KR20180037893A - Composition and polyamideimide composite and polyamideimide film and electronic device - Google Patents

Abstract

The present invention relates to: an alkoxysilane group-modified polyamideimide precursor; a composition comprising an oligosilica compound as a condensation reaction product of an organosilane diol and an alkoxysilane compound; a polyamideimide composite obtained from the composition; a polyamideimide film; and an electronic device including the same. One embodiment provides a film-forming composition capable of improving optical and mechanical properties.

Description

Technical Field The present invention relates to a composition, a polyamideimide composite, a polyamideimide film, and an electronic device. More particularly,

Compositions, polyamideimide composites and polyamideimide films and electronic devices.

As portable electronic devices, such as smart phones and tablet PCs, are becoming more and more diverse, display devices are required to be flexible as well as thin and lightweight, as well as bendable and foldable.

Currently, display devices mounted on portable electronic devices use hard glass to protect the display module. However, glass is not flexible enough to be applied to flexible display devices. Accordingly, a transparent film made of a polymer material capable of replacing glass has been studied.

One embodiment provides a composition for film formation that can improve optical and mechanical properties.

Another embodiment provides a film-forming composite capable of improving optical and mechanical properties.

Another embodiment provides a film that can improve optical and mechanical properties.

Another embodiment provides an electronic device comprising the film.

According to one embodiment, there is provided a composition comprising a polyamideimide precursor modified with an alkoxysilane group and an oligosilica compound that is a condensation reaction product of an organosilane diol and an alkoxysilane compound.

The composition may comprise trace amounts of water up to about 100 ppm.

The composition may not contain water.

The organosilane diol may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 8 cycloalkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkoxy Or a substituted or unsubstituted C6 to C20 aryl group,

n is an integer of 1 to 10;

At least one of R ¹ and R ² in Formula 1 may be a substituted or unsubstituted C6 to C20 aryl group.

The alkoxysilane compound may be trialkoxysilane, tetraalkoxysilane or a combination thereof.

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

The oligosilica compound can be obtained by a non-condensation reaction of the organosilane diol and the alkoxysilane compound in the presence of an alkaline earth metal hydroxide.

The oligosilica compound may be included in an amount of about 0.1% to 30% by weight based on the total amount of the composition.

The oligosilica compound may be included in an amount of about 5% to 20% by weight based on the total amount of the composition.

The alkoxysilane group modified polyamideimide precursor may be a reaction product of a polyamideimide precursor obtained from an anhydride, a diamine compound and a dicarboxylic acid derivative with a reactive organosilane compound.

The reactive organosilane compound may be represented by the following general formula (2).

(2)

In Formula 2,

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, provided that at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group,

L is a single bond, a substituted or unsubstituted C1 to C12 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C12 heteroarylene group,

A is -NH ₂ , an anhydride group or a carboxylic acid group.

The reactive organosilane compound may include gamma aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinianhyde or combinations thereof.

According to another embodiment, there is provided a polyamideimide composite comprising a cured product of the composition.

The cured product may include a polyamideimide matrix and an oligosilica compound bonded or dispersed in the polyamideimide matrix.

The composite may comprise from 4% to 14% by weight of Si relative to the total content of the composite.

According to another embodiment, there is provided a polyamideimide film comprising the polyamideimide composite.

The polyamide-imide film may have a transmittance of about 70% or more and a haze of about 2.0 or less with respect to light having a wavelength of 430 nm.

The yellowness index (YI) of the polyamide-imide film may be about 3.5 or less.

According to another embodiment, there is provided an electronic device comprising the polyamide-imide film.

According to another embodiment, there is provided a process for preparing a polyamideimide precursor, which comprises preparing a polyamideimide precursor, preparing a polyamideimide precursor modified with an alkoxysilane group by reacting the polyamideimide precursor with a reactive organosilane compound, Preparing an oligosilica compound by the non-hydropolymerization reaction of the polyamideimide film, mixing the alkoxysilane group-modified polyamideimide precursor and the oligosilica compound, and curing the mixture And a manufacturing method thereof.

The step of preparing the oligosilica compound may be carried out in the presence of an alkaline earth metal hydroxide.

The optical properties and mechanical properties of the polyamide-imide film can be improved.

1 is a cross-sectional view of a display device according to an embodiment.
2 is a cross-sectional view of a display device according to another embodiment.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, the structures actually applied may be implemented in various different forms and are not limited to the embodiments described herein.

Unless otherwise defined herein, 'substituted' means that the hydrogen atom in the compound is substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group , A C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 hetero arylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, An alkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

Hereinafter, " combination " includes two or more blends and two or more laminated structures.

Hereinafter, the term " imide " includes not only an imide but also an imide which is a precursor of an imide and an imide.

Not in the "silica" is not limited to SiO _2, SiO say the connection-based materials, depending on the context, silica, SiO _x (x is 1.5 to 2.5), siloxane (siloxane), and / or an organic substituent (Hydrogen, aryl, alkyl, etc.), or an organic material such as siloxane.

The composition according to one embodiment comprises a polyamideimide precursor modified with an alkoxysilane group and an oligosilica compound that is a condensation reaction product of an organosilane diol and an alkoxysilane compound.

The composition is substantially free of water. For example, the water content in the composition is very low, not more than 100 ppm. 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 alkoxysilane group-modified polyamideimide precursor may include a reaction product of a condensation product having at least one end of the acid with a reactive functional group such as a martial art, an amine group, and / or a carboxylic acid group, and a reactive organosilane compound.

As an example, the condensation polymerization product can be obtained from an acid dianhydride, a diamine monomer and a dicarboxylic acid derivative.

The acid dianhydride may be represented by the following formula A:

(A)

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.

A ₁ in formula (A) 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⁾ =, wherein 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 each independently represents a hydrogen, a 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 (A) above, 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 (A) 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 monomer may be represented by the following formula (B).

[Chemical Formula B]

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 (B), 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 is hydrogen, halogen, a substituted or unsubstituted C 1 to C 10 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;

In formula (B), A < ₂ > can 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 monomer 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 monomer 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 diamine monomers may be used alone or in a mixture of two or more as necessary.

Specific examples of the dicarboxylic acid derivatives that can be used include 4,4'-biphenyl dicarbonyl chloride (BPCL), terephthaloyl chloride (TPCL) Lt; / RTI >

For example, the condensation polymerization product may be produced by reacting a tetracarboxylic acid dianhydride represented by the following formula A-1, a diamine monomer represented by the following formula B-1 and a dicarboxylic acid derivative represented by the following formula C-1 Can be obtained.

[A-1]

[Formula B-1]

[Chemical formula C-1]

X ¹ -CO-R ² -CO-X ²

In the above formulas A-1 to C-1, L, R ² , R ⁶ to R ¹⁰ , R ¹² , R ¹³ and n 3 to n 8 are as described above, and X ¹ and X ² each independently may be halogen .

For example, the tetracarboxylic acid dianhydride represented by the above formula (A-1) can be obtained by reacting, for example, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , BPDA), 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, 6FDA, or a combination thereof, and the compound represented by the formula (B-1) The diamine compound may be, for example, 2,2'-bis (trifluoromethyl) benzidine (TFDB), and the dicarboxylic acid derivative represented by the above formula (C-1) 4,4'-biphenyl dicarbonyl chloride (BPCL), terephthaloyl chloride (TPCL), or a combination thereof.

For example, the condensation polymerization product may include about 0.1 to 0.7 mole of the tetracarboxylic dianhydride and about 0.3 to 0.9 mole of the dicarboxylic acid derivative per mole of the diamine compound.

The condensation polymerization can be carried out by stirring the acid dianhydrides, diamine monomers and dicarboxylic acid derivatives at a predetermined temperature (for example, 50 degrees Celsius 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 dicarboxylic acid derivative and the diamine monomer are first reacted to form an amide structural unit, and an additional anhydride is added thereto to react the amide structural unit and the amic acid structural unit to form a polyamideimide precursor Can be obtained.

For example, an oligomer (hereinafter referred to as 'amide group-containing oligomer') having an amide group and ending with an amino group at both ends is first prepared by reacting the dicarboxylic acid derivative and the diamine monomer, The polyamideimide precursor can be obtained by reacting the polyamideimide precursor with an anhydride as a diamine compound.

For example, the condensation polymerization may be carried out in a solution containing a condensation polymerization catalyst, if desired. For solution polymerization, the polymerization solvent may be any solvent known for the preparation of polyamideimide precursors.

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, diamines and dicarboxylic acid derivatives 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 having a reactive functional group (e.g., anhydride, amine and / or carboxylic acid residue) at one or both terminals is reacted with a reactive organosilane compound to obtain a polyamideimide precursor modified with an alkoxysilane group.

The reactive organosilane compound may be represented by, for example, the following formula (2).

(2)

In Formula 2,

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, provided that at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group,

L is a single bond, a substituted or unsubstituted C1 to C12 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C12 heteroarylene group,

A is -NH ₂ , an anhydride group or a carboxylic acid 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 polyamideimide precursor are stirred in any solvent (e.g., dimethylacetamide (DMAc), etc.) at a temperature of less than 100 degrees Celsius, such as less than 50 degrees Celsius, A polyamideimide precursor modified with a silane group can be obtained.

The content of the reactive organosilane compound is such that the content of the polyamideimide precursor having a reactive functional group (eg, anhydride group, amine group or carboxylic acid group) at one or both ends and the content of the polyamidoimide precursor having an alkoxysilane May be appropriately selected in consideration of the content of the compound. 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, amine, or carboxylic acid residue) of the polyamideimide precursor, 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 polyamideimide precursor modified with an alkoxysilane group may react with the hydroxyl group or the alkoxy group of the oligosilica compound.

The oligosilica compound comprises 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. As an example, the alkoxysilane compound may be trialkoxysilane, tetraalkoxysilane, or a combination thereof. For example, the alkoxysilane compound may be tetramethoxysilane, tetraethoxysilane, 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:

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 8 cycloalkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkoxy Or a substituted or unsubstituted C6 to C20 aryl group,

n is an integer of 1 to 10;

For example, at least one of R ¹ and R ² in Formula 1 may be a C6 to C20 aryl group. By using an organosilane diol substituted with an aryl group as described above, the hydrophobic property can be enhanced and the dispersibility can be improved when mixed with the polyamideimide precursor.

For example, the organosilane diol may 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.

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, while 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. The alkaline earth metal hydroxide may be, for example, barium hydroxide or strontium hydroxide, but is not limited thereto. This embodiment is carried out in a non-water condensation reaction, and water is not added.

Generally, 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, transmittance). 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, a composition comprising an organosilyl silica precursor obtained by a non-hydrosol-reactive reaction, even when comprised of a lesser amount of silica, exhibits improved optical properties (e.g., increased light transmittance and reduced ≪ / RTI > yellow index). 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 more than 3 parts by weight, per 100 parts by weight of the alkoxysilane group-modified polyamideimide precursor, Or 4 parts by weight 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 alkoxysilane group-modified polyamideimide precursor. 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. The polyamideimide precursor, which is a precursor of polyamideimide, is sensitive to the presence of moisture. In particular, when the polyamideimide precursor is heated in the presence of water, the main chain is decomposed to lower the molecular weight of the polyamideimide in the final polymer composite, which may lead to deterioration of physical properties of a molded article (for example, a film) have. In addition, as the content of the organosilica precursor produced by the hydrolysis of the Suzuki reaction increases, the final composition will contain an increased amount of water, which increases the viscosity of the polyamideimide precursor solution Which is disadvantageous in view of fairness and handleability.

In a non-limiting example, the hydroxyl group of the silanediol and the alkoxy group of the alkoxysilane can undergo a non-hydrolytic condensation reaction (e.g., 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, etc.) before mixing with the modified polyamideimide precursor.

The composition is obtained by mixing the modified polyamideimide precursor and the oligosilica compound (formed by the non-hydrolytic condensation reaction).

The oligosilica compound may be included in an amount of about 0.1% to 30% by weight based on the total amount of the composition. Within this range, for example, about 5% to 20% by weight can be included.

The above composition can be optionally made into a film or the like and then dried. 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 polyamideimide composite wherein organosilica (e.g., nanoparticles thereof) is dispersed. During the optional drying and curing, the polyamideimide precursor may be converted to a polyamideimide and the oligosilica compound may form a silica network, and in particular, the reactor (e.g., an alkoxy group or a hydroxyl group) of the organosilicon precursor may be a polyamide Lt; RTI ID = 0.0 > alkoxysilane < / RTI >

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

Curing of the composition can be carried out by heating the composition to a temperature sufficient to cure the polyamideimide. 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.

The cured product may include a polyamideimide matrix and an oligosilica compound bonded or dispersed in the polyamideimide matrix.

The polyamideimide matrix may comprise, for example, amide structural units and imide structural units.

For example, the polyamideimide matrix may include a structural unit represented by the following formula (D) and a structural unit represented by the following formula (E).

[Chemical Formula D]

In the above formula (D)

L may be a single bond, -CONH-, -Ph-CONH-Ph-, or -NHCO-Ph-CONH-, wherein Ph may be substituted or unsubstituted phenylene,

R ² is a divalent organic group containing one or more substituted or unsubstituted aromatic rings, in which two or more aromatic rings are bonded to each other to form a fused ring, or two or more aromatic rings are single bonds, O, S, S (= O) ₂ , C = O, C (= O) NH, CR ^a (OH), SiR ^b R ^c or (CR ^d R ^e ) _p , Wherein R ^a to R ^e are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group,

R ⁶ and R ⁷ can each independently be an electron withdrawing group and can be, for example, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ or -CO ₂ C ₂ H ₅ Work Can,

R ⁸ and R ⁹ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C3 to C30 heterocyclic group, a halogen, a hydroxy group, a substituted or unsubstituted silyl group,

n3 may be an integer of 0 to 4, n5 may be an integer of 0 to 3, n3 + n5 may be an integer of 0 to 4,

n4 may be an integer of 0 to 4, n6 may be an integer of 0 to 3, n4 + n6 may be an integer of 0 to 4,

(E)

In the above formula (E)

R ¹⁰ is the same or different in each repeating unit, and each independently represents a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 cycloaliphatic group, a substituted or unsubstituted C6- C30 aromatic organic group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ¹¹ is the same or different from each other in each repeating unit, and each independently contains a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a condensed ring; (O) ₂ , Si (CH ₃ ) ₂ , (CH ₂ ) ₂ , or the like, wherein at least two aromatic organic groups are a single bond, a substituted or unsubstituted fluorenyl group, O, S, ) _p (where 1? _p? 10), (CF ₂ ) _q where ₁ ? _q ? 10, C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or C Can,

R ¹² and R ¹³ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C3 to C30 heterocyclic group, a halogen, a hydroxy group, a substituted or unsubstituted silyl group,

n7 and n8 may each independently be an integer of 0 to 3;

For example, the structural unit represented by the formula (D) may include a structural unit represented by the following formula (D-1), a structural unit represented by the following formula (D-2), or a combination thereof, but is not limited thereto.

[Formula D-1]

[Formula D-2]

For example, the structural unit represented by the formula (E) may include a structural unit represented by the following formula (E-1), a structural unit represented by the following formula (E-2), or a combination thereof, but is not limited thereto.

[E-1]

[Formula E-2]

For example, the polyamideimide matrix may include a structural unit represented by the formula (D) and a structural unit represented by the formula (E) in a ratio of 90:10 to 10:90. Within the above range, for example, the structural unit represented by the formula (D) and the structural unit represented by the formula (E) may be contained in a ratio of 90:10 to 30:70. Within the above range, for example, the structural unit represented by the formula (D) and the structural unit represented by the formula (E) may be contained in a ratio of 90:10 to 50:50. For example, the structural unit represented by the formula (D) may be larger than the structural unit represented by the formula (E).

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 polyamideimide matrix when viewed by transmission electron microscopy.

 In the polyamideimide 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 within this range, the composite may exhibit improved optical properties in terms of transmittance, yellowness (measured in accordance with ASTM D1925), haze and pencil hardness (measured in accordance with ASTM D3363).

The polyamideimide composite may have an (average) transmittance of at least about 70%, such as at least about 75%, such as at least about 80%, such as at least about 85%, in the visible region of the wavelength range of 300-800 nm, For example, 75% or more, YI 3.5 or less, and haze of 2.0 or less, such as 1.5 or less, and the pencil hardness may be 2H or more, for example, 3H or more. For example, the polyamideimide composite can simultaneously satisfy light transmittance of 70% or more, YI of 3.5 or less, haze of 2.0 or less, and pencil hardness of 2H or more.

The polyamideimide composite may have a modulus of at least about 5.2 GPa. The modulus can be achieved by increasing the inter-polymer chain packing of the amide-imide copolymer comprising an amide structural unit and an imide structural unit. The polyamideimide composite may have a modulus within the above range, for example, from about 5.2 GPa to 10.0 GPa, and may have a modulus within the above range, for example, from about 5.3 GPa to 9.0 GPa, To 8.0 GPa, and may have a modulus within the above range of, for example, about 5.5 GPa to 7.0 GPa. The polyamideimide composite may have improved mechanical properties by having a modulus in the above range.

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. Thus, the composite can solve the problem that the polyamide-imide film shows deterioration of optical properties and physical properties in a subsequent high-temperature process. For example, the polyamideimide composite may have a coefficient of thermal expansion (CTE) of 150 ppm / degree or less, for example, 130 degrees centigrade or less, obtained by heating the specimen under a load of 0.05N at a temperature of 30 degrees centigrade to 400 degrees centigrade at a rate of 10 degrees / ppm / day < / RTI >

In other embodiments, the film comprises the polyamideimide complex.

The film may have a thickness of about 20 [mu] m to 100 [mu] m. Within this range, it may have a thickness of about 30 탆 to 95 탆.

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, 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, a flat panel display will be described as an example of an electronic device with reference to the drawings.

1 is a cross-sectional view of a display device according to an embodiment.

Referring to FIG. 1, a display device 100 according to an embodiment includes a display panel 50 and a window 10A.

The display panel 50 may be, for example, an organic light emitting display panel or a liquid crystal display panel, and may be, for example, a Ben double display panel, a foldable display panel, or a rollerable display panel.

The window 10A may be the above-described polyamideimide film or a polyamideimide film. The window 10A can be disposed on the observer side.

A further layer may be interposed between the display panel 50 and the window 10A and may further comprise, for example, a single layer or a plurality of polymeric layers (not shown) and optionally a transparent adhesive layer (not shown) have.

2 is a cross-sectional view of a display device according to another embodiment.

Referring to FIG. 2, the display device according to the present embodiment includes a display panel 50, a window 10A, and a touch screen panel 70 positioned between the display panel 50 and the window 10A.

The display panel 50 may be, for example, an organic light emitting display panel or a liquid crystal display panel, and may be, for example, a Ben double display panel, a foldable display panel, or a rollerable display panel.

The window 10A may be the above-described polyamideimide film or a polyamideimide film. The window 10A can be disposed on the observer side.

The touch screen panel 70 is disposed adjacent to the window 10A and the display panel 50 and recognizes the change of the touch position and position when a human hand or an object is touched through the window 10A and outputs a touch signal . The driving module (not shown) can check the position of the touch point from the output touch signal, check the icon displayed at the position of the detected touch point, and perform a function corresponding to the checked icon, Can be displayed on the display panel 50.

Other layers may be interposed between the touch screen panel 70 and the window 10A and may further include, for example, a single layer or multiple layers of polymeric layers (not shown) and optionally a transparent bonding layer (not shown) have.

Other layers may be interposed between the touch screen panel 70 and the display panel 50, and may further include, for example, a single layer or a plurality of polymer layers (not shown) and optionally a transparent bonding layer (not shown) .

The display device can be applied to various electronic devices, for example, smart phones, tablet PCs, cameras, touch screen devices, and the like, but is not limited thereto.

The embodiments described above will be described in more detail by way of examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Preparation of amide group-containing oligomer

Synthetic example

Bis (trifluoromethyl) benzidine (TFDB) 1 (1 g) was added to 700 g of N, N-dimethylacetamide as a solvent in a round bottom flask The remaining TFDB was rinsed with 50 ml of dimethylacetamide (DMAC) and dissolved in terephthaloyl chloride (0.12 mol, 39.2 g) and 2.8 molar equivalent of pyridine (0.343 mol, , TPCL) 0.7 molar equivalent (0.086 mol, 17.4 g) was added in four portions to a TFDB solution at 25 DEG C and stirred vigorously for 15 minutes.

The resulting solution was then stirred for 2 hours in a nitrogen atmosphere and then added to a 7L NaCl solution containing 350 g of NaCl and stirred for 10 minutes. The solids are then filtered and resuspended and re-filtered twice in 5 L of deionized water. Subsequently, the final filtrate is appropriately pressurized to remove the remaining water as much as possible, and dried at 90 캜 and under vacuum for 48 hours to obtain an amide group-containing oligomer represented by the following formula (F). The number-average molecular weight of the resulting amide group-containing oligomer was about 997.

[Chemical Formula F]

Preparation of composition

Manufacturing example

[1] Preparation of polyamideimide precursor

(0.0152 mole) of the amide group-containing oligomer obtained in the synthesis example and 143 ml of dimethylacetamide (DMAc) were added to a 250 ml four-necked double-walled reactor equipped with a mechanical stirrer preliminarily heated to 30 ° C and a nitrogen inlet. Subsequently, the solution was stirred at 30 ° C and under nitrogen atmosphere until the oligomer completely dissolved, and then 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (0.0068 mole) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) Lt; / RTI > Then, 10 ml of dimethylacetamide (DMAc) is further added thereto, and the solution is stirred for 48 hours to obtain an amide-amic acid copolymer solution having a solid concentration of 16 wt%. After the temperature was lowered to 25 ° C, 4.6 g of acetic anhydride was added to the amide-amic acid copolymer solution, and the mixture was stirred for 30 minutes. Then, 3.6 g of pyridine was added and stirred for 48 hours to obtain a polyamideimide precursor.

[2] End capping treatment with alkoxysilane:

 Gamma aminopropyltrimethoxysilane was added to the polyamideimide precursor prepared in [1] and stirred at 25 ° C to cap the anhydride terminal of the polyamideimide with an alkoxysilane to obtain a polyamideimide precursor modified with an alkoxysilane group . The content of gamma-aminopropyltrimethoxysilane is 2.0 to 2.3 times based on the difference in the molar content of the diamine and the anhydride.

[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 Lt; 0 > C for 5 hours. Methanol is removed from the reaction mixture obtained using a reduced pressure evaporator to obtain a reactive oligosilica compound.

[4] Preparation of Composition

As shown in Table 1, the reactive oligosilica compound obtained in [3] was added to the alkoxysilane group-modified polyamideimide precursor prepared in [2] at 0 to 20% by weight and stirred to prepare a composition. The Si content in the composition is 4.3 wt%.

Preparation of polyamideimide film

The composition thus obtained was coated on a glass substrate and heat-treated in a nitrogen atmosphere at a temperature of 300 DEG C for 60 minutes to prepare an 80 mu m-thick polyamideimide film containing an oligosilica.

evaluation

The optical properties and mechanical properties of the polyamide-imide films thus prepared are evaluated.

Transmittance, yellowness, and haze are determined by measuring the light transmittance (%) of the polyamide-imide film using a Minolta Spectrophotometer CM-3600d. The light transmittance (%) may be an average light transmittance in a visible light region of about 300 nm to 800 nm.

The pencil hardness is measured according to ASTM D3363 standard using a pencil hardness tester and a Mitsubishi pencil.

The modulus (elastic modulus) is measured with an Instron 3365 (Instron) film specimen, 10 mm wide and 50 mm long at room temperature, stretched at a rate of 25 mm / min and measured with an ASTM D882 standard five times per sample.

Oligosilica
Content (% by weight) Permeability
(%) Yellowness
Hayes Pencil hardness Modulus (GPa) Example 1 5 88.4 3.4 1.0 3H 5.4 Example 2 10 88.4 3.1 1.1 3H 5.8 Example 3 15 88.7 3.0 0.8 3H 5.6 Example 4 20 88.4 3.3 1.2 2H 5.2 Comparative Example 1 0 88.0 3.8 1.3 H 5.1

Referring to Table 1, it can be confirmed that the polyamide-imide films according to Examples 1 to 4 have improved optical characteristics and mechanical properties as compared with the polyamide-imide films according to Comparative Example 1.

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, but is capable of various modifications within the scope of the appended claims, the accompanying drawings, It is natural to belong.

10A: Window
50: Display panel
70: Touch screen panel
100: display device

Claims (22)

An alkoxysilane group-modified polyamideimide precursor, and
The oligosilica compound which is the condensation product of the organosilane diol and the alkoxysilane compound
≪ / RTI >
The method of claim 1,
Wherein the composition comprises a minor amount of water of up to 100 ppm.
The method of claim 1,
Wherein the composition does not comprise water.
The method of claim 1,
Wherein the organosilane diol is represented by the formula:
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 8 cycloalkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkoxy Or a substituted or unsubstituted C6 to C20 aryl group,
n is an integer of 1 to 10;
5. The method of claim 4,
Wherein at least one of R ¹ and R ² in Formula 1 is a substituted or unsubstituted C6 to C20 aryl group.
The method of claim 1,
Wherein the alkoxysilane compound is a trialkoxysilane, tetraalkoxysilane or a combination thereof.
The method of claim 6,
Wherein the alkoxysilane compound is tetramethoxysilane, tetraethoxysilane, or a combination thereof.
The method of claim 1,
Wherein the oligosilica compound is obtained by non-hydrolytic condensation reaction of the organosilane diol and the alkoxysilane compound in the presence of an alkaline earth metal hydroxide.
The method of claim 1,
Wherein the oligosilica compound is present in an amount of from 0.1% to 30% by weight based on the total amount of the composition.
The method of claim 1,
Wherein said oligosilica compound is comprised between 5% and 20% by weight based on the total amount of said composition.
The method of claim 1,
Wherein the alkoxysilane group modified polyamideimide precursor is a reaction product of a polyamideimide precursor obtained from an anhydride, a diamine compound and a dicarboxylic acid derivative with a reactive organosilane compound.
12. The method of claim 11,
Wherein the reactive organosilane compound is represented by the following formula:
(2)

In Formula 2,
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, provided that at least one of R ₁ to R ₃ is a C ₁ to C 6 alkoxy group,
L is a single bond, a substituted or unsubstituted C1 to C12 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C12 heteroarylene group,
A is -NH ₂ , an anhydride group or a carboxylic acid group.
The method of claim 12,
Wherein the reactive organosilane compound comprises gammaaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinianhyde or a combination thereof.
14. A polyamideimide composite comprising a cured composition of any one of claims 1 to 13.
The method of claim 14,
The cured product
Polyamideimide matrix, and
The oligosilica compound bonded or dispersed in the polyamideimide matrix
≪ / RTI >
16. The method of claim 15,
Wherein said composite comprises from 4% to 14% by weight of Si relative to the total content of said composite.
A polyamideimide film comprising the polyamideimide composite of claim 14.
The method of claim 17,
A transmittance to light having a wavelength of 430 nm of not less than 70% and a haze of not more than 2.0.
The method of claim 17,
And the yellowness index (YI) is 3.5 or less.
An electronic device comprising the polyamide-imide film according to claim 17.
Preparing a polyamideimide precursor,
Preparing a polyamideimide precursor modified with an alkoxysilane group by reacting the polyamideimide precursor with a reactive organosilane compound,
Preparing an oligosilica compound by non-hydrolytic condensation reaction of an organosilane diol and an alkoxysilane compound,
Mixing the alkoxysilane group-modified polyamideimide precursor with the oligosilica compound, and
Curing the mixture
≪ / RTI >
22. The method of claim 21,
Wherein the step of preparing the oligosilica compound is carried out in the presence of an alkaline earth metal hydroxide.

Images