TWI376392B - Polyimide resin and liquid crystal alignment layer and polyimide film using the same - Google Patents

Description

1376392 IX. Description of the Invention: [Technical Field] The present invention relates to a colorless and transparent polyimide resin, and a liquid crystal alignment layer and a polyimide film using the resin. 5 [prior art]

In general, 'polyalkylene amine (PI) resin is related to high heat resistant resin obtained by ring closure and dehydration reaction of polyglycolic acid at high temperature, and polyamine acid is transmitted through aromatic dianhydride and aromatic Obtained by solution polymerization of a diamine or an aromatic diisocyanate. In the preparation of the polyamine resin, the aromatic 10 succinic anhydride includes, for example, pyromellitic dianhydride (PMDA) or bismuth dibenzoate (BPDA); and the aromatic diamine includes, for example, oxidized two Aniline (ODA), p-phenylenediamine (p_PDA), m-phenylenediamine (m_pDA), methylene diphenylamine (MDA), and diaminophenyl hexafluoropropane (HFDA). Because the insoluble, refractory, and ultra-high heat-resistance polyamidamide resins have excellent properties such as heat resistance, oxidation resistance, radiation resistance, low temperature resistance, and chemical resistance, they are used in various applications. The field includes advanced heat-resistant materials such as automotive materials, aerospace materials or aerospace materials, and electronic materials such as insulating coating agents, insulating films, semiconductors, or electrode protective films for TFT-LCDs. Recently (polyimine resin has been used as a display material, for example, a conductive filler is mixed with a polymer, or a conductive filler is coated on the surface of the film of the composite film, the optical fiber or liquid crystal alignment layer is formed, and the transparent electrode Membrane) However, the high aromatic ring density of the polyamidene resin interacts with charge transfer to cause it to become brown or yellow, so that the light transmittance in the visible light range is annoyingly reduced. The yellow or brown color of the polyamide resin makes it difficult to apply in fields requiring transparency. In order to solve these problems, many methods for purifying monomers and high-purity solvents for polymerization have been realized, but the improvement effect on light transmittance is not large. U.S. Patent No. 5,053,480 discloses a process for the replacement of an aromatic dianhydride using an alicyclic dianhydride component. Although this method improves the transparency and color of the liquid phase or the film phase compared with the purification method, it is still limited in terms of improving the light transmittance, and thus the high light transmittance cannot be achieved, and the thermal and mechanical properties thereof are also Getting worse. It is described in U.S. Patent Nos. 4,595,548, 4, 601, 036, 4, 458, 024, 4, 895, 972, 5,158, 083, 5, 093, 453, 5, 218, 077, s, s, s, s, s, s, s, s, s, s, s, s. Regarding the preparation of a polyamidomine having a novel structure, the light transmittance and the color transparency are improved in a range in which the thermal properties are not significantly lowered. The main purpose is to use a linking group having, for example, -0, _8〇2_ or CH2•, The alignment (PP〇Siti〇n) is linked to a bend caused by a meta position (m_p〇siti0n), or an aromatic diacid field and an aromatic diamine monomer having a substituent such as a _CF3. However, such a melamine has been found to be insufficient for use in a semiconductor insulating film, a TFMXD, and an electrode guard soft display substrate in terms of mechanical properties, yellow index, and visible light transmittance. SUMMARY OF THE INVENTION Accordingly, the present invention provides a poly-stylish amine resin which is colorless and transparent and has excellent mechanical properties and thermal stability. </ RTI> A 1376392 using the resin is also provided.

A liquid crystal alignment layer and a polyimide film. According to a first embodiment of the present invention, there is provided a polyamidamide resin prepared by polymerizing an aromatic dianhydride and an aromatic diamine. The aromatic dianhydride comprises 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride 5 (2,2,-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 6-FDA^〇 4_(2,5-monooxytetrazol-β-furan-3-yl)-1,2,3,4-tetrazinene-1,2-dioxalic anhydride (4-(2,5-out (^加11)^(11'〇£1»^11-3-)^1)-1,2,3,4-tetrahydronaphthalene-l,2-dicarboxylic anhydride, TDA), and the aromatic diamine Included as a compound, or a mixture of two or more compounds, selected from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'- Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-TFDB), 3,3'-bis(trifluoromethyl)-4,4,-diamine-based stupid (3,3 '-bis (trifluoromethy 1)_4,4 '-diaminobipheny 1,3,3 '-TFDB), 4,4'-bis(3-aminophenoxy)diphenylphosphonium 15 (4,4'-bis(3- Aminophenoxy)diphenylsulfone, DBSDA), bis(3-aminophenyl)砚〇^(3-&amp;111丨11〇卩1^11丫1)3111!'〇116,3-008) and double (4- Aminophenyl) hinders 0^(4-&amp;111^1〇卩11611丫1)5111£01^,4-〇〇 8). In the polyamidamide resin of the first embodiment, the aromatic diamine may further comprise a compound or a mixture of two or more compounds selected from the group consisting of 2,2'-bis[4 (4- Aminophenoxy)phenyl]hexafluoropropane (2,2,-bis[4(4-aminophenoxy)phenyl]hexafluoropropane, 4-BDAF), 2,2'-bis[3 (3-aminophenoxyl) Phenyl] hexafluoropropane (2,25-bis[3(3-aminophenoxy)phenyl]hexafluoropropane, 3-BDAF), 1,3-bis(3-aminophenoxy)benzene 8 1376392 (l, 3-bis(3-aminophenoxy)benzene, APB-133), 1,3-bis(4-aminophenoxy)benzene (1,3_bis(4-aminophenoxy)benzene, APB-134), M_double ( 4-, 4-bis(4-aminophenoxy)benzene, APB-144, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane 5 ( 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 6-HMDA). In the first embodiment, the amount of 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6-FDA) may be 1 to 1 based on the total amount of the aromatic dianhydride. 99 mole percentage (mol%). In the polyamidamide resin of the first embodiment, based on the total amount of diamines, from 2,2'-bis(Triditymethyl)-4,4'-diaminobiphenyl (2) , 2'-TFDB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-amino group a compound selected from the group consisting of diphenyl sulfone (DBSDA), bis(3-aminophenyl) sulfone (3-DDS), and bis(4-aminophenyl) sulfone (4-DDS) or A mixture of two or more selected compounds is used in an amount of from 15 to 90 mole percent (mol%). According to a second embodiment of the present invention, there is provided a liquid crystal alignment layer comprising the above polyamidamide resin. The liquid crystal alignment layer of the second embodiment may have a pretilt angle of 〇 to 2 degrees. According to a third embodiment of the present invention, there is provided a polyimine film comprising the above polyamidamide resin. The polyamidamine film of the third embodiment has a light transmittance measured by an ultraviolet spectrophotometer on a basis of a film thickness of 50 to 1 μm, and may have a wavelength equal to or greater than a wavelength of 380 to 780 nm. An average transmittance of 85%, and an average transmittance of 88% or more at a wavelength of 551 to 780 nm. The polyamidamine film of the third embodiment has a light transmittance measured by an ultraviolet spectrophotometer on the basis of a film thickness of 5 Å to 1 〇〇μη1, and may have a wavelength equal to or greater than a wavelength of 55 〇 nm. The light transmittance of 88% may have a light transmittance equal to or greater than 85% at a wavelength of 5 〇〇 nm, and may have a light transmittance equal to or greater than 50% at a wavelength of 42 〇 nm. The polyamidamine film of the third embodiment may have a yellow index (yeu〇w index) of 荨 or less than 15 on the basis of a film thickness of 5 Å to 1 Å μηη. The polyimide film of the third embodiment may have a dielectric constant of 3 (?) or less at 1 GHz on a basis of a film thickness of 5 Å to 1 Å μη. The polyamidamine film of the third embodiment may have an average coefficient of thermal expansion (CTE of 5 〇ppm or less) at 50 to 2 〇〇〇C on a basis of a film thickness of 5 Å to 1 〇〇 μηη. ). The polyimide film of the third embodiment may have a modulus equal to or greater than 3.0 GPa on a basis of a thickness of 50 to 100 μm. The polyimide film of the third embodiment may have 50 °/ or less of 400 nm on a basis of a film thickness of 50 to 100 μm. UV cut off wavelength. The invention can provide a polyimide resin which is colorless, transparent and has excellent mechanical properties and thermal stability, and thus can be used in various fields, including a semiconductor insulating film, a TFT-LCD insulating film, a passivation film, and a liquid crystal alignment layer. , optical communication materials, protective films for solar cells, and flexible display substrates. The present invention also provides a liquid 1376392 crystal alignment layer and a polyimide film using the polyamidamine resin. - BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows a liquid crystal 5 alignment layer produced using the polyamidamide resin of the present invention. * * Symbols used in the drawings indicate 氺氺 1, 2 glass substrate 4 liquid crystal molecules α pretilt angle [Embodiment] 3 alignment layer 5 liquid crystal layer The present invention will be described in detail later. The present invention relates to a polyamidamine resin composed of a copolymer of a diamine and a diacid needle, and a liquid crystal alignment layer and a poly-aniline film using the resin. In particular, 15 is a colorless and transparent polyimide resin, and a liquid crystal alignment layer and a polyimide film using the resin. For this purpose, the aromatic dianhydride used in the present invention substantially comprises 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane succinic anhydride (6-FDA) and 4-(2,5). - Dihydrotetrahydrofuran_3_yl)_1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid 2-indole (TDA). The FDA is used in an amount of from 1 to 99 mole percent (mol%), preferably from 1 to 9 mole percent, based on the total amount of the dianhydride. Therefore, a poly-proline which is transparent and has high visible light transmittance, low ultraviolet absorption and yellowness index, and high viscosity can be prepared. 1376392. The aromatic diamine used in the present invention substantially comprises a compound or a mixture of two or more compounds selected from the group consisting of 2,2'-bis(trifluoromethyl)-4,4'- Diaminobiphenyl (2,2'-TFDB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3'-TFDB), 4,4' - bis(3-amino phenoxy-5)diphenyl sulfone (DBSDA), bis(3-aminophenyl)indole (3-DDS) and • bis(4-aminophenyl)sulfone (4 -DDS). Further, the aromatic diamine may further comprise a compound or a mixture of two or more compounds selected from the group consisting of 2,2'-bis[4(4-aminophenoxy)phenyl]hexa Fluoropropane (4-BDAF), 2,2'-bis[3 (3-amino-10-phenoxy)phenyl]hexafluoropropane (3-BDAF), 1,3-bis(3-aminophenoxyl) Base) benzene (APB-133), 1,3-bis(4-aminophenoxy)benzene (APB-134), 1,4-bis(4-aminophenoxy)benzene (octa-6-) 144) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6-HMDA). In this regard, based on the total amount of diamine, from 2,2,-bis(trifluorofluorene15-yl)-4,4'-diaminobiphenyl (2,2'-TFDB), 3,3 ,-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3'-TFDB), 4,4,-bis(3-aminophenoxy)diphenyl sulfone (DBSDA) a compound selected from bis(3-aminophenyl)indole (3-DDS) and bis(4-.aminophenyl)-(4-DDS), or selected as two or more compounds The mixture may be used in an amount of from 10 to 90 mol% to 20 parts by mole, preferably from 20 to 80 mol%. Therefore, high light transmittance and transparency can be achieved and electrical properties and thermal properties can be improved. The dianhydride and the diamine are dissolved in an organic solvent in an equivalent molar amount, and then reacted to prepare a polyaminic acid solution. The reaction conditions are not particularly limited, but include a reaction at a negative temperature of 20 to 80 ° C, a temperature of 12 1376392, and a reaction time of 2 to 48 hours. Further, the reaction is preferably carried out in an inert gas atmosphere of argon or nitrogen, and the organic solvent used for the solution polymerization of the monomer is not particularly limited as long as the polylysine can be dissolved therein. The commonly known reaction 5 solvent uses one or more polar solvents selected from the group consisting of m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and diterpene. Ethyl acetamide (DMAc), dimethyl sulfoxide (0 River 80), acetone and diethyl acetate. Further, a low boiling point solvent such as tetrahydrofuran (THF) or chloroform' or a low absorption solvent such as γ-butyrolactone may also be used. 10 The amount of the organic solvent to be used is not particularly limited, and in order to obtain a polyamic acid solution having an appropriate molecular weight and viscosity, the organic solvent is preferably used in an amount of 50 to 95% by weight based on the total amount of the polyamic acid solution. (wt%) 'More preferably from 7 to 9 weight percent. The polyamic acid solution thus obtained is amidoximinated to prepare a b glass transition temperature of 200 to 350. (: Polyimide resin. In order to form a liquid crystal alignment layer using the polyamic acid prepared by using the above monomer, the polyamic acid is applied to a glass substrate by spin coating or roller coating ( For example, indium tin oxide glass (IT 〇 glass), and then thermally hardened at 8 〇 cc for 5 minutes, and at 25 〇. The temperature is thermally hardened for 2 , minutes, 2 〇 to complete the polya during the removal of the solvent. a hydrazide reaction whereby a film (having a thickness of about 1 Å to 100 Åm) is formed on a glass substrate. To improve the coating ability or surface slab, and to apply to a processing process, the (4) polyamine's system is diluted to have 1 The viscosity of the appropriate coating solution is up to 5 、. The solvent used for the dilution is not limited to the solvent used for the polymerization. 13 丄376392 The commonly known dilution solvents are the following polar dissolution examples, one of which can be used alone. Alternatively, they may be used in combination, for example, N-methyl | pyrrolidone. Amine (DMAc) y~ (ΝΜΡ), bis-f-carbamamine (DMF), dimethylethene butyrate, and di-n-butoxyethanol. In order to effectively form a liquid crystal alignment layer, it is made from the above monomers.

The acid coating solution can be prepared by one or more of the following coating solution processes: 1. a process using a polyaminic acid solution; ίο~2. The polyphthalic acid polymer is thermally hardened and/ Or chemical hardening, a process of preparing a coating solution by a polyamination reaction, a precipitation to form a resin, and a process of dissolving in an organic solvent; stone 3. making the poly-proline polymer pass through 2 items of heat hardening and / or chemical, chemical, to carry out polyimidization reaction (no resin), and then the solution process;

&gt; Kunming the solution of the first and second or third items, and further the preparation process; and adding (/glutinous) the resin of the second item to the polyamine solution of the first item, and further preparing the coating The process of the solution. 2〇_The coating solution prepared by the above process can be subjected to a coating process:::Prophet&quot; one or more filtration steps using a filter and an ionizer having a pore diameter in the range of 0.1 to 5 μm . In the example of the invented polyamido resin for forming a liquid crystal alignment layer, apricot is a stable pretilt angle. The term "pretilt angle" refers to an angle at which the liquid crystal is preliminarily tilted for the reaction rate of the electromigration to 14 1376392 when the field voltage is applied to the liquid crystal and the liquid crystal is aligned in a predetermined direction. The liquid crystal alignment layer containing the polyacrylamide resin of the present invention exhibits a stable pretilt angle of 〇 to 2 degrees, and thus can be applied to an alignment layer of a plane _(^plane Switching, IPS) mode having a pretilt angle of less than 2 degrees. . 5 In addition, when the polyamidamine film is produced by using a polyaminic acid solution, a filler may be added to the polyaminic acid solution to enhance the properties of the polyamidamine film, including slidability, thermal conductivity, and electrical conductivity. Sex and corona resistance. There are no special restrictions on the filling, but specific examples include sulphur dioxide, oxidized chin, layered dioxo prior, carbon nanotubes, oxygen her, nitrogen cut, nitrogen fine, scale ^

10 calcium, calcium phosphate and mica. The particle size of the L 15 filler is not particularly limited depending on the nature of the film to be modified and the type of the filler to be added. The average particle diameter of the filler is preferably in the range of from 〇1 to 50 μm, more preferably in the range of from 〇〇〇5 to 25, in the range of from 0.01 to 1 〇 μηη. In this case, the polyacrylamide film is fortunately and easily modified, and also exhibits good surface conductivity and mechanical properties. The amount of the filler may be determined by the nature of the film to be modified and the particle diameter of the filler -' but is not particularly limited. The amount of the filler added is 〇., to 20 parts by weight, preferably 20 parts by weight, based on 100 parts by weight of the poly-branched acid solution. iU is more, the method of adding the filler is not particularly limited, but the age is said to be included in the polyfluorene reaction or after the addition of the filler to the poly-proline solution, after the polymerization of the amine W solution, using three The pro-grinding machine mixes the filler, and the crucible solution containing the filler is mixed. 1376392 The method for producing a polyimide film using the polyamic acid solution prepared in this manner is not particularly limited, and any known conventional methods can be employed. The methylene amination of the polyaminic acid solution includes, for example, thermal amidation and chemical imipenem, wherein chemical amidation is particularly effective. The chemical sulfoxide 5 is added to the polyaminic acid solution by using a dehydrating agent, including an acid anhydride such as acetic anhydride, and an imidization catalyst, including a tertiary amine such as isoquinoline, picoline or pyridine. Come in. The chemical imidization can be carried out together with the thermal aramidation. The heating conditions vary depending on the type of the polyamic acid solution and the thickness of the film. 10 by heating the polyamic acid solution on the substrate at 80 to 200 ° C, preferably at 100 to 180 ° C, to activate the dehydrating agent and the mercaptoamide catalyst, and to partially harden and dry to obtain a gelled polylysine film, separating the polyproline film from the substrate, and heating the gelled film at 2 to 4 Torr (&gt;c for 5 to 400 seconds) to obtain a poly The thickness of the polyimide film obtained by the present invention is not particularly limited, but the film thickness is preferably in the range of 1 Å to 25 Å μm in consideration of the field of application, and more preferably In the range of 25 to 150 μm, the polyamidamine film produced by the present invention has a light transmittance measured by an ultraviolet spectrophotometer at a film thickness of 1 〇 〇 at a wavelength of 2 〇 550 nm. The light transmittance is equal to or greater than 88%; the light transmittance at a wavelength of 5 等于 is equal to or greater than 85%; the light transmittance at a wavelength of 420 nm is equal to or greater than 50%. Further, at a wavelength of 38 〇 to 78 〇 The average light transmittance at 11 〇 1 is equal to or greater than 85%, and equal to or greater than 88% at a wavelength of 551 to 78 〇 nm. + 1376392 Polyaluminium The film has a yellow index equal to or less than 15 on the basis of a thickness of 50 to 100 4 „1. The polyalkylene film of the present invention which is similar to the light transmittance and the yellow index can be applied to general use. The yellow polyimide film is difficult to apply, and the transparency is high. 5. The protective film of the TFT-LCD or the diffusion plate and the coating layer, such as the interlayer of the TFT-LCD, the gate insulating layer (Gate) Insulator) and liquid crystal alignment layer. When transparent polyimide is applied to the liquid crystal alignment layer, it helps to increase the porosity, thereby producing a TFT-LCD with high contrast, and transparent polyamine can also be applied. The flexible display substrate of the present invention has a dielectric constant of 3.0 or less at 1 GHz, and thus can be used as a semiconductor passivation film. The average thermal expansion coefficient (CTE) of the polyimide film at 50 to 200 ° C is 50 ppm or less. If the average thermal expansion coefficient exceeds 15 50 PPm, when the polyimide film is applied to the thin film transistor (TFT) thin film electricity placed on the 4 film In the TFT ARRAY process, the polyacrylamide film may shrink or expand with different process temperatures, resulting in failure to achieve alignment in the electrode doping process. In addition, the film cannot be flattened and may be wound up. Therefore, when the coefficient of thermal expansion is lowered, the TFT process may be performed more accurately. The poly-mineral amine film of the present invention has a modulus equal to or greater than 3.0 GPa. In this example, the polyimide film may be more It is easily applied to the Roll to Roll process of flexible display substrates. When the polyimide film is used as a base film of a flexible display and a soft copper foil substrate (FCCL), it is a press roll press. At this time, since the film is subjected to the pulling force when the film is wound by the drum and released from the drum, the film having a modulus of less than 3.0 GPa may be broken. The 5 poly-branched amine film of the present invention has a 鄕 cutoff wavelength of 4 〇〇 nm or less according to the transmittance measurement using an ultraviolet spectrophotometer. Therefore, the polyacrylamide film of the present invention can be used as a surface protective film for solar cells. The following examples are given to further understand the present invention, but the examples are not to be construed as limiting the invention. 10 &lt;Example 1&gt; Once the nitrogen gas was passed through a reaction apparatus equipped with a mixture of H, a population, a dropping funnel, a temperature controller, and a condenser, the 33.5386 g of Ν, Ν -: methyl ethylamine (DMAc) was added to the round bottom flask, and the temperature of the reaction apparatus was lowered to 〇QC, and then 3 62922 15 g (0.007 mol) of 4_BDAF and 〇7449 g (〇〇〇3) The 3D DDS of Mohr is dissolved therein. Keep this solution at 0. The temperature of the crucible. 3.1097 g (0.007 mol) of 6_FDA and 7890078 g (〇 3 mol) of TDA were added to the solution, and the mixture was stirred for 1 hour until 6_FDA and TDA were completely dissolved. The solid content of this solution was 2% by weight 2 〇 (wt%). The obtained solution was stirred at room temperature for 8 hours to give a polyaminic acid solution having a viscosity of 2200 cps at 23 °C. Thereafter, a polyamic acid solution having a thickness of 500 to 1 μm was applied to the glass substrate using a Doctor Blade, and dried at a temperature in a vacuum oven for 1 hour, and dried at a temperature of 60 ° C. 2 hours to produce 1763392 a Self Standing Film. Next, let the film be at 5 per minute in a high temperature supply box. The heating rate of 匚 was hardened for 3 hours at 8 ° C, 1 hour at 100 ° C, 1 hour at 200 ° and 30 minutes at 3 ° C to produce a thickness of 50 μηι and 1 〇〇. Μιη poly-branched 5 amine film. &lt;Example 2&gt; As in the example, 3.62922 g (0.007 mol) of 4-BDAF was dissolved in 33.5386 g of DMAc, and yttrium, 7449 g (0.007 mol) of 4-DDS' was completely dissolved. Next, 3 j〇97 g (0.007 mol) 1 〇 of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added to the solution' and the solution was stirred for 1 hour until the 6-FDA and TDA were completely dissolved. . The solid content of this / gluten solution was 20 weight percent (wt%). Then, the obtained solution was stirred at room temperature for 8 hours to give a polyaminic acid solution having a viscosity of 2100 cps at 23 °C. 15 Thereafter, a polyimide film was produced in the same manner as in Example 1. &lt;Example 3&gt; As in Example 1, 2.04631 g (〇, 007 mol) of aPB-133 and 0.7449 g (0.003 mol) of 3_DDS were completely dissolved in gram of DMAc. Add 3.10975g (〇〇〇7mole) of 6 fda and ^曰90078g (ο·mole) of TDA to the solution in sequence and the solution of the solution = H, until '6_ ship and dish completely Dissolved. This dissolved solid contained f as 20 weight percent (wt%). Then, the obtained solution was scrambled for 8 hours at room temperature to give a polyaminic acid solution having a viscosity of 23 cc at the measurement of ePs. 19 Thereafter, a polyimide film was produced in the same manner as in Example 1. &lt;Example 4&gt; As in Example 1, 2.04631 g (0.007 mol) and 0.7449 g (〇.〇03 mol) of 4 DDS were completely dissolved in 27 2〇696 5 g of DMAc. 3.1 975 gram (0.007 mole) of 6-FDA and 0.90078 gram (0.003 mole) of TDA were sequentially added to the solution, and the obtained solution was stirred for a few hours until 6_FDA and TDA were completely dissolved. The solid content of the obtained solution was 2% by weight (wt%). Then, the solution was stirred at room temperature for 8 hours to give a polyaminic acid solution having a viscosity of 1 〇 1950 cps at 23 °C. Thereafter, a polyimide film was produced in the same manner as in Example 1. &lt;Examples As in Example 1 ' 2.24161 g (0.007 mol) of 2,2,-TFDB and 0.7449 g (0.003 mol) of 3-DDS, dissolved in 27.98796 g of 15 DMAC. 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added to the mixture, and the solution was stirred for 1 hour until the 6-FDA and TDA were completely dissolved. This solution had a solid content of 20% by weight (wt%). Then, the solution was stirred at room temperature for 8 hours to give a polyfluorene 20-amino acid solution having a viscosity of 2 〇〇〇 cps at 23 °C. Thereafter, a polyimide film was produced in the same manner as in Example 1. &lt;Example 6&gt; As in the example, 2.24161 g (0.007 mol) of 2,2,_TFDB and 0.7449 g (0.003 mol) of 4-DDS were completely dissolved in 27.98796 20 1376392 g of DMAc_. 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added to the solution, and the solution was stirred for 1 hour until the 6-FDA and TDA were completely dissolved. The solution had a solid content of 20% by weight (wt%). Then, the solution was stirred at room temperature for 8 hours to give a polyacetic acid solution having a point of 2000 cps at 23 °C. Thereafter, a polyimide film was produced in the same manner as in Example 1. &lt;Comparative Example 1&gt; As in Example 1, 5.1846 g (0.01 mol) of 4_BDAF was dissolved in 108.55 gram of DMAc, after which (4425 g (0.01 mol) of 6-FDA was added to the solution. Stirring the solution i hours until 6_FDA is completely dissolved. The solid content of this solution is 20 weight percent (wt%) &lt;) Then, this solution is pulverized at room temperature for 8 hours to produce a viscosity of 1300 cps at 23 ° C. Polylysine solution. 15 Thereafter, a polyimide film was produced in the same manner as in Example 1, and the film thicknesses were 25 μm, 50 μm and 1 Å, respectively. &lt;Comparative Example 2&gt; As in the example, 2.9233 g (0.01 mol) of ΑΡΒ·133 was dissolved in 29.482 g of DMAc, and then 4425 g (0.01 mol) of 2 〇6_FDA was added to the solution. The solution was stirred for 1 hour until the 6-FDA was completely dissolved. The solid content of this solution was 20% by weight (wt% h, and then the solution was stirred for 8 hours at a temperature to give a polyamic acid solution having a viscosity of 1200 cps at 23 ° C. Thereafter, The polyimide film was produced in the same manner as in Example 1. 1376392 &lt;Comparative Example 3&gt; As in Example 1, 2.4830 g (0.01 mol) of the 3-DDS system was dissolved in 27.702 g of DMAc, followed by 4.4425 g (0.01 mol) The FDA-FDA is added to the solution. The solution is stirred for 1 hour until the 6-FDA finish 5 is completely dissolved. The solid content of this solution is 20 weight percent (wt%). Then, the solution is at room temperature. The mixture was stirred for 8 hours to give a polyamine solvent solution having a viscosity of 1300 cps. Then, a polyimide film was produced in the same manner as in Comparative Example 1. &lt;Comparative Example 4&gt; 10 As Example 1 2.4830 g (〇.〇1 mol) of the 4-DDS was dissolved in 27.702 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added to the solution. The solution was stirred for 1 hour until 6 - FDA is completely dissolved. The solid content of this solution is 20 weight percent (wt%). Then This solution was stirred at room temperature for 8 hours to give a polyamic acid solution having a viscosity of 1400 cps at 23 ° C. Thereafter, a polyimide film was produced in the same manner as in Comparative Example 1. &lt; Comparative Example 5&gt; As in Example 1, 2.0024 g (〇.〇1 Moel) of the 3,3'-ODA system was dissolved in 25.7796 g of DMAc, followed by 4.4425 g (〇.〇1 Molar) 20 of 6- The FDA was added to the solution, and the obtained solution was stirred for 1 hour until the 6-FDA was completely dissolved. The solid content of the solution was 2% by weight (wt%). Then, the solution was stirred at room temperature for 8 hours. A polyaminic acid solution having a dot of 16 〇〇 cps at 23 ° C was produced. Thereafter, a polyimide film was produced in the same manner as in Comparative Example 1. 22 1376392 &lt;Comparative Example 6&gt; 2.0024 g (0.01 mol) of 4,4,_〇DA was dissolved in 16 J344 g of DMAc, after which 2.1812 g (0 01 mol) of PMDA was added to the solution, and the obtained solution was stirred for a few hours until 5 6-FDA completely dissolved" The solid content of this solution is 2% by weight (wt%). Then, at room temperature This solution was stirred for 8 hours to give a polyamic acid solution having a viscosity of 2500 poise at 23 ° C. Thereafter, a polyimide film was produced in the same manner as in Comparative Example 1. The above examples and comparative examples The properties of the obtained polyamidamine film, 10 were measured in the following manner. The results are summarized in the following table 丨 to Table 5 ^ (1) Transmittance and 50% cut-off wavelength using the external light spectrophotometer (Varian Technology Co., Ltd., Varian; model CarylOO) to measure each poly Asia Visible light transmittance of amidoxime and 50% cutoff wavelength. 15 (2) Yellow index The yellow index is measured in accordance with the ASTM E313 standard. (3) Modulus Using Instron's Universal Testing Machine (Universal)

Testing Machine), model Model 1000, measures modulus according to jis κ 6301 standard 20. (4) Glass transition temperature (Tg) The glass transition temperature was measured using a scanning thermal differential analyzer (DSC 'ΤΑ instrument, model Q2〇〇). (5) Thermal expansion coefficient (CTE) 23 The thermal expansion coefficient was measured at 50 to 200 Torr using a thermomechanical analyzer (TMA, ΤΑ instrument, model Q4 〇〇) according to the thermomechanical analysis method (TMA-Method). (6) Dielectric constant 5 The dielectric constant is measured in accordance with ASTM D150. (7) Pretilt Angle Use γ-butyrolactone as a dilution solvent to dilute the polyamines of each sample and comparative example to a viscosity of 1〇 to 50 cps, and then use a particle size of 2μηη, 〇·45 Filters of μιη and 0.2 μηι were filtered with an ion filter, and then the resulting polyamine solution was coated on a glass substrate (indium tin oxide glass) (coating conditions: spin coating, 400 to 4,000 rpm) , 10 to 40 seconds). Each polyamine solution on the glass substrate was attached to 8 Torr. (The temperature is hard-hardened at a temperature of 5 minutes, and then thermally hardened at a temperature of 250 ° C for 20 minutes, thereby completing the polyamidation reaction during the removal of the solvent. Thereby, the film having a thickness of 1 〇〇 nm 15 That is, formed on the glass substrate. The glass substrates U, 2) coated by this method are respectively positioned as the upper substrate and the lower substrate, and thereafter the liquid crystal molecules (4) are introduced into the space between the glass substrates (1, 2). 'To produce liquid crystal cells containing liquid crystal layer (5) (as shown in the first figure). The pretilt angle of each liquid crystal cell was measured by a crystal rotation method (Crystal Rotation 2 Method). The results are shown in Table 5 below. 24 1376392 [Table 1] Light transmittance composition Mohby film thickness (μπι) 380 nm to 551 nm to 550 500 420 780 nm 780 nm lilll 1 6-FDA+TDA/4-BDAF+3-DDS 7:3 :7:3 50 85.6 88.9 88.7 86.4 63.1 2 6-FDA+TDA/4-BDAF+4-DDS 7:3:7:3 50 85.7 89.0 88.8 87.4 63.8 Fan 3 6-FDA+TDA/APB-133+3 -DDS 7:3:7:3 50 87.3 89.6 89.4 89.0 75.4 Example 4 6-FDA+TDA/APB-133+4-DDS 7:3:7:3 50 86.8 88.9 88.7 88.2 75.8 5 6-FDA+TDA/ 2,2,-TFDB+3-DDS 7:3:7:3 50 88.5 90.3 89.9 89.2 71.5 6 6-FDA+TDA/2,2,-TFDB+4-DDS 7:3:7:3 50 88.4 90.1 89.6 89.2 70.7 1 6-FDA+TDA/4-BDAF+3-DDS Γ7Ϊ3:7:3 100 85.1 88.3 88.2 85.5 59.8 2 6-FDA+TDA/4-BDAF+4-DDS 7:3:7:3 100 85.2 88.6 88.4 86.0 60.2 Fan 3 6-FDA+TDA/APB-13 3+3-DDS PwiT 100 86.8 89.9 89.8 87.5 70.1 Example · 4 6-FDA+TDA/APB-13 3+4-DDS 7:3:7 :3 100 86.0 88.7 88.3 86.7 70.3 5 6-FDA+TDA/2,2,-TFDB+3-DDS 7:3:7:3 100 87.8 89.9 89.4 88.0 67.8 6 6-FDA+TDA/2,2,- TFDB+4-DDS 7:3:7:3 100 87.8 89.7 89.2 88.3 66.5 [Table 2]

Composition Mohrby Film Thickness (μιη) Yellow Index 50% Cutoff Wavelength (nm) Modulus (GPa) Tg (°C) CTE (ppm/ °C) Dielectric Constant, lGHz Example 1 6-FDA+TDA/4 -BDAF+3-DDS 7:3:7:3 50 6.7 394 3.05 234 48.8 2.60 2 6-FDA Ten TDA/4-BDAF+4-DDS 7:3:7:3 50 6.5 394 3.09 241 47.9 2.61 3 6 -FDA+TDA/APB-133+3-DDS 7:3:7:3 50 4.6 388 3.0 212 46.7 2.70 4 6-FDA+TDA/APB-133+4-DDS 7:3:7:3 50 4.4 396 3.0 260 46.4 2.70 5 6-FDA+TDA/2,2'-TFDB+3-DDS 7:3:7:3 50 1.86 380 3.04 245 46 2.8 6 6-FDA+TDA/2,2,-TFDB+4 -DDS 7:3:7:3 50 2.45 384 3.02 247 44 2.86 Example 1 6-FDA+TDA/4-BDAF+3-DDS 7:3:7:3- 100 7.5 397 3.09 • 47.9 2 6-FDA+ TDA/4-BDAF+4-DDS 7:3:7:3 100 7.5 396 3.14 47.1 • 3 6-FDA+TDA/APB-133+3-DDS ^:3:7:3 100 5.8 393 3.12 - 46.0 - 4 6-FDA+TDA/APB-133+4-DDS 7:3:7:3 100 5.7 398 3.17 • 45.6 _ 5 f-FDA+TDA/2,2,-TFDB+3-DDS 7:3:7 :3 100 2.83 385 3.12 45 • 6 6-FD A+TD A/2,2,-TFDB+4-DDS 7:3:7:3 100 3.35 388 3.1 43 - 25 1376392 [Table 3]

Light transmittance composition Mohr ratio film thickness (μιη) 380 nm to 551 nm to 550 nm 500 nm 420 nm 780 nm 780 nm 1 6-FDA/4-BDAF 10:10 25 82.8 90.0 87.2 86.0 63.1 than 2 6- FDA/APB-133 lorio 25 84.4 89.3 87.8 86.0 77.3 Compared with 3 6-FDA/3-DDS 10:10 25 84.3 88.6 89.7 88.6 66.5 Fan 4 6-FDA/4-DDS 10:1ο 25 84.6 89.4 90.5 90.0 72.5 Example 5 6-FDA/3,3,-ODA 10:10 25 84.9 89.8 90.0 87.6 77.1 6 PMDA/ODA ιο:Το~^ 25 56.6 85.2 73 35.0 0.05 1 6-FDA/4-BDAF 10:10 50 82.2 89.7 86.8 85.1 60.0 to 2 6-FDA/APB-133 10:10 50 83.8 88.8 87.2 84.8 73.2 Compared to 3 6-FDA/3-DDS 10:10 50 83.7 88.2 89.1 87.6 63.1 Fan 4 6-FDA/4-DDS 10:10 50 83.9 89.1 90.0 89.1 69.4 Example 5 6-FDA/3,3,-ODA ΓϊοΤΐο- 50 84.3 89.3 89.2 86.3 73.8 6 PMDA/ODA 10:10 50 56.0 84.5 69.2 33.1 0 1 6-FDA/4-BDAF 10:10 100 81.6 89.2 86.3 84.3 51.2 Ratio 2 6-FDA/APB-133 10:10 100 83.1 88.1 86.7 84.3 63.3 Compare 3 6-FDA/3-DDS 10:10 100 83.1 87.8 88.5 87.0 53.5 Fan 4 6-FDA/4-DDS 10:10 100 83.2 88.8 89.5 88.6 58.6 Example 5 6-FDA/3,3,- ODA 10:10 100 83.5 88.7 88.8 85.4 62.1 6 PMDA/ODA 10:10 100 ' - - [Table 4] Composition Mohby Film Thickness (μιη) Yellow Index 50% Carrier Wavelength (nm) Modulus (GPa) Tg (°C) CTE (ppm/°C) Dielectric constant / 1GHz 1 6-FDA/4-BDAF 10:10 25 9.7 411 3.0 263 52.3 2.5 Ratio 2 6-FDA/APB-133 10:10 25 5.5 395 3.05 206 47.1 2.7 Compared with 3 6-FDA/3-DDS 10:10 25 1.82 388 3.1 270 47 3.0 Fan 4 6-FDA/4-DDS 10:10 25 1.68 382 3.1 310 46 3.1 Example 5 6-FDA/3, 3'-ODA 10:10 25 5.29 396 3.0 244 41 2.73 6 PMDA/ODA 10:10 25 91.7 514 3.0 No 26 3.3 1 6-FDA/4-BDAF 10:10 50 11.2 L 413 3.06 • 51.1 than 2 6- FDA/APB-133 10:10 50 6-9, 398 3.11 • 46.0 vs 3 6-FDA/3-DDS 10:10 50 2.95\ 392 3.16 • 45.3 Fan 4 6-FDA/4-DDS 10:10 50 386 3.17 45.1 Example f&gt; 6-FDA/3,3'-ODA 10:10 50 6.46 399 3.05 39.6 • 6 PMDA/ODA 10:10 50 - 3.12 25.0 - 26 1376392 Comparative Example 1 6-FDA/4-BDAF 10: 10 100 23.4 415 3.09 48.8 2 6-FDA/APB-133 10:10 100 14.2 401 3.14 44.5 . _3 6-FDA/3-DDS 10:10 100 4.54 396 3.20 44.9 4 6-FDA/4-DDS 10:10 100 4.26 390 3.22 _ 44.6 . 5 6-FDA/3,3,-ODA 10:10 100 14.26 405 3.13— _ 39.1 6 PMDA/ODA 10:10 100 - - - _ [Table 5] Component Mohr Pretilt (degrees) 1 6-FDA+TDA/4-BDAF+3-DDS 7:3:7:3 1.5 2 6-FDA+TDA/4-BDAF+4- DDS 7:3:7:3 1.5 Example 3 6-FDA+TDA/APB-133+3-DDS 7:3:7:3 1.4 4 6-FDA+TDA/APB-133+4-DDS 7:3: 7:3 1.4 5 6-FDA+TDA/2,2'-TFDB+3-DDS 7:3:7:3 1.4 One - 6 6-FDA+TDA/2,2'-TFDB+4-DDS 7: 3:7:3 1.5 1 6-FDA/4-BDAF 10:10 3.5 2 6-FDA/APB-133 10:10 3.2 Comparison 3 6-FDA/3-DDS Γ 10:10 Γ /3.1 Example 4 6- FDA/4-DDS 10:10 3.1; b 6-FDA/3,3'-ODA 10:10 --, I, /'_ 9 7 6 PMDA/ODA ΤοΓΓο- 1.2 Properties from light transmittance and yellow index As a result of the measurement, it is apparent that the polyiminamide film of the present invention has a film thickness of 5 〇 5 or 100 in the visible light range, and its light transmittance is equal to or greater than 88 Å at a wavelength of 550 nm; At 500 nm, the light transmittance is equal to or greater than 85%; n times the network TMG%; in addition, at the wavelength, the average light transmittance is equal to or greater than 85%, and at a wavelength of 55 The average light transmittance from 1 to 78 〇 nm is equal to or greater than 88%; and, its yellow index is always low. Therefore, it was confirmed that the polyiminamide film of the present invention has high transparency. In the comparative example, regardless of the thickness of the film, the average transmittance of the example when moving to the visible leg in the visible range is equal to 27 1376392

10 15

Or greater than 85%. Further, in Comparative Example 6, a polyimide film having a film thickness of equal to or greater than 90 μm could not be produced. The polyamidamine film produced in the example of the present invention has a light transmittance of 5〇% at a wavelength of 400 nm or less, and finally realizes a colorless transparent poly Asian having excellent visible light transmittance. The polyimide film of the invention can be used as a surface protective film for solar cells. In addition, since the average coefficient of thermal expansion of polyweilai is equal to or less than 50 ppm, the height is of a high degree of dimensionality, and is equal to or greater than the film property &amp; U t〇 _ process required thin = 1 = 2 Ming polyimide film can also be used to manufacture soft TFT test, with equal or = = can be used as a semiconductor passivation film" with equal to or less than 2 Degree _=^ manufactured liquid crystal alignment layer, with an alignment layer for the pattern. This month b is used as a plane conversion (IPS) 28 1376392. BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows a liquid crystal alignment layer produced using the polyamidamide resin of the present invention. 5 [Description of main component symbols] 1, 2 glass substrate 3 alignment layer 4 liquid crystal molecules 5 liquid crystal layer α pretilt angle

29

Claims (1)

1376392 Diaminobiphenyl (2,2'-butane 06), 3,3,-bis(trifluoromethyl)-4,4'-diamine% phenyl (3,3'-TFDB), 4,4'-bis(3-aminophenoxy)diphenylfluorene' (DBSDA), bis(3-aminophenyl)indole (3-DDS) and bis(4-aminophenyl)sulfone (4-DDS) A selected compound, or a mixture of two or more than five selected compounds, in an amount of from 10 to 90 mole percent. A liquid crystal alignment layer comprising the polyamidamide resin according to any one of claims 1 to 4. &gt; 6. The liquid crystal alignment layer according to claim 5, which has a pretilt angle of 〇 to 2 degrees. A polyiminamide film comprising the polyamidamine resin according to any one of claims 1 to 4. 8. The polyamidamine film according to claim 7, wherein the light transmittance is measured by an ultraviolet spectrophotometer at a wavelength of 380 to 780 on the basis of a film thickness of 50 to 1 〇〇μηη. At nm, the film has an average light transmittance equal to or greater than 85%, and at a wavelength of 551 to 780 rmi, the 臈&gt; has an average light transmittance equal to or greater than 88%. 9. The polyamidamine film according to claim 7, wherein the light transmittance is measured by an ultraviolet spectrophotometer at a wavelength of 50 to 1 μm, at a wavelength of 55 〇 nm. When the film has a transmittance of 2% or more, 该%, the film has a light transmittance equal to or greater than 85% at a wavelength of 50〇11111, and the film has a wavelength equal to or greater than a wavelength of 420 nm. 5〇% transmittance. 10. If the application is as described in item 7 of the full-time enclosure, the film has a yellow phase of 31 which is equal to or less than 15 on the basis of a film thickness of 50 to 10 〇Mm. The polyacrylamide film having a thickness as described in the patent application No. 7 has a dielectric constant equal to 3. 制 at 1 GHz on the basis of the film or small; ^ to 1 GG μΠ1. The thicker household. The poly-arylene film according to the seventh item of the fourth patent system, under the film, the film is from % to fine on the basis of 5 Torr to 100 μm in summer. The temperature of c has an average coefficient of thermal expansion equal to or less than 50 ppm. U.S. Patent No. 7, U.S. Patent Application Serial No. 7, which has a modulus of 50 Å to 1 Å, and has a modulus equal to or greater than 3 〇 GPa. The polyamidamine film according to claim 7, wherein the light transmittance is measured by an ultraviolet spectrophotometer having a thickness of 50 to 1 μm, and the film has a ratio of 4 or less. 50% cut off wavelength of 〇〇nm. 32