TWI226363B - Liquid crystal aligning film composition used for liquid crystal display - Google Patents

Abstract

The present invention is to provide a kind of liquid crystal aligning film composition used for liquid crystal display (LCD), in which the liquid crystal aligning film composition used for LCD is a polyimide resin oligomer (A) having the structural formula (I) as shown in the following, wherein m is an interger of 1, 2, and 3, R is selected one of from aromatic and cyclicaliphatic, X is selected from the group containing amide, ester, and ether etc., Y is the group of containing cholesterol structure; this polyimide resin oligomer (A) through an induced process and the second reagent (B) are mixed together to produce an aligning thin film of liquid crystal molecule.

Description

1226363

[Previous technology] Liquid crystal displays (LCD) have played a very important role in the photovoltaic industry, and have developed rapidly in recent years. With the gradual application of electronic products, the demand for liquid crystal displays has also increased rapidly, ranging from big brothers and personal digital assistants (PDAs) that personally carry with them to laptop computers and LCD monitors. It can be seen that the electronic production σσ of liquid crystal display applications has become more promising in recent years due to the advancement of process technology and the input of related materials industries. At present, the most widely used alignment method in the liquid crystal display industry is to rub the substrate coated with the alignment film (a 1 i gn i ng fi 1 m) in a certain direction with mechanical force, which can make the liquid crystal molecules uniform. And the stable alignment effect is called rubbing treatment (rubbing treatment). The advantages of this method are good mass production and stable alignment effect. But at present, the rubidium molecular film as an alignment film is often not strong enough. After rubbing, it is often separated from the substrate or cracks are generated. When assembled into a liquid crystal display and driven by voltage, this "wound" alignment film will adsorb Ionic charge; when the applied voltage is released, residual voltage is accumulated (residue 11age). Residual voltage will cause image retention on the day (image

1226363 _Case No. 90112828 Amended 5. The description of the invention (2) The phenomenon of stacking occurred, and at the same time, the contrast (contrast) was reduced. In addition, because the alignment film is not resistant to brushing, many fine particles and dust are generated, which will cause partial discharge under the voltage application state, which may damage the alignment film itself and indium tin oxide (indium). tin oxide (1 to 0) electrode or thin film transistor (TFT). At the same time, large and small defects formed on the surface of the alignment film are more likely to cause scattered phase distortion and light scattering, thereby reducing the display quality. Especially in the process of super twisted nematic liquid crystal displays (STN-LCD), a stronger brushing and a larger process allowable width are required. Therefore, the requirements for the brushing resistance of the alignment film will be higher. Ordinary liquid crystal display alignment agents are almost composed of polyimide (ρ ο 1 yimide). This polymer can be obtained chemically through the addition polymerization of dianhydride and bisamine. The species is closely related to the characteristics of the resulting polyimide product. U.S. Patent No. 5 6 9 8 1 35 discloses a method of increasing the dianhydride of several aliphatic dianhydrides to increase the abrasion resistance of an alignment film. However, the introduced aliphatic acid anhydride has poor reactivity, thus increasing the difficulty of the synthesis reaction. Japanese Patent Application No. 9-1 8 5 0 6 5 has not been examined. Japanese patent discloses that thermal bridging compounds are used to increase the rubbing resistibility of the alignment film, but the maximum residual voltage is still It is too high to be used in high-end liquid crystal displays.

1226363 __Case No. 90 chat 8__ Year, month, and day of the amendment V. Description of the invention (3) ^ ~ ^ ~ " 1 To make the alignment film achieve better electrical requirements, such as high charge retention, low DC residual potential, etc. , You can refer to Japanese unrequested patent Sho 64 4 472 0, Japanese unrequested patent JP-A 10-183118, U.S. Patent No. 5 8 5 8 2 74 and U.S. Patent ^ The method disclosed in Patent No. 5 9 5 4 9 9 9 is, for example: mixing a poly amic acid resin with a soluble polyimide resin solution in a certain ratio. Characteristics, polyamic acid has low DC residual potential, brush resistance, low image residue, and good printability; while soluble polyimide has the advantages of high voltage retention and low roasting, w degree, etc. After mixing, it should improve the electrical performance; however, the Z-soluble polyfluorene imine part is less resistant to brushing, so there are still serious problems such as dust and film peeling. ^ In addition, U.S. Patent No. 5 9 549 9 9 discloses a method for protecting the pretilt angle, which is beneficial to the introduction of long-chain alkanes in a solvent-soluble polyimide moiety. The disadvantage of this method is that because the long-chain alkyl group cannot effectively cause steric obstacles, the long chain itself is easy to rotate, the pretilt angle is unstable, and the alignment uniformity is reduced. Furthermore, it is not easy for everyone to worry about the pre-tilt angle control. [Explanation 1] The main purpose of the present invention is to solve the above-mentioned defects and to avoid the existence of the above-mentioned defects. The present invention provides a liquid crystal alignment film composition for a liquid crystal display, which is unlikely to produce scratches or powders. Another object of the present invention is to provide a liquid crystal alignment film composition for a liquid crystal display, which can maintain a high charge retention rate and a low DC residual potential. 9

1226363 _Case No. 90112828_Year_Month_Revision_ ‘V. Description of the invention (4) To the film composition, no residual image. Another object of the present invention is to provide a liquid crystal alignment film composition for a liquid crystal display, which can meet the high and low pretilt angles of various displays. Another object of the present invention is to provide a liquid crystal alignment film composition for a liquid crystal display, which is easy to synthesize. In order to achieve the above object, the present invention uses a polyimide resin oligomer (A) having a cholesterol structure to induce moderate cross-linking through an induction process and then mixes it with a second reagent (B) to produce an easily synthesized, Alignable liquid crystal molecular film that is resistant to brushing and meets the high and low pretilt angles of various displays. It is not easy to produce brush & abrasion marks or dust, no residual image, and easy synthesis reaction. The detailed description and technical contents of the present invention are described below with reference to the drawings: A liquid crystal alignment film composition for a liquid crystal display, the composition includes: a polyimide resin recruiting polymer (A), which is moderately produced through an induction process After cross-linking and mixing with a second reagent (B), alignable liquid crystal molecules are produced, as shown in "Figure 1", which is a structural diagram of a polyimide resin oligomer according to the present invention, where m is 1 An integer of 2, 2, and 3, R may be selected from one of aromatic compounds and cyclic aliphatics, X is selected from the group consisting of amine groups, ester groups, ether groups, and the like, Y is a group containing a cholesterol structure ^ Group, in which the polyimide resin oligomer (A) accounts for 1% to 30% by weight of the total resin solution, and preferably 6 to 20%. The group Y of the cholesterol structure may be selected from one of the following compounds: androsterone and its derivatives, cholesterol and its derivatives, corticosterone acetate and its derivatives, epi-androgen ifone

Page 10 1226363 Amendment No. 90112828 V. Explanation of the Invention (5) (epiandrosterone) and its derivatives, ergosterol estrone and its derivatives, methyltestosterone and its derivatives , Lanosterol and its derivatives, mestranol and its derivatives, pregsterone and its derivatives, / 3-Sitosterol and its derivatives, stigmasterol and its derivatives Derivatives, testosterone and its derivatives, (estryl amine) and its derivatives, norethisterone and its derivatives, pregnenoryl chloride and its derivatives, and (17- (1, 5-dimethyl- hexyl) -10, 13-dimethyl-hexadecahydro-cyc1 openta [a] phenanthrene) and the like. A second reagent (B), which may be selected from one of the following compounds: polyamic acid, soluble polyimide resin, a mixture of polyamic acid and soluble polyimide resin, wherein the soluble polyimide resin is The weight ratio of polyamic acid is 1/4 ~ 4/1, and the best is 1/3 ~ 3/1. "Figure 2" shows the structure of the polyamic acid of the present invention, where R 1 is A tetravalent organic group, R2 is a divalent organic group, η is a positive integer, as shown in the "third figure", which is the structure diagram of the soluble polyfluorene imine resin of the present invention, in which R 3 is a tetravalent organic group, R 4 is a divalent organic group, and η is a positive integer. The induction process includes anionic initiated polymerization, heating initiated polymerization, peroxide added to initiate polymerization, UV light initiated polymerization, and T-ray initiated polymerization. [Example 1, Example] Two kinds of diamine compounds benzene-l, 4-diamine 26 · 7g and 3,5-diamino-benzoic acid—17— (1,5—dimethyl—hexyl) —

1226363 __90112828_year month day_ «V. Description of the invention (6) 10,13-dimethyl-hexadecahydr〇-cyclopenta [a] phenanthren- 3-yl ester 14.3g with two diacid anhydride compounds benz〇 [l, 2-c ; 4, 5-c '] difuran-l, 3,5,7-tetraone 52 · 3g and furan-2,5-dione 6.7g were put into the reactor, nitrogen was passed through, and anhydrous N-fluorenyl group was added Chrysanthemone (NMP) 400g, at a temperature of 120 ~

After heating at 160 ° C for 10 to 12 hours, a polyimide solution can be finally obtained. After adding 1000 g of methanol to produce a white precipitate, the precipitate was washed with methanol, filtered, and dried at 40 ° C to obtain a white polyimide resin powder. 0.6 g of polyimide resin powder was dissolved in 9.4 g of anhydrous N-methyl say σ each ketone to form a lotion bath-type poly ^ imine solution (ρ I-1), and this solution was taken ρ I_ 1 3 〇g, add 2,2, -azobis (isobutyronitrile) 0.5g, put into the reactor, pass in nitrogen, and heat for 5 ~ 6 hours at a temperature of 90 ~ 1 10 ° C to obtain a solution (PI-1-1). One of 2,6-bis [4- (4-aminophenoxy) phenyl] propane 14.6 g of a diamine compound and 5, 5'-bi isobenxofurany 1 -1, 3, 1, 2, 3, -tetraone 10.3 g Anhydride compounds are put into the reaction mixture, and nitrogen gas is passed in, and anhydrous n-methyl roxoxone is added, and the reaction is performed at room temperature for about 3 hours to form a polyamic acid solution (PAA-1). The weight ratio of the solution (PI-1-1) to the polyamic acid solution (pAA — 1) is 1: 9 '. After mixing, it is diluted to a mixed resin solution (M — 1) with a solid content of 5%. The solution was coated on the cleaned I TO substrate, and then heated to 200 ~ 250 C to complete drying. The substrate was taken out and cooled to room temperature. [Example 2, Example]

Page 121226363 Amendment No. 90112828 V. Description of the Invention (7) diamino-benzoic acid-17- (1, 5-dimethyl-hexyl)-10, 13-dimethyl-hexadecahydro-cyclopenta [a] phenanthren-3-yl ester 0.99g of two diamine compounds were placed in the reactor. Under nitrogen, 120g of m-cresol and 2.0g of quinoline were added. After stirring and dissolving, benzo [l, 2-c; 4,5-c was added. '] difuran-l, 3,5,7-tetraone 16.92g, and then heated at a temperature of 50 ~ 170 ° C for 4 hours to obtain a polyimide alignment membrane solution, adding 1 0 0 0 alcohol to produce white After precipitation, the precipitate was washed with methanol, filtered, and dried to obtain a white polyimide resin powder. 0.6 g of the polyimide resin powder was taken and dissolved in 9.4 g of r-butyrolactone. Soluble polyfluorene imine solution (PI-2). 14.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane diamine compound and 5,5'-biisobenxofuranyl -1,3,1 ', 3' -tetr a one 10.3 g of dianhydride compound Put it into the reactor, pass in nitrogen gas, and add anhydrous N-fluorenyl phosphinolone, and react at room temperature for about 3 hours to form a polyphosphonic acid solution (PAA-1). After the soluble polyfluorene imine solution (PI-2) and the polyamidic acid solution (PAA-1) are mixed in a weight ratio of 3: 1, the mixed solution and the solution (PI-; 1-1 ) Mix at a weight ratio of 9: 1, and dilute to a mixed resin solution (M-2) with a solid content of 5%. Apply this alignment film solution to the cleaned ITO substrate and heat it in an oven for 2 0 ~ 2 50 ° C to dry completely, remove the substrate and cool to room temperature. [Example 3, Example] Two diamine compounds benzene-1,4-diamine 26.7g and 3; 5-diamino-benzoic acid-17 ~ (l, 5-dimethyl-hexyl)-

Page 13 1226363 Case No. 90112828 Amendment V. Description of the Invention (8) 10, 13-dimethyl-hexadecahydr0-cyclopenta [a] phenanthren-3-yl ester 14.3 g and two diacid anhydride compounds benz〇 [l, 2- c; 4,5-c '] difuran-l, 3,5,7-tetraone 52.3 g and furan-2,5-dione 6.7 g were placed in the reactor, nitrogen was passed through, and anhydrous N-fluorenyl group was added Scopolone (NMP) 4 0 0 g, at a temperature of 120 ~

After heating at 160 ° C for 10 to 12 hours, a polyimide solution can be finally obtained. After adding 100 g of methanol, a white precipitate was generated, and the precipitate was washed with methanol, filtered, and dried at 40 ° C to obtain a white polyimide resin powder. 0.6 g of polyfluorene imide resin powder was dissolved in 9.4 g of anhydrous N-fluorenylpyrrolidone to form a solvent-soluble polyfluorene imine solution (PI _ 1), and a photosensitizer such as thioxanthone was added. A solution (PI-1-2) was obtained. 14.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane diamine compound and 5, 5 '-biisobenxofuranyl-1,3,1', 3 '-tetraone 10.3 g of dianhydride The compound was placed in a reactor, and nitrogen was introduced, and anhydrous N-methylpyrrolidone was added, and reacted at room temperature for about 3 hours to form a polyamidic acid solution (PAA-1).

The weight ratio of the solution (PI-Bu 2) to the polyamic acid solution (PAA-1) is 1: 9 '. After mixing, it is diluted to a mixed resin solution (M-3) with a solid content of 5%, and this alignment film solution is used. It is coated on the cleaned I TO substrate, heated and baked until completely dried, and irradiated with UV light to crosslink. [Example 4, Example] 26.7 g of benzene-l, 4-diamine and 3,5-diamino-benzoic acid-17- (l, 5-dimethyl-hexyl) -10,13-dimethyl-hexadecahydrO-cycl 〇penta [a] phenanthren-3-yl ester 14.3 g two diamine compounds and benzo [l, 2-c; 4,5-c ']

Page 14 1226363 Case No. 90112828 Amended in May V. Description of Invention (9) difuran-1,3,5,7-tetraone 52 · 3 g and furan-2,5-dione 6 · 7 g Into the reactor, pass in nitrogen, and add anhydrous N-fluorenyl group (400 g) (NMP), heated at a temperature of 120 ~ 160 ° C for 10 ~ 1 2 hours, and finally obtain polyfluorene Imine solution. After adding 100 g of methanol, a white precipitate was generated, and the precipitate was washed with methanol, filtered, and dried at 40 ° C to obtain a white polyimide resin powder. 0.6 g of polyfluorene imide resin powder was dissolved in 9.4 g of anhydrous N-methylpyrrolidone to form a solvent-soluble polyfluorene imine solution (p I -1), and the solvent-soluble polyfluorene was taken 30 g of amine solution 'Added 0.5 g of barbituric acid, put it into the reactor, nitrogen gas, and heated at a temperature of 100 ~ 150 ° C for 0 · 5 ~ 6 hours to obtain a solution (PI-1-3) . Diamine compound of 2,2-bis [4- (4-aminophen〇xy) phenyl] propane 14.6 g and 5,5'-biisobenxofuranyl-l, 3, l ', 3'-tetraone diacid anhydride compound 10.3 g was put into the reactor, and nitrogen gas was added, and anhydrous N-fluorenylpyrrolidone was added, and the reaction was performed at room temperature for about 3 hours to form a polyamidic acid solution (PAA-1). The weight ratio of the solution (PI-1-3) to the polyamic acid solution (PAA-1) is 9: 1. After mixing, it is diluted to a mixed resin solution (M-4) with a solid content of 5%. This alignment film The solution was coated on the cleaned ITO substrate, and then heated in an oven at 200 ~ 250 ° C until it was completely dried. The substrate was taken out and cooled to room temperature. [Example 5 and Example] Two diamine compounds, benzene-1, 4-diamine 27.9 g, and 3, 5-diamino-benzoic acid-17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-hexadecahydro -cyclopenta [a] phenanthren-3-yl ester 11.7g | ^ benzo [l, 2-c; 4,5-c ']

Page 15 1226363 ___Case No. 90112828_Yuanyue Yuezheng V. Description of the invention (10) difuran-l, 3, 5, 7-tetraone 52.3 g and furan-2, 5-dione 6. 7 g The dianhydride compound was put into the reactor, nitrogen was passed in, and 40 g of anhydrous N-fluorenylpyrrolidone (NMP) was added, and heated at a temperature of 120 to 160 ° C for 10 to 12 hours, and finally obtained Polyimide solution. After adding 100 g of methanol to produce a white precipitate, the precipitate was washed with methanol, filtered, and dried at 40 ° C to obtain a white polyimide resin powder. 0.6 g of polyimide resin powder > was hydrolyzed to 9.4 g of anhydrous N-methyl. A solvent-soluble polyfluorene imine solution (PI -1) * was formed in each of the 17 compounds, and a solvent-soluble polyfluorine imide solution 3 (^) was added, and 2,2'-32〇1 ^ 3〇3 was added. 13111 ^]: 01141 ^ 16〇.58, put it into the reactor, pass nitrogen gas, and heat it at a temperature of 90 ~ 110 ° C for 5 ~ 6 hours to obtain a solution (PI_: 1-1) *. 4 etc. 2, 2 — bis [4 — (4-amin〇phenoxy) phenyl] proparie diamine compound 14.6 g with [5,5'-biisobenxofuranyl -1,3,1 ', 3'-tetraone] 10.3 g of the dianhydride compound was put into the reactor, and nitrogen gas was added, and anhydrous N-methyl was added. This proxidone was reacted at room temperature for about 3 hours to form a polyamine solution (paa-1). The solution (PI-1-1) * and the polyamic acid solution (PAA-1) have a weight ratio of 1: 9, and after mixing, dilute to a mixed resin solution (M — 1) * with a solid content of 5%. This alignment film solution is coated on the cleaned 丨 τ〇 substrate, and the box is heated from 2000 to 250 ° C to complete drying, the substrate is taken out and cooled to room temperature. [Example 6 〕 29.2 g of benzene-1,4-diamine and two diamines Compound 3 ’5 diamino-benzoic acid-17- (1,5-dimethyl-hexyl) -Α, ··· 3 dimethyl —hex ίΐ d ecahydro — cyclopenia [a]

Page 16Ϊ226363 Amendment_Case No. 9Q112828 V. Description of the invention (11) phenanthren-3_yl ester 9.0 g and two dianhydride compounds benzo [l, 2-c; 4,5-c '] difuran-i, 3,5 , 7-tetra〇ne 52.3 g and furan-2, 5-dione 6.7 g were placed in the reactor, nitrogen was passed through, and anhydrous N-methylpyrrole acid j (NMP) 400 g, At temperature} 2〇 ~

After heating at 160 ° C for 10 to 12 hours, a polyimide solution can be finally obtained. After adding 100 g of methanol, a white precipitate was generated, and the precipitate was washed with methanol, dried over and dried at 40 ° C to obtain a white polyimide resin powder. 0.6 g of polyimide resin powder was dissolved in 9.4 g of anhydrous N-methylpyrrolidone to form a solvent-soluble polyfluorene imine solution (p I — 丨) * *, taking the solvent-soluble type 30 g of polyimide / cereal, added 2, 2-azobis (isobutyirori): ile) 0.5 g 'into the reactor, pass in nitrogen, and heat at a temperature of 90 to 5 for 6 to 6 hours To obtain a solution (PI-1—1) **. A 1-fe compound 2,2-bis [4- (4-aminophenoxy) phenyl] propane 14.6 g and a dianhydride compound 5,5, _biisobenxofuranyl-1,3,1,, 3, -tetraone ΐ〇 · 3 Put g into the reaction Is, pass in nitrogen, and add anhydrous N-fluorenyl-u-ketone, and react at room temperature for about 3 hours to form a polyamino acid solution (pAA-1).

Solution (PI-1-1) ** and polyamine solution (PAA — 1) in a weight ratio of 1: 9, and after mixing, diluted to a mixed resin solution (μ-1) with a solid content of 5% * *, This alignment film solution was coated on the cleaned 丨 τ 〇 substrate, heated in an oven at 200 ~ 250 ° C to complete drying, the substrate was taken out and cooled to room temperature 0 [Example 7, Example] benzene-1 2,4-diamine 26.7 g and two diamine compounds 3, 5-diami no-benzoic acid-17- (1,5-dimethyl-hexyl)-

$ 17page case number 90112828 1226363 _ V. Description of the invention (12) 10,13-dimethyl-hexadecahydro-cycl〇penta [a] phenanthren-3-yl ester 14. 3 g with two diacid anhydride compounds benz〇 [ l, 2-c; 4,5-c '] difuran-l, 3,5,7-tetraone 52.3g and furan-2,5-dione 6.7g were put into the reactor, and nitrogen gas was passed through, 400 g of anhydrous N-methylpyrrolidone (NMP) was added at a temperature of 120 to 160. (: Indirect heating for 10 to 12 hours, finally a polyimide solution can be obtained. After adding 1000 g of methanol, a white precipitate is generated. The precipitate is washed with methanol, filtered, and dried at 40 ° C. A white polyimide resin powder can be obtained. 0.6 g of polyimide resin powder is dissolved in 9.4 g of anhydrous N-methyl. This σ forms a solvent-soluble polyimide solution (ρ I -1), take 30 g of a solvent-soluble polyfluorene imine solution, add 0.5 g of 2,2'-azobis (isobutyronitrile), put it in a reactor, and introduce nitrogen gas at a temperature of 90-110 °. The solution (PI-: 1-1) can be obtained by heating for 5 to 6 hours. The monoamine compound 2,2-bis [4- (4-aminophenoxy) phenyl] propane 14.6 g and ([5,5 '-biisobenxofuranyl- 1,3, Γ, 3'-tetraone]) 10. 3g of the dianhydride compound is put into the reactor, nitrogen is introduced, and anhydrous N-methyl is added. This t; each ketone, reacts at room temperature for about 3 Hours, a polyamine solution (pa A-1) is formed. The weight ratio of the solution (PI-1-1) to the polyamino acid solution (pAA_!) Is 3: 9 7 'After mixing, dilute to a solid content of 5% Mixed resin solution (μ -1) * * * 'Apply this alignment film solution to the cleaned 丨 τ 〇 substrate, and heat it in an oven at 200 ~ 250 ° C until it is completely dry, remove the substrate and cool to room Temperature 0

[Example 8, Comparative Example] Preparation of PAA-1 without mixing 2,2 bis [4- (4-aminophenoxy) phenyl] propane

Page 18 1226363 __ Case No. 90112828_ Year J____ V. Description of the Invention (13) 14.6 g of diamine compound and 5,5'-biisobenxofuranyl -1,3,1 ', 3'-tetraone 10.3 g of dianhydride The compound was placed in a reactor, nitrogen was passed, and anhydrous N-fluorenyl was added. This ketorone is reacted at room temperature for about 3 hours to form a polyamidic acid solution (PAA-1). Apply the (PAA-1) solution on the cleaned IT0 substrate, heat it in an oven at 200 ~ 250 ° C until it is completely dry, remove the substrate and cool to room temperature. [Example 9, Comparative Example] 4,4'-11161:] ^ 16116-1) 13-〇-13〇1111 (1: [116 13.69 8 and 3,5-diamino-benzoic acid-17- (1 ， 5-dimethyl-hexyl) -10, 13-dimethyl-hexadecahydro-cyclopenta [a] phenanthren-3-yl ester 0.99 g Two kinds of diamine compounds were put into the reactor, and m-cresol was added under nitrogen flow. 1 2 0 g and quinoline 2.0 g, after dissolving, add benzo [l, 2-c; 4,5-c '] difuran-l, 3,5,7-tetraone 16.92 g, then at a temperature of 50 to 1 After heating at 70 ° C for 4 hours, a polyimide alignment film solution can be obtained. After adding 1000 g of alcohol to produce a white precipitate, the precipitate is washed with methanol, filtered, and dried to obtain a white polymer. Pyrene imine resin powder, 0.6 g of polyimide resin powder was dissolved in 9.4 g of T-butyrolactone, and a soluble polyfluorene imide solution (PI Γ 2) was prepared. 2,2-bis [4- (4-aminophenoxy) phenyl] propane 14.6 g of diamine compound and dianhydride compound [5, 5, -biisobenxofuranyl-1,3, Γ, 3'-tetraone] 10 · 3 g was put into the reactor, Pass in nitrogen and add none N-fluorenylpyrrolidone, reacted at room temperature for about 3 hours to form a polyfluorenic acid solution (PAA-1). Soluble polyfluorenimine solution (PI-2) and polyfluorenic acid solution (PAA -

1226363 _ Case No. 90112828 _ year month day__ V. Description of the invention (14) 1) After mixing in a weight ratio of 3: 1, dilute to a mixed resin solution with a solid content of 5%, and apply this alignment film solution Place it on the cleaned I TO substrate, heat it in an oven at 200 ~ 250 ° C until it is completely dry, remove the substrate and cool to room temperature. In order to test the characteristics of the present invention, the IT 0 substrate, which has been coated with the alignment film solution, baked to dryness and cooled to room temperature, is subjected to the following evaluation experiments: I. Alignment film pretilt angle measurement: The film is oriented, and finally a test liquid crystal cell is made. The Merck model is ZL 1-2 2 9 3 liquid crystal, and finally sealed with a sealant, and the pre-tilt angle is measured. Π · Alignment measurement: The liquid crystal cell for driving test is observed by polarizing microscope without abnormal domain. ΙΠ · Measurement of the toughness of the alignment film: The glass plate test piece containing the alignment film was prepared, and the film thickness of the alignment film was about 0. 0 5 ~ 0 · 1 5 / zm, fixed brushing conditions (pushing amount 0 5 nun, the rotation speed of the drum is 1000 rpm, the number of orientations is 40 times, the platform movement speed is 10 cm / mi η), the surface of the film is brushed, and finally the polarizing film is used to observe and compare the alignment film brushing. Surface state before and after. IV. DC residual potential measurement: After a fixed DC voltage is applied to the liquid crystal element, the maximum voltage remaining in the liquid crystal element is measured. V. Measurement of charge retention rate: After the test liquid crystal cell has been treated, '60 Hz 'IV electricity is applied' and its charge retention rate is measured.

Page 20 1226363 _Case No. 90112828_year month__ V. Description of the invention (15) "Figure 4" is the test result of the embodiment of the present invention, "Figure 5" and "Sixth Figure" are conventional techniques Polarized light microscope image of the toughness measurement of the alignment film and polarized light microscope image of the toughness measurement of the alignment film of the present invention. Therefore, it can be known that the weight percentage of the polyimide resin aggregate in the total resin solution is 1 to 30% It is preferably 6 to 20%. The second reagent (B) may be selected from one of the following compounds: polyamidic acid, soluble polyimide resin, a mixture of polyamic acid and soluble polyimide resin, Among them, the weight ratio of soluble polyfluorene imine resin to polyamino acid is 1/4 ~ 4/1, and most preferably 1/3 ~ 3/1. Although the present invention has been disclosed in the preferred embodiment as above, it is not used to limit the present invention. Any person skilled in the art can make some changes and decorations without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application.

Page 1226363 Case No. 90112828 Amendment Brief Description of the Drawings Figure 1 Structure diagram of the polyimide resin oligomer of the present invention. Fig. 2 Structure diagram of a polyamic acid of the present invention. Fig. 3 is a structural diagram of a soluble polyfluoreneimide resin according to the present invention. Fig. 4 Test results of an embodiment of the present invention. Fig. 5 Polarized light microscope image for measuring the toughness of the conventional alignment film. Fig. 6 is a polarized light microscope image for measuring the toughness of the alignment film of the present invention.

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Claims (1)

1226363 Case No. 90Π 2828 Revised ^, application for patent scope 1 · A liquid crystal alignment film composition for a liquid crystal display, the composition of the composition is as follows: (A)-polyimide resin oligomer, its structural formula is as follows As shown in I: m is an integer of 1, 2, or 3, R may be selected from one of aromatic compounds and cyclic aliphatics, X may be selected from the group consisting of amido, ester, and ether groups, and Y is A group of cholesterol structure; (B)-a second reagent; and (C) an induction process, the polyimide resin polymer is subjected to the induction process to cause moderate cross-linking, and the induction process is used to make the structure ( I) The method of opening the double bond and opening the double bond includes anion-initiated polymerization, heating-initiated polymerization, addition of peroxide-initiated polymerization, ultraviolet (UV) -initiated polymerization, and τ-ray initiation Polymerization. 2. The liquid crystal alignment film composition for a liquid crystal display according to item 1 of the scope of the patent application, wherein the polyimide resin oligomer contains a cholesterol structure-containing group Y, and may be selected from one of the following compounds: androstone (androsterone) compounds (and their derivatives), cholesterol (cholesterol), corticosterone acetate / lipid (corticosterone acetate), epi-androsterone (ep i androsterone), ergotristerol and sterol ( Page 23 1226363 _Case No. 90112828 _ Amendment Date __ Sale Six, Patent Application Range ergosterol estrone), Methyl 1 testosterone, Lanosterol, Mestranol, Pregsterone, Sitosterol ), Stigmasterol, testosterone, estry 1 amine, norethisterone, pregnenory1 ch1 oride, and 17- (1,5-dimethy 1-hexy1) -10, 13-dimethyl-hexadecahydro-cyclopenta [a ] phenanthrene ° 3 · The liquid crystal alignment film composition for a liquid crystal display according to item 1 of the scope of application for a patent, wherein the weight percentage of the polyfluorene imine resin aggregate to the total resin solution is 1 to 30% . 4. The liquid crystal alignment film composition for a liquid crystal display according to item 3 of the scope of the patent application, wherein the weight percentage of the polyfluorene imide resin oligomer in the total resin solution is preferably 6 to 20%. 5. The liquid crystal alignment film composition for a liquid crystal display according to item 1 of the scope of application for a patent, wherein the second agent may be selected from the group consisting of polyamic acid, soluble polyimide resin, polyamino acid, and soluble polyimide A group of amine resin mixtures. 6. The liquid crystal alignment film composition for a liquid crystal display according to item 4 of the scope of the patent application, wherein the structural formula of the polyamino acid is as shown in the following formula: lead R1 is a tetravalent organic group, R2 is a divalent organic group, and 11 is a positive integer. 7 · Liquid crystal display for liquid crystal display as described in item 4 of the scope of patent application Page 24 1226363 Case No. 90112828 _η Amendment t. Scope of patent application To the film composition, the structure of the soluble polyfluorene imine resin is as shown in the following formula π: (Π) R3 is a tetravalent organic group, R4 is a divalent organic group, and η is a positive integer. 8. The liquid crystal alignment film composition for a liquid crystal display according to item 4 of the scope of application for a patent, wherein a weight ratio of the soluble polyimide resin to the polydonkey acid is 20 to 80%. 9. The liquid crystal alignment film composition for a liquid crystal display according to item 8 of the scope of the patent application, wherein the weight ratio of the soluble polyimide resin to the polyamic acid is preferably 25 to 75%. Page 25