligosilica compound, and curing.

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