KR20190054843A - Polyimides and optoelectronic devices comprising the same - Google Patents

Abstract

According to one embodiment of the present invention, provided is a polyimide polymer represented as chemical formula 1. The polyimide polymer provided in one embodiment of the present invention has excellent heat resistance, chemical resistance and photoelectric properties. A polymer film containing the polyimide polymer has a low surface roughness and an excellent printability for conductive glass or metals. In addition, the present invention has an excellent photoreactive property in a long wavelength area of 300 nm or more and even in a low amount of light of 50-1,000 mJ/cm^2. Moreover, a pyrolysis initiating temperature of a photocured polymer film is 250°C or more, a photoelectric coefficient (r_33) of a photoelectric device comprising the polymer film has an excellent range of values, and an excellent aging stability at high temperatures. In addition, the present invention provides a low gaseous emission property at high temperatures, an electric insulation, an excellent solvent resistance and an excellent boding property to various substrates, thereby being useful in application of photoelectric devices such as optical modulators and optical switches.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide polymer and a photoelectric device including the same,

To a polyimide polymer and a photoelectric device including the same.

Optical signals such as optical modulators, optical switching, optical memories, optoelectronic circuits, wavelength conversion, electric field sensors, THz wave generation and reception, and holograms are the most important elements for implementing optical information processing systems. And control devices.

As the photoelectric material for these implementations, an inorganic crystal such as lithium niobate (LiNbO ₃ ) is used as a material, but it has a disadvantage in that it is difficult to exhibit processability and photoelectric property at a high temperature. Therefore, in order to realize the next-generation ultra-high-speed optical communication, development of a new material capable of overcoming this is required.

On the other hand, the organic polymer material can be applied to a large area by a solution process, and the electro-optic coefficient (r ₃₃ ) can be improved relatively easily, which is highly applicable as an electro-optical material for next-generation optical communication.

However, as is well known, in order for a polymer material to have electro-optical properties, the entire system must have asymmetry. For this purpose, a full-field poling method has been used in which a polarized material is polarized by applying a DC electric field near a glass transition temperature of a polymer material, and then cooled under application of an electric field to fix an oriented polarization.

As one of the problems of the electro-optical material using a polymer, there is a relaxation phenomenon in which the initial electro-optical characteristic decreases after the poling. Reduction of such relaxation phenomenon is very important in order to be used for manufacturing a long-time reliable device. For this purpose, introduction of a side chain into a chromophore or development of a technique using a polymer having a high glass transition temperature is being carried out. Thus, the thermal stability was slightly improved by doping polyamic acid with a low molecular photoelectric functional compound, but the glass transition temperature was lowered by the addition of photoelectric compound.

Also, synthesis of nonlinear optically active diamine or photoelectric functional polymer through Mitsunobu reaction has been reported. In the case of a photopolymer based on acrylic or polycarbonate, the improvement of the photoelectric coefficient is relatively easy due to the low glass transition temperature, while in the case of the time stability, it is only several hundred hours in the temperature range of 80-100 ° C.

Among these polymer electro-optic materials, an electro-optical material comprising polyimide as a base polymer has a relatively high glass transition temperature (T _g ) and is excellent in thermal stability. However, such a polyimide-based electrooptic polymer also has a disadvantage in that it deteriorates the long-term stability of the photoelectric device due to a decrease in the photoelectric property due to the chromophore disorder caused by the poling process when the process is performed at a high temperature of 100 ° C or higher or for a long time. There is

However, in order to be applied to devices such as a light control device and a next-generation silicon photonics, stability over time at 100 占 폚 or higher and stability against a process solution are highly required.

Patent Document 1 (Korean Patent No. 10-0284814) discloses a photo-crosslinkable polyimide-based polymer compound having non-linear optical properties and a manufacturing method thereof. In the case of the photoelectric material proposed in the related art, The photoelectric coefficient decreased to about 50% of the initial value.

Patent Document 2 (US Patent No. 5,223,356) discloses a photoelectric material into which a photo-curable polyvinylcinnamate is introduced, and Patent Document 3 (US Patent No. 7390857) discloses a photoelectric material in a temperature range of 130-200 占 폚 Thermal crosslinking polymer technology was developed through thermal curing.

However, most of the photoelectric polymer materials developed to date have not provided enough heat resistance to withstand the manufacturing or use temperature of optical communication devices and semiconductors, and are required to improve characteristics for long-term use at high temperatures have.

Accordingly, the inventors of the present invention have developed a polyimide copolymer exhibiting excellent heat resistance, chemical resistance and photoelectric properties, and confirmed that it exhibits excellent photoelectric coefficient and thermal stability by applying it to a photoelectric device, thereby completing the present invention.

An object of one aspect of the present invention is to provide a photoelectric polyimide copolymer excellent in stability at a high temperature and with high chemical resistance.

Another object of the present invention is to provide an optoelectronic device that provides stability and chemical resistance over time at a temperature of 250 DEG C or higher.

In order to achieve the above object, in one aspect of the present invention,

There is provided a polyimide polymer represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

는

,

,

또는

이고, 상기 A₁은 단결합, -(CH₂)_p-, -O-, -CO-, -S-, -SO₂-, -C(CH₃)₂-, -C(CF₃)₂-, -Si(CH₃)₂-,

,

또는

이고, p는 1-5이고,

The

,

,

or

And wherein A ₁ represents a single _{bond, - (CH 2) p -} , -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 _{-, -Si (CH 3) 2} -,

,

or

, P is 1-5,

는

,

,

또는

를 포함하고, X는 -O-(C=O)-, -(C=O)-O-, -NH(C=O)-, -(C=O)-NH-, -O-, -S-, -N(C=O)₂CH₂CH- 또는 -CH₂-O(C=O)-이고, Y₁ 내지 Y₃는 각각 독립적으로 수소(H), C_1-30의 알킬 또는 C_5-30의 아릴이고, R₀는 C_1-30의 알킬 또는 C_5-30의 아릴이고, t는 1-20의 정수이고,

The

,

,

or

(C = O) -O-, -NH (C = O) -, - (C = O) -NH-, -O-, - S-, -N (C = O) 2 CH 2 CH- , or _{-CH 2 -O (C = O)} - a, Y ₁ to Y ₃ are each independently hydrogen (H), a C _1-30 alkyl or C _0-30 aryl, R ₀ is C _1-30 alkyl or C _5-30 aryl, t is an integer of 1-20,

는

,

,

또는

이고, R₁은

이고, R₂는 수소(H), C_1-5의 직쇄 알킬 또는 C_3-5의 분지쇄 알킬이고, Z₁은 CR₇ 또는 질소(N)이고, Z₂는

,

또는

이고, Z₃는 CR₇ 또는 질소(N)이고, Z₄는 NR₇, 황(S) 또는 산소(O)이고, Z₅는

이고, R₃ 내지 R₇은 각각 독립적으로 수소(H), 할로, 시아노(CN), 니트로(NO₂), C_1-5의 직쇄 알킬, C_3-5의 분지쇄 알킬 또는 할로겐 치환된 C_1-5의 알킬이고, q는 1-5의 정수이고,

The

,

,

or

, R < ₁ >

And, R ₂ is hydrogen (H), a straight chain alkyl or branched alkyl of C _3-5 of C _1-5, Z ₁ is CR ₇ or nitrogen (N), Z ₂ is

,

or

And, Z ₃ is CR ₇ or nitrogen (N) and, Z ₄ is NR _7, a sulfur (S) or oxygen (O), Z ₅ is

And R ₃ to R ₇ are each independently selected from the group consisting of hydrogen (H), halo, cyano (CN), nitro (NO ₂ ), C _1-5 linear chain alkyl, C _3-5 branched chain alkyl, C _1-5 alkyl, q is an integer of 1-5,

n is an integer of 1-500,

m is an integer of 1-500.)

In another aspect of the present invention,

Dianhydride; At least one aromatic diamine selected from the group consisting of compounds represented by the following formulas (2), (3), (4) and (5) And an aromatic diamine comprising bishydroxyphenyl; (step 1); And

There is provided a process for producing a polyimide polymer represented by the above formula (1), which comprises a step (step 2) of producing a polyimide polymer using the polymer produced in the above step 1 and a compound represented by the following formula (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the above Chemical Formulas 2 to 6,

X, Y ₁ , Y ₂ , Y ₃ , R ₂ , Z ₁ , Z ₂ , q and t are as defined in the formula (1)).

Further, in another aspect of the present invention

There is provided a polymer membrane comprising the polyimide polymer represented by the above formula (1).

Further, in another aspect of the present invention

There is provided a photoelectric device including the polymer film.

The polyimide polymer provided in one aspect of the present invention has an effect of exhibiting excellent heat resistance, chemical resistance, and photoelectric characteristics. The polymer film containing the polyimide polymer has a low surface roughness and is excellent in printing property against conductive glass or metal. In addition, it has excellent photoreaction characteristics even in a long wavelength region of 300 nm or more and a low light amount of 50-1,000 mJ / cm ² .

In addition, the photocatalytic coefficient of the photoelectric device including the polymer film (r ₃₃ ) exhibits a good range of values, and the stability at a high temperature is remarkably excellent even when the photocurable polymer film has a pyrolysis initiation temperature of 250 ° C or more . In addition, it is effective for application of photoelectric devices such as optical modulators and switches because of its low gas emission characteristics at high temperatures, electrical insulation, excellent solvent resistance, and adhesion properties to various substrates.

1 is a nuclear magnetic resonance spectrum of the polyimide polymer prepared in Example 1,
2 is a thermogravimetric curve of a polymer film obtained by photo-curing the polyimide polymer prepared in Example 1,
FIG. 3 is a graph showing a change with time at a high temperature measured after heat treatment of the photoelectric device manufactured from the polyimide polymer produced in Example 1 and Comparative Example 1 at a temperature of 150 ° C.,
FIG. 4 is a graph showing a change with time at a high temperature measured after heat treatment of the photoelectric device manufactured from the polyimide polymer produced in Example 1 and Comparative Example 1 at a temperature of 200 ° C.,
FIG. 5 is a comparative chart of film thickness variations for the process solution of the polyimide polymer prepared in Example 1 and Comparative Example 1. FIG.

In one aspect of the invention,

There is provided a polyimide polymer represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

는

,

,

또는

이고, 상기 A₁은 단결합, -(CH₂)_p-, -O-, -CO-, -S-, -SO₂-, -C(CH₃)₂-, -C(CF₃)₂-, -Si(CH₃)₂-,

,

또는

이고, p는 1-5이고,

The

,

,

or

And wherein A ₁ represents a single _{bond, - (CH 2) p -} , -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 _{-, -Si (CH 3) 2} -,

,

or

, P is 1-5,

는

,

,

또는

를 포함하고, X는 -O-(C=O)-, -(C=O)-O-, -NH(C=O)-, -(C=O)-NH-, -O-, -S-, -N(C=O)₂CH₂CH- 또는 -CH₂-O(C=O)-이고, Y₁ 내지 Y₃는 각각 독립적으로 수소(H), C_1-30의 알킬 또는 C_5-30의 아릴이고, R₀는 C_1-30의 알킬 또는 C_5-30의 아릴이고, t는 1-20의 정수이고,

The

,

,

or

(C = O) -O-, -NH (C = O) -, - (C = O) -NH-, -O-, - S-, -N (C = O) 2 CH 2 CH- , or _{-CH 2 -O (C = O)} - a, Y ₁ to Y ₃ are each independently hydrogen (H), a C _1-30 alkyl or C _0-30 aryl, R ₀ is C _1-30 alkyl or C _5-30 aryl, t is an integer of 1-20,

는

,

,

또는

이고, R₁은

이고, R₂는 수소(H), C_1-5의 직쇄 알킬 또는 C_3-5의 분지쇄 알킬이고, Z₁은 CR₇ 또는 질소(N)이고, Z₂는

,

또는

이고, Z₃는 CR₇ 또는 질소(N)이고, Z₄는 NR₇, 황(S) 또는 산소(O)이고, Z₅는

이고, R₃ 내지 R₇은 각각 독립적으로 수소(H), 할로, 시아노(CN), 니트로(NO₂), C_1-5의 직쇄 알킬, C_3-5의 분지쇄 알킬 또는 할로겐 치환된 C_1-5의 알킬이고, q는 1-5의 정수이고,

The

,

,

or

, R < ₁ >

And, R ₂ is hydrogen (H), a straight chain alkyl or branched alkyl of C _3-5 of C _1-5, Z ₁ is CR ₇ or nitrogen (N), Z ₂ is

,

or

And, Z ₃ is CR ₇ or nitrogen (N) and, Z ₄ is NR _7, a sulfur (S) or oxygen (O), Z ₅ is

And R ₃ to R ₇ are each independently selected from the group consisting of hydrogen (H), halo, cyano (CN), nitro (NO ₂ ), C _1-5 linear chain alkyl, C _3-5 branched chain alkyl, C _1-5 alkyl, q is an integer of 1-5,

n is an integer of 1-500,

m is an integer of 1-500.)

Hereinafter, the polyimide polymer according to the present invention will be described in detail.

In general, the polyimide polymer (or resin) refers to a high heat resistant resin produced by condensation polymerization of an aromatic tetracarboxylic acid dianhydride or a derivative thereof with an aromatic diamine or an aromatic diisocyanate followed by imidization. The polyimide polymer may have various molecular structures depending on the type of monomers used and is generally prepared by polycondensation using an aromatic tetracarboxylic acid dianhydride and an aromatic diamine. Most polyimide resins are insoluble and insoluble ultra high heat resistant resins and have the following characteristics. This is because of excellent heat resistance and oxidation resistance, high usable temperature, long-term usable temperature of about 260 占 폚, excellent heat resistance characteristic of short-term usable temperature of about 480 占 폚, radiation resistance, excellent low temperature characteristic and excellent chemical resistance.

However, in the case of the polyimide polymer having photoelectric characteristics developed up to now, there is a problem that the side chain introduced for the purpose of improving the photoelectric coefficient is not fixed and the long-term stability at high temperature is low.

At this time, the polyimide polymer provided in one aspect of the present invention may contain aromatic diamine and bishydroxyphenyl-containing aromatic diamine having excellent photoreactivity even at a long wavelength of at least 300 nm and at a low light intensity of 50 mJ / cm ² as a soluble polyimide polymer Was introduced as a monomer, and at the same time a photoelectric functional group was introduced into the side chain.

In a specific example, the polyimide polymer may have an intrinsic viscosity of 0.1-5.0 dL / g, may be 0.6-5.0 dL / g, may be 0.9-5.0 dL / g, may be 0.6-4.0 dL / g, And may be 0.9-4.0 dL / g, and may be 0.9-2.5 dL / g. In addition, the polyimide polymer may have a weight average molecular weight of 5,000-500,000 g / mol. Further, the polyimide polymer may be a glass transition temperature (T _g) is the temperature range of 150-250 ℃. Furthermore, the polyimide polymer can be prepared by reacting an aprotic polar solvent such as dimethylacetamide (DMAc), dimethylformamide (DMF), N -methyl-2-pyrrolidone (NMP), acetone, And can easily dissolve at room temperature for organic solvents such as meta-cresol and the like. In particular, it exhibits a high solubility of 10% by weight or more at room temperature even for a low-absorbent solvent such as tetrahydrofuran (THF), gamma-butyrolactone (GBL) and the like.

는

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

및

등을 포함할 수 있다. 이때, 상기 r은 1-20일 수 있으며, 1-10일 수 있고, 1-5일 수 있다.Further, for example, in the polyimide polymer,

The

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

And

And the like. Here, r may be 1-20, may be 1-10, and may be 1-5.

Further, for example, the polyimide polymer may be produced using a dianhydride monomer, an aromatic diamine monomer containing a photoreactive group, an aromatic diamine monomer containing bishydroxyphenyl, and a photoelectric compound. In addition to the above-mentioned diamine monomers, aromatic diamine monomers commonly used in the art can be further used.

In this case, the aromatic diamine monomer containing the photoreactive group may be used in an amount of 1-99 mol% based on 100 of the total diamine monomer used. The aromatic diamine monomer containing bishydroxyphenyl may be used in an amount of from 1 to 99 mol% based on 100 of the total diamine monomer used.

For example, the dianhydride monomer may be a tetracarboxylic dianhydride and may include pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride (BPDA), benzophenone-3,4-3 ', 4'-tetracarboxylic dianhydride (BTDA), diphenylsulfone-3,4-3', 4'-tetracarboxylic acid dianhydride (DSDA), 4,4 '- (2,2'-hexafluoroisopropylidene) diphthalic dianhydride (6FDA), m ( p ) Carboxylic acid dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (CBDA), 1-carboxydimethyl-2,3,5-cyclopentanetricarboxylic acid-2,6,3 , 5-dianhydride (TCAAH), cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride (CHDA), butane-1,2,3,4-tetracarboxylic acid dianhydride (BuDA) 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride (CPDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic acid dianhydride (DOC DA), 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetralin-1,2-dicarboxylic acid dianhydride (DOTDA), bicyclooctene- -Tetracarboxylic dianhydride (BODA) and naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTDA), and the like.

For example, the aromatic diamine monomer containing the photoreactive group may be selected from siloxane diamine derivatives, furyl- (acryloyloxy) 3,5-diaminobenzoate, 3,5-diaminobenzenesinnamate and coumaronyl 3,5- Diaminobenzoate, and mixtures of two or more thereof.

For example, the bishydroxyphenyl-containing aromatic diamine monomer is an aromatic diamine monomer containing two or more hydroxy groups, and includes diaminoresorcinol (DAR), 4,4-diamino-3,3-dihydro (DDB), 2,2-bis- (3-amino-4-hydroxyphenyl) propane (BAP), 2,2- (6FAP), and the like, or a mixture of two or more thereof.

Examples of the aromatic diamine monomer that is conventionally used include para-phenylenediamine (PPD), meta-phenylenediamine (MPD), 2,4-toluenediamine (TDA), 4,4'-diaminodiphenyl Methane (MDA), 4,4'-diaminodiphenyl ether (DPE), 3,4'-diaminodiphenyl ether (3,4'-DPE), 3,3'- Diaminobiphenyl (TB), 2,2'-dimethyl-4,4'-diaminobiphenyl ( m- TB), 2,2'-bis (truculuoromethyl) -4,4'- diamino (TFMB), 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide (TSN), 4,4'- diaminobenzophenone (BTDA), 3,3'-diaminobenzophenone (3,3'-BTDA), 4,4'-diaminodiphenylsulfide (ASD), 4,4'-diaminodiphenylsulfone (ASN), 4,4'- diaminobenzanilide (DAMG), 1,3-bis (4-aminophenoxy) 2,2-dimethylpropane (DANPG), 1,2-bis [2- (4-aminophenyl) fluorene (FDA), 5 (6) -amino-1- (4-aminomethyl) 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4'-bis (4-aminophenoxy) biphenyl and 4,4'- Bis (4-aminophenoxyphenyl) propane (BAPP), 2,2-bis (3-aminophenoxyphenyl) propane (BAPP- (4-aminophenoxy) phenyl] sulfone (BAPS), bis [4- (3-aminophenoxy) phenyl] sulfone (BAPS- Hexafluoropropane (HFBAPP), 3,3'-dicarboxy-4,4'-diaminodiphenylmethane (MBAA), 4,6-dihydroxy-1,3-phenylenediamine (DADHB) Dihydroxy-4,4'-diaminobiphenyl (HAB), 2,2-bis (3-amino-4-hydroxyphenyl) hexaprylopropane (6FAP), 3,3'- (TAB), 1,6-diaminohexane (HMD), 1,3-bis (3-aminophylphenyl) -1,1,3,3-tetramethylsiloxane , 1-amino-3-aminomethyl-3,5 , 5-trimethylcyclohexane (DAIP), 4,4'-methylenebis (4-cyclohexylamine) (DCHM), 1,4- aminocyclohexane (DACH), bicyclo [2,2,1] heptanebis (Methylamine) (NBDA), tricyclo [3,3,1,13,7] decane-1,3-diamine 13AD, 4-aminobenzoic acid- (5-aminophenyl) -5-aminobenzoxazole (5ABO), 9,9-bis [4- (4-aminophenoxy) phenyl) fluorene (BAOFL), 2,2- 4,4'-diaminobiphenyl (3,3 ', 4,4'-bis (4-aminophenoxy) biphenyl-3,3'-disulfonic acid (pBAPBDS), bis -Aminophenyl) hexafluoropropane (HFDA), 5-diaminobenzoic acid, 2,4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid and 2,2-diaminobenzenesulfonic acid Or a mixture of two or more.

In one embodiment, the photofunctional compound is selected from the group consisting of N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenyl azo) 4 - ((4 - ((2-hydroxyethyl) amino) phenyl) diazenyl) -5-nitrobenzonitrile, 2- Phenyl) diazenyl) -5-nitrobenzonitrile, 2- (methyl (4 - ((2,3,5,6-tetrafluoro-4-nitrophenyl) ) Diazenyl) phenyl) amino) ethan-1-ol, 6- (Methyl 4- ((2,3,5,6-tetrafluoro-4-nitrophenyl) Ol, 2- (methyl (4 - ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) phenyl) amino) ethan- ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) phenyl) amino) hexan- Diazenyl) phenyl) amino) ethan-1-ol, 6- (methyl (4 - ((perfluoropyridin- (4 - ((2- (trifluoromethyl) pyridin-4-yl) diazenyl) phenyl) amino) ethan- Pyridin-4-yl) diazenyl) phenyl) amino) hexan-1-ol and mixtures of two or more thereof.

In another aspect of the present invention,

Dianhydride; At least one aromatic diamine selected from the group consisting of compounds represented by the following formulas (2), (3), (4) and (5) And an aromatic diamine comprising bishydroxyphenyl; (step 1); And

There is provided a process for producing a polyimide polymer represented by the following formula (1), which comprises a step (step 2) of producing a polyimide polymer using the polymer produced in the step 1 and a compound represented by the following formula (6).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the above Chemical Formulas 1 to 6,

,

,

, X, Y₁, Y₂, Y₃, R₀, R₂, Z₁, Z₂, n, m, q 및 t는 상기 화학식 1에서의 정의와 같다.)

,

,

, X, Y ₁ , Y ₂ , Y ₃ , R ₀ , R ₂ , Z ₁ , Z ₂ , n, m, q and t are as defined in the above formula (1)

Hereinafter, the method for producing the polyimide polymer according to the present invention will be described in detail for each step.

First, in the process for producing a polyimide polymer according to the present invention, step 1 is a step of reacting dianhydride; At least one aromatic diamine selected from the group consisting of compounds represented by formulas (2), (3), (4) and (5); And an aromatic diamine including bishydroxyphenyl, to prepare a polymer.

The polyimide polymer according to the present invention can be prepared by dissolving a dianhydride monomer, a diamine monomer or the like in a polar organic solvent. In particular, it is produced using an aromatic diamine monomer containing an aromatic diamine monomer containing a photoreactive group represented by the general formulas (2) to (5) and bishydroxyphenyl.

In this case, for example, an organic solvent may be used in the step 1, and the organic solvent may be selected from the group consisting of meta-cresol, N -methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc) Gamma-butyrolactone, 2-butoxyethanol and 2-ethoxyethanol. Methanol, tetrahydrofuran, and dioxane, or a mixture of two or more solvents.

For example, the dianhydride in step 1 may be at least one selected from the group consisting of pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride (BPDA) , 4'-tetracarboxylic acid dianhydride (BTDA), diphenylsulfone-3,4-3 ', 4'-tetracarboxylic dianhydride (DSDA), 4, 4'- (2,2'-hexafluoroisopropylidene) diphthalic dianhydride (6FDA), m ( p ) -terphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, Cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (CBDA), 1-carboxydimethyl-2,3,5-cyclopentanetricarboxylic acid-2,6,3,5-dianhydride TCAAH), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (CHDA), butane-1,2,3,4-tetracarboxylic acid dianhydride (BuDA) 4-cyclopentanetetracarboxylic dianhydride (CPDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA), 4- (2,5-dioxotetrahydrofuryl-3 -Tetralin-1,2-dicarboxylic acid dianhydride (DOTDA), bicyclooctene-2,3,5,6-tetracarboxylic acid dianhydride (BODA) and naphthalene- 5,8-tetracarboxylic dianhydride (NTDA), and the like, or a mixture of two or more thereof.

Further, for example, the aromatic diamine containing the compound represented by the general formulas (2) to (5) in the step 1 may be a siloxane diamine derivative, a furyl- (acryloyloxy) 3,5-diaminobenzoate, Benzene cinnamate and coumaronyl 3,5-diaminobenzoate.

,

,

및

등의 1 종 또는 2 종 이상의 혼합물일 수 있으나, 상기 비스하이드록시페닐을 포함하는 방향족 디아민은 2 개 이상의 하이드록시기를 가지는 방향족 디아민이라면 이에 제한되는 것은 아니다.In addition, for example, the aromatic diamine containing bishydroxyphenyl in step 1 above is an aromatic diamine monomer having two or more hydroxy groups, and includes diaminoresorcinol (DAR), 4,4-diamino-3,3 Dihydroxybiphenyl (DDB), 2,2-bis- (3-amino-4-hydroxyphenyl) propane (BAP), 2,2- Fluoropropane (6FAP), and the like, or a mixture of two or more thereof. As a specific example,

,

,

And

, And the aromatic diamine containing bishydroxyphenyl is not limited to an aromatic diamine having two or more hydroxy groups.

In addition, in the above step 1, a polymer can be produced by further using an aromatic diamine monomer which has been conventionally used. For example, para-phenylenediamine (PPD), meta-phenylenediamine (MPD), 2,4-toluenediamine (TDA), 4,4'- diaminodiphenylmethane (MDA) Diaminodiphenyl ether (DPE), 3,4'-diaminodiphenyl ether (3,4'-DPE), 3,3'-dimethyl-4,4'-diaminobiphenyl (TB) ( M- TB), 2,2'-bis (tributylmethyl) -4,4'-diaminobiphenyl (TFMB), 3,7- Diaminobenzothiophene-5,5-dioxide (TSN), 4,4'-diaminobenzophenone (BTDA), 3,3'-diaminobenzophenone (3,3'-BTDA), 4 , 4'-diaminodiphenylsulfide (ASD), 4,4'-diaminodiphenylsulfone (ASN), 4,4'-diaminobenzanilide (DABA) (DAMEG), 1,3-bis (4-aminophenoxy) 2,2-dimethylpropane (DANPG), 1,2-bis [2- (4-aminophenoxy) ethoxy] (FID), 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane (PIDN), 1,4- Bis (4-aminophenoxy) benzene (T (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB) Aminophenoxy) biphenyl (BAPB), 4,4'-bis (3-aminophenoxy) biphenyl (BAPB-M), 2,2- (3-aminophenoxy) phenyl] propane (BAPP-M), bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- Sulfone (BAPS-M), 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (HFBAPP), 3,3'-dicarboxy-4,4'-diaminodiphenyl Methane (MBAA), 4,6-dihydroxy-1,3-phenylenediamine (DADHB), 3,3'-dihydroxy-4,4'- diaminobiphenyl (HAB) (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 3,3 ', 4,4'-tetraaminobiphenyl (TAB), 1,6- diaminohexane 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethylsiloxane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (DAIP) '-Methylenebis (4-cyclo (NBDA), tricyclo [3, 3, 1, 13, 7] heptane bis (methylamine) Aminophenyl ether (APAB), 2- (4-aminophenyl) -5-aminobenzazole (5ABO), 9,9-bis [4 (3-aminophenoxy) phenyl) fluorene (BAOFL), 2,2-bis (3-bis (3-sulfoproxy) -4,4'- diaminobiphenyl (4-aminophenoxy) biphenyl-3,3'-disulfonic acid (pBAPBDS), bis (4-aminophenyl) hexafluoropropane (HFDA), 5-diaminobenzoic acid, 4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2,2-diaminobenzenesulfonic acid and the like, and one or more aromatic diamine monomers may be further used.

Next, in the method for producing a polyimide polymer according to the present invention, Step 2 is a step of preparing a polyimide polymer by using the polymer prepared in Step 1 and the compound represented by the following Chemical Formula 6.

In the step 2, a photoelectric compound is introduced into the side chain of the polymer produced in the step 1, and the reaction is carried out using the compound represented by the formula (6).

For example, the compound represented by the general formula (6) in the step 2 is a photoelectric compound such as N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenyl azo) (2 - ((2-hydroxyethyl) (methyl) amino) phenyl) diazenyl) -5-nitrobenzonitrile 2- ((4 - ((2, 3, 5, 6-tetrahydrobenzoyl) phenyl) diazenyl) Phenyl) amino) ethan-1-ol, 6- (methyl (4 - ((2,3,5,6-tetrafluoro-4-nitro Phenyl) amino) ethane-1-ol, 2- (methyl (4 - ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) Ol, 6- (methyl (4 - ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) phenyl) amino) hexan- ((Perfluoropyridin-4-yl) diazenyl) phenyl) amino) ethan- 4-yl) diazenyl) phenyl) amino) ethane, which is a starting material, Ol and 6- (methyl (4 - ((2- (trifluoromethyl) pyridin-4-yl) diazenyl) phenyl) amino) hexan- .

Further, in another aspect of the present invention,

There is provided a polymer membrane comprising the polyimide polymer represented by the above formula (1).

The polymer film containing the polyimide polymer provided by the present invention has a low surface roughness, excellent printability to conductive glass or metal, and excellent heat resistance and photoelectric characteristics.

In addition, more than 300 nm, the long wavelength region of 300-400 nm and 20-1,000 mJ / cm ^2, preferably 30-500 mJ / cm ^2, and more preferably excellent in low-light amount of about 50-100 mJ / cm ² Exhibits photoreaction characteristics.

Furthermore, for example, the polymer film preferably has a light curing degree of 10% or more. When the polymer film is photo-cured, it can exhibit remarkably excellent thermal stability.

The thermal decomposition temperature of the polymer film may be 250 ° C or higher, 250 ° C or higher, and 280 ° C or higher.

Further, in another aspect of the present invention,

There is provided an optoelectronic device including the above polymer film.

In the photoelectric device provided in the present invention, when the photoelectric coefficient is 20-50 pm / V and the heat treatment is performed at a temperature of 150 ° C for 500 hours, the initial photoelectric coefficient is maintained at 95% and 200 ° C for 1 hour And when it is heat-treated, excellent stability at a high temperature with aging stability of 90% or more is provided. In addition, it is useful for manufacturing devices such as optical modulators and switches because of its low gas emission characteristics at high temperatures, electrical insulation, and adhesion properties to various substrates.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

< Manufacturing example  1> 3,5- Diamino benzyl Shinnamate (3,5- diamino -benzyl cinnamate ) Synthesis of

(1) Add 100 ml of ethanol to a hydrogenation reactor and dissolve 10 g of 3,5-dinitrobenzyl alcohol. After adding 1 g of Pd / C (5%) as a catalyst, a reduction reaction was carried out at a pressure of 3.5 atm for 5-6 hours. Thereafter, the reaction mixture from which Pd / C has been removed by using a membrane filter is concentrated under reduced pressure, and the obtained solid is recrystallized in ethanol to obtain a product.

(2) In a 500 ml round-bottomed flask equipped with an ice bath, 6 g of 3,5-dinitrobenzyl alcohol was added, and 240 ml of 1,4-dioxane ) / Water (H ₂ O) (volume ratio 4/1) mixed solvent was added and dissolved. Then, 13.8 g of sodium carbonate (Na ₂ CO ₃ ) and 14.8 g of di-tert-butyl dicarbonate t-BOC) were added and stirred for 5 minutes. Then, the temperature was raised to room temperature, and stirring was continued for 6-7 hours. Then, the reaction mixture was filtered to remove sodium carbonate, and diluted by adding 200 ml of ethyl acetate to the reaction mixture. The polar solvent in ethyl acetate was removed using brine, and finally the solution with water removed by anhydrous MgSO ₄ was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Subsequently, ethyl acetate was used as a recrystallization solvent to obtain a white solid, di-tert-butyl 5- (hydroxymethyl) -1,3-phenylene dicarbamate (di-tert-butyl 5- -phenylene dicarbamate.

(3) To a 500 ml round-bottomed flask equipped with an ice bath was added di-tert-butyl 5- (hydroxymethyl) -1, 3-phenylene dicarbamate 3-phenylene dicarbamate (6 g) was dissolved in 250 ml of m-cresol (MC), and then 3.5 g of cinnamoyl chloride was added and stirred. 4 g of triethylamine (TEA) was slowly injected at a temperature of 0 ° C, the temperature was raised to room temperature, and stirring was continued for 12 hours. Thereafter, the polar solvent in the metacresol was removed using a brine solution, and finally the solution, from which moisture was removed with anhydrous magnesium sulfate, was concentrated under reduced pressure to prepare a reaction product containing a trace amount of impurities. The residue was purified by column chromatography (ethyl acetate (EA): hexane (Hx) = 1: 4) to obtain 3,5-bis (tert-butoxycarbonylamino) benzyl cinnamate (tert-butoxycarbonylamino) benzyl cinnamate).

(4) 6 g of 3,5-bis (tert-butoxycarbonylamino) benzyl cinnamate was placed in a 500 ml round-bottom flask, and 200 ml of metacresol After dissolution, 100 ml of triflouroacetic acid (CF ₃ COOH) was added and the mixture was stirred at room temperature for 4 hours. Thereafter, the reaction mixture was concentrated under reduced pressure to remove volatile substances and diluted with 250 ml of methacrole. The diluted reaction mixture was neutralized with sodium hydrogencarbonate, and the polar solvent in the metacresol was removed by using brine. Finally, the water-removed solution was concentrated under reduced pressure to prepare a reaction product containing a small amount of impurities . And then purified by column chromatography (EA: Hx = 3: 2) to prepare a yellow liquid compound, 3,5-diamino-benzyl cinnamate.

< Manufacturing example  2> 3-Biphenyl-4-yl- Acrylic  Acid 3,5- Diamino - benzyl  Synthesis of 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzyl ester

(1) In a 250 ml round-bottomed flask equipped with a reflux condenser, 2 g of biphenyl-4-carbaldehyde was added, dissolved in 100 ml of benzene, and then triphenyl phosphorane ) Derivative (4.2 g) was added thereto, followed by heating under reflux for 8 hours at a temperature of 80 ° C. At this time, the triphenyl phosphorane derivative is prepared by reacting an alkyl phosphonium salt prepared from triphenyl phosphate and ethyl bromo acetate with n-butyl lithium was synthesized by deprotonation. Next, the reaction mixture was cooled to room temperature, and the polar solvent in benzene was removed using brine. Finally, the solution, from which moisture was removed with anhydrous magnesium sulfate, was concentrated under reduced pressure to prepare a reaction product containing trace impurities. The residue was purified by column chromatography (EA: Hx = 1: 4) to obtain 3-biphenyl-4-yl-acrylic acid ethyl ester as a white solid .

(2) 4.55 g of 3-biphenyl-4-yl-acrylic acid ethyl ester was added to a 250 ml round-bottomed flask, and 100 ml of tetrahydrofuran (THF ) / Ethanol (EtOH) / water (H ₂ O) (volume ratio 1/1/1) mixed solvent was added and dissolved. Then, 5 g of lithium hydroxide was added and stirred for 2 hours. Thereafter, the reaction mixture was neutralized by titration with hydrochloric acid, and the precipitate was filtered and dried to obtain a white solid, 3-biphenyl-4-yl-acrylic acid.

(3) 2 g of 3-biphenyl-4-yl-acrylic acid was dissolved in 200 ml of metacresol in a 500 ml round bottom flask, and 2 ml of oxalyl chloride And the mixture was stirred. 2-3 drops of dimethylformamide were added and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction mixture was concentrated under reduced pressure to remove volatiles, and 3-biphenyl-4-yl-acryloyl chloride, a yellow solid compound, was obtained.

(4) To a 500 ml round-bottomed flask equipped with an ice bath was added di-tert-butyl 5- (hydroxy methyl) -1, 3- dihydroxy- 3-phenylene dicarbamate (3.02 g) was dissolved in 250 ml of metacresol, and then 2.0 g of 3-biphenyl-4-yl-acryloyl chloride was added thereto and stirred . Then, 1.1 g of triethylamine was slowly added at a temperature of 0 ° C, the temperature was raised to room temperature, and stirring was continued for 12 hours. The polar solvent in the metacresol was removed from the reaction mixture using brine, and finally the water-removed solution with magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing a small amount of impurities. The residue was purified by column chromatography (EA: Hx = 1: 4) to give 3-biphenyl-4-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino- benzyl ester (3- biphenyl-4-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino-benzyl ester.

(4) To a 500 ml round bottom flask was added 3-biphenyl-4-yl-acrylic acid 3, 5-bis-tert- 5-bis-tert-butoxycarbonylamino-benzyl ester) was dissolved in 200 ml of metacresol, and then 100 ml of trifluoroacetic acid was added thereto. The mixture was stirred at room temperature for 4 hours. The reaction mixture was then concentrated under reduced pressure to remove volatiles and diluted with 250 ml of metacresol. The diluted reaction mixture was neutralized with sodium hydrogencarbonate, and the polar solvent in the metacresol was removed by using brine. Finally, the water-removed solution was concentrated under reduced pressure to prepare a reaction product containing a small amount of impurities . The residue was purified by column chromatography (EA: Hx = 3: 2) to obtain 3-biphenyl-4-yl- acrylic acid 3,5-diamino-benzyl ester.

< Manufacturing example  3> 3-Naphthalen-2-yl- Acrylic  Acid 3,5- Diamino - benzyl  Synthesis of 3-Naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester

(1) In a 500 ml round-bottomed flask, 2 g of 3-naphthalene-1-yl acrylic acid was dissolved in 200 ml of metacresol and dissolved in oxalyl chloride 2 ml was added and stirred. Then 2-3 drops of N, N-dimethylformamide (DMF) were added, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction mixture was concentrated under reduced pressure to remove volatiles, and 3-naphthalen-1-yl-acryloyl chloride as a yellow solid compound was obtained.

(2) To a 500 ml round-bottomed flask equipped with an ice bath was added di-tert-butyl 5- (hydroxy methyl) -1 , 3-phenylene dicarbamate) was dissolved in 250 ml of metacresol, to which 2.01 g of 3-naphthalen-1-yl-acryloyl chloride was added and stirred . Then, 1.51 g of triethylamine was slowly injected at a temperature of 0 ° C, and then the temperature was raised to room temperature and stirring was continued for 12 hours. Then, the polar solvent in the metacresol was removed using a brine solution. Finally, the solution, from which moisture was removed with anhydrous magnesium sulfate, was concentrated under reduced pressure to prepare a reaction product containing a trace amount of impurities. The residue was purified by column chromatography (EA: Hx = 1: 4) to obtain 3-naphthalen-2-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino ester -yl-acrylic acid 3,5-bis-tert-butoxycarbonyl amino benzyl ester.

(3) To a 500 ml round bottom flask was added 3-naphthalen-2-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino ester (3-naphthalen- -tert-butoxycarbonyl amino benzyl ester) was dissolved in 200 ml of metacresol, 100 ml of trifluoroacetic acid was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was then concentrated under reduced pressure to remove volatiles and diluted with 250 ml of metacresol. The diluted reaction mixture was neutralized with sodium hydrogencarbonate, and the polar solvent in the metacresol was removed by using brine. Finally, the water-removed solution was concentrated under reduced pressure to prepare a reaction product containing a small amount of impurities . The crude product was purified by column chromatography (EA: Hx = 3: 2) to give 3-naphthalen-2-yl-acrylic acid 3,5-diamino- acid 3,5-diamino-benzyl ester.

< Example  1 > Preparation of polyimide polymer 1

Step 1: In a 1 L reactor equipped with a stirrer, a temperature controller, a nitrogen inlet, a dropping funnel and a condenser, 10.7 g (0.04 mol) of 3,5-diamino Benzyl cinnamate and 14.6 g (0.04 mol) of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) were dissolved in a metacresol solvent of 547 g as a reaction solvent, 35.5 g (0.08 mol) of 4,4 '- (2,2'-hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was slowly added while passing nitrogen gas. At this time, the solid content was fixed at 10% by weight, the reaction temperature was raised to 80 캜, held for 2 hours, heated to 150 캜 and held for 3 hours. The resulting polymer solution was added to an excess amount of methanol to separate the solid, followed by filtration and drying in a vacuum dryer at 80 DEG C for 12 hours to obtain a polymer.

Step 2: 1.48 g (2 mmol) of the polymer obtained in the above step 1 was dissolved in 30 ml of tetrahydrofuran (THF) and then 1.95 g (6 mmol) of N-methyl-N- (2- 1.57 g (6 mmol) triphenylphosphine and 1.04 g (6 mmol) diethyldiazocarboxylate (DEAD) were added at room temperature for 3 days Lt; / RTI &gt; After completion of the reaction, the product was precipitated in excess amount of methanol, and the product was filtered and dried in a vacuum dryer at 80 ° C for 12 hours to prepare a polyimide polymer.

< Example  2 > Preparation of polyimide polymer 2

The amount of N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline, triphenylenphosphine and diethyldiazocarboxylate used in Step 2 of Example 1 was 1.30 (4 mmol), 1.05 g (4 mmol), and 0.69 g (4 mmol) of the compound shown in the above formula (1).

< Example  3> Preparation of polyimide polymer 3

The amount of N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline, triphenylenphosphine and diethyldiazocarboxylate used in Step 2 of Example 1 was set to 0.98 The polyimide polymer was prepared in the same manner as in Example 1 except that the amount of the compound obtained was 3 g (3 mmol), 0.78 g (3 mmol), and 0.52 g (3 mmol).

< Example  4> Preparation of polyimide polymer 4

Diaminobenzyl cinnamate prepared in Preparation Example 1 was used instead of 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzoic acid obtained in Preparation Example 2 in Step 1 of Example 1, Polyimide polymer was prepared in the same manner as in Example 1 except that 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  5> Preparation of polyimide polymer 5

Except that 3,5-diaminobenzyl cinnamate prepared in Preparation Example 1 was used instead of 3-biphenyl-4-yl-acrylic acid 3,5-diamino- Polyimide polymer was prepared in the same manner as in Example 2 except that 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  6> Preparation of polyimide polymer 6

The procedure of Example 3 was repeated except that 3,5-diaminobenzyl cinnamate prepared in Preparation Example 1 was used instead of 3-biphenyl-4-yl-acrylic acid 3,5-diamino- Polyimide polymer was prepared in the same manner as in Example 3 except that 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  7> Preparation of polyimide polymer 7

3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester prepared in Preparation Example 3 instead of 3,5-diaminobenzyl cinnamate prepared in Preparation Example 1 in Step 1 of Example 1 Polyimide polymer was prepared in the same manner as in Example 1 except that 3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  8> Preparation of polyimide polymer 8

3-naphthalene-2-yl-acrylic acid 3,5-diamino-benzyl ester prepared in Preparation Example 3 was used instead of 3,5-diaminobenzyl cinnamate prepared in Preparation Example 1 in Step 1 of Example 2 Polyimide polymer was prepared in the same manner as in Example 2 except that 3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  9> Preparation of polyimide polymer 9

3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester prepared in Preparation Example 3 instead of 3,5-diaminobenzyl cinnamate prepared in Preparation Example 1 in Step 1 of Example 3 Polyimide polymer was prepared in the same manner as in Example 3 except that 3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester was used as a monomer.

< Example  10> Preparation of polyimide polymer 10

1.12 g (3 mmol) of 2- (methyl (4- ((2-hydroxyphenyl) azo) aniline was used in the place of N-methyl- (Molecular weight: 372 g / mol) was introduced as a photo-functional substituent, the above-mentioned compound was synthesized in the same manner as in item A polyimide polymer was prepared in the same manner as in Example 1.

< Example  11> Preparation of polyimide polymer 11

(2-hydroxyethyl) (methyl) amino) phenyl) diazenyl) -5-nitrobenzonitrile in step 2 of Example 2 above, 1.49 g (4 mmol) (Molecular weight: 372 g / mol) was added to a solution of 2 - [(4 - ((2,3,5,6-tetrafluoro-4- cyanophenyl) diazenyl) phenyl) amino) ethan- A polyimide polymer was prepared in the same manner as in Example 2, except that the polyimide polymer was introduced as a substituent.

< Example  12> Preparation of polyimide polymer 12

Instead of 2 - ((4 - ((2-hydroxyethyl) (methyl) amino) phenyl) diazenyl) -5-nitrobenzonitrile in step 2 of Example 3 above, 2.23 g (Molecular weight: 372 g / mol) was added to a solution of 2 - [(4 - ((2,3,5,6-tetrafluoro-4- cyanophenyl) diazenyl) phenyl) amino) ethan- Polyimide polymer was prepared in the same manner as in Example 3, except that the polyimide polymer was introduced as a substituent.

The structures of the polyimide polymers prepared in Examples 1 to 12 are shown in Table 1 below.

Chemical structural formula Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

Example 10

Example 11

Example 12

< Comparative Example  1>

Step 1: While slowly passing nitrogen gas through a 1 L reactor equipped with a stirrer, a thermostat, a nitrogen inlet, a dropping funnel and a condenser, 29.2 g (0.08 mol) of 2,2-bis- Hexafluoropropane (6FAP) was dissolved in 547 g of metacresol solvent as a reaction solvent. 35.5 g (0.08 mol) of 4,4 '- (2,2' -Hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA) was slowly added. At this time, the solid content was fixed to 10% by weight, the reaction temperature was raised to 80 캜, held for 2 hours, heated to 150 캜 and maintained for 3 hours. The resulting polymer solution was added to an excess amount of methanol to separate the solid, followed by filtration and drying in a vacuum dryer at 80 DEG C for 12 hours to obtain a polymer.

Step 2: 1.48 g (2 mmol) of the polymer obtained in the above step 1 was dissolved in 30 ml of tetrahydrofuran (TFH), and then 1.95 g (6 mmol) of N-methyl-N- (2- 1.57 g (6 mmol) triphenylphosphine and 1.04 g (6 mmol) diethyldiazocarboxylate (DEAD) were added at room temperature for 3 days Lt; / RTI &gt; After completion of the reaction, the product was precipitated in excess amount of methanol, and the product was filtered and dried in a vacuum dryer at 80 ° C for 12 hours to prepare a polyimide polymer.

< Comparative Example  2>

The amount of N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline, triphenylenphosphine and diethyldiazocarboxylate used in Step 2 of Comparative Example 1 was 1.30 (4 mmol), 1.05 g (4 mmol), and 0.69 g (4 mmol) of the compound of Preparation Example 1 were used.

< Comparative Example  3>

The amount of N-methyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline, triphenylenphosphine and diethyldiazocarboxylate used in Step 2 of Comparative Example 1 was 0.98 g, 3 mmol), 0.78 g (3 mmol), and 0.52 g (3 mmol) of a polyimide polymer.

< Experimental Example  1> Analysis of polyimide polymer synthesis results

In order to confirm the results of the synthesis of the polyimide polymers according to the present invention, the polyimide polymers prepared in Examples 1 to 12 and Comparative Examples 1 to 3 were measured by nuclear magnetic resonance spectroscopy (1H NMR spectroscopy) And the results are shown in Table 2 and FIG.

The intrinsic viscosity was determined by dissolving the polyimide polymer in N- methyl-2-pyrrolidone (NMP), measuring the solution viscosity thereof, and calculating the viscosity of each solution.

[Equation 1]

_{η inh = ln (t / t} 0) / c

(In the above formula (1)

η _inh is the intrinsic viscosity, c is the concentration (g / 100 ml), t is the drop time of the intermediate pressure solution, and t ₀ is the fall time of the NMP.

Intrinsic viscosity (dL / g) Photoelectric functional group substitution ratio (%) Example 1 2.35 99 Example 2 2.35 48 Example 3 2.35 28 Example 4 0.92 99 Example 5 0.92 51 Example 6 0.92 29 Example 7 1.76 100 Example 8 1.76 49 Example 9 1.76 29 Example 10 0.95 99 Example 11 0.95 49 Example 12 0.95 27 Comparative Example 1 0.56 98 Comparative Example 2 0.56 50 Comparative Example 3 0.56 29

As shown in Table 2, the intrinsic viscosity of the polyimide polymers prepared in Examples 1 to 12, which are the polyimide polymers according to the present invention, was 0.95-2.35 dl / g, and the film moldability Were found to be very good. It is also confirmed that the substitution rate can be controlled by changing the conditions of the substitution reaction.

Further, as shown in FIG. 1, the polyimide polymer prepared in Example 1, which is a polyimide polymer according to the present invention, can be confirmed to have been synthesized normally through a structural analysis using a nuclear magnetic resonance spectrometer.

< Experimental Example  2> Characterization of polymer membrane and photoelectric device including polyimide polymer

Manufacturing of optoelectronic devices

0.15 g of polyimide polymer was added to 0.85 g of cyclohexanone and dissolved by stirring for 24 hours. The prepared solution (15% by weight of 1 g solution) is filtered using a filter having a size of 0.2 탆 and then left at room temperature for 30 minutes to remove air bubbles. A polymer membrane was formed by coating a 1 μm thick polyimide polymer on a 20 mm × 20 mm glass plate coated with key ring-shaped indium tin oxide (ITO) using a spin coater. (500 rpm / 5 sec, 1,000 rpm / 3 sec, 1,500 rpm / 2 sec, 2,000 rpm / 30 sec, 1,500 rpm / 2 sec, 1,000 rpm / 3 sec, and 500 rpm / 5 sec).

Thereafter, a glass plate coated with a polymer membrane containing a polyimide polymer was placed on a hot plate at 210 DEG C for 30 minutes to remove the solvent remaining in the polymer membrane. Then, a keyhole-shaped mask is coated on the device from which the solvent is removed (polymer film-coated ITO substrate) so as to have a shape of indium tin oxide of 90 ^° and then put in a chamber of a gold thin film deposition chamber together with a gold wire . The chamber was made to a high vacuum of 3 × 10 ^-6 torr or less, and a gold thin film having a thickness of 50 nm was formed on the polymer film by applying voltage to the gold wire at a speed of 0.1 nm / s.

Then, the polymer film of the device where the gold thin film is formed and the polymer film of the overlapping part of the indium tin oxide are removed, thereby forming a passage through which the voltage can be applied to the lower part of the polymer film. Then, a device is inserted into a poling machine, and a jig capable of applying voltage between positive charge and negative charge is contacted with indium tin oxide and gold thin film, respectively.

Finally, a voltage of 100 V / [mu] m is applied to the device and the temperature inside the poling machine is gradually raised to a temperature of 130-220 [deg.] C. Keep at that temperature for 30 minutes and then gradually lower the temperature to 100 ° C. The device was kept at 60-100 V / um while the temperature was changed. The device in the poling machine was taken out at a temperature of 100 ° C and then cooled at room temperature for 1 minute to produce a photoelectric device. The photocatalytic reaction was performed by exposing the photoelectric device to ultraviolet rays having a wavelength of 300-460 nm.

(1) Analysis of pyrolysis characteristics

The pyrolysis characteristics of the photopolymerized thin film were evaluated by a thermogravimetric analyzer (TGA). The results are shown in Table 3 and FIG.

(2) Characteristic evaluation of photoelectric device

In the photoelectric device, the copper wires were soldered using the indium tin oxide portion and the gold thin film portion with the indium wire and the soldering iron, and then a voltage of 2 V was applied thereto to obtain an electrooptic coefficient (photoelectric coefficient; r ₃₃ ) And the results are shown in Table 3 below.

(3) Stability evaluation of photoelectric device at high temperature with aging

In order to evaluate the stability of the photoelectric device at a high temperature with time, the photoelectric device including the polyimide polymer of Example 1 and Comparative Example 1 was placed in an oven and subjected to heat treatment at 150 占 폚 and 250 占 폚. The results are shown in FIG. 3 and FIG.

Applied polymer Pyrolysis temperature (℃) Glass transition temperature (캜) The photoelectric coefficient (r ₃₃ , pm / V) Example 1 278 185 48 Example 2 265 182 34 Example 3 260 175 30 Example 4 285 182 45 Example 5 270 178 40 Example 6 270 175 35 Example 7 280 182 42 Example 8 275 180 38 Example 9 265 180 31 Example 10 270 185 48 Example 11 268 180 35 Example 12 260 178 28 Comparative Example 1 230 170 12 Comparative Example 2 220 175 10 Comparative Example 3 210 175 8

As shown in Table 3 and FIG. 2, the polymer membrane comprising the polyimide polymer according to the present invention exhibited excellent pyrolysis initiation temperature of 250 ° C or more, and pyrolysis products at 200 ° C were hardly observed.

In addition, as shown in Table 3, FIG. 3 and FIG. 4, in the case of the photoelectric device in which the polymer film containing the polyimide polymer according to the present invention was formed, the photoelectric coefficient was at least 28 pm / V, The photoelectric coefficient of the polymer membrane including the polymer was much higher than that of the photoelectric coefficient of 8-12 pm / V. In particular, in the case of the photoelectric device in which the polymer membrane including the polyimide polymer of Example 1 was formed, pm / V.

Further, it was confirmed that the initial photoelectric characteristics were 95% and 90% or more, respectively, even after the heat treatment at 150 ° C. for 500 hours and at 250 ° C. for 1 hour.

< Experimental Example  3> Evaluation of stability for process solvent

In order to confirm the stability of the polyimide polymer according to the present invention with respect to the process solvent, the photopolymerized film prepared using the polyimide polymer prepared in Examples 1 to 3 and the polyimide polymer prepared in Comparative Example 1 And the chemical stability of the photoresist (PR) and the photoresist stripper were evaluated. The results are shown in Table 4 and FIG. 5, respectively.

division Solubility measurement results Organic solvent Comparative Example 1 Example 1 Example 2 Example 3 N-methyl-2-pyrrolidone Available Insolvency Insolvency Insolvency Dimethylacetamide Available Insolvency Insolvency Insolvency Dimethylformamide Available Insolvency Insolvency Insolvency Acetone Available Insolvency Insolvency Insolvency Tetrahydrofuran Available Insolvency Insolvency Insolvency 2.38% tetramethylammonium
Hydroxide Available Insolvency Insolvency Insolvency Potassium hydroxide solution Available Insolvency Insolvency Insolvency PR stripper Available Insolvency Insolvency Insolvency

As shown in Table 4, it was confirmed that the polymer membrane comprising the polyimide polymer prepared in Examples 1 to 3 according to the present invention exhibited excellent solvent resistance. As a result of the decrease in the solubility of the polymer by the photo-crosslinking reaction, it can be applied to a multilayer array device or the like exposed to various process solvents.

5, the polymer film containing the polyimide polymer prepared in Example 1 according to the present invention exhibited a very low thickness variation of 5% or less under photoresist treatment process conditions (70 캜, 60 seconds of immersion) . &Lt; / RTI &gt;

Thus, the polyimide polymer according to the present invention, the polymer film containing the same, and the photoelectric device fabricated therefrom can be used as various optical components, switches and optical modulators used in optical communication devices due to excellent chemical resistance and heat resistance It is possible to provide a high heat-resistant material which is suitable for application and at the same time requires fine pattern formation characteristics.

In addition, since the polyimide polymer according to the present invention has excellent stability at a high temperature, the organic photoelectric polymer device having the photoelectric material core layer and the clad layer can be manufactured using the polyimide polymer of the present invention. According to the present invention, it is possible to manufacture a small-sized, high-efficiency optical modulator, increase the speed of optical communication, and reduce power consumption. In addition, the conventional multistage photoresist coating process can be shortened.

Claims (12)

A polyimide polymer represented by the following formula (1)

[Chemical Formula 1]

(In the formula 1,

The

,

,

or

And wherein A ₁ represents a single _{bond, - (CH 2) p -} , -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 _{-, -Si (CH 3) 2} -,

,

or

, P is 1-5,

The

,

,

or

(C = O) -O-, -NH (C = O) -, - (C = O) -NH-, -O-, - S-, -N (C = O) 2 CH 2 CH- , or _{-CH 2 -O (C = O)} - a, Y ₁ to Y ₃ are each independently hydrogen (H), a C _1-30 alkyl or C _0-30 aryl, R ₀ is C _1-30 alkyl or C _5-30 aryl, t is an integer of 1-20,

The

,

,

or

, R &lt; ₁ &gt;

And, R ₂ is hydrogen (H), a straight chain alkyl or branched alkyl of C _3-5 of C _1-5, Z ₁ is CR ₇ or nitrogen (N), Z ₂ is

,

or

And, Z ₃ is CR ₇ or nitrogen (N) and, Z ₄ is NR _7, a sulfur (S) or oxygen (O), Z ₅ is

And R ₃ to R ₇ are each independently selected from the group consisting of hydrogen (H), halo, cyano (CN), nitro (NO ₂ ), C _1-5 linear chain alkyl, C _3-5 branched chain alkyl, C _1-5 alkyl, q is an integer of 1-5,
n is an integer of 1-500,
and m is an integer of 1-500).
The method according to claim 1,
remind

The

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

And

, Wherein r is 1-20. 2. The polyimide polymer according to claim 1,
The method according to claim 1,
Wherein the polyimide polymer has an intrinsic viscosity of 0.1-5.0 dL / g and a weight average molecular weight of 5,000-500,000 g / mol.
Dianhydride; At least one aromatic diamine selected from the group consisting of compounds represented by the following formulas (2), (3), (4) and (5) And an aromatic diamine comprising bishydroxyphenyl; (step 1); And
A process for producing a polyimide polymer represented by the following formula (1), comprising the step of preparing a polyimide polymer using the polymer prepared in the above step 1 and a compound represented by the following formula (6)

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the above Chemical Formulas 1 to 6,

,

,

, X, Y ₁ , Y ₂ , Y ₃ , R ₂ , Z ₁ , Z ₂ , n, m, t and q are as defined in claim 1).
5. The method of claim 4,
The dianhydride in step 1 above may be selected from the group consisting of pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride (BPDA) 4,4 ', 4'-tetracarboxylic acid dianhydride (DSDA), 4,4'- (tetraacetic acid dianhydride (BTDA) Hexafluoroisopropylidene) diphthalic dianhydride (6FDA), m ( p ) -terphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, cyclobutane- , 2,3,4-tetracarboxylic dianhydride (CBDA), 1-carboxydimethyl-2,3,5-cyclopentanetricarboxylic acid-2,6,3,5-dianhydride (TCAAH), cyclo Hexane-1,2,4,5-tetracarboxylic dianhydride (CHDA), butane-1,2,3,4-tetracarboxylic dianhydride (BuDA), 1,2,3,4-cyclopentane Tetracarboxylic dianhydride (CPDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA), 4- -Dioxotetrahydrofuryl-3-yl) -tetralin -1,2-dicarboxylic dianhydride (DOTDA), bicyclopentene-2,3,5,6-tetracarboxylic acid dianhydride (BODA) and naphthalene-1,4,5,8-tetracarboxyl And at least one member selected from the group consisting of acid dianhydride (NTDA).
5. The method of claim 4,
(2-hydroxyethyl) -4- (4-nitrophenylazo) aniline, N-ethyl-N- 2 - ((4- (2-hydroxyethyl) amino) phenyl) diazenyl) -5-nitrobenzonitrile, (Methyl) (4 - ((2,3,5,6-tetrafluoro-4- (2-hydroxyethyl) amino) phenyl) diazenyl) Phenyl) amino) ethan-1-ol, 6- (methyl (4- ((2,3,5,6-tetrafluoro-4-nitrophenyl) diazenyl) phenyl) amino ), Hexan-1-ol, 2- (methyl (4 - ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) (4 - ((2,3,5,6-tetrafluoro-4-cyano) diazenyl) phenyl) amino) hexan- Phenyl) amino) ethan-1-ol, 6- (methyl (4 - ((perfluoropyridin-4-yl) diazenyl) Yl) phenyl) amino) ethan-1-ol and 6- (methyl (4- (2- ((2- (trifluoromethyl) pyridin-4-yl) diazenyl) phenyl) amino) hexan-1-ol.
A polymer membrane comprising a polyimide polymer represented by the following formula (1): &lt; EMI ID =

[Chemical Formula 1]

(In the formula 1,

,

,

, n and m are the same as defined in claim 1).
8. The method of claim 7,
Wherein the polymer film has a light curing degree of 10% or more.
8. The method of claim 7,
Wherein the polymer membrane has a thermal decomposition temperature of 250 ° C or higher.
10. A photoelectric device comprising the polymer membrane of claim 7.
11. The method of claim 10,
Wherein the photoelectric coefficient of the photoelectric device is 20-50 pm / V.
11. The method of claim 10,
Wherein the stability of the photoelectric device at high temperature with aging is at least 90% after heat treatment at a temperature of 200 캜 for one hour.

Images