KR20140071884A - Novel polyimide, preparation method thereof and organic insulating layer using the same - Google Patents

Abstract

The present invention relates to a novel polyimide having excellent insulation and heat resistance, a method for producing the same, and an organic insulating film including the same. The novel polyimide according to the present invention has an excellent effect in exhibiting blue color at 496 nm, excellent thermal resistance against high temperature by having a high glass transition temperature of about 350°C or more and a 5% weight pyrolysis temperature of 500°C or more, and excellent electrical insulation by having a dielectric constant of 3 or smaller at 1 to 1000 kHz. Accordingly, the novel polyimide according to the present invention can be used as a material of a blue organic light-emitting diode and can also be usefully used as a material for an organic insulating film or a flexible metal coil layer (FMCL) film for electronic devices such as light-emitting diodes (LED) and organic thin film transistors (OTFT).

Description

TECHNICAL FIELD The present invention relates to a novel polyimide polymer, a method for producing the same, and an organic insulating film using the polyimide polymer.

The present invention relates to a novel polyimide polymer having excellent insulating properties and heat resistance, a method for producing the same, and an organic insulating film using the same.

With the rapid development of the display industry, many researches related to fabrication of light emitting diodes (LEDs), thin film transistors, liquid crystal alignment films, and the like have been conducted. Particularly, since these insulating films form an interface with a semiconductor and crystallinity and shape of the semiconductor depend on the interface characteristics of the insulating film, they are regarded as a core part of the finally produced electronic device characteristics. It is emphasized.

In general, organic insulating materials conventionally used in insulating films for electronic devices include polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polymethyl methacrylate (PMMA), and polyimide (PI).

However, in the case of a polyvinyl alcohol (PVA) or polyvinyl phenol (PVP) system among the organic insulators, application of a curing agent to a flexible substrate is limited due to the polymerization reaction of the polymer at a high temperature. In addition, when the organic insulating film is applied to a thin film transistor, there is a problem such as leakage current due to hydroxy group and hysteresis (hysteresis), because it contains a hydroxy (OH) group in the structure even after curing.

On the other hand, polyimide (PI) is an insoluble and infusible ultra-high temperature resistant resin, and has excellent heat resistance and oxidation resistance, high usable temperature, excellent electrochemical and mechanical properties, excellent radiation resistance, excellent low temperature processability for low temperature curing catalyst, And has been widely used for electric wiring coating materials and electric insulating materials. Especially, recently, due to the development of electronic industry and the tendency to lighten electronic products, the application fields thereof have been continuously expanded to provide interlayer insulating films for module boards, chip carrier tapes, A flexible printed circuit board (FPCB), a liquid crystal alignment film, a heat-resistant adhesive, and the like.

In particular, a flexible printed circuit board (FPCB) is a flexible printed circuit board used for mounting electronic components and semiconductors used in electronic products, and is a flexible printed circuit board that is used for mounting a cellular phone, a camera, a flat panel display, , Military equipment, medical equipment, and the like. The polyimide polymer is a flexible metal foil laminated film (FMCL) such as a flexible copper clad laminate (FCCL) used as a disc material for such a flexible printed circuit board , flexible metal clad laminate. The polyimide substrate is used in the form of a composite of an aromatic polyimide film / sheet, a metal film (for example, a copper film, an aluminum film), or an adhesive such as an epoxy.

On the other hand, the polyimide used for the insulating film for electronic devices and the flexible metal foil laminated film is required to have high heat resistance against high temperature generated when using a circuit board due to low permittivity, process temperature and integration of devices, Studies on the polyimide polymerization having a dielectric constant have been actively conducted.

First, studies on an organic insulating film using a polyimide polymer having a low dielectric constant have been known (Patent Documents 1 and 2 and Non-Patent Document 1).

Next, studies on a flexible metal foil laminated film using a polyimide polymer have been known (Patent Document 3).

The inventors of the present invention have been interested in a polymer compound having excellent heat resistance and insulation properties and have been studying a compound for an organic insulating film while the novel polyimide polymer according to the present invention has an effect of heat resistance and insulation properties , And blue light emission, thus completing the present invention.

Japanese Laid-Open Patent Publication No. 1998-52559; Japanese Patent Application Laid-Open No. 1999-349683; Korean Patent No. 10-0867528.

Macromol. Symp. 199, (2003), 321.

It is an object of the present invention to provide a novel imide polymer.

Another object of the present invention is to provide a method for producing a novel polyimide polymer.

It is another object of the present invention to provide novel diamine intermediates of the polyimide polymers.

Another object of the present invention is to provide a process for producing the diamine intermediate.

It is another object of the present invention to provide novel dianhydride intermediates of the polyimide polymers.

It is another object of the present invention to provide a process for the preparation of said dianhydride intermediates.

It is still another object of the present invention to provide an organic insulating film containing a novel polyimide polymer.

Another object of the present invention is to provide a flexible metal foil laminated film produced using the novel polyimide polymer.

It is still another object of the present invention to provide a polyimide polymer for a fluorescent blue light emitting material.

In order to achieve the above object,

The present invention provides a novel polyimide polymer represented by the following general formula (1).

[Chemical Formula 1]

,

및 n은 본 명세서에서 정의한 바와 같다).
(In the above scheme,

,

And n are as defined herein.

In addition, the present invention relates to a process for producing a compound represented by the following formula 1,

Reacting a diamine compound represented by the formula (2) and a dianhydride compound represented by the formula (3) to prepare an amic acid polymer represented by the formula (4) (step 1); And

A process for producing a novel polyimide polymer represented by the formula (1), comprising the step (2) of preparing the polyimide polymer represented by the formula (1) by heat treating the amic acid polymer represented by the formula (4) to provide.

[Reaction Scheme 1]

,

및 n은 본 명세서에서 정의한 바와 같다).
(In the above scheme,

,

And n are as defined herein.

Further, the present invention provides a diamine intermediate compound of the polyimide polymer represented by the formula (1), represented by the following formula (2a).

(2a)

Wherein X and Y are as defined in this specification and the compound of formula (2a) is a compound of formula (2).

The present invention also relates to a process for producing a compound represented by the following formula 2,

There is provided a process for preparing a diamine intermediate compound of a polyimide polymer represented by the formula (2a), which comprises reacting a dibromo compound represented by the following formula (5) with a boronic acid compound represented by the formula (6)

[Reaction Scheme 2]

Wherein X and Y are as defined in this specification and the compound of formula (2a) is a compound of formula (2).

Further, the present invention provides a dianhydride intermediate compound of the polyimide polymer represented by the above formula (1) represented by the following formula (3a).

[Chemical Formula 3]

Wherein X and Y are as defined herein and the compound of formula (3a) is a compound of formula (3).

The present invention also relates to a process for preparing a compound represented by the following formula (3)

Reacting a compound represented by the formula (7) with a compound represented by the formula (8) to prepare a boronic acid compound represented by the formula (9) (step 1); And

A step (2) of coupling the boronic acid compound of formula (9) and the dibromo compound of formula (5) prepared in step 1 to prepare a dianhydride compound of formula (3a) To provide a process for preparing a dianhydride intermediate compound of a polyimide polymer to be displayed.

[Reaction Scheme 3]

Wherein X and Y are as defined herein and the compound of formula (3a) is a compound of formula (3).

Further, the present invention provides an organic insulating film containing a compound represented by the following general formula (1).

[Chemical Formula 1]

,

및 n은 본 명세서에서 정의한 바와 같다)
(In the formula 1,

,

And n are as defined herein)

The present invention also provides a flexible metal-clad laminate film (FMCL) prepared by applying a novel polyimide polymer represented by the following formula (1) on at least one surface of a conductive metal film and curing the same.

[Chemical Formula 1]

,

및 n은 본 명세서에서 정의한 바와 같다)
(In the formula 1,

,

And n are as defined herein)

Further, the present invention provides a novel polyimide polymer for a blue light emitting organic device represented by the following formula (1).

[Chemical Formula 1]

,

및 n은 본 명세서에서 정의한 바와 같다).
(In the formula 1,

,

And n are as defined herein.

The novel polyimide polymer according to the present invention is excellent in the effect of emitting blue at 496 nm, has a high glass transition temperature of about 350 ° C or higher and a thermal decomposition temperature of 5% by weight of not less than 500 ° C, Has a low dielectric constant of 2.9 or less at 1 to 1000 kHz, and thus has an excellent electrical insulation property. Therefore, the novel polyimide polymer according to the present invention can be used not only as a material for a blue organic light emitting device but also as an organic insulating film for electronic devices such as a light emitting diode (LED), an organic thin film transistor (OTFT), or a flexible metal foil laminated film ) Material and the like.

FIG. 1 is a photograph of a manufacturing process of a metal-insulator-metal (MIM) structure device and a manufactured electrode-dielectric-electrode structure device (in FIG. 1, (1) (2) is a glass substrate coated with a thin film of polyimide polymer prepared in Example 3 on the substrate of (1), (3) is a glass substrate coated with a thin film of polyimide polymer prepared in (Au) electrode is coated on the glass substrate.
2 is a graph showing the glass transition temperatures (T _g ) of Examples 3 and 4 according to the present invention.
3 is a graph showing the thermal decomposition temperatures (Td _{5 %} ) of Examples 3 and 4 according to the present invention.
4 is a graph showing dielectric constants according to frequency of a metal-insulator-metal (MIM) structure element coated with the polyimide polymer thin film prepared in Example 3 according to the present invention.
5 is a graph showing the UV and photoluminescence (PL) spectra of the polyimide polymer prepared in Example 3 according to the present invention.
6 is a diagram showing the structure of a flexible metal foil laminated film (FMCL) comprising a novel polyimide polymer according to the present invention (in Fig. 6, (1) is a novel polyimide polymer film according to the present invention, (2) is a metal film).

Hereinafter, the present invention will be described in detail.

The present invention provides a novel polyimide polymer represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

는

,

,

,

,

,

,

,

,

,

,

또는

이고;

The

,

,

,

,

,

,

,

,

,

,

or

ego;

는

,

,

,

,

,

또는

이고, 이때,

또는

중 하나는 반드시 안트라센 중심을 갖는 치환기이며; 및

The

,

,

,

,

,

or

Lt; / RTI >

or

Lt; / RTI > is a substituent having an anthracene center; And

n is an integer of 10 to 1000;

Preferably, the novel polyimide polymer is a compound represented by the following general formula (1A) or (1B).

≪ EMI ID =

(Formula 1A is a compound of Formula 1)

≪ RTI ID = 0.0 &

(Formula 1B is a compound of Formula 1).

In addition, the present invention relates to a process for producing a compound represented by the following formula 1,

Reacting a diamine compound represented by the formula (2) and a dianhydride compound represented by the formula (3) to prepare an amic acid polymer represented by the formula (4) (step 1); And

A process for producing a novel polyimide polymer represented by the formula (1), comprising the step (2) of preparing the polyimide polymer represented by the formula (1) by heat treating the amic acid polymer represented by the formula (4) to provide.

[Reaction Scheme 1]

,

및 n은 상기 화학식 1에서 정의한 바와 같다).
(In the above scheme,

,

And n are the same as defined in the above formula (1)).

Hereinafter, the above manufacturing method will be described in detail for each step.

First, step 1 of the present invention is a step of reacting a diamine compound represented by the formula (2) and a dianhydride compound represented by the formula (3) to prepare an amic acid polymer. More specifically, step Reacting with an amine group of a diamine represented by the general formula (2) to produce an amic acid polymer represented by the general formula (4) containing an amide bond while breaking the anhydride ring of the hydride.

At this time, the organic solvent which can be used may be tetrahydrofuran (THF), dioxane, dimethylformamide (DMF), toluene, N-methylpyrrolidone (NMP) or the like which does not adversely affect the reaction, N-methylpyrrolidone can be used.

The reaction temperature may be in the range of -20 to 10 ° C, preferably -10 to -5 ° C.

Next, the step 2 according to the present invention is a step of preparing the polyimide polymer represented by the formula (1) by heat-treating the amic acid polymer represented by the formula (4) prepared in the step 1, more specifically, And then subjecting the amic acid polymer represented by the formula (4) to high temperature heat treatment to prepare a polyimide polymer represented by the formula (1) by dehydration of an amide group and a carboxylic acid group in the compound structure of the formula (4).

At this time, the step 2 may be carried out in a high temperature atmosphere, preferably at a reaction temperature of 300 to 400 ° C.

Further, the present invention provides a diamine intermediate compound of the polyimide polymer represented by the formula (1), represented by the following formula (2a).

(2a)

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl;

Y is hydrogen or 4- (t-butyl) phenyl; And

The compound of formula (2a) is a compound of formula (2).

Herein, the compound represented by the formula (2a) according to the present invention is one selected from the group consisting of compounds represented by the following formulas (2b) to (2d).

(2b)

[Chemical Formula 2c]

(2d)

The present invention also relates to a process for producing a compound represented by the following formula 2,

There is provided a process for preparing a diamine intermediate compound of a polyimide polymer represented by the formula (2a), which comprises reacting a dibromo compound represented by the following formula (5) with a boronic acid compound represented by the formula (6)

[Reaction Scheme 2]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl, Y is hydrogen or 4- (t-butyl) phenyl, and the compound of formula ).

Hereinafter, a method for preparing the diamine intermediate compound represented by Formula 2a will be described in detail.

The preparation method according to the present invention is a method for preparing a compound represented by the formula (2a) by performing a Suzuki reaction of a dibromo compound represented by the formula (5) and a boronic acid compound represented by the formula (6) in the presence of a palladium catalyst and a base .

At this time, the available palladium (Pd) (0) catalyst is tetrakis triphenylphosphine palladium _{(Pd (PPh 3) 4)} , bis triphenylphosphine palladium (Ⅱ) chloride _{(PdCl 2 (PPh 3) 2} ), palladium (ⅱ) chloride (PdCl _2), palladium (ⅱ) acetate _{(Pd (OCOCH 3) 2)} , [1,1- bis (diphenyl phosphine) ferrocene] dichloropalladium (ⅱ) (PdCl ₂ (dppf) ) May be used. Preferably however use of tetrakis triphenylphosphine palladium _{(Pd (PPh 3) 4)} , but the embodiment is not limited thereto.

In addition, usable bases include sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium ethoxide (NaOEt), sodium acetate (NaOAc), potassium butoxide (KOBu), potassium acetate (KOAc) , Potassium phosphate (K ₃ PO ₄ ), and cesium carbonate (Cs ₂ CO ₃ ). Preferably, sodium carbonate (Na ₂ CO ₃ ) can be used, but is not limited thereto.

Further, the usable organic solvent is selected from the group consisting of distilled water, tetrahydrofuran (THF), toluene, ethanol, 1,4-dioxane, dimethylformamide (DMF), dimethylsulfoxide (DMSO) Mixed solution may be used. Preferably, tetrahydrofuran (THF) can be used, but is not limited thereto.

Further, the present invention provides a dianhydride intermediate compound of the polyimide polymer represented by the above formula (1) represented by the following formula (3a).

[Chemical Formula 3]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl, Y is hydrogen or 4- (t- butyl) phenyl, and the compound of formula 3a is a compound of formula 3 ).

Here, the compound represented by the formula (3a) according to the present invention is one selected from the group consisting of compounds represented by the following formulas (3b) to (3d).

(3b)

[Chemical Formula 3c]

(3d)

The present invention also relates to a process for preparing a compound represented by the following formula (3)

Reacting a compound represented by the formula (7) with a compound represented by the formula (8) to prepare a boronic acid compound represented by the formula (9) (step 1); And

A step (2) of coupling the boronic acid compound of formula (9) and the dibromo compound of formula (5) prepared in step 1 to prepare a dianhydride compound of formula (3a) To provide a process for preparing a dianhydride intermediate compound of a polyimide polymer to be displayed.

[Reaction Scheme 3]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl, Y is hydrogen or 4- (t- butyl) phenyl, and the compound of formula 3a is a compound of formula 3 ).

Hereinafter, the preparation method of the dianhydride intermediate compound represented by Formula 3a will be described in detail.

The step 1 of the present invention is a step of reacting a compound represented by the formula (7) with a compound represented by the formula (8) to prepare a boronic acid compound represented by the formula (9), more specifically, a compound represented by the formula And a Suzuki reaction of a diborane compound represented by the general formula (8) are carried out to prepare a boronic acid compound represented by the general formula (9).

At this time, the available palladium (Pd) (0) catalyst is tetrakis triphenylphosphine palladium _{(Pd (PPh 3) 4)} , bis triphenylphosphine palladium (Ⅱ) chloride _{(PdCl 2 (PPh 3) 2} ), palladium (ⅱ) chloride (PdCl _2), palladium (ⅱ) acetate _{(Pd (OCOCH 3) 2)} , [1,1- bis (diphenyl phosphine) ferrocene] dichloropalladium (ⅱ) (PdCl ₂ (dppf) ) May be used. Preferably, [1,1-bis (diphenylphosphine) ferrocene] dichloropalladium (II) (PdCl ₂ (dppf)) may be used, but is not limited thereto.

In addition, usable bases include sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium ethoxide (NaOEt), sodium acetate (NaOAc), potassium butoxide (KOBu), potassium acetate (KOAc) , Potassium phosphate (K ₃ PO ₄ ), and cesium carbonate (Cs ₂ CO ₃ ). Preferably, potassium acetate (KOAc) can be used, but is not limited thereto.

Further, the usable organic solvent is selected from the group consisting of distilled water, tetrahydrofuran (THF), toluene, ethanol, 1,4-dioxane, dimethylformamide (DMF), dimethylsulfoxide (DMSO) Mixed solution may be used. Preferably, dimethylsulfoxide (DMSO) may be used, but is not limited thereto.

Next, step 2 according to the present invention is a step of coupling the boronic acid compound of formula (9) prepared in step 1 and the dibromo compound of formula (5) to prepare a dianhydride compound represented by formula (3a) , And more particularly to a process for preparing a compound represented by the general formula (3a) by performing a Suzuki reaction of a boronic acid compound represented by the formula (9) and a dibromo compound represented by the formula (5) in the presence of a palladium catalyst and a base.

At this time, the available palladium (Pd) (0) catalyst is tetrakis triphenylphosphine palladium _{(Pd (PPh 3) 4)} , bis triphenylphosphine palladium (Ⅱ) chloride _{(PdCl 2 (PPh 3) 2} ), palladium (ⅱ) chloride (PdCl _2), palladium (ⅱ) acetate _{(Pd (OCOCH 3) 2)} , [1,1- bis (diphenyl phosphine) ferrocene] dichloropalladium (ⅱ) (PdCl ₂ (dppf) ) May be used. Preferably however use of tetrakis triphenylphosphine palladium _{(Pd (PPh 3) 4)} , but the embodiment is not limited thereto.

In addition, usable bases include sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium ethoxide (NaOEt), sodium acetate (NaOAc), potassium butoxide (KOBu), potassium acetate (KOAc) , Potassium phosphate (K ₃ PO ₄ ), and cesium carbonate (Cs ₂ CO ₃ ). Preferably, sodium carbonate (Na ₂ CO ₃ ) can be used, but is not limited thereto.

Further, usable organic solvents include, but are not limited to, distilled water, tetrahydrofuran (THF), toluene, ethanol, 1,4-dioxane, dimethylformamide (DMF), dimethylsulfoxide (DMSO) Ethoxyethane (DME) or a mixed solution thereof may be used. Preferably, dimethoxyethane (DME) can be used, but is not limited thereto.

Further, the present invention provides an organic insulating film for electronic devices comprising a compound represented by the following formula (1).

[Chemical Formula 1]

,

및 n은 상기 화학식 1에서 정의한 바와 같다).
(In the formula 1,

,

And n are the same as defined in the above formula (1)).

As a result of thermogravimetric analysis (TGA measurement) and differential scanning calorimetry (DSC measurement) of the novel polyimide polymer represented by the formula (1) according to the present invention 1 and 2, The polyimide polymer has a high glass transition temperature (T _g ) of about 350 ° C or higher and a pyrolysis temperature (Td _{5 %} ) of at least 500 ° C. Further, the dielectric constant of the polyimide polymer according to the present invention was measured and found to have a low dielectric constant (k) of 2.9 or less at a frequency of 1 to 1000 kHz. From this, it can be seen that the novel polyimide polymer according to the present invention has excellent heat resistance and low dielectric constant (see Experimental Example 1 and Experimental Example 2).

Therefore, the novel polyimide polymer according to the present invention does not decompose even at a high temperature, stably maintains its shape, and has excellent electrical insulating properties through low dielectric constant. Therefore, the polyimide polymer according to the present invention can be used as a light emitting diode ), An organic thin film transistor (OTFT), and the like.

The organic insulating layer for electronic devices according to the present invention can be manufactured by a spin coating method, a bar coating method, an inkjet printing method, or a dipping method, but is not limited thereto.

In addition, the thickness of the organic insulating film for electronic devices according to the present invention can be controlled within a range of 30 to 300 nm.

If the thickness of the polyimide polymer exceeds the above-mentioned range, the insulating property of the organic insulating film is greatly deteriorated. If the thickness is too large, the driving voltage of the electronic device including the polyimide polymer according to the present invention is increased.

Further, the present invention provides a flexible metal-clad laminate film (FMCL) prepared by applying a novel polyimide polymer represented by the following formula (1) to at least one side of a conductive metal film and curing the same.

[Chemical Formula 1]

,

및 n은 상기 화학식 1에서 정의한 바와 같다).
(In the formula 1,

,

And n are the same as defined in the above formula (1)).

The flexible metal-clad laminate film (FMCL) according to the present invention can be produced by applying intermediate compounds of the polyimide polymer represented by the formula (1) on a film substrate made of a conventional conductive metal, , The polyimide polymer film 1 is laminated on the metal film 2 as shown in Fig. 6, for example, by thermally polyimidizing by heating stepwise at a temperature in the range of about 80 to 400 DEG C A flexible metal foil laminated film (FMCL) containing a polyimide polymer can be produced.

As a result of thermogravimetric analysis (TGA measurement) and differential scanning calorimetry (DSC measurement) of the novel polyimide polymer represented by Formula 1 according to the present invention, the polyimide polymer has a high glass transition temperature (T _g ), and the thermal decomposition temperature (Td _{5 %} ) was confirmed to be 500 ° C or higher. Further, the dielectric constant of the polyimide polymer according to the present invention was measured and found to have a low dielectric constant (k) of 2.9 or less at a frequency of 1 to 1000 kHz. From this, it can be seen that the novel polyimide polymer according to the present invention has excellent heat resistance and low dielectric constant (see Experimental Example 1 and Experimental Example 2).

Therefore, the novel polyimide polymer according to the present invention does not decompose even at a high temperature, stably maintains its shape, and has an excellent electrical insulation property through a low dielectric constant. Therefore, the polyimide polymer according to the present invention is a flexible metal foil laminated film (FMCL) material.

In the flexible metal foil laminated film (FMCL) according to the present invention, the conductive metal may be selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, iron, aluminum, molybdenum, tungsten, Can be used.

The present invention also provides a novel polyimide polymer for a blue light emitting organic device represented by the following general formula (1).

[Chemical Formula 1]

,

및 n은 상기 화학식 1에서 정의한 바와 같다).
(In the formula 1,

,

And n are the same as defined in the above formula (1)).

The blue light emitting polymers that have been developed to date have many improvements in terms of lifetime and brightness. The main cause is heat. As a result, the polyimide polymer represented by the formula (1) according to the present invention was found to have a high glass transition temperature of about 350 ° C or higher. In addition, the polyimide polymer according to the present invention was confirmed to emit blue light through the UV and photoluminescence (PL) spectral results. From the results, it can be seen that the polyimide polymer represented by the formula (1) according to the present invention has excellent heat resistance and excellent blue light emission effect (see Experimental Example 1 and Experimental Example 3).

Therefore, the polyimide polymer represented by the formula (1) according to the present invention is excellent in the effect of emitting blue light and excellent in heat resistance, so that it has excellent lifetime and brightness improvement effect. Therefore, it is useful as a material for blue light emitting organic devices Can be used.

Hereinafter, the present invention will be described in detail with reference to Production Examples, Examples and Experimental Examples.

However, the following Production Examples, Examples and Experimental Examples are merely illustrative of the present invention, and the content of the present invention is not limited by Production Examples, Examples and Experimental Examples.

< Manufacturing example  1 > 2,6- die -t- Butyl anthracene  Produce

Trifluoroacetic acid (TFA, 150 mL) was injected into a three-necked reactor equipped with a stirrer and a condenser. Anthracene (27 g) was dispersed in the reactor, and t -butanol (54 mL) Followed by reflux stirring for one day. Thereafter, the solution was cooled to room temperature, the liquid was removed as much as possible, and then a lump-shaped organic material having a yellowish black solution was dispersed in hexane (or pentane). Water was added to the reaction mixture to separate the white organic layer and the water layer, and the separated organic layer was further washed twice with water and then filtered. The filtered organic layer was washed with hexane (or pentane) and dried to obtain the desired compound (18 g, 40%).

^{1 H NMR (300 MHz, CDCl} 3): δ 8.32 (s, 2H), 7.94-7.91 (d, 2H), 7.87-7.86 (d, 2H), 7.56-7,53 (dd, 2H), 1.45 ( s, 18H).

< Manufacturing example  2> 9,10- Dive Lomo -2,6- die -t- Butyl anthracene  Produce

The compound prepared in step 1 (17.5 g, 60 mmol) was dissolved in dichloromethane (DCM, 260 mL) and then cooled to 0 ^° C. Bromine (6.8 mL) was dissolved in dichloromethane (DCM, 200 mL), added dropwise to the reaction while maintaining the temperature at 0 ^° C, stirred at room temperature overnight, and then stirred overnight. After stirring was completed, sodium bisulfite aqueous solution (Na ₂ S ₂ O ₅ , 3.4 g / H ₂ O 30 mL) was added and stirred for 30 minutes to remove residual bromine. Then, sodium bicarbonate aqueous solution (NaHCO 3 ₃ , 12.2 g / H ₂ O 150 mL) was added dropwise to neutralize. The neutralized reaction product was subjected to layer separation to extract an organic layer, and the organic layer was washed with water and then dried with magnesium sulfate. The dried organic layer was dried under reduced pressure, and the resulting solid was filtered and dried to obtain the title compound (17 g, 36 mmol, 60%).

¹ H NMR (300 MHz, CDCl ₃ ):? 8.52-8.49 (d, 2H), 8.47-8.46 (d, 2H), 7.73-7.69 (dd, 2H), 1.49 (s, 18H).

< Example  1 > 9,10- Bis (4- Aminophenyl ) -2,6- die -t- Butyl anthracene  Produce

A 2 L two-necked reactor was charged with a condenser, a vacuum and a nitrogen injection device, and THF (600 mL) was introduced, and the compound (9.0 g) and 4- (4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl) benzamine (9.2 g) was dissolved. To the reaction was added a 2M sodium carbonate aqueous solution (Na ₂ CO ₃ ) and tetrakis triphenylphosphine palladium (Pd (PPh ₃ ) ₄ , 924 mg). Thereafter, the mixture was heated under reflux in a nitrogen atmosphere for 4 days. When the reaction was completed, it was cooled to room temperature, added to water (400 mL), and then the organic layer was separated. The layered organic layer was dried over magnesium sulfate and purified by column chromatography to obtain the desired compound (6.3 g, 58%).

^{1 H NMR (300 MHz, DMSO} -d 6): δ 7.67-7.64 (dd, 4H), 7.49-7.48 (dd, 2H), 7.07-7.05 (d, 4H), 6.82-6.80 (d, 4H), 5.26 (s, 4H), 1.23 (s, 18H).

< Example  2> 9,10-Bis [4- ( Isobenzofuran -1,3- Dieonil )] - 2,6- die -t- Butylant Manufacture of Larsen

Step 1: 5- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane -2 days) Isobenzofuran -1,3- this Manufacture of onions

(10 g, 44 mmol), bis (pinacorate diborane, 10.2 g, 40 mmol), [1, 1 -bis (Diphenylphosphine) ferrocene] dichloropalladium (II) / metylene chloride complex (1 g) and potassium acetate (12 g, 120 mmol) were dissolved in dimethylsulfoxide (DMSO), and the mixture was stirred at 80 DEG C for 8 hours. After completion of the stirring, the reaction was cooled, a small amount of water was added to the reaction mixture, The filtrate was diluted with ethyl acetate (EA), activated charcoal was added, and the product was decolorized by filtration. The decolored filtrate was washed with water, and then sodium sulfate (Na ₂ SO ₄ ), The organic solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (5.0 g, 82%).

^{1 H NMR (300 MHz, DMSO} -d 6): δ 8.23 (dd, 1H), 8.14 (s, 1H), 8.09 (dd, 1H), 1.34 (s, 12H).

Step 2: 9,10-Bis [4- ( Isobenzofuran -1,3- Dieonil )] - 2,6- die -t- Butyl anthracene  Produce

(5 g, 11 mmol) and 5- (4,4,4-tetrahydro-2H-1,5-benzodiazepine) prepared in Preparation Example 2 were placed in a 2 L 2-neck reactor equipped with a condenser, Dioxaborolan-2-yl) isobenzofuran-1,3-dione (6.3 g, 23 mmol) was dissolved. To the reaction was added a 2M sodium carbonate aqueous solution (Na ₂ CO ₃ ) and tetrakis triphenylphosphine palladium (Pd (PPh ₃ ) ₄ , 513 mg). Thereafter, the mixture was heated under reflux in a nitrogen atmosphere for 4 days. When the reaction was completed, it was cooled to room temperature, added to water (200 mL), and then the organic layer was separated. The layered organic layer was dried over magnesium sulfate and purified by column chromatography to obtain the desired compound (3.8 g, 60%).

¹ H NMR (500 MHz, CDCl ₃ ):? 7.70 (t, 2H), 7.69 (dd, 2H), 7.52 (d, 2H), 7.47 (d, 2H), 1.22

Mass (M &lt; + &gt;): 582.

< Example  3> Production of polyimide polymer-1

Step 1: Amic acid  polymer( PAA ) -1

The compound (1.4 g, 3.0 mmols) prepared in Example 1 was dissolved in N-methylpyrrolidone (20.9 g) in the presence of nitrogen and cooled to 0 ° C with ice water. Thereafter, 4,4'-oxydiphthalic anhydride (ODPA, 0.9 g, 3.0 mmols) was added dropwise, and about 5^oC for 24 hours to obtain the desired compound.

Intrinsic viscosity (solvent: NMP, concentration: 0.5 g / dL, measuring temperature: 30 ^° C): 1.45;

Kinematic viscosity: 3100 cps;

^{1 H NMR (300 MHz, DMSO} -d 6): δ 10.6 (br.s, 2H), 8.09-6.84 (. Br m, 18), 1.24-1.23 (br s, 18H.).

Step 2: Preparation of polyimide polymer-1

The amic acid polymer-1 prepared in the above step 1 was spin-cast on a glass substrate and then heat-treated at 90 ° C for 10 minutes and at 250 ° C for 40 minutes to obtain a target compound.

IR:? _Max (cm ^-1 ): 3329, 3059 2962, 2912, 2871, 1776, 1723, 1609, 1515, 1478, 1363, 1269, 1225, 1085, 821, 734.

< Example  4> Production of polyimide polymer-2

Step 1: Preparation of amamic acid polymer (PAA) -2

The compound (1.4 g, 3.0 mmols) prepared in Example 1 was dissolved in a solution (21 g) of N-methylpyrrolidone (6.3 g) dissolved in DMF (14.7 g) in the presence of nitrogen, 0.0 &gt; 0 C. &lt; / RTI &gt; The compound (1.7 g, 3.0 mmols) prepared in Example 2 was added dropwise in this order and stirred at room temperature for 24 hours to obtain the desired compound.

Intrinsic viscosity (solvent: DMF / NMP, concentration: 0.5 g / dL, measuring temperature: 30 ^o C): 0.9;

Kinematic viscosity: 2700 cps;

¹ H NMR (300 MHz, DMSO-d ₆ ):? 10.92 (s, 1H), 10.7 (s, 1H), 8.24-7.45 (br.m, 26), 1.32-1.14 (br.

Step 2: Preparation of polyimide polymer-2

The amic acid polymer-2 prepared in the above step 1 was spin-cast on a glass substrate, and then heat-treated at 90 ° C for 10 minutes and at 400 ° C for 40 minutes to obtain a target compound.

IR:? _Max (cm ^-1 ): 3063, 2967, 2906, 2875, 1369, 1729, 1617, 1514, 1369, 1260, 1223, 1089, 817, 668.

< Experimental Example  1 > New  Measurement of glass transition temperature and pyrolysis temperature of polyimide polymer

In order to evaluate the heat resistance of the novel polyimide polymer according to the present invention, the following experiment was conducted.

In order to evaluate the heat resistance of the polyimide polymer according to the present invention, the glass transition temperature and the thermal decomposition temperature were measured. At this time, the glass transition temperature (T _g ) of the polyimide polymer prepared in Example 3 and Example 4 was measured under a nitrogen (N ₂ ) at 10 ° C / min using a differential scanning calorimeter (DSC measurement, TA instrument) (TGA, TA instrument 2950, USA). The results are shown in FIG. 2. The results are shown in FIG. 2, and the results are shown in FIG. % by weight decrease in the occurring pyrolysis temperature (Td _5%) to 10 ℃ / min in a nitrogen (N ₂₎ temperature rise measured by up to 800 ℃, the results are shown in Fig.

2 is a graph showing the glass transition temperatures (T _g ) of Examples 3 and 4 according to the present invention.

3 is a graph showing the thermal decomposition temperatures (Td _{5 %} ) of Examples 3 and 4 according to the present invention.

As shown in FIG. 2 and FIG. 3, the glass transition temperature (T _g ) of the novel polyimide polymer prepared in Example 3 and Example 4 according to the present invention was found to be about 350 ° C or higher and the pyrolysis temperature Td _{5 %} ) was confirmed to be over 500 ° C. This means that even at a high temperature of 300 DEG C or more, the thermosetting stability is excellent without morphological deformation and decomposition.

Therefore, the novel polyimide polymer according to the present invention has excellent thermal stability at a high temperature, and thus can be effectively used as an organic insulating film for an electronic device or a material for a blue organic light emitting device.

< Experimental Example  2 > New  Measurement of Dielectric Constant of Polyimide Polymer

In order to evaluate the dielectric properties of the novel polyimide polymer according to the present invention as an organic insulating material, the following experiment was conducted.

First, a device having a metal-insulator-metal (MIM) structure was fabricated. At this time, gold (Au) was deposited by using an indium tin oxide (ITO) electrode as a lower electrode and a shadow mask as a top electrode, and the thickness of the organic insulating film was adjusted to 300 nm. More specifically, the amic acid polymer prepared in Step 1 of Example 3 was spin-coated on an ITO electrode (thickness: 180 nm), heat-treated at 90 ^° C for 10 minutes, and then heat-treated at 250 ° C for 40 minutes To the polyimide polymer of Example 3. Thereafter, gold (Au) having a diameter of 2 cm and a thickness of 40 nm was thermally deposited on the polyimide polymer thin film under a vacuum of about 10 ^-6 torr using a shadow mask to form an electrode-dielectric-electrode MIM) device was completed. The prepared electrode-dielectric-electrode (MIM) device measures the capacitance at a frequency of 1 to 1000 kHz using an impedance relay (Agilent Technologies 4294A Precision Impedence analyzer) and substitutes it into the following equation to obtain a dielectric constant Respectively. The measurement results are shown in Fig.

4 is a graph showing dielectric constants according to frequency of a metal-insulator-metal (MIM) structure element coated with the polyimide polymer thin film prepared in Example 3 according to the present invention.

As shown in Fig. 4, the polyimide polymer according to the present invention has a low dielectric constant of 2.85 to 2.9 at a frequency of 1 to 1000 kHz. From this, it can be seen that the novel polyimide polymer according to the present invention has excellent dielectric properties because it has a low dielectric constant of 3 or less.

Accordingly, the novel polyimide polymer according to the present invention has excellent thermal stability at a high temperature, and has excellent electrical insulation characteristics through low dielectric constant, so that it can be effectively used as an organic insulating film for electronic devices.

< Experimental Example  3 > New  Evaluation of luminescence of polyimide polymer

In order to evaluate the luminescent effect of the novel polyimide polymer according to the present invention as the material of the organic light emitting device, the following experiment was conducted.

First, UV-Vis spectrum (UV / VIS Spectrophotometer, Agilent 8453) of the polyimide polymer film of Formula 1 prepared in Example 3 was measured. Thereafter, the light was irradiated at a wavelength of 380 nm and excited. Then, PL (PL / PLE Measuring System for Phosphor) was measured. The results are shown in FIG.

5 is a graph showing the UV and photoluminescence (PL) spectra of the polyimide polymer prepared in Example 3 according to the present invention.

As shown in Fig. 5, the polyimide polymer according to the present invention was found to emit light at a blue emission wavelength band of 496 nm. From this, it can be seen that the polyimide polymer according to the present invention emits blue light.

Accordingly, the novel polyimide polymer according to the present invention has excellent thermal stability at a high temperature, and is excellent in the effect of emitting blue light at 496 nm, so that it can be effectively used as a material for a blue organic light emitting device.

Claims (15)

A novel polyimide polymer represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

(In the formula 1,

The

,

,

,

,

,

,

,

,

,

,

or

ego;

The

,

,

,

,

,

or

Lt; / RTI &gt;

or

Lt; / RTI &gt; is a substituent having an anthracene center; And

and n is an integer of 10 to 1000).
The method according to claim 1,
The novel polyimide polymer is represented by the following general formula (1A) or (1B):
&Lt; EMI ID =

(Formula 1A is a compound of Formula 1)
&Lt; RTI ID = 0.0 &

(Formula 1B is a compound of Formula 1).
As shown in Scheme 1 below,
Reacting a diamine compound represented by the formula (2) and a dianhydride compound represented by the formula (3) to prepare an amic acid polymer represented by the formula (4) (step 1); And
A process for producing a polyimide polymer represented by the formula (1), comprising the step (2) of preparing the polyimide polymer represented by the formula (1) by heat treating the amic acid polymer represented by the formula (4) Manufacturing method:
[Reaction Scheme 1]

(In the above scheme,

,

And n are as defined in claim 1).
A diamine intermediate compound of the polyimide polymer represented by the general formula (1)
(2a)

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl;
Y is hydrogen or 4- (t-butyl) phenyl; And
The compound of formula (2a) is a compound of formula (2).
5. The method of claim 4,
Wherein the compound represented by Formula 2a is a compound represented by Formula 2b to Formula 2d:
(2b)

[Chemical Formula 2c]

(2d)

.
As shown in Scheme 2 below,
A process for preparing a diamine intermediate compound of a polyimide polymer represented by formula (2a), which comprises reacting a dibromo compound represented by the following formula (5) with a boronic acid compound represented by the formula (6)
[Reaction Scheme 2]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl;
Y is hydrogen or 4- (t-butyl) phenyl; And
The compound of formula (2a) is a compound of formula (2).
A dianhydride intermediate compound of a polyimide polymer represented by the formula (1)
[Chemical Formula 3]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl;
Y is hydrogen or 4- (t-butyl) phenyl; And
The compound of formula (3a) is a compound of formula (3).
8. The method of claim 7,
Wherein the compound represented by the formula (3a) is a compound represented by the following formula (3b) to (3d):
(3b)

[Chemical Formula 3c]

(3d)

.
As shown in Scheme 3 below,
Reacting a compound represented by the formula (7) with a compound represented by the formula (8) to prepare a boronic acid compound represented by the formula (9) (step 1); And
A step (2) of coupling the boronic acid compound of formula (9) and the dibromo compound of formula (5) prepared in step 1 to prepare a dianhydride compound of formula (3a) Method of preparing a dianhydride intermediate compound of a polyimide polymer to be displayed:
[Reaction Scheme 3]

(Wherein X is t-butyl, trimethylsilyl or 4- (t-butyl) phenyl;
Y is hydrogen or 4- (t-butyl) phenyl; And
The compound of formula (3a) is a compound of formula (3).
1. An organic insulating film for electronic devices comprising a compound represented by the following formula
[Chemical Formula 1]

(In the formula 1,

,

And n are as defined in claim 1).
11. The method of claim 10,
Wherein the organic insulating layer is formed by any one method selected from the group consisting of a spin coating method, a bar coating method, an ink jet printing method, and a dipping method.
11. The method of claim 10,
Wherein the organic insulating film has a thickness of 30 to 300 nm.
A flexible metal-clad laminate film (FMCL) is produced by coating a new polyimide polymer represented by the following formula (1) on at least one surface of a conductive metal film and then curing it.
[Chemical Formula 1]

(In the formula 1,

,

And n are as defined in claim 1).
14. The method of claim 13,
Wherein the conductive metal is one selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, iron, aluminum, molybdenum, tungsten, alloys thereof and mixtures thereof.
1. A novel polyimide polymer for a blue light emitting organic device represented by the following Formula 1:
[Chemical Formula 1]

(In the formula 1,

,

And n are as defined in claim 1).

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