TW473497B - Low pretilt angle polyamic acid alignment materials - Google Patents

Abstract

A polyamic acid liquid crystal alignment materials comprises of aromatic tetracarboxylic acid derivatives which are polymerized by a non-polar aromatic dianhydride and selected diamines. The claimed liquid crystal alignment materials applying to liquid crystal device show excellent coating property, adhesion property and stability. The liquid crystal cell assembling by coating and heat curing of the claimed polyamic acid alignment materials, converted into cyclized polyimide alingment layer shows a pretilt angle value less than 2 degrees. The liquid crystal cells performing low pretilt angle property are applied in high duty twisted nematic (TN) liquid crystal display devices.

Description

473497

473497 LCD monitor. This product has good coatability, and it meets the requirements of the production method for commercialization. In order to achieve the purpose of the previous disclosure, Ying poly S & amino acid alignment raw pretilt angle is lower than 2. Yuan polyphosphonic acid, to make a pretilt corneal transistor acid solution closed high pretilt angle% aliphatic but its process into a linear super Twisted aziridine type (ch i ra The shortcomings of this conventionally known twisted direction, low pretilt alignment film is invented again, adhesive character. This hair can use Λ_A. _ Case No. 87113084 V. Description of the invention (2 ) Membrane's use of the amount of siloxane to control the wide viewing angle, super twisted nematic and thin profit JP 0 5 3 1 3 1 6 9-A Controlling the alignment film with polyamines, but only applicable to the alignment film coated with symmetrical aroma polymer) to control the pretilt angle. This patent, JP0 72872 35-A plus the pretilt angle, is only applicable to the patent JP 0 6 1 8 0 4 5 1-A using a poly-alignment film for optical smectic crystals' but its It has not been mass-produced. Due to the nature of the angle, it cannot be applied to high-specification alignment film materials. A novel alignment film material has another object of the invention to provide a curved nematic material. The production of high-transparency alignment film materials is new in the device. A kind of angle that can produce repeated single corrections, but it is only suitable for LCD monitors. Japan specializes in the degree of polyimide. In addition, W093006045-A is too complicated in polymer (amph i pha tic), and has low practicality. It is structured in alignment film, but its liquid crystal display. Polyamide-imide 1 smet ic liquid crystal display alignment film material is not low Pre-tilted LCD. The main object of the present invention is to provide an angle (< 2.0 degrees) characteristic. This material can be used for high-order twisting purposes to provide an alignment film, stability, # 刷 磨 性, and another purpose is to provide-an industrial method manufacturing, in line with the invention of a liquid crystal display film material and its manufacturing method . According to the present invention, a 0-degree alignment film material is

473497 Case No. 87113084 V. Explanation of the invention (3) 〇 II 0 0 人 八 II -II coch2ch2oc

ο IIc- Η "

/ XX

Wherein R is a bisamine group and the molar ratio x: y is 0.8 to 1.2. In the repeating unit of the alignment film material according to the present invention, κ is a bisamine group, which may be selected from the group consisting of a phenyl type bisamine group and two or two types of bis-type bismuth group which are suitable for the Λ-type double-strand type phenyl group. The amino structure is, for example: (a)

Η I Η -Ν ~ (〇 ^ Ν- (b) (c) (d) Ν- {〇) η (Η Η

The alignment membrane material invented by Nan Wenhong of Ben and Phenyl is a specially designed non-polar phenyl dihepatic diamine for polymerization reaction, preferably a condensation polymerization reaction, to generate a polyamino acid solution 'to be polymerized. After the amino acid is coated on the substrate, it is closed to form a polyimide by baking. Used in the polymer of the present invention

473497

473497 _ Case No. 87113084_ Year Month_g_ Amendment V. Description of the invention (5) The greater the viscosity, the higher the viscosity. When the mol ratio of dianhydride to bisamine is less than 1, a suitable end cap functional group can be added to make up for the difference and reduce the oxidation caused by the mol ratio not equal to 1. Phenomenon, and the applicable terminal functional group is selected from phthalic anhydride, maleic anhydride, aniline, and cyclo-hexyl amine. In order to match processability, the alignment film material of the present invention is diluted with an organic solvent to 4% to 10% by weight of an organic solvent to adjust the viscosity to facilitate subsequent alignment film processing processes. The applicable organic solvent is selected from the group consisting of N-methyl pyrrolidone (NMP); m-cresol; r-butylactone; N, N- N, N-dimethyl acetamide (DMAC); N, N-dimethyl formamide (DMF); ethylene glycol monobutyl ether , BC); diethylene glycol monoethyl ether (diethy 1 eneg 1 yc ο 1 m ο η oethy 1 ether, EC) and mixtures thereof, wherein ethylene glycol monobutyl ether and diethylene glycol monoethyl ether The amount should be controlled below ninety percent by weight. The present invention also provides a method for preparing a polyamic acid alignment film material, which is obtained by polymerizing a phenyl dianhydride and a bisamine, and is preferably performed by a condensation reaction. The polymerization reaction takes about 3 minutes to 24 hours to form polyamic acid, and a more suitable time is between 10 minutes to 6 hours. The temperature required for the polymerization is between -20 ° C and 120 ° C, and a more suitable temperature is between 0 ° C and 60 ° C. After the completion of the polymerization reaction, polyamic acid is obtained. The degree of polymerization is 10 to 5,000, the more suitable degree of polymerization is 40 to 250, the weight average molecular weight is 2,000 to 2,000,000, and the more suitable weight average molecular weight is 8,000 to 1,000.

473497 __Case number 87113084 __Year Month and Day___ V. Description of the invention (6) 5 0, 0 0 0. If necessary in the production method of the present invention, before adding the diamine, nitrogen gas can be introduced and extracted by means of evacuation, or even repeated several times to remove moisture such as oxygen from the reaction vessel. Thereafter, the dianhydride can be added in batches, for example in three additions to increase the molecular weight and viscosity of the polymer. In addition, in order to increase the polymerization degree and decrease the reaction time of the polymerization reaction of the present invention, a part of catalyst may be added. The applicable catalyst is selected from triethylamine (TEA), diethylamine, and n-butylamine ( n-butylamine); and d-pyridine. The function of the catalyst is to adjust the pH value of the solution and have a catalytic function, which can increase the polymerization degree and viscosity and reduce the reaction temperature. The solid content of the polymer to form the polyamino acid, that is, the weight percentage of the polymer relative to the solvent should be between 10% and 30%. After the reaction is completed, in order to adjust the viscosity or dilution to control the film thickness factor, the solid content should be adjusted to between 4% and 10%. The step of reacting polyamidate to form fluorene imine requires dehydration and ring closure. The commonly used method is high-temperature cyclization. The cyclization temperature is between 150 ° C and 400 ° C. The more suitable cyclization temperature is between 180 ° C and 320 ° C. The conversion time is between 3 minutes and 6 hours. Alignment membrane material In order to improve the adhesiveness of the alignment membrane, a small amount of silane coupling agent can be added. The commonly used coupling agent of Shixiyuan is selected from 3-aminopropyl trimethoxy silane); 3-aminopropyl triethoxy silane; 2-aminopropyl triethoxy silane; 2-aminopropyl trimethoxy silane;

Page 10 473497

^ 烧 基 # 肖 ropyl triethGxy sUane) and its mixing method Draw out, then add ethylene glycol and viscosity Moore number into a small amount of temperature, make, pure agent, miscellaneous materials, baking agent, and degree And nitrogen, and then use 丄 M M pumping method II of water and oxygen, and then add phenyl dianhydride after mixing, in order to maintain the high molecular weight Mole number at f to increase the molecular weight of bisamine, you can add After the temperature is controlled, the purification process is performed. The amine is dissolved in acetic acid, acetone, toluene, etc., and the washed solution is placed at a high temperature of 1700, and the solubility and viscosity of n-fluorenyl 1% pyrrolidone reach an appropriate range. Predecessor. Taking "preparing polyamic acid according to the present invention" as the first step, pass in a stirred reaction tank and repeat this step three times to remove the reaction volume of the diamine, and add a solvent to dissolve it. Adding Shuangxi ’can be divided into three additions, with a total of 0.8 to 1.2 (mole ratio). At this time, the catalyst is triethylamine, etc., and the reaction time is 3 minutes to 24 hours. The non-solvent can be dried with electronic grade water, acetone, toluene, etc. Thereafter, for example, by adding a Shibuya coupler through dilution, an alignment film having an appropriate film thickness after baking can be added. Therefore, the present invention provides an alignment film material having a liquid crystal material arranged at a low pretilt angle. The alignment film material is coated into an alignment film through a commercial coating machine such as blade coating, spin coating, etc., which meets the requirements of industrial alignment film modulation. In order to determine that the novel alignment film material of the present invention can produce an alignment film with a low pretilt angle, the alignment film material of the present invention has a low pretilt angle characteristic by making a liquid crystal cell and testing the pretilt angle. The liquid crystal sample is prepared by cleaning two pieces of indium antimony oxide (I T 0) glass and then coating the surface with the compound of the present invention.

Page 11 4/4 / Case No. 871 彳 如 Λ- Amendment V. Description of the Invention (8) Coating method to film material can be baked and baked at high temperature to form polyimide knife coating or spin coating After the prognosis, the liquid crystal cell is assembled, filled with liquid crystal, two-way film, and cooled by cooling the 'bristles and rubbing Bias Angle Tester (TBA). Using a pretilt angle tester (Tilt below 2 degrees, the pretilt angle of the invention can be achieved. If the measured pretilt angle is proved by this method to be the low pretilt angle of the present invention 4, the alignment film material that can be invented can produce a low pretilt angle. For non-polar phenyltetracarboxylic acid groups, the / pretilt ^ characteristics The principle is to produce a regular arrangement from the back, so that it can be matched with f㈣imine I and the effect of the friction angle of the bristles, so that the control = to the low pre-weighted vinyl 'improves wear resistance', reduces brush marks, and transparency Good: The foregoing and other objects and features of the present invention will be more prominent through the description of the examples. It should be understood that it is intended to illustrate the operation results of the present invention under better conditions, rather than === to the invention The scope is not limited, and the others are not deviated from the spirit of the invention. The modifications and changes are intended to be protected by the present invention. Example 1 In a 1 liter four-necked reaction bottle, a condensing tube, a thermometer, a feeding tube and a stirring rod were inserted, and nitrogen was added, and 3.2 4 g was added. Phenylene diamine (p ~ phenylene diamine) and 70 g of n-methylpyrrolidone solvent, stir for about 10 minutes 'add 3.94 g of ethylene glycol anhydrous 1,2,4 benzenetrimethyl ester, repeat this step 2 times' the last 1 After the second addition, add 15 g of n-pyridyl pyrrolidone,

Page 12 473497 _ cable number 87113084_ year month date-V. Description of the invention (9) Stir for 3 hours and precipitate with a large amount of toluene to obtain a solid 'confirmed by 1 R spectrum as a polyamic acid, its repeating unit The structure is as follows:

0 II

〇

After adding 46. 25 g of ethylene glycol butyl ether and 138, 75 g of n-methylpyrrolidone, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour to obtain a pale yellow polyamine solution, the viscosity is 50C.P., solid content is 7.5% 'weight average molecular weight is 29,800, and its pretilt angle is 0.92 degrees. Example 2 In a 1 liter four-necked reaction flask, a condenser tube, a thermometer, a feed tube and a stirring rod were respectively inserted, and nitrogen gas was added thereto. 5. Olg 4,4'-aniline (4, 4 '-oxy di am i ne) and 70 g of n-fluorenyl Ⅱ slightly burned ketone solvent, mixed for about 10 minutes, added 3. 35 g of ethylene glycol anhydrous 1,2,4 benzenetrimethyl ester, repeat this step twice, After the last addition, 10 g of n-methylpyrrolidone was added and mixed for 6 hours to 'precipitate with a large amount of toluene' to obtain a solid, which was confirmed to be polyamic acid by IR spectrum. The structure of the repeating unit is as follows:

With the addition of 120 g of ethylene glycol butyl ether and 360 g of n-methylπ-pylonolone

Page 13 473497 _ Case No. 87113084. Year _g ---------- V. Description of the invention (10) 0. lg of 3-aminopropyltrimethoxysilane, stirred for 1 hour 'to get β 7 7 度。 Light yellow polyamic acid solution, viscosity is 25C. P., solid content is 4%, weight average molecular weight is 2 1, 6 0 0, measured its pretilt angle is 1. 7 7 degrees. Example 3 In a 1 liter four-necked reaction flask, a condensing tube, a thermometer, a feeding tube and a stirring rod were respectively inserted, and nitrogen was passed in, and 5.10 g of 3 '3 -dimethyl-4,4'-diamine was added. Benzodibenzol (〇4〇11 ^ (1 丨 116) and 7 (n-methyl methyl ketone burning ketone solvent, stir for about 10 minutes, add 3.2 lg of ethylene glycol anhydrous 丨, 2 '4 Benzo Trimethyl Ester 'was repeated twice, and after the last addition, 15 g of n-fluorenylpyrrolidone was added, stirred for 6 hours, and poured into a large amount of toluene to obtain a solid, which was confirmed by IR spectrum to be polyamino acid. The structure of the repeating unit is as follows:

After adding 46.25 g of ethylene glycol butyl ether and 138.75 g of n-fluorenylpyrrolidone, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour to obtain a pale yellow polyamino acid solution, the viscosity is 7. CP, the solid content was 7.5%, the weight average molecular weight was 39,400, and its pretilt angle was measured to be 1.52 degrees. Example 4 In a 1-liter four-neck reaction flask, a condenser tube, a thermometer, a feed tube and a stirring rod were respectively inserted, and nitrogen gas was passed in, and 7.8 g of 2, 2′-di (4, (4-aminobenzyloxy) was added. (Phenyl) benzene) (2,2-bis- (4- (4-aminophenoxy) phenyl)

Page 14 473497 87113084_year month date_ five 'invention description (11) pr 〇pane) and 70 g of n-methylpyridine than slightly burned ketone solvent, stirred for about 10 minutes, force σ into 2. 52g of ethylene Alcohol anhydrous 1,2,4 benzenetrimethyl ester 'Repeat this step twice, add 15 g of n-pyridylpyrrolidone after the last addition, stir for 6 hours, and precipitate with a large amount of toluene' to obtain a solid, with IR spectrum The structure of the repeating unit proved to be polyamino acid:

After adding 90 g of ethylene glycol butyl ether and 270 g of n-methylpyrrolidone, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour, a pale yellow polyamino acid solution was obtained with a viscosity of 3 0 C _ 32 °。 P., the solid content is 4%, the weight average molecular weight is 28, 90 0, and its pretilt angle is 1.32 degrees. Example 5 In a 1-liter four-necked reaction flask, a condensing tube, a thermometer, a feeding tube, and a stirring rod were respectively inserted into nitrogen, and 2.82 g of phenylenediamine and 0.58 g of 4, 4'-aniline and 70 g were added. N-methylpyrrolidone solvent, stir for about 10 minutes, add 3.88g of ethylene glycol anhydrous h 2,4 benzenetrimethyl ester, repeat this step twice, and add 15g of n-pyridylpyrrolidone after the last addition , Stirred for 3 hours, precipitated with a large amount of ammonium, to obtain a solid, confirmed by IR spectrum as polyamic acid, the structure of its repeating unit is as follows:

Page 15 473497 _____ Case No. 87113084__ Month η King £ 5. Description of Invention (12)

〇〇 After adding 46. 25g of ethylene glycol butyl ether and 138.75g of n-fluorenyl to 17 ketones, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour, a pale yellow poly The amino acid solution has a viscosity of 80C. P. and a solid content of 7.5%. The weight-average molecular weight is 46, 8 0 ', and its pretilt angle is 0.83 degrees. Example 6 In a 1-liter four-necked reaction flask, insert the condenser tube 'thermometer', the feed tube and the stirring rod 'through nitrogen, and add 7.02 g of 2,2'-bis (4- (4aminophenoxy) Benzene) propane and 0.4 g of 3,3'-dimethyl-4,4, diamine bisbenzene and 70 g of n-pyridylpyrrole for brewing I solvent, stirred for about 10 minutes, and added 2. 52 g of ethylene glycol Anhydrous 1,2'4 trimethyl ester. Repeat this step twice. After the last addition, add 15 g of n-methylsmolanone and stir for 3 hours. Precipitate with a large amount of toluene. The spectrum was confirmed to be polyamic acid, and the structure of its repeating unit is as follows:

Page 16 473497 87113084, year V. Description of the invention (13)

HO—

〇 〇 II II ooc ^ c ^ oc- oh3c? / X / C-N- ^ O: ^ ΟΟη ^ Υ Η XC-〇H II ο Η 0 Cli \ -〇Η Correction

Η CH, Q9 After adding 58.75g of ethylene glycol butyl ether and 1.76.25g of n-fluorenylpyrrolidine, 0.1 g of 3-aminopropyltrioxolite, it was lightly stirred for 1 hour and lightened. 58 度。 Yellow polyamic acid solution, viscosity of 40 C. P., solid content of 6%, weight average molecular weight of 3, 8 0 0, measured its pretilt angle of 1. 58 degrees. Comparative Example 1 In a 1 liter four-neck reaction flask, 'insert a condenser tube, a thermometer, a feed tube, and a stirring rod', and pass in nitrogen gas, add 3.89 g of phenylenediamine and 70 g of n-pyridyl pyrrolidone solvent, and stir for about 10 minutes. Add 3. 6 5 g of 4,4'-diacid dianhydride (4,4, -oxydiphthalic anhydride), repeat this step 2 times, add 15 g of n-methylpyrrolidone after the last addition, and stir for 3 After hours, a large amount of toluene was precipitated to obtain a solid, which was confirmed to be polyamic acid by IR spectrum. The structure of its repeating unit is as follows:

Page 17 473497 Case No. 87113084 __ Month and Day __ϋ V. Description of the invention (14)

After adding 46. 25g of ethylene glycol butyl scale and 138.75g of n-pyridyl ketone, each of the ketones, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour to obtain pale yellow polyfluorene 11 度。 Acid solution, the viscosity is 6 〇c · p., The solid content is 7.5% 'weight average molecular weight is 3,600, and its pretilt angle is 4.11 degrees. Comparative Example 2 In a 1-liter four-neck reaction flask, a condenser tube, a thermometer, a feed tube and a stirring rod were inserted, and nitrogen was passed through. 7.247 g of 4,4'-aniline acid and 70 g of n-pyridylpyrrolidone solvent were added. Stir for about 10 minutes, add 2. 5 7 9 g of pyromellitic dianhydride 'Repeat this step 2 times, add 1 n-methylpyrrolidone' after the last addition. After 1 hour, a large amount of toluene was precipitated to obtain a solid, which was confirmed to be polyamine by 1 R spectrum. The structure of the repeating unit is as follows:

After adding 46.25g of ethylene glycol butyl ether and 1 38.75g of methyl methyl D to P each of the ketones' 0.1 g of 3-aminopropyltrimethoxysilane, stirred for 1 hour, simmered in light stomach yellow / Chromamic acid solution, viscosity is 9 0 C. Ρ., Solid content is 7. 5%; 1: 1 ^ ^

Page 18 473497 Case No. 87113084 Revision V. Description of the invention (15) The molecular weight is 50, 0 0 0, and its pretilt angle is 4 · 14 °. Comparative Example 3 In a 1-liter four-necked reaction flask, a condenser tube, a thermometer, a feeding tube and a stirring rod were respectively inserted, and nitrogen gas was added thereto, and 6.16 g of 3, 3'-dimethyl-4, 4'-diamine was added. Diphenylbenzene and 70 g of n-methylpyrrolidone solvent 'were stirred for about 10 minutes, and 2.99 g of difluorenone tetracarboxylic dianhydride (3, 3', 4, 4 '-benzophenone tetracarboxy1ic di anhydr i de), repeat this step twice, add 15 g of n-pyridylpyrrolidone after the last addition, stir for 6 hours, and precipitate with a large amount of toluene to obtain a solid, which is confirmed by IR spectrum as polyamino acid, which The structure of the repeating unit is as follows:

HO -C II o

〇 H Ο Ο 0 h3c II II 丨 丨 'τ

r〇H o After adding 6.25 g of ethylene glycol butyl ether and 138.75 g of n-methylpyrrolidone '0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour, a pale yellow polyamine solution was obtained. The viscosity is 80 C. P ·, the solid content is 7.5% 'weight average molecular weight is 47, 500, and its pretilt angle is 3.96 degrees. Comparative Example 4 In a 1 liter four-necked reaction flask, a condenser tube, a thermometer, a feeding tube and a stirring rod were respectively inserted, and 8.92 4 g of 2, 2'-bis (4- (4 —aminobenzyloxy) was added under nitrogen. ) Benzene) propane and 70g of n-methylpyrrolidone solvent, stir about

Page 19, 473497, Case No. 87113084, 3 ^ · V. Description of the invention (16) tetracarboxylic dianhydride), repeat this dream 2 times, 'After dare to add once, add 15 g of n-methylpyrrolidone, stir 3 After hours of precipitation with a large amount of toluene, a solid was obtained, which was confirmed to be polyamine by IR spectrum. The structure of its repeating unit is as follows:

After adding 46. 25 g of ethylene glycol butyl ether and 1 38. 75 g of fluorenylpyrrolidone, 0.1 g of 3-aminopropyltrimethoxysilane, and stirring for 1 hour, a light yellow polyamino acid solution was obtained. 'The viscosity is 80 C. P., the solid content is 7.5%, the weight average molecular weight is 45, 500, and its pretilt angle is 3.56 degrees. In summary, the good alignment film material of the present invention has a low pre-angle characteristic, can be applied to high-order twisted nematic liquid crystal displays, and it is manufactured by using polymerization, which has good mass productivity and industrial practical value. It should be suitable for Application for issuing = conditions for profit. Various changes and modifications according to the patent of the present invention ’order should still fall within the scope of the present invention, p / W, q / two.

Claims (1)

The number 87113084 The number 87113084 °° · π *. 1 a Its polyamic acid structure can be represented by the following 1. A poly (amino acid) alignment membrane material The general unit of the repeating unit is represented by: L〇 ο II HO —ϊ ο where R is a bisamino group and the molar ratio x: y is 0.8 to 1.2. 2. The alignment film material of item 1 of the patent application scope is suitable for generating a pretilt angle below 2.0 degrees. 3. The alignment film material according to item 1 of the application, wherein the bisamino group R is selected from the group consisting of a phenyl-type bisamine group and two or more phenyl-type bisamine groups. 4. The alignment film material according to item 1 of the patent application, wherein the bisamino group R is selected from the following bisamine groups and mixtures thereof: Page 21 2001.10. 08. 021 H · / Scope of patent application ^ > > §2113084 _Ά Amendment (a) (b) (c) (d) (e) ν- ^ Ο ^ Ο ^-^ Ο ^ -ν-; 5. For example, the application of patent No. 3 to phenyl dianhydride and ammonium, the alignment membrane material, wherein polyamine amino R & & amine is obtained by polymerization reaction. 6. For example, the scope of the formazan patent 坌, aligning film materials with phenyl dianhydride and bisamine j, in which the polyamido acid is based on the scope of the patent application. Ethylene glycol anhydrous U, 4 stupid: A bidirectional membrane material of item A, in which the phenyl double liver is ethylene glycol bis (anhydro-trimeliitate). For example, the alignment film of the scope of application for the fifth item of the following groups and their mixtures: needle, T-bisamine is selected from Page 22 2001.10.08. 022 Λ 473497 __ Case No. 87113084_ Amendment Date 6. Patent application scope (a) (b) 2ην- <^-νη2; 2ην-(^ 〇) -〇- ^ 〇 ) -νη2; (c) (d), hn- ^ 〇)-(〇) ^-nh2; 2hn- (〇 ^ 〇 ^ 〇) -nh2; 9. For example, the alignment film material of the scope of application for patent, wherein the polymerization degree of polyamic acid is 10-5, 00. 10. The alignment film material according to item 1 of the scope of patent application, wherein the degree of polymerization of polyamic acid is 40 ~ 250. 11. For example, the alignment film material of the first patent application range, wherein the weight average molecular weight of the polyamic acid is 2,000 ~ 2,000,000. 12. For example, the alignment film material of the scope of patent application, wherein the weight average molecular weight of the polyamic acid is 8,000 ~ 50,000. Page 23 2001.10.08. 023