JP6813275B2 - Compositions, composites produced from them, and films and electronic devices containing them. - Google Patents

Description

The present invention relates to compositions, composites from which they are produced, and films and electronic devices containing them.

Polyimide is a kind of high-performance polymer and contains a cyclic imide and an aromatic ring in the main chain. Polyimide has relatively excellent thermal stability, mechanical and optical properties, and has gained considerable importance in advanced technical fields such as microelectronics, aviation and separation technology. For example, polyimide has been found to be useful as a transparent substrate (for example, a flexible substrate) or a flexible transparent protective film in various display devices and electronic elements such as light emitting diodes or complementary metal oxide semiconductor sensors. There is. For this reason, the development of polyimide-based materials with improved optical properties such as yellow index, translucency, and haze is required.

This type of polyimide-based material may be exposed to high temperatures during the process for final products such as displays or electronic devices. For example, a method of manufacturing an organic light emitting diode (LED) includes a step of treating a substrate at a high temperature of about 350 ° C. or higher for a predetermined 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, the optical physical properties (transparency, haze, yellow index) of the material may be significantly deteriorated. For example, high temperature heat treatment may cause a packing phenomenon between chains or within chains due to the movement of polymer chains. As a result, a charge transfer complex (hereinafter referred to as CTC) is formed, which is considered to be one of the causes of yellowing by predominantly absorbing visible light in a low wavelength region. There is. After the heat treatment, the polyimide substrate may exhibit reduced mechanical properties. For this reason, there is a need to develop a material for a polyimide substrate that can maintain its original physical properties (for example, optical and mechanical properties such as transmittance and yellow index) even after a high temperature process.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for producing a polyimide composite which exhibits improved optical physical characteristics and retains the original physical characteristics even after high temperature treatment. That is.

Another object of the present invention is to provide a polyimide composite film produced from the above composition.

Still another object of the present invention is to provide an electronic device including the polyimide composite film.

The composition according to one embodiment of the present invention devised to achieve the above-mentioned object contains a polyamic acid and an oligosilica compound modified with an alkoxysilane group (alkoxysilyl group), and Si in the composition. The atomic content is 15% by weight or less based on the total weight of the solid content of the composition. The polyamic acid modified with the alkoxysilane group contains a reaction product between the polyamic acid dianhydride and the polycondensation product of the diamine and the reactive organic silane compound. The oligosilica compound contains a condensation reaction product of an organic silanediol and an alkoxysilane compound. The content of water in the composition can be 100 ppm or less. For example, the composition is substantially free of water.

The polycondensation product of the acid dianhydride and the diamine preferably contains an acid dianhydride represented by the following general formula 1 and a polycondensation product of the diamine of the following general formula 2. Preferably has a residue that reacts with the reactive organic silane compound at at least one end.

In the formula, A ₁ is a substituted or unsubstituted tetravalent C5-C24 aliphatic ring group, a substituted or unsubstituted tetravalent C6-C24 aromatic ring group, and a substituted or unsubstituted tetravalent. It is a residue selected from the heteroaromatic ring groups of C4 to C24, and the aliphatic, aromatic ring group or heteroaromatic ring group exists alone, or two or more are bonded to each other to form a polycyclic type. A ring is formed, or two or more selected from the two or more said aliphatic rings or the aromatic ring and the heteroaromatic ring are single-bonded, −O−, −S−, −C (= O). −, −CH (OH) −, −S (= O) ₂ −, −Si (CH ₃ ) ₂ −, − (CH ₂ ) _p − (Here, 1 ≦ p ≦ 10), − (CF ₂ ) _q − (where 1 ≦ q ≦ 10), C1 to C10 linear or branched aliphatic aliphatic groups, C1 to C10 fluoroalkyl groups, C6 to C20 aromatic hydrocarbon groups, and C6. It is linked by an alkylene group of C1 to C10 having one or more substituents selected from the aliphatic hydrocarbon groups of ~ C20, -C (= O) NH-, or a combination thereof.

In the formula, A2 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 A residue selected from the heteroaromatic ring group of C24 and -L-SiR _2- O-SiR _2- L (where L is a single bond or an alkylene group of C1 to C10), and is the above aliphatic group. Alternatively, the aromatic ring groups exist alone, or two or more of them are joined 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. Bonding, -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 aliphatic hydrocarbon groups, C1 to C10 fluoro. A divalent alkylene group of C1 to C10 having one or more substituents selected from an alkyl group, an aromatic hydrocarbon group of C6 to C20, and an aliphatic hydrocarbon group of C6 to C20, -C (= O) NH. -Or they are connected by a combination of these.

In the general formula 1, A ₁ is preferably any one of the following.

During the ceremony
X ^{1 to} X ⁸ are the same or different, and are independently bonded to each other directly, −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), -C (CH) ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= O) NH-,
Z ¹ is -O-, -S-, or -NR ^300- (where R ³⁰⁰ is hydrogen or an alkyl group of C1-C5),
Z ² and Z ³ are the same or different, and independently of each other, -N = or -C (R ³⁰¹ ) = (where R ³⁰¹ is an alkyl group of hydrogen or C1 to C5, but Z ² and Z ³ Z ³ is not -C (R ³⁰¹ ) = at the same time),
R ^{30 to} R ⁵⁰ and R ^{54 to} R ⁶⁰ are the same or different, and independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ^{51 to} R ⁵³ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aromatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups. Yes,
k30, k31 and k32 are independently integers of 0 to 2.
k33, k35, k36, k37, k39, k42, k43, k44, k46, k54 and k57 are each independently an integer of 0 to 3.
k34 is 0 or 1,
k38, k45, k50, k55 and k56 are independently integers from 0 to 4, respectively.
k40, k41, k47, k48 and k49 are independently integers from 0 to 5, respectively.
k58, k59 and k60 are independently integers from 0 to 8.

In the general formula 2, A2 is preferably represented by any one of the following.

During the ceremony
X ^{10 to} X ¹⁶ are the same or different, and are independently bonded to each other directly, −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), -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 independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ⁸⁷ and R ⁸⁸ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aliphatic organic group, or substituted or unsubstituted C6 to C20 aromatic organic group. Yes,
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are each independently an integer of 0-4.
k71, k72, k85 and k86 are independently integers of 0 to 3, respectively.
k84, k89 and k90 are independently integers from 0 to 10.

The acid dianhydride and the polycarboxylic dianhydride product of the diamine are 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] octo-7-ene-. 2,3,5,6-tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) ) Diphthalic acid dianhydride (6FDA), 4,4'-oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 4- (2,5-dioxo tetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (DTDA), 1,2,4,5-benzenetetracarboxylic dianhydride; 1,2,3,4-benzenetetracarboxylic dianhydride Anhydride; 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 1,2,4,5-naphthalene Tetetracarboxylic dianhydride; 1,2,5,6-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 2,3,6,7-naphthalenetetracarboxylic Acid 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'-diphenyltetracarboxylic 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) sulfone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl Spherone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; bis (3,4-dicarboxyphenyl) sulfonate dianhydride; 4,4'-bis (2, 3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3', 4,4'-ben Zophenonetetracarboxylic dianhydride; 2,2', 3,3'-benzophenonetetracarboxylic dianhydride; 2,3,3', 4'-benzophenonetetracarboxylic 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-carboxyphenyl) 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- (2,2) 3-dicarboxyphenoxy) phenyl] propanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propanedianhydride; [4- (2,3-dicarboxyphenoxy)- 4'-(3,4-dicarboxyphenoxy) diphenyl] propanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propanedianhydride; 2 , 3,4,5-thiophentetracarboxylic dianhydride; 2,3,5,6-pyrazinetetracarboxylic dianhydride; 1,8,9,10-phenanthenetetracarboxylic dianhydride; 3,4 , 9,10-Perylenetetracarboxylic dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride; 1,1-bis (3,4-dicarboxyphenyl) -1 −phenyl-2,2,2-trifluoroethanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropanedianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethanedianhydride; 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl ] Diphenyl ether dianhydride, or an acid dianhydride selected from a mixture thereof, and
2,2'-bis (trifluoromethyl) benzidine (TFDB, 2,2'-bistrifluoromethyl-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-amino) Phenyl) ethane; 2,2'-diamino-diethylsulfide; bis (4-aminophenyl) sulfide; 2,4'-diamino-diphenylsulfide; 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-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-adamantan; bis [2- (3-aminophenyl) hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1'-di Adamantane; 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-in; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis (3-aminophenyl) decafluoropentane; 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] Diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (BACH), 4,4'-(hexafluoroisopropyridene) bis ( From p-phenyleneoxy) dianiline, 4,4'-(hexafluoroisopropyridene) bis (4-phenoxyaniline) (6FIDDA), 9,9-bis (4-aminophenyl) fluorene (BAPF), and mixtures thereof. Containing the hydrolytic product of the diamine of choice, said anhydride residue, amine residue, or both at one or both ends It is preferable to have.

The polycondensation products of the acid dianhydride and the diamine are 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), bis (3,4-dicarboxyphenyl) hexafluoropropanedi. Contains a polycondensation product of an acid dianhydride selected from an anhydride (6FDA) or a mixture thereof and 2,2'-bis (trifluoromethyl) benzidine (TFDB), and is anhydrous at one or both ends. It preferably has a substance residue, an amine residue, or both.

The reactive organic silane compound is preferably a compound represented by the following general formula 3.

In the formula, L is a single-bonded, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof. A is a -NH ₂ or an acid anhydride group, and R _{1 to} R ₃ are independently alkyl groups of C1 to C6 or alkoxy groups of C1 to C6, but R _{1 to} R. one or more of the _3, an alkoxy group C1 -C6.

The reactive organic silane compound is preferably gamma-aminopropyltrimethoxysilane (γ-APS), aminophenyltrimethoxysilane, 3- (triethoxysilyl) propyl oxalic acid anhydride, or a combination thereof.

The content of the reactive organic silane compound is preferably 0.01 mol or more and 10 mol or less per 1 mol of the alkoxysilane compound.

The organic silanediol is preferably represented by the following general formula 4.

In the formula, n is an integer of 1 to 10, and R ₁ and R ₂ are independently alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and 3 to 8 carbon atoms, respectively. It is an alkyl group having 1 to 20 carbon atoms, 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 substituted by the cycloalkyl group of.

The alkoxysilane compound is preferably tetramethoxysilane, tetraethoxysilane, or a mixture thereof.

The condensation reaction between the organic silanediol and the alkoxysilane compound is preferably a non-hydrocondensation reaction carried out in the presence of an alkaline earth metal hydroxide.

The content of the alkoxysilane compound per mol of the organic silanediol is preferably 2 to 10 mol.

The content of the oligosilica compound per 100 parts by weight of the polyamic acid modified with the alkoxysilane group is preferably 1 to 10 parts by weight.

In other embodiments, the polyimide composite comprises a cured product of the composition described above. In the polyimide composite, the content of Si atoms is preferably 15% by weight or less based on the total weight of the polyimide composite. The content of the Si atom is preferably determined by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM / EDX).

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

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

The polyimide composite preferably has a transmittance of 65% or more and a haze of 1% or less with respect to light having a wavelength of 430 nm.

The polyimide composite has a coefficient of thermal expansion (CTE) of 150 ppm / ° C. or less obtained by heating a sample of the composite from 30 ° C. to 400 ° C. at a rate of 10 ° C./min under a load of 0.05 N. It is preferable to have.

In another embodiment, the film comprises the polyimide composite.

In yet another embodiment, the electronic element comprises the film.

The electronic element is preferably 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, the method for producing a polyimide composite consists of a step of preparing a polyamic acid by a reaction between an acid dianhydride and a diamine, and a reaction of the polyamic acid with a reactive organic silane compound by an alkoxysilane group. A step of preparing a modified polyamic acid, a step of preparing an oligosilica compound by a non-hydrocondensation reaction between an organic silanediol and an alkoxysilane compound, and a step of preparing an oligosilica compound modified by the alkoxysilane group and the oligosilica. Includes a step of mixing the compounds and a step of curing.

The polyimide composite produced from the composition according to one embodiment of the present invention exhibits improved optical physical properties (eg, translucency, yellow index, and haze value), and the deterioration of physical characteristics caused by the high temperature step. To suppress or prevent.

It is a figure which shows typically the production reaction scheme of the polyimide composite by one non-limiting embodiment. It is a graph which shows the thermomechanical analysis test result of the polyimide of Comparative Example 1 and the polyimide composite of Examples 1-3. It is a figure which shows the transmission electron microscope image of the polyimide composite produced by an Example. It is a figure which shows the transmission electron microscope image of the polyimide composite produced by the comparative example.

Hereinafter, one embodiment of the present invention will be specifically described. However, this is presented merely as an example, and the present invention is not limited thereto, and the present invention is defined by the scope of claims described later.

As used herein, unless otherwise specified, "substitution" means that one or more hydrogen atoms contained in a given functional group or compound are halogen atoms (-F, -Cl, -Br or -I". ), A hydroxy 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 Differently, each independently is an alkyl group of C1 to C10), amidino group, hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted ring. Group organic groups (eg, cycloalkyl groups), substituted or unsubstituted aryl groups (eg, benzyl group, naphthyl group, fluorenyl group, etc.), substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted Alternatively, it means that it is substituted with one or more substituents selected from the group consisting of an unsubstituted heteroaryl group and a substituted or unsubstituted heterocyclic group, and these substituents are connected to each other to form a ring. Form.

In the present specification, unless otherwise specified, "alkyl group" means an alkyl group of C1 to C30, specifically, an alkyl group of C1 to C15, and "cycloalkyl group" means C3. ~ C30 means cycloalkyl group, specifically, C3 to C18 cycloalkyl group, "alkoxy group" means C1 to C30 alkoxy group, specifically C1 to C18. The "alkyl group" means the ester group of C2 to C30, specifically, the ester group of C2 to C18, and the "ketone group" means the ketone group of C2 to C30. Specifically, it means a ketone group of C2 to C18, and "aryl group" means an aryl group of C6 to C30, and specifically, means an aryl group of C6 to C18. "Alkyl group" means an alkyl group of C2 to C30, and specifically, an alkyl group of C2 to C18.

Here, "alkylene" is a straight-chain or branched-chain saturated aliphatic hydrocarbon group, having a valence of at least 2, and depending on the selection, within a range in which the valence of the alkylene group does not exceed. Is substituted by one or more substituents.

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

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

In the present specification, the "reactive organic silane compound" is a functional group that reacts with a reactive functional group (for example, an anhydride group or an amine group) contained in a condensation reaction product of acid dianhydride and diamine. Refers to an organic silane compound having.

As used herein, the term "polyamic acid modified with an alkoxysilane group" refers to a polyamic acid modified to have an alkoxysilane group.

As used herein, the term "alkoxysilane group" refers to a group derived from a silane having one or more alkoxy groups (for example, one, two, three, four, etc.) (for example, alkoxysilyl). Say.

Here, the term "silica" is not limited to SiO ₂ , but refers to the material of the Si—O connection base, and depending on the context, silica is SiO _x (x is 1.5 to 2.5), siloxane (siloxane). ), And / or organic materials such as silica or siloxane with organic substituents (hydrogen, aryl, alkyl, etc.).

The composition according to one embodiment of the present invention contains a polyamic acid and an oligosilica compound modified with an alkoxysilane group, and the content of Si atoms in the composition is the total weight of the solid content of the composition. As a standard, it is 15% by weight or less. The composition is substantially free of water. For example, the content of water in the composition is 100 ppm or less. The water content in the composition is due to the amount of water unavoidably contained in the production of the composition (for example, a trace amount of water contained in the reactant or solvent). Here, the solid content is related to the content of the polymer, and here, it refers to the content of diamine and acid dianhydride contained in the composition. The content of Si is calculated from the content of the component (or reaction raw material) constituting the solid content in the composition.

The polyamic acid modified with the alkoxysilane group is a condensed polymerization product of acid dianhydride and diamine having a reactive functional group such as an anhydride group and / or an amine group at least one end (for example, at least). It contains a reaction product between a polyamic acid) having an anhydride group and / or an amine group at one end and a reactive organic silane compound.

The acid dianhydride is represented by the following general formula 1.

In the formula, A ₁ is a substituted or unsubstituted tetravalent C5-C24 aliphatic ring group, a substituted or unsubstituted tetravalent C6 to C24 aromatic ring group, and a substituted or unsubstituted tetravalent. It is a residue selected from the heteroaromatic ring groups of C4 to C24, and the aliphatic, aromatic ring group or heteroaromatic ring group exists alone, or two or more are bonded to each other to form a polycyclic type. A (aromatic) ring is formed, or two or more selected from the two or more said aliphatic rings or the aromatic ring and the heteroaromatic ring are single-bonded, -O-, -S-, -C. (= O)-, -CH (OH)-, -S (= O) _2- , -Si (CH ₃ ) ₂ -,-(CH ₂ ) _p- (here, 1 ≤ p ≤ 10),- (CF ₂ ) _q − (where 1 ≦ q ≦ 10), C1 to C10 linear or branched aliphatic hydrocarbon groups, C1 to C10 fluoroalkyl groups, C6 to C20 aromatic hydrocarbons. group, and one or more substituents C1~C10 alkylene group having a group (e.g., selected from a finger ring aromatic hydrocarbon groups C6 to C20, -CR ₂ - as, R is independently hydrogen, a C1~C10 fat Group hydrocarbon groups, C6-C20 aromatic hydrocarbon groups, or C6-C20 aliphatic hydrocarbon groups, but R is not hydrogen at the same time), -C (= O) NH-, or a combination thereof. It is connected.

In the general formula 1, A ₁ is preferably any one of the following.

In the formula, X ^{1 to} X ⁸ are the same or different, and are independently bonded to each other directly, −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), − C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= O) NH-,
Z ¹ is -O-, -S-, or -NR ^300- (where R ³⁰⁰ is hydrogen or an alkyl group of C1-C5),
Z ² and Z ³ are the same or different, and independently of each other, -N = or -C (R ³⁰¹ ) = (where R ³⁰¹ is an alkyl group of hydrogen or C1 to C5, but Z ² and Z ³ Z ³ is not -C (R ³⁰¹ ) = at the same time),
R ^{30 to} R ⁵⁰ and R ^{54 to} R ⁶⁰ are the same or different, and independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ^{51 to} R ⁵³ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aromatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups. Yes,
k30, k31 and k32 are independently integers of 0 to 2.
k33, k35, k36, k37, k39, k42, k43, k44, k46, k54 and k57 are each independently an integer of 0 to 3.
k34 is 0 or 1,
k38, k45, k50, k55 and k56 are independently integers from 0 to 4, respectively.
k40, k41, k47, k48 and k49 are independently integers from 0 to 5, respectively.
k58, k59 and k60 are independently integers from 0 to 8.

In general formula 2, A2 is preferably represented by any one of the following:

In the formula, X ^{10 to} X ¹⁶ are the same or different, and are independently bonded to each other directly, −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), − 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 independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ⁸⁷ and R ⁸⁸ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aliphatic organic group, or substituted or unsubstituted C6 to C20 aromatic organic group. Yes,
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are each independently an integer of 0-4.
k71, k72, k85 and k86 are independently integers of 0 to 3, respectively.
k84, k89 and k90 are independently integers from 0 to 10.

In one embodiment, in the general formula 1, A ₁ is selected from:

Each L is the same or different, and independently, 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), -CR _2- (here, 1 ≤ q ≤ 10) In, R is the same or different, and independently, hydrogen, a linear or branched aliphatic hydrocarbon group of C1 to C10, an aromatic hydrocarbon group of C6 to C20, or a finger ring group of C6 to C20. Although it is a hydrocarbon group, both Rs are not hydrogen), -C (CF ₃ ) _2- , -C (CF ₃ ) (C ₆ H ₅ )-or -C (= O) NH-
The aromatic ring is not substituted, or one or more hydrogens are C1-C15 alkyl groups, -F, -Cl, -Br, -I, C1-C15 haloalkyl groups, C1-C15 alkoxy. Substituted by a group, an aryl group of C6 to C12, an allyloxy group of C6 to C12, a nitro group, a hydroxy group, or a combination thereof, * is a portion connected to the carbon of the carbonyl group.

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

Non-limiting examples of the acid dianhydride represented by the general formula 1 include 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and bicyclo [2.2.2] octo-. 7-ene-2,3,5,6-tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-( Hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 4,4'-oxydiphthalic acid dianhydride (ODPA), pyromellitic dianhydride (PMDA), 4- (2,5-dioxo tetrahydrofuran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (DTDA), 1,2,4,5-benzenetetracarboxylic dianhydride; 1,2,3,4-benzene Tetetracarboxylic dianhydride; 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 1,2,4 , 5-Naphthalenetetracarboxylic dianhydride; 1,2,5,6-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 2,3,6,7 -Naphthalenetetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Anhydride; 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,2', 3,3'-diphenyltetracarboxylic dianhydride; 4, 4'-bis (3,4-dicarboxyphenoxy) diphenyl dianhydride; bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dian Anhydroide; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (2,3-di) Carboxoxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; bis (3,4-dicarboxyphenyl) dianhydride; 4,4'- Bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3', 4,4' -Benzophenonetetracarboxylic dianhydride; 2,2', 3,3'-benzophenonetetracarboxylic dianhydride; 2,3,3', 4'-benzophenonetetracarboxylic 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-carboxyphenyl) 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- (2,2) 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-propanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propanedianhydride 2.3,4,5-thiophentetracarboxylic dianhydride; 2,3,5,6-pyrazinetetracarboxylic dianhydride; 1,8,9,10-phenanthrenetetracarboxylic dianhydride; 3,4,9,10-Perylenetetracarboxylic dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride; 1,1-bis (3,4-dicarboxyphenyl) ) -1-phenyl-2,2,2-trifluoroethanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropanedianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethanedianhydride; 4,4'-bis [2- (3,4-dicarboxyphenyl) Hexafluoroisopropyl] diphenyl ether dianhydride can be mentioned. Such acid dianhydride monomers can be synthesized by known methods or are commercially available. The acid dianhydride may be used alone or as a mixture of two or more, if necessary.

The diamine is represented by the following general formula 2.

In the formula, A2 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 A residue selected from the heteroaromatic ring group of C24 and -L-SiR ^2- O-SiR ^2- L (where L is a single bond or an alkylene group of C1 to C10), and is the above aliphatic group. Alternatively, the aromatic ring groups exist alone, or two or more of them are joined to each other to form a polycyclic (aromatic) ring, or two or more of the aliphatic rings or two or more of the aromatics. Single ring, -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 aliphatic hydrocarbon groups, C1 A divalent alkylene group of C1 to C10 having one or more substituents selected from a fluoroalkyl group of ~ C10, an aromatic hydrocarbon group of C6 to C20, and an aliphatic hydrocarbon group of C6 to C20 (eg,- As CR _2- , R is independently hydrogen, an aliphatic hydrocarbon group of C1 to C10, an aromatic hydrocarbon group of C6 to C20, or a finger ring hydrocarbon group of C6 to C20, but R is simultaneously. It is linked by (not hydrogen), -C (= O) NH- or a combination thereof.

In the general formula 2, A2 is preferably one of the following.

In the formula, X ^{10 to} X ¹⁶ are the same or different, and are independently bonded to each other directly, −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), − C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= O) NH-,
R70 to R86 and R89 to R90 are the same or different, and independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups. ,
R ⁸⁷ and R ⁸⁸ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aliphatic organic group, or substituted or unsubstituted C6 to C20 aromatic organic group. Yes,
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are each independently an integer of 0-4.
k71, k72, k85 and k86 are independently integers of 0 to 3, respectively.
k84, k89 and k90 are independently integers from 0 to 10.

In one embodiment, in general formula 2, A2 is selected from:

In the above formula, L is the same or different, and is 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), −CR ₂ − (here, R Are the same or different, and independently, hydrogen, linear or branched aliphatic hydrocarbon groups of C1 to C10, aromatic hydrocarbon groups of C6 to C20, or finger ring hydrocarbon groups of C6 to C20. However, the two Rs are not both hydrogen), with -C (CF ₃ ) _2- , -C (CF ₃ ) (C ₆ H ₅ )-or -C (= O) NH-. Yes,
X is the same or different and independently of 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. Yes,
The aromatic or finger ring group ring is not substituted, or one or more hydrogens are C1-C15 alkyl groups, -F, -Cl, -Br, -I, C1-C15 haloalkyl groups, C1-. Substituted by an alkoxy group of C15, an aryl group of C6 to C12, an allyloxy group of C6 to C12, a nitro group, a hydroxy group, or a combination thereof, * is a portion connected to nitrogen.

In another embodiment, the A2 is selected from, but is not limited to:

In one embodiment of the invention, the diamine is one or more selected from the following compounds.

In the formula, R ^{32 to} R ⁵² are the same or different, and independently, hydrogen, halogen, nitro group, substituted or unsubstituted C1 to C15 alkyl group, substituted or unsubstituted C1 to C15 alkoxy group, respectively. Substituted or unsubstituted C1-C15 fluoroalkyl groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstituted C3-C15 heterocycloalkyl groups, substituted or unsubstituted C3-C15 oxy A cycloalkyl group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted C6-C15 oxyaryl group, or a substituted or unsubstituted C2-C15 heteroaryl group.
X ² to X ¹² are the same or different and are independently a single bond, a substituted or unsubstituted alkylene group of C1 -C10, a substituted or unsubstituted C1 -C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 allylene groups, SO ₂ , O, CO or a combination thereof.
n35 to n37 and n40 to n49 are any one of the integers 0 to 4.
n38 and n39 are any one of integers 0 to 3.

As a non-limiting example, the diamine has the following general formula:

Specific examples of diamine monomers that can be used 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-diethylsulfide; 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) 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) -be Phenyl; 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-adamantan; bis [2 -(3-Aminophenyl) Hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1'-diadamantane; N- (3-aminophenyl) -4-aminobenzamide; 4-aminophenyl-3-aminobenzoe -To; 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) phenylhexafluoropropane; 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) porcine-1-en-3-in; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis (3-aminophenyl) ) Decafluoropentane; 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, 2,2'-bis ( Trifluoromethyl) benzidine (TFDB), diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (BACH), 4,4'-(hexafluoroisopropyridene) bis (4-phenoxyaniline) (6FIDDA) and Examples include, but are not limited to, 9,9-bis (4-aminophenyl) fluorene (BAPF). The diamine may be used alone, or may be used as a mixture of two or more kinds, if necessary.

In one embodiment of the present invention, the polycondensation product of the acid dianhydride and the diamine is 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), bis (3,4-di). It contains a polycondensation product of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and an acid dianhydride selected from carboxyphenyl) hexafluoropropane dianhydride 6FDA) or a mixture thereof.

The polycondensation is carried out by stirring the acid dianhydride and the diamine in an air atmosphere or an inert gas atmosphere at a predetermined temperature (for example, 50 ° C. or lower). The conditions and usual mechanism of such condensation polymerization are well known. The polymerization method is not particularly limited and may be appropriately selected.

For example, the polycondensation is carried out in a solution containing a polycondensation catalyst, depending on the selection. In the case of solution polymerization, any solvent known for producing polyamic acids can be used as the polymerization solvent. Examples of the solvent include, but are not limited to, bipolar aprotic solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide, gamma-butyrolactone, and monochlorobenzene. Examples of the polycondensation catalyst include, but are not limited to, paratoluenesulfonic acid. When the given acid dianhydride monomer is added to the given diamine monomer at a predetermined temperature in the presence of a predetermined catalyst, depending on the selection, in the above-mentioned polymerization solvent such as a bipolar aprotonic solvent, The condensation reaction is carried out by the parental attack of the amino group on the carbonyl carbon of the anhydride group. The polymerization time and temperature may also be appropriately selected according to the type of monomer used.

For example, the polymerization is carried out at a temperature of 50 ° C. or lower, for example, −20 ° C. to 30 ° C. for 30 minutes or longer, for example, 1 hour or longer. The concentration of the monomer in the solution may be appropriately selected and is not particularly limited. Acid dianhydrides and diamine monomers can be easily produced by known synthetic methods or are commercially available. The molar ratio of acid dianhydride to diamine (acid dianhydride / diamine) is adjusted so that the polycondensation product has an anhydride residue at one or both ends. For example, the content of acid dianhydride is in the range of 0.8 to 0.99, for example 0.9 to 0.97, per mole of diamine.

The polycondensation product (eg, polyamic acid) having a reactive functional group (eg, anhydride and / or amine residue) at one or both ends reacts with the reactive organic silane compound by the alkoxysilane group. Obtain a modified polyamic acid. In a non-limiting example, referring to FIG. 1, the reactive functional group (eg, amino group) of the reactive organic silane compound reacts with the anhydride group of the polycondensation product and the alkoxysilane at the end of the chain. Obtain a polyamic acid having a group.

The reactive organic silane compound is preferably a compound represented by the following general formula 3.

In the formula, L is a single-bonded, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof. A is a -NH ₂ or an acid anhydride group, and R _{1 to} R ₃ are independently alkyl groups of C1 to C6 or alkoxy groups of C1 to C6, but R _{1 to} R. one or more of the _3, an alkoxy group C1 -C6.

Examples of the reactive organic silane compound include, but are not limited to, γ-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane and 3- (triethoxysilyl) propyl oxalic acid anhydride.

The reaction conditions between the reactive organic silane compound and the polycondensation product are not particularly limited. For example, a reactive organic silane compound (eg, aminoalkoxysilane) and a polyamic acid in an arbitrary solvent (eg, dimethylacetamide (DMAc)) at a temperature of 100 ° C. or lower, for example, 50 ° C. or lower, or 30 ° C. or lower. To obtain a polyamic acid modified with an alkoxysilane group.

The content of the reactive organic silane compound includes the content of a polyamic acid having a reactive functional group (for example, an anhydride group or an amine group) at one or both ends and the alkoxysilane compound contained in the oligo silica compound described later. Select appropriately in consideration of the content of. For example, the content of the reactive organic silane compound ranges from 1 to 1.5 mol per mol 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 (for example, the content of aminoalkoxysilane) is 0.01 to 10 mol, for example, 0.1 mol to 3 mol, per mol of the alkoxysilane compound contained in the oligosilica compound. , 0.5 mol to 2 mol, or 0.8 mol to 1.5 mol, but is not limited thereto.

The polyamic acid modified by the alkoxysilane group reacts with the hydroxy group or the alkoxy group of the oligosilica compound.

The oligosilica compound contains a condensation reaction product of an organic silanediol and an alkoxysilane compound.

The alkoxysilane compound includes monoalkoxysilane, dialkoxysilane, trialkoxysilane, tetraalkoxysilane, or a combination thereof. In one embodiment of the present invention, an oligosilica compound is produced through a non-hydrocondensation reaction, and the produced oligosilica compound is mixed with the above-mentioned polycondensation product to obtain a composition.

The organic silanediol is preferably a compound represented by the following general formula 4.

In the formula, n is an integer of 1 to 10, and R ₁ and R ₂ are independently alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and 3 to 8 carbon atoms, respectively. It is an alkyl group having 1 to 20 carbon atoms, 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 substituted by the cycloalkyl group of.

For example, the silanediol is diphenylsilanediol, diisobutylsilanediol, silanol-terminated polydimethylsiloxane, silanol-terminated polydimethylsiloxane, silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer, silanol-terminated polydiphenylsiloxane, silanol-terminal polydiphenylsiloxane, silanol. Terminal polytrifluoropropylmethylsiloxane or a mixture thereof. When diphenylsilanediol is used as the silanediol, an optically transparent oligosilica compound solution is obtained.

The alkoxysilane compound is preferably tetramethoxysilane, tetraethoxysilane, or a mixture thereof.

Due to the transparency of the oligosilica compound or due to the improved optical properties of the complex produced, the content of the alkoxysilane compound per mol of the organic silanediol is 1-10 mol. .. The non-hydrocondensation reaction using only the alkoxysilane compound provides an opaque oligosilica compound, whereas the use of the above-mentioned contents of the alkoxysilane compound and silanediol controls the rate of the non-hydrogen sol-gel reaction, for example. As a result, a transparent viscous solution containing the oligosilica compound is obtained.

The condensation reaction of the organic silanediol and the alkoxysilane compound is a non-hydrocondensation reaction in the presence of an alkaline earth metal hydroxide, for example, a non-hydrozol-gel reaction. That is, in the embodiment of the present invention, the composition for producing a polyimide composite does not contain water.

Conventionally, a composition containing an oligosilica compound produced by a hydrolysis condensation reaction requires a large amount of silica in order to improve optical physical properties (for example, permeability). When such a large amount of silica is contained, a decrease in the mechanical properties of the final complex is unavoidable. For example, the final complex has a remarkable increase in brittleness.

In contrast, the composition containing the organosilica precursor obtained by the non-hydrous sol-gel reaction has improved optical properties of the produced complex, even when it contains a lower content of silica. (For example, increased light transmittance and decreased yellow index) are shown. In the composition according to one embodiment of the present invention, the content of the oligosilica compound is 1 part by weight or more, for example, 2 parts by weight or more and 3 parts by weight per 100 parts by weight of the polyamic acid modified by the alkoxysilane group. Or more, or 4 parts by weight or more. For example, the content of the oligosilica compound is 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 by the alkoxysilane group. Since the optical physical properties can be improved by adding a small amount of oligosilica compound in this way, it is possible to provide a composite of improved quality while suppressing the influence of silica particles on mechanical physical properties such as brittleness of the composite as much as possible. can do.

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 such a non-hydrated sol-gel reaction significantly shortens the time required for producing a composition for producing a complex and producing a complex. When the oligosilica compound is produced by a non-hydrous sol-gel reaction, the composition containing the oligosilica compound does not contain water and a solvent for the sol-gel reaction. Therefore, the viscosity of the composition does not decrease due to water and the solvent, which improves the productivity in the manufacturing process of the composite and facilitates the handling of the composition.

In contrast, when the oligosilica compound produced by the hydrosol-gel reaction is included, the final composition will necessarily contain water. Polyamic acids, which are precursors of polyimide, are sensitive to the presence of water. In particular, when the polyamic acid is heated in the presence of moisture, the main chain is decomposed and the molecular weight of the polyimide in the final polymer composite is reduced, which is a molded article containing the produced polymer composite (eg,). , Film) leads to deterioration of physical properties. When the content of the organosilica precursor produced by the hydrosol-gel reaction is increased, the final composition contains a further increased amount of water, and such an increased amount of water is a polyamic acid solution. It causes a decrease in the viscosity of silica, which is disadvantageous in terms of processability and handleability.

As a non-limiting example, with reference to FIG. 1, the hydroxyl group of the silanediol and the alkoxy group of the alkoxysilane undergo a non-hydrocondensation reaction (eg, with the release of alcohol) to form a crosslinked silica precursor. The non-hydrocondensation reaction is 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 catalyst is, but is not limited to, 0.0001 to 10 mol%. The non-hydrocondensation reaction is carried out for 10 minutes or more, for example, 30 minutes to 5 hours, but is not limited thereto. The reaction temperature is 0 ° C. or higher and 200 ° C. or lower, but is not limited thereto. For example, the reaction is carried out at room temperature. The alcohol produced by the condensation reaction is removed by a suitable method (eg, vacuum evaporation) prior to mixing with the modified polyamic acid.

The modified polyamic acid and the oligosilica compound (formed by the non-hydrocondensation reaction) are mixed to obtain a composition. The obtained composition is produced by a film or the like and dried, depending on the selection. Drying is carried out at 50 ° C. to 200 ° C., but is not limited thereto. Drying is carried out in a nitrogen atmosphere, but is not limited to this. The composition is optionally dried and cured to provide a polyimide composite in which organosilica (eg, its nanoparticles) are dispersed. During the optional drying and curing, the polyamic acid is converted to polyimide and the oligosilica compound forms a silica network, in particular the reactive groups (eg, alkoxy or hydroxy groups) of the organosilica precursor. It reacts with alkoxysilane at the end of polyamic acid to form a crosslinked bond.

Therefore, another embodiment of the present invention relates to a polyimide composite containing a cured product of the composition described above.

Curing of the composition is carried out by heating the composition to a temperature sufficient to cause imidization of the polyamic acid. The temperature is in the range of 50 ° C. or higher, for example, 80 ° C. to 400 ° C., but is not limited thereto. Curing takes place in a nitrogen atmosphere, but is not limited to this. The composition solved the problem of a decrease in permeability during high-temperature curing, and the composite obtained by curing was significantly improved as compared with the composition containing the oligosilica compound which is a hydrosol-gel reaction product. Shows transparency, reduced coefficient of thermal expansion, and improved heat resistance. In particular, the above-mentioned effects can be obtained even when the content of silica in the complex is low.

In one embodiment of the present invention, the cured product does not contain silica particles having a size of 200 nm or more (particularly, a size of 150 nm or more) when observed with a transmission electron microscope (TEM). In one embodiment of the invention, the cured product does not contain a domain of oligosilica separated from the polyimide matrix when observed with a transmission electron microscope. The content of Si in the polyimide composite is, for example, in the range of 4% by weight to 14% by weight based on the total weight of the composite. When Si is contained within such a range, the complex exhibits improved optical properties in terms of transparency, yellow index, and haze. The polyimide composite has a transmittance of 65% or more, for example, 68% or more, and a haze of 1% or less, for example, 0.5% or less with respect to light having a wavelength of 430 nm. For example, the polyimide composite simultaneously satisfies a light transmittance of 70% or more, a YI of 12 or less, and a haze of 5% or less.

In addition, the composite exhibits significantly improved heat resistance at a high temperature of more than 300 ° C., for example, about 400 ° C. Therefore, the composite solves the problem that the polyimide film exhibits deterioration in optical properties and physical properties in the subsequent high temperature step. For example, the polyimide composite has a coefficient of thermal expansion (CTE) of 150 ppm / ° C. or less obtained by heating a test piece from 30 ° C. to 400 ° C. at a rate of 10 ° C./min under a load of 0.05 N, for example. It is 130 ppm / ° C or less.

In another embodiment, the film comprises the polyimide composite.

In yet another embodiment, the electronic element comprises the film. The film is used as a substrate for an electronic device, an insulating film, a dielectric film, a flat film, a protective film, and the like.

The electronic element is 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 examples. However, the examples below are merely examples for explaining embodiments of the present invention, and these do not limit the scope of the present invention.

I. Production of Composition and Complex (Example 1)
[1] Production of poly (amic acid):
N-Methyl-2-pyrrolidone (NMP) was charged into the reactor under a nitrogen atmosphere. 2,2'-bistrifluoromethyl-4,4'-biphenyldiamine (TFDB) is added to and dissolved in the reactor to dissolve 2,2'-bistrifluoromethyl-4,4'-biphenyldiamine (TFDB) solution. Manufactured. 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) in the 2,2'-bistrifluoromethyl-4,4'-biphenyldiamine (TFDB) solution 2,2'-bistrifluoro Addition was made so that the molar ratio with methyl-4,4'-biphenyldiamine (TFDB) was 0.9 to 0.99: 1 (TFDB: BPDA), and the reaction was carried out at 25 ° C. for 48 hours to obtain a polyamic acid. Obtained.

[2] Terminal capping treatment with aminoalkylsiloxane:
Gammaaminopropyltrimethoxysilane was added to the solution containing the polyamic acid prepared in item [1], and the mixture was stirred at 25 ° C. and the ends of the anhydride of the polyamic acid were capped with alkoxysilane. The content of gammaaminopropyltrimethoxysilane was increased 2.0 to 2.3 times based on the difference in molar content between diamine and dianhydride.

[3] Production of oligosilica compound (using non-hydrocondensation reaction):
10 g (0.066 mol) of tetramethoxysilane and 3.57 g (0.0165 mol) of diphenylsilanediol were placed in a flask, and barium hydroxide was further added thereto at a content of 0.2 mol% with respect to 1 mol of tetramethoxysilane. After addition with, the mixture was stirred at 80 ° C. for 5 hours. Methanol was removed from the reaction mixture obtained using a vacuum evaporator to obtain an oligosilica compound.

[4] Production of composition and production of composite by curing the composition:
A composition was obtained by mixing and stirring a predetermined amount of polyamic acid produced in item [2] and whose end was capped with aminosiloxane, and a predetermined amount of oligosilica compound obtained in item [3]. .. The Si content of the composition was 4.3% by weight.

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

(Examples 2 to 5)
Except that a predetermined amount of polyamic acid whose ends were capped with aminosiloxane and a predetermined amount of oligosilica compound were mixed to obtain a composition in which the Si content in the composition was as shown in Table 1, respectively. The composition and the polyimide composite were produced in the same manner as in Example 1.

(Comparative Example 1)
The composition and polyimide were produced in the same manner as in Example 1 except that a composition consisting of a polyamic acid whose end was capped with aminosiloxane was used without adding an oligosilica compound.

(Comparative Examples 2-3)
Except that a predetermined amount of polyamic acid whose ends were capped with aminosiloxane and a predetermined amount of oligosilica compound were mixed to obtain a composition in which the Si content in the composition was as shown in Table 1, respectively. The composition and the polyimide composite were produced in the same manner as in Example 1.

(Comparative Example 4)
Except that a predetermined amount of polyamic acid with uncapped ends and a predetermined amount of oligosilica compound were mixed to obtain a composition in which the Si content in the composition was as shown in Table 1, respectively. The composition and the polyimide composite were produced in the same manner as in the method of Example 1.

(Comparative Example 5 and Comparative Example 6)
A silica precursor produced by a hydrous sol-gel reaction was used in place of the oligosilica compound produced by a non-hydrated sol-gel reaction, except that the silica content of the composition was as shown in Table 1 below. , A composition was produced in the same manner as in the method of Example 1, and a silica-containing polyimide composite was obtained from this.

II. Analysis of characteristics and evaluation of physical properties of the manufactured complex 1. Measurement of Translucency of Complex For the composites obtained in Examples 1-5 and Comparative Examples 1-6, the total wavelength transmittance (%) and the total wavelength transmittance (%) with respect to light of 300 to 800 nm and The transmittance (%) for light having a wavelength of 430 nm was measured.

A part of the sample was cut into a width of 50 mm and a length of 50 mm, and the transmittance was measured using a spectrophotometer CM-3600d manufactured by Minolta.

The results are summarized in Table 1.

2. 2. Measurement of Yellow Index of Complex The yellow index (YI) of the complexes obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was measured 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 spectrophotometer CM-3600d manufactured by Minolta.

The results are summarized in Table 1.

3. 3. Measurement of haze of complex The haze of the complexes obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was measured 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 haze was measured using a spectrophotometer CM-3600d manufactured by Minolta.
The results are summarized in Table 1.

4. Measurement of Coefficient of Thermal Expansion of Complex The coefficient of thermal expansion (CTE) of the composites obtained in Examples 1 to 3 and Comparative Example 1 was measured by the following method.

A part of the sample was cut into a width of 5 mm and a length of 30 mm, and the coefficient of thermal expansion (CTE) was measured using a thermomechanical analyzer Q400 manufactured by TA Instruments. The sample was hooked on a crystal hook, a force of 0.050 N was applied, and then the sample was heated from 30 ° C. to 400 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere. The coefficient of thermal expansion value was determined in the range of 50 ° C. to 400 ° C.

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

5. Analysis of Complex by Transmission Electron Microscope The complex of Example 4 and the complex of Comparative Example 4 were analyzed by a transmission electron microscope using a Tecnai G2 device manufactured by FEI Company, and the results are shown in FIGS. 3 and 4. Each is shown.

The results in Table 1 suggest that the complexes of Examples 1-5 exhibit improved optical properties as compared to the composites of Comparative Examples. For example, the composites of Example 1 and Example 4 have a Si content of 4.3% and 13.9%, respectively, but with approximately 14% and 27% higher permeability (430 nm) than Comparative Example 1. In contrast to (in wavelength), the composite of Comparative Example 6 has a Si content of approximately 25% by weight, but exhibits a transmittance (at a wavelength of 430 nm) that is only 10% higher than that of Comparative Example 1. .. That is, the composites of Examples 1-5 show improved optical properties such as higher transmittance, even if they contain a reduced content of silica (extremely even in the short wavelength region). As a result, the optical physical properties of the composite are improved while not affecting other mechanical physical properties such as brittleness.

As is clear from the results of Comparative Example 6, the content of silica to be added must be much higher (eg, 3 times) in order to obtain the same light properties as the non-hydroactive reaction using the hydrous reaction.

As is clear from the results of Table 2 and FIG. 2, the composites of Examples 1 to 3 had significantly lower thermal expansion (particularly during high temperature heat treatment at 400 ° C.) than the polyimide of Comparative Example 1. May show a coefficient of CTE. Therefore, it is suitably applied to an optical element (for example, a transparent substrate or a translucent film) in a manufacturing process including a subsequent heat treatment at a high temperature, such as a manufacturing process of an organic light emitting diode (LED).

Although the preferred embodiments of the present invention have been described in detail above, the scope of rights of the present invention is not limited to these, and those skilled in the art using the basic concepts defined in the claims below. Various modifications and improvements also belong to the scope of the present invention.

Claims (22)

It contains a polyamic acid and an oligosilica compound modified with an alkoxysilane group, and the content of Si atoms in the composition is 15% by weight or less based on the total weight of the solid content of the composition.
The polyamic acid modified by the alkoxysilane group contains an acid dianhydride and a reaction product between a polycondensation product of diamine and a reactive organic silane compound, and the oligosilica compound is an organic silane diol and A composition containing a non- hydrocondensation reaction product of an alkoxysilane compound. The composition according to claim 1, wherein the water content of the composition is 100 ppm or less. The polycondensation product of the acid dianhydride and the diamine contains the polyanhydride represented by the following general formula 1 and the polycondensation product of the diamine of the following general formula 2, and the reactivity is at least one end. The composition according to claim 1 or 2, which has a functional group that reacts with an organic silane compound:

In the formula, A ₁ is the same or different, and independently, substituted or unsubstituted tetravalent C6 to C24 aliphatic ring groups, substituted or unsubstituted tetravalent C6 to C24 aromatic ring groups, respectively. Alternatively, it is a substituted or unsubstituted tetravalent 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 joined to each other to form a fused ring, or two or more rings are directly bonded, or -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 ≤ 1 ≤ q ≦ 10), C1-C10 linear or branched aliphatic aliphatic group groups, C1-C10 fluoroalkyl groups, C6-C20 aromatic hydrocarbon groups, and C6-C20 finger ring group hydrocarbon groups. By an alkylene group of C1 to C10 having one or more substituents selected from, -C (CF ₃ ) _2- , -C (CF ₃ ) (C ₆ H ₅ )-, or -C (= O) NH- It is connected and

In the formula, A2 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 It is a heteroaromatic ring group of C24, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group exists alone, or two or more rings are joined to each other to form a fused ring, or Two or more rings are directly bonded, or -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), linear or branched C1 to C10 C1 to C10 having one or more substituents selected from the aliphatic hydrocarbon group of the chain, the fluoroalkyl group of C1 to C10, the aromatic hydrocarbon group of C6 to C20, and the finger ring group hydrocarbon group of C6 to C20. alkylene _{group, -C (CF 3) 2 -} , - C (CF 3) (C 6 H 5) -, or -C (= O) are connected by NH-. The composition according to claim 3, wherein A ₁ is one of the following in the general formula 1.


During the ceremony
X ^{1 to} X ⁸ are the same or different, and are independently bonded to each other directly, −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), -C (CH) ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= O) NH-,
Z ¹ is -O-, -S-, or -NR ^300- (where R ³⁰⁰ is hydrogen or an alkyl group of C1-C5),
Z ² and Z ³ are the same or different, and independently of each other, -N = or -C (R ³⁰¹ ) = (where R ³⁰¹ is an alkyl group of hydrogen or C1 to C5, but Z ² and Z ³ Z ³ is not -C (R ³⁰¹ ) = at the same time),
R ^{30 to} R ⁵⁰ and R ^{54 to} R ⁶⁰ are the same or different, and independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ^{51 to} R ⁵³ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aromatic organic groups, or substituted or unsubstituted C6 to C20 aromatic organic groups. Yes,
k30, k31 and k32 are independently integers of 0 to 2.
k33, k35, k36, k37, k39, k42, k43, k44, k46, k54 and k57 are each independently an integer of 0 to 3.
k34 is 0 or 1,
k38, k45, k50, k55 and k56 are independently integers from 0 to 4, respectively.
k40, k41, k47, k48 and k49 are independently integers from 0 to 5, respectively.
k58, k59 and k60 are independently integers from 0 to 8.
* Is the portion connected to the carbon of the carbonyl group. The composition according to claim 3 or 4, wherein A2 of the general formula 2 is any one of the following:

During the ceremony
X ^{10 to} X ¹⁶ are the same or different, and are independently bonded to each other directly, −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), -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 independently, halogen, substituted or unsubstituted C1 to C10 aliphatic organic groups, or substituted or unsubstituted C6 to C20 aromatic groups. It is an organic group
R ⁸⁷ and R ⁸⁸ are the same or different, and independently, hydrogen atom, halogen, substituted or unsubstituted C1 to C10 aliphatic organic group, or substituted or unsubstituted C6 to C20 aromatic organic group. Yes,
k70, k73, k74, k75, k76, k77, k78, k79, k80, k81, k82 and k83 are each independently an integer of 0-4.
k71, k72, k85 and k86 are independently integers of 0 to 3, respectively.
k84, k89 and k90 are independently integers from 0 to 10.
* Is the part connected to nitrogen. The acid dianhydride and the polycarboxylic dianhydride product of the diamine are 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] octo-7-ene-. 2,3,5,6-tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) ) Diphthalic acid dianhydride (6FDA), 4,4'-oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 4- (2,5-dioxo tetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (DTDA), 1,2,4,5-benzenetetracarboxylic dianhydride; 1,2,3,4-benzenetetracarboxylic dianhydride Anhydride; 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 1,2,4,5-naphthalene Tetetracarboxylic dianhydride; 1,2,5,6-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 2,3,6,7-naphthalenetetracarboxylic Acid 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'-diphenyltetracarboxylic 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) sulfone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl Spherone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; bis (3,4-dicarboxyphenyl) sulfonate dianhydride; 4,4'-bis (2, 3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3', 4,4'-ben Zophenonetetracarboxylic dianhydride; 2,2', 3,3'-benzophenonetetracarboxylic dianhydride; 2,3,3', 4'-benzophenonetetracarboxylic 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-carboxyphenyl) 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- (2,2) 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-propanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propanedianhydride 2.3,4,5-thiophentetracarboxylic dianhydride; 2,3,5,6-pyrazinetetracarboxylic dianhydride; 1,8,9,10-phenanthrenetetracarboxylic dianhydride; 3,4,9,10-Perylenetetracarboxylic dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride; 1,1-bis (3,4-dicarboxyphenyl) ) -1-phenyl-2,2,2-trifluoroethanedianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropanedianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethanedianhydride; 4,4'-bis [2- (3,4-dicarboxyphenyl) Hexafluoroisopropyl] diphenyl ether dianhydride, or an acid dianhydride selected from a mixture thereof, and
2,2'-bis (trifluoromethyl) benzidine (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-diethylsulfide; bis (4) -Aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; bis (3-aminophenyl) sulfone; bis (4-aminophenyl) sulfone; 4,4'-diamino-dibenzyl sulfoxide; bis (4-amino) Phenyl) 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) -Phenyl) -benzene; 1,4-bis (1,1-dimethyl-5-amino-pentyl) -benzene; 1,4-bis (4-aminophenoxy) -benzene; o-xylylene diamine; m-xyl Rangeamine; p-xylylenediamine; 3,3'-diamino-benzophenone;4,4'-diamino-benzophenone;2,6-diamino-pyridine;3,5-diamino-pyridine; 1,3-diamino-adamantan Bis [2- (3-aminophenyl) hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1'-diadamantan; 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) phenylhexafluoropropane 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) porcine-1-en-3-in; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis ( 3-Aminophenyl) decafluoropentane; 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane (BACH), 4,4'-(hexafluoroisopropyridene) bis (4-phenoxyaniline) (6FIDDA), 9,9-bis (4-aminophenyl) fluorene (BAPF), and a reduced polymerization product of diamine selected from mixtures thereof,
The composition according to any one of claims 1 to 5, which has a functional group that reacts with the reactive organic silane compound at one end or both ends. The composition according to any one of claims 1 to 6, wherein the reactive organic silane compound is a compound represented by the following general formula 3.

In the formula, L is a single-bonded, substituted or unsubstituted alkylene having 1 to 12 carbon atoms, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C1 to C12 heteroarylene, or a combination thereof. A is a -NH ₂ or an acid anhydride group, and R _{1 to} R ₃ are independently alkyl groups of C1 to C6 or alkoxy groups of C1 to C6, but R _{1 to} R. one or more of the _3, an alkoxy group C1 -C6. The reactive organic silane compound is any one of claims 1 to 7, which is gamma aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propyl oxalic acid anhydride, or a combination thereof. The composition according to. The composition according to any one of claims 1 to 8, wherein the content of the reactive organic silane compound is 0.01 mol to 10 mol per 1 mol of the alkoxysilane compound. The organic silanediol is represented by the following general formula 4 and is represented by the following general formula 4.

In the formula, n is an integer of 1 to 10, and R ₁ and R ₂ are independently alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and 3 to 8 carbon atoms, respectively. Alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms substituted with the cycloalkyl group of
The composition according to any one of claims 1 to 9, wherein the alkoxysilane compound is tetramethoxysilane, tetraethoxysilane, or a mixture thereof. The composition according to any one of claims 1 to 10, wherein the condensation reaction between the organic silanediol and the alkoxysilane compound is a non-hydrocondensation reaction in the presence of an alkaline earth metal hydroxide. The composition according to any one of claims 1 to 11, wherein the content of the alkoxysilane compound per 1 mol of the organic silanediol is 2 to 10 mol. The composition according to any one of claims 1 to 12, wherein the content of the oligosilica compound per 100 parts by weight of the polyamic acid modified with the alkoxysilane group is 1 to 10 parts by weight. A complex containing a cured product of the composition according to any one of claims 1 to 13. The composite according to claim 14, wherein the cured product has a size of 200 nm or more when observed with a transmission electron microscope and does not contain a silica domain separated from the polyimide matrix. The composite according to claim 14, wherein the cured product does not contain a silica domain separated from the polyimide matrix when observed with a transmission electron microscope. The complex according to any one of claims 14 to 16, wherein the complex has a Si content of 4% by weight to 14% by weight based on the total weight of the complex. The complex according to any one of claims 14 to 17, wherein the composite has a transmittance of 65% or more and a haze of 1% or less with respect to light having a wavelength of 430 nm. The composite is claimed to have a coefficient of thermal expansion (CTE) of 150 ppm / ° C. or less obtained by heating a sample of the composite from 30 ° C. to 400 ° C. at a rate of 10 ° C./min under a load of 0.05 N. Item 2. The complex according to any one of Items 14 to 18. A film containing the complex according to any one of claims 14 to 19. An electronic device comprising the film according to claim 20. Method for producing polyimide composite including the following steps:
The step of preparing a polyamic acid by the reaction between the acid dianhydride and the diamine,
A step of reacting the polyamic acid with a reactive organic silane compound to prepare a polyamic acid modified with an alkoxysilane group, and
A step of preparing an oligosilica compound by a non-hydrocondensation reaction between an organic silanediol and an alkoxysilane compound,
A step of mixing the polyamic acid modified with the alkoxysilane group and the oligosilica compound, and a step of performing curing.