TWI275630B - Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them - Google Patents

Abstract

To provide a vertical orientation type composition having excellent heat resistance, transparency, surface hardness and vertical orientation, to provide a liquid crystal oriented film using the same, and to provide a liquid crystal cell. The vertical orientation type composition containing a low polar polyamic acid resin, the liquid crystal oriented film and the liquid crystal sell using the same are provided. In more detail, a new polyamic acid-mixed composition has excellent heat resistance, surface hardness, transparency and liquid crystal orientation and prepared by mixing a polyamic acid derivative with a low polar polyamic acid resin in a proper ratio, wherein the low polar polyamic acid resin is prepared by solution-polymerizing an acid dianhydride with aromatic diamines containing an imide ring-containing side chain-having aromatic diamine. The liquid crystal oriented film has low surface roughness and highly excellent printability, heat resistance and transparency using the polyamic acid composition. The liquid cell has a pretilt angle of above 89 DEG and a voltage retention of above 99%.

Description

1275630 发明, invention description: The present invention relates to a vertical alignment type composition containing a low polarity polyphthalic acid resin and a liquid crystal alignment film and a liquid crystal cell using the vertical alignment type composition, more specifically, The present invention relates to a novel polyphthalic acid mixed composition, and a liquid crystal alignment film having a very excellent low surface roughness, printability, heat resistance and transparency using the polyamic acid mixed composition, and using the same A liquid crystal unit cell having a pretilt angle of 89 degrees or more and a voltage holding ratio of 99% or more of the polyaminic acid mixed composition. The novel polylysine mixed composition has excellent heat resistance, surface hardness, transparency, and alignment of liquid crystals, and is obtained by mixing a low-polarity polyamic acid resin and a poly-proline derivative at an appropriate ratio. The low-polarity polyacrylic acid resin is obtained by solution polymerization from a dianhydride (containing an alicyclic dianhydride) and an aromatic diimide (an aromatic diamine having a sulfhydryl ring side chain group). . [Prior Art] In general, a polyimine resin refers to an aromatic tetracarboxylic acid or a derivative thereof which is polycondensed by an amidation reaction with an aromatic diamine or an aromatic diisocyanate. Heat resistant resin. The polyimine resin can have various molecular structures depending on the kind of the monomer to be used. Usually, the aromatic tetracarboxylic acid component may be pyromellitic dianhydride (PMDA) or bisphthalic acid dianhydride (BPDA), and the aromatic diamine component may be p-phenylene diamine (p-PDA). M-phenylenediamine (m-PDA), 4,4-oxydiphenylamine (ODA), 4,4-methylenediphenylamine (MDA), 2,2-diaminophenylhexafluoropropane (HFDA) , bis-aminophenoxydiphenyl hydrazine (m-BAPS), p-diaminophenoxydiphenyl hydrazine (;?-; 6 VIII? 3), 1,4-diaminophenoxybenzene ( TPE-Q), l,3-diaminophenoxybenzene (butyl?-11), 2,2-diaminophenoxyphenylpropane (BAPP), 2,2-diaminophenoxy Phenyl hexafluoropropane (HFBAPP) or the like is obtained by condensation polymerization. Most of the polyimide resin is insoluble and infusible. The high heat resistant resin has (1) excellent heat and oxidation resistance, (2) high temperature, 1275630 (3) and long period of about 260 °C. The temperature and the short-term temperature of about 480 ° C can be used, and the temperature is excellent in heat resistance, (4) radiation resistance, (5) excellent low-temperature characteristics, and (6) excellent chemical resistance. However, only the polyimine resin has such a characteristic, which is caused by the formation of a charge transfer complex, has low light transmittance in the visible light field, and is difficult to be applied to a field requiring transparency. The problem exists. Therefore, various types of main chain type aliphatic polyimine resins have been produced and used in fields requiring excellent light penetration such as liquid crystal alignment films. The polyimine resin for liquid crystal alignment film which has been introduced into the alicyclic group in the main chain has been developed so that a long burnt chain group is introduced into the side chain in order to exhibit a pretilt angle, and a representative one can be dissolved. A soluble polyimine resin and a polyaminic acid resin in a solvent. However, in the case of a soluble polyimine resin, there is a problem of poor printability due to poor solubility in a usual organic solvent, and a polymethylamine-based alignment film has a voltage holding ratio (VHR, v〇) due to high surface polarity. Ltage h〇ldingchuan (4) reduces the disadvantages. However, in order to apply it as an alignment film that can adapt to various driving methods, it is required to control the pretilt angle. For the purpose of sexuality, transparency, and transparency, the use of polyimine-based trees has low solubility and low voltage retention. It has been found that a low-polarity alicyclic polyglycine is derived. The composition is not only 'and has excellent heat resistance, and the present invention has been completed. The composition has excellent heat resistance and a direct alignment type composition. The above-mentioned vertical alignment type composition has excellent printability and richness, and has excellent pretilt angle. In order to solve the problem of the light transmittance and the problem of the liquid crystal alignment film, the present inventors have intensively studied the proline resin, with an aromatic or a solution. Under the certain ratio, the mixed agent has excellent solubility, surface hardness and vertical alignment. The purpose of the present invention is to provide a surface hardness and vertical alignment. The other object of the present invention is to provide a A liquid crystal alignment film having a low surface coarseness and a liquid crystal cell having a voltage retention of 4 1275630. According to an embodiment of the present invention, the present invention provides a mixture of low polarity side chains represented by the following formula (1) A vertical alignment type composition comprising a proline resin and a polyglycine derivative represented by the following formula (2).

[Chemical Formula 2]

In the formula

)OC )〇Λ〇( )σ°τ〇( )03⁄4 (6)

One or two or more kinds of tetravalent groups of Dr ° ° ° ° ° C ch3 must contain one selected from the structural formula 1275630 (a), (b), (c), (d), and (e) Species or two or more alicyclic tetravalent groups; and each of the steroids selected from CF3 ' > , , ~<0>-8(f)

0-ss^N^gQ (CH 2)nCH 3 (where n is a natural number in the range of 1 to 30), or two or more kinds of divalent groups, and the above-mentioned formula (f) The aromatic divalent group of the side chain of the succinimide; the "natural number of the range", in addition, according to the invention. The composition of the polyamic acid mixture described above provides a smear cell. According to the present invention, a liquid crystal alignment film and a liquid are provided, and a mixed composition of polyglycine is provided, and the poly 6 1275630 urethane mixed composition has a right side polar side chain, which not only has a non-:: Amino acid, which has a novel structure and low use as a demanding property and a high pretilt angle, is a liquid alignment film for TFT_TN and STN LCD and various tip heat-resistant structural materials which are used for the characteristics of the 赦 瞪 瞪 久 久 久 久[Embodiment] The present invention will be described in detail below. The second aspect of the present invention relates to a vertical alignment type composition, which is a polyglycine tree containing a low-polarity side chain represented by tm·(1). , a lysine derivative of the formula (2), which is represented by the formula (2). A liquid crystal alignment film or a liquid crystal cell having excellent heat resistance, transparency, surface hardness, high voltage holding ratio, and pretilt angle, is formed by coating a vertical alignment type composition, and then a formula (1) The polyamic acid resin containing a low-polarity side chain is used, and the poly-proline derivative represented by the above formula (2) is used in a mixing ratio of 1 to 99% by weight: to 99% by weight. The present invention relates to a polyamic acid resin containing a low-polarity side chain represented by the above formula (1) and a poly-proline derivative represented by the above formula (2), which is an aromatic tetracarboxylic acid or a derivative thereof. The aromatic diamine or the aromatic diisocyanate is obtained by polycondensation, and may have various molecular structures depending on the kind of the monomer to be used. Usually, the aromatic tetracarboxylic acid monomer may be selected from pyromic acid dianhydride. (PMDA), diphenyl ketone tetracarboxylic dianhydride, hydroxybiphenyldicarboxylic dianhydride, biphenyl dicarboxylic acid dianhydride (BPDA), and hexafluoroisopropylidene dianhydride dianhydride are used. Further, the aromatic diamine monomer can usually be selected from p-phenylene diamine (P-PD). A), m-phenylenediamine (m-PDA), 4,4-oxydiphenylamine (ODA), 4,4-methylenediphenylamine (MDA), 2,2-diaminophenyl hexafluoropropane (HFDA), m-diaminophenoxydiphenyl hydrazine (m-BAPS), the word bis, aminophenoxydiphenyl MQ9-BAPS), 1,4-diaminophenoxybenzene (TPE- Q), 1,3-diaminophenoxybenzene (TPE-R), 2,2-diamino-p-phenylene phenylpropane (BAPP), 2,2-diaminophenoxyphenyl hexa Fluoropropane a (HFBAPP) or the like is used. 1275630, the present invention relates to a poly-proline derivative represented by the low-polarity side acid tree represented by the above formula (1) and the above formula (2), except for the former = The aromatic monomer also contains the above structural formula: an aliphatic tetracarboxylic dianhydride monomer and a diamine monomer having the above structural formula === subf = aromatic diamine as an essential component: Ϊ Polymerization manufacturing. The above-mentioned (1) is a poly-aromatic dianhydride containing a low-polarity side chain. The usual aromatic tetra-(tetra) monomer is: acid: contains an aliphatic tetracarboxylic dianhydride, and is selected. Free U2,3, deducted butane tetracarboxylic dianhydride [CBDA, (a)], 1,2,3,4-cyclopropane tetracarboxylic dianhydride [CPDa 5-(2,5-dioxotetrahydrofuranyl) -3·Methylcyclohexane-U2-dicarboxylic acid II [DOCDA, (c)], 4-(2,5-di-oxytetrahydrofuranyl)·tetrahydroindole-1,2·dicarboxylate Acid dianhydride [DOTDA; (d)], and one or more aliphatic tetracarboxylic dianhydrides of octene-2,3_5,6•tetracarboxylic dianhydride [BOD A ; (e)] Essential ingredients. In the case of ^, the amount of the aliphatic tetracarboxylic dianhydride represented by the above structural formulae (a) to (6) is based on the total diacid anhydride monomer! ~99% of the range is used. When the polyamic acid resin containing a low-polarity side chain represented by the former formula (1) has a side bond group having an aliphatic group, it also combines the characteristics of a burnt amber quinone imide group. The diamine monomer, in addition to the usual aromatic diamine monomer, also contains the alkyl amber-bromide-substituted pericyrene-free diamine represented by the above structural formula (f) as an essential component for the polymerization. Manufacturing. In this case, the amount of the aromatic diamine represented by the above structural formula (f) is in the range of 1 to 99 mol% based on the total diamine monomer. Thereby, the novel mixture prepared by using the aromatic diamine represented by the above (f) as an essential monomer is obtained by mixing with a polyaminic acid resin (introduction of a succinate substituted with a low polarity alkyl group) The side chain group is mixed to improve transparency, printability, and mechanical properties, and the electrooptical characteristics of the liquid crystal cell made using the above composition are particularly improved. The polyamic acid resin containing a low-polarity side chain represented by the above formula (1) has a weight average molecular weight (Mw) of 5,000 to 15 Å, a 〇〇〇g/mole range, and an intrinsic viscosity of 0·1~ In the range of 1.5dL/g, the glass transition temperature is 1275630 15 0~300 C fe. Also a soluble polyimine resin represented by the former formula (1), p-dimethylacetamide (DMAc), dimercaptocarboxamide (DMF), N-mercapto-2-pyrrolidone An organic solvent such as (NMP), an aprotic polar solvent such as acetone or ethyl acetate, such as m-phenol, has a property of being easily dissolved at normal temperature. Further, since the polyphthalic acid derivative represented by the above formula (2) is used as a dianhydride single-system, the aliphatic tetracarboxylic anhydride represented by the structural formulae (a) to (e) is an essential monomer, and therefore It is possible to produce a poly-proline derivative which can improve the mechanical properties and minimize the deterioration of the scratch resistance while also improving the printability. The polyamic acid derivative represented by the above formula (2) is prepared by solution polymerization from the composition of the aforementioned monomers, and has a weight average molecular weight (Mw) of 10,000 to 200,000 g/mole, and an intrinsic viscosity of 〇3~ 2 〇dL / g range 'glass transition temperature is 200 ~ 40 (TC range, yttrium imidation 200 ~ 300 ° C range characteristics. Then the formula (2) represented by the poly-proline derivative again ' π 1 river Such as dimethyl acetamide (DMA), dimercaptoamine (DMF), Ν 曱 _2 _2 " pyrrolidone (ΝΜΡ), acetone, ethyl acetate and other aprotic polar cresols and other organic The solvent has a property of being easily soluble at room temperature. I. Low-boiling solvent such as dihydrofuran (THF) or chloroform, and r~-like = 疋. For a solvent, it has a high solubility of 10% by weight or more at room temperature. It also shows high solubility. Moreover, it is made by using a method generally used in the field, coating a human fire, a poly-proline resin represented by a low-polarity side chain, and a precursor acid derivative (1). The liquid crystal alignment film or liquid jin indicates the result of the optical characteristics of the brewing, and the pretil angle is 87. The price of the voltage is 98.0 ~ 99 q. The range voltage (residual-DC) is in the range of 1 〇〇 ~ 400 mV. As the above %, the residual electricity is in the maintenance of poly-proline In addition to the excellent characteristics of the original, the characteristics of the two characteristics are excellent, so it can be used as a heat-resistant material with various types of =w and liquid crystal space, aviation and other cutting-edge industries. Instruments, Electronics, (Example) The present invention will be described in detail by the following examples, which are not limited thereto, and may be variously modified and modified within the scope of the technical idea of the present invention. [Manufacturing Example 1] 1- Preparation of (3,5-diaminophenyl)-3-(1-hexene)-succinimide (DN-IM-6) while slowly passing nitrogen through a 250 mL reaction equipped with a stirrer and a nitrogen injection device After dissolving 9.2 g (0.05 mol) of 3,5-dinitroaniline in 50 mL of acetic acid as a reaction solvent, 9.1 g (0.05 mol) of 2-hexen-1-yl group was added by nitrogen gas. - Succinic anhydride, refluxed for 24 hours. After cooling the reaction solution at normal temperature, a precipitated solid was obtained.

The solid obtained above was recrystallized from methyl alcohol to obtain 12.7 g of 1-(3,5-diaminophenyl)-3-(1-hexene)-succinimide (DN-IM- 6) (yield 73%). [Production Example 2] Production of 1-(3,5-diaminophenyl)-3-(1-octene)-succinimide (DN-IM-8) except for the use of 〇.5 g (0.05 mol) The same reaction as in the above Production Example 1 was carried out except that 2-octene-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-octene)-amber imine (DN-IM-8). The solid obtained above was recrystallized from decyl alcohol to obtain 1 3 · 1 g of 1-(3,5-diaminophenyl)-3-(1-octene)-succinimide (DN- IM-8) (yield 70%).

[Manufacturing Example 3] Production of 1-(3,5-diaminophenyl)-3-(1-decene)·sodium bromide (DN-IM-10) except for the use of 11.9 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-decene-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl)- 3-(1-decene)-succinimide (DN-IM-10). The solid obtained above was recrystallized from decyl alcohol to obtain 14.5 g of 1-(3,5-diaminophenyl)-3-(1-decene)-succinimide (〇>1 -1]\1-10) (yield 70%). [Manufacturing Example 4] Production of 1-(3,5-diaminophenyl)-3-(1-dodecene)-succinimide (DN-IM-12) 10 1275630 In addition to the use of 13.3 g (0.05 Mo The same reaction as in the above Production Example 1 was carried out except that 2-dodecen-1-yl-succinic anhydride of the ear was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminobenzene). Benzyl-3-(1-dodecene)-succinimide (DN-IM-12). The solid obtained above was recrystallized from decyl alcohol to obtain 14.0 g of 1-(3,5-diaminophenyl)-3-(1-dodecene)-succinimide (DN-IM). -12) (yield 65%). [Production Example 5] Production of 1-(3,5-diaminophenyl)-3-(1-tetradecene)-succinimide (DN-IM-14) except for the use of 14.7 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-tetradecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-tetradecene)-succinimide (DN-IM-14). The solid obtained above was recrystallized from methanol to obtain 14.9 g of 1-(3,5-diaminophenyl)-3-(1-tetradecene)-succinimide (DN-IM-14). ) (yield 65%). [Manufacturing Example 6] Production of 1-(3,5-diaminophenyl)-3-(1-hexadecenyl)-succinimide (DN-IM-16) except for the use of 16.1 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-hexadecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-hexadecenyl)-succinimide (DN-IM-16). The solid obtained above was recrystallized from decyl alcohol to obtain 1 5.4 g of 1-(3,5-diaminophenyl)-3-(1-hexadecenyl)-succinimide (DN-IM). -16) (yield 63%). [Production Example 7] Production of 1-(3,5-diaminophenyl)-3-(1-octadecene)-succinimide (DN-IM-18) except 17.5 g (0.05 m) was used. The same reaction as in the above Production Example 1 was carried out except that 2-octadecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-octadecene)-amber imine (DN-IM-18). The solid obtained above was recrystallized from decyl alcohol to obtain 16.2 g of 11 1275630 (3,5-amine-aldolyl octadecene)-succinimide (DN-IM-18) (yield 63%) ). [Production Example 8] Production of U(3,5-diaminophenyl)-3-hexyl-succinimide (DA-IM-6) ^ Dn*IM-6 6,9 g (0.02 mol) dissolved in i〇〇mL of NMP and ethanol (1/3 volume ratio), and 〇 & pd / c (5%) catalyst (in the carbon particles, coated with 5% of the amount of I bar metal catalyst After the hydrogen reactor was simultaneously charged, the reduction reaction was carried out at 60 C for 2 hours. After the reaction product was filtered, the reaction solvent was distilled under reduced pressure.

The above-obtained solid was recrystallized in a co-solvent of hexane/ethyl acetate to prepare 3.18 g of 1-(3,5-diaminophenyl)-3-hexyl-succinimide (DA-IM). -6) (yield 55%) 〇 [Production Example 9] K (3,5-diaminophenyl)-3-octyl-succinimide (DA-IM-8) was produced in addition to 7.5 g. (〇·02 Moer) dn-IM-8 The same reaction as in the above Production Example 8 was carried out except for DN-IM-6 to obtain a diamine-based group -3 -octyl-succinimide (da_im- 8). The solid obtained above was recrystallized from methanol to obtain 3 · 6 8 g of 1-(3,5-diaminophenyl)-3-octyl-succinimide (Da-IM-8) ( Yield 5 8%) ° [Production Example 10] 1-(3,5-diaminophenyl)-3-indolyl-succinimide

(DA-IM-10) Production The same reaction as in the above Production Example 8 was carried out except that 8.1 g of DN-IM-10 was used instead of DN-IM-6 to obtain a diamine phenyl group. )-3-mercapto-pyrazine (DA-IM-10). The solid obtained above was recrystallized from decyl alcohol to obtain 4 to 15 g of 1-(3,5-diaminophenyl)-3-indolyl-succinimide (DA-IM-10) ( Yield 60%) ° [Production Example 11] Production of 1-(3,5-diaminophenyl)_3-dodecyl-succinimide (DA-IM-12) except 8.6 g (〇. The same reaction as in the above Production Example 8 was carried out except that DN-IM-12 was used instead of DN-IM-6 to obtain 1-(3,5-diamine 12 1275630 phenyl)-3-dodecane. Alkyl-succinimide (dA-IM-12). The solid obtained above was recrystallized from hexane/ethyl acetate to give 4.48 g of 1-(3,5-diaminophenyl)-3 -doderyl-dipperimide (DA- IM-12) (yield 60%). [Production Example 12] M3,5-diaminephenyl)-3-tetradecylsuccinimide (DA-IM-14) was produced except that 9.2 g (0.02 mol) of DN-IM-14 was used. The same reaction as in the above-mentioned Production Example 8 was carried out, except for DN-IM-6, to obtain the crude diamine phenyl)-3-tetradecyl-succinimide (DA-IM-14). The solid obtained above was recrystallized from decyl alcohol to obtain 5.6 g of 1-(3,5-diaminophenyl)-3-tetradecyl-succinimide (DA-IM-14) ( Yield 70%). [Production Example 13] M3,5-diaminephenyl)-3-hexadecyl-succinimide (DA-IM-16) was produced except that 9.8 g (0. 〇 2 mol) of DN was used. The same reaction as in the above Production Example 8 was carried out except that DN-IM-6 was used to obtain 1-(3,5·diaminophenyl)-3-hexadecyl-succinimide (DA-IM). -16). The solid obtained above was recrystallized from hexane/ethyl acetate to obtain 6.01 g of 1-(3,5-diaminophenyl)·3 -hexadecyl-succinimide (DA-IM). -16) (yield 70%). [Production Example 14] Production of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DA-IM-18) except for the use of 10.3 g (〇.〇2 Mo) The same reaction as in the above Production Example 8 was carried out except that DN-IM-18 was used instead of DN-IM-6 to obtain 1-(3,5-diaminophenyl)-3-octadecyl-succinimide ( DA-IM-18). The solid obtained above was recrystallized from hexane/ethyl acetate to give 6.87 g of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DA-IM). -18) (yield 75%). The diamine monomers DA-IM-6 to 18 having the low-polarity alkyl-substituted amber imine side chain group obtained in the above Production Examples 8 to 14 can be confirmed to have a yield of 50% after recrystallization. The above 'and shows that it has very good storage stability in the air. 13 Ϊ 275630 [Production Example 15] Production of polyamic acid anhydride (PAA-1) containing a low-polarity side chain, while slowly passing nitrogen gas through a 250 mL equipped with a stirrer, a temperature adjusting device, a nitrogen gas injection device, and a cooler In the reactor, 9.15 g of (u,5-diaminophenyl)-3-octadecane was dissolved in N-methyl-2-pyrrolidone as a reaction solvent. After the base-succinimide (DA-IM-18), 5.28 g (0.02 mol) of 5-(2,5-dioxytetrahydrofuran)-3-A was slowly added by nitrogen. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and while stirring at a reaction temperature of 〇 ° C or lower for 24 hours, a polyaminic acid solution (PAA-1) was obtained. [Production Example 16] Production of polyamic acid anhydride (pAA-2) containing a low-polarity side chain, while slowly passing nitrogen gas through a 25 mL reaction equipped with a stirrer, a temperature adjusting device, a nitrogen gas injection device, and a cooler 1. Dissolve 9.15 g of 1-(3,5-diaminophenyl)-3-octadecane in N-mercapto-2-pyrrolidone as a reaction solvent. After the base-succinimide (DA-IM-18), a solid 3.92 g (0.02 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was slowly added while passing nitrogen. . At this time, the solid content concentration (s〇Hd content) was fixed at 20% by weight, and while stirring at a reaction temperature of 〇°c or lower for 24 hours, a polyaminic acid solution (paA-2) was obtained. [Production Example 17] Production of polyacrylic acid (PAA-3) While slowly passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen gas injection device, N-mercaptopyrrolidone as a reaction solvent was used. After dissolving 19.8 g (0.1 mol) of methylenediphenylamine, a solid 19.6 g (〇1 mol) of 12,3,4·cyclobutane tetracarboxylic dianhydride was slowly added while passing nitrogen. At this time, the solid content concentration (s〇lid content) was fixed at 15 wt%, and the reaction temperature was kept under the crucible for 36 hours to obtain a polyaminic acid solution (PAA-3). [Production Example 18] Production of soluble polyamido resin (SPI) while passing nitrogen gas slowly through a 25 〇 mL reactor equipped with a stirrer, a temperature adjustment device, a nitrogen gas injection device, and a cooler, as a reaction Dissolving 9.15 g (0.02 mol) of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide in N-mercapto-2-pyrrolidone dissolved in 14 1275630 After (DA-IM-1 8), a solid 5·28 g (0·02 mol) of 5-(2,5-dioxotetrahydrofuran)-3-fluorenyl group was slowly added while passing nitrogen gas. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and the mixture was stirred for 24 hours while maintaining the reaction temperature at 0 ° C or lower to obtain a polyamic acid solution.

To the above polyamic acid solution, 6.12 g (0.06 mol) of acetic anhydride and 0.1 g (0.1 mol) of pyridine were added, and after stirring at room temperature for 24 hours, stirring at 120 ° C for 3 hours, and then washing with methanol. Several times, a soluble polyamine resin (SPI) was obtained. [Example 1] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-2) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 1.97 g of the low-polar side chain-containing polypolymer of the above-mentioned Production Example 15 was dissolved in 80 g of N-mercapto-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The proline resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 17 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 2] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-3) containing a low-polarity side chain

While slowly passing nitrogen through a 100 mL reactor equipped with a stirrer and a nitrogen injection device, 80 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2 - 4·16 6 g of the polyamic acid resin solution containing the low-polarity side chain of the above-mentioned Production Example 15 and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were dissolved in butoxyethanol, and stirred for 24 hours. A solution with a viscosity of 25 cps was obtained. [Example 3] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-4) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device Dissolved in a solution of 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. 15 1275630 16.073 g of the low-polarity side chain of the above-mentioned production example 15 The polyamic acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 4] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-5) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 100 mL reactor equipped with a stirrer and a nitrogen gas injection device. Dissolving 3 7 · 5 0 3 g of the above-mentioned production example 15 in 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent The polyamic acid chain resin solution of the low polarity side chain and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 c ps. [Example 5] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-6) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 87.5 g of the above-mentioned production example 15 having a low-polarity side chain was dissolved in 75 g of N-mercapto-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. A solution of the amino acid resin and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 6] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-7) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 337.3 g of the low-polarity side chain-containing polyamine contained in the above-mentioned Production Example 15 was dissolved in 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 7] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-8) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device Dissolve 0.765 g of 16 1275630 in 80 g of N-mercapto-2-pyrrolidone as a diluent solvent, 120 g of butyrolactone, and 60 g of 2-n-butoxyethanol. The polyfluorene-containing polyfluorene of the above-mentioned Production Example 16. The amino acid resin solution and 5 μg of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 8] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-9) containing a low-polarity side chain

While slowly passing nitrogen through a 100 mL reactor equipped with a stirrer and a nitrogen injection device, 80 g of N-methyl-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxy group as a diluent solvent were used. LMeg was dissolved in hexan. The poly-proline lysate solution containing the low-polarity side chain of the above-mentioned Production Example 16 and 5 〇g of the polyamic acid solution of the above-mentioned Production Example 17 were stirred for 24 hours to obtain a viscosity of 25 cps. Solution. [Example 9] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-10) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 1000 mL reactor equipped with a stirrer and a gas injection device. Dissolving 々.bGg in 80 g of N-methyl-2-pyrrole ketone, l2 〇g 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent, and the low-polarity side chain of the above-mentioned production example 16 The polyamic acid resin solution and 5 μg of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 1 0] Manufacture of a mixture of a poly (amino acid) resin and a polyaminic acid (BPAA-11) containing a low-polarity side chain

While slowly passing nitrogen through a l〇〇〇mL reactor equipped with a stirrer and a nitrogen injection device, 75 g of N-methyl-2-pyrrolidone as a diluent solvent, 120 g of 7-butane, and 6 〇g2 - n-butoxyethanol dissolved l6. 〇 5g The polyamic acid resin solution containing the low polarity side chain of the above-mentioned production example 16 and 5 〇g of the polyamic acid solution of the above-mentioned production example 17 were stirred for 24 hours. A solution having a viscosity of 25 cps was prepared. [Example 11] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-12) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 10,000 mL reactor equipped with a stirrer and an atmosphere injection device. Dissolving 17 1275630 37.5 〇 3 g of the low-polarity side chain of the above-mentioned Production Example 16 in 75 g of N-methyl-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent The polyamic acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 1 2 ] A mixture of a polyamic acid resin having a low-polarity side chain and a poly-aracine acid? Manufacture of eight people-13)

Nitrogen gas was slowly passed through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device while being used as a diluent solvent for 75 g of N-methylpirolone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol. 87.5 g of the polyamic acid resin solution containing the low-polarity side chain of the above-mentioned Production Example 16 and 5 μg of the polyamic acid solution of the above-mentioned Production Example 17 were dissolved, and stirred for 24 hours to obtain a solution having a viscosity of 25 cp. . [Example 1 3] Production of a mixture of a polyamic acid resin containing a low-polarity side chain and a poly-aracine acid (BPAA-14) while passing nitrogen gas through a reaction of 1000 mL equipped with a mixer and a nitrogen injection device 337*3g of the low-polar side chain of the above-mentioned production example 16 was dissolved in 75 g of N-methylbihadone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The proline resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

[Comparative Example 1] Production of a polyamic acid resin (PAA_1) containing a low-polarity side chain, while slowly passing nitrogen gas through a 25 OmL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, as a reaction solvent Dissolving 9.15 g of 1-(3,5-diaminophenyl)-3-octadecyl-spholeimide in N-methyl-2-pyha-β- ketone After (DA-IM-18), slowly add 5.28 g of solid (5,5-dioxanthene) to the solid. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was kept at 〇 ° C for 24 hours while maintaining the reaction temperature to obtain a polyaminic acid solution (PAA-1). [Comparative Example 2] Production of a polyamic acid resin (PAA-2) containing a low-polarity side chain while slowly passing nitrogen gas through a 25 OmL reactor equipped with a stirrer, a nitrogen gas injection device, and an 18 1275630 cooler 9.15 g (0.02 mol) of 1-(3,5-diaminophenyl)-3-octadecyl-sodium imine (dissolved in the reaction solvent) in methyl 2-pyrrolidone ( After DA-IM-18), a solid 3.92 g (0.02 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid was added slowly through the atmosphere. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was kept at 0 ° C or lower for 24 hours to obtain a polyaminic acid solution (PAA-2). [Comparative Example 3] Production of polyacrylic acid (PAA-3) while passing nitrogen gas slowly through a 500 mL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, while using N-methyl-2 as a reaction solvent After dissolving 19·8 g (0.1 mol) of the hydrazine diphenylamine in the pyrrole group, 19.6 g (0.1 mol) of 1, 2, 3, 4 was slowly added to the solid by nitrogen gas. - Huan Ding Hyun four acid and two wild. At this time, the solid content of the solid content was fixed at 15% by weight, and the reaction temperature was maintained at 〇 for 3 hours while stirring to obtain a polyaminic acid solution (PAA-3). [Comparative Example 4] Production of polyaminic acid (PAA-4) containing soluble polyimine, while passing nitrogen gas slowly through a 500 mL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, as a diluent solvent 〇 〇 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N 3 9 5 g of the above-mentioned soluble polyimide solution of Production Example 18 was stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Experimental Example 1] The solutions prepared in accordance with the above Examples 1 to 13 and Comparative Examples 1 to 4 were applied to an ITO glass plate at a thickness of 0.05 to 0.2 μm, and then thermally cured at a temperature of 230 ° C for 30 minutes. The physical properties of the obtained polyimide film of the polyimide derivative are shown in Table 1 below. 19 1275630 [Table l] Component (% by weight) f Temple composition PA A-1 PAA-2 PAA-3 Intrinsic viscosity*) Surface tension pencil (dL/g) (dyne/cm) Hardness 1 BPAA-2 5 95 1.10 37.6 5H 2 BPAA-3 10 90 0.86 37.2 4H 3 BPAA-4 30 70 0.74 36.8 3H 4 BPAA-5 50 50 0.56 36.5 3H 5 BPAA-6 30 70 0.43 36.4 3H Real 6 BPAA-7 90 10 0.34 36.4 1H Shi 7 BPAA-8 2 98 1.38 37.6 5H Example 8 BPAA-9 5 95 1.16 37.1 5H 9 BPAA-1 0 10 90 0.94 36.2 4H 10 BPAA-1 1 30 70 0.86 36.3 4H 11 BPAA-12 50 50 0.76 36.3 3H 12 BPAA-13 30 70 0.58 36.3 3H 13 BPAA-1 4 90 10 0.49 36.3 2H Ratio 1 PAA-1 100 0.15 36.4 1H Compared to 2 PAA-2 100 0.2 36.3 2H Example 3 PAA-3 100 1.50 47.5 5H 4 SPAA SPI (5 : PAA3 (95) 1.26 36.6 1H *) Using NMP as a solvent, it was measured at a concentration of 0.5 g/dL at 30 °C. As shown in the above Table 1, it can be confirmed that all of the polyamic acid resins containing the low-polarity side chain of the present invention have a transparent pumpkin-colored transparent resin, and have an intrinsic viscosity of 0.49 to 1.38 dL/g, which is formed by solvent casting. The aforementioned resin has very excellent film formability and mechanical properties. Further, the pencil hardness of the polyimide film of the present invention was in the range of 1H to 5 ,, and the average was 3 Η and uniform, and the comparative examples 1, 2 and 4 were markedly lowered. The surface tension of the film tends to decrease as the content of the diamine introduced into the side chain of the amber quinone imine (the side chain group containing the ring of the imine ring introduced) is decreased, and it is shown in 36.2 to 37.2 dyne. A uniform value of /cm. [Experimental Example 2] 20 1275630 The solution obtained in the above Examples 1 to 1 3 4 7 » R + a, YJ J and Comparative Examples 1 to 4, 徂: at::, the solution viscosity was 20~~, borrowed By film:

Pm, 25 seconds) to make a film. Subsequently, after the liquid crystal cell was formed by . . . , the liquid crystal cell obtained by the above was measured as shown in Table 2 below. Observing the alignment state of the liquid crystal by a polarizing microscope using a polarizing microscope, and determining the capacitance of the liquid crystal panel by changing the Dc bias side by using a crystal rotation method (pretilt angles of each liquid crystal cell) When the capacitance change rate of the CV hysteresis curve is 2〇%, the voltage difference between the same capacitance is used as a reference to determine the residual voltage (residual DC) ° [Table 2] Area distribution to the film pretilt angle (degrees) VHR (%) R·D · C(mV) After pre-friction friction (normal temperature) Example 1 BPAA-2 89.6 90.0 99.7 154 ^^ Example 2 BPAA-3 8 9.6 89.4 99.5 258 'Example 3 BPAA-4 89.6 89.5 99.3 272 — ^' Example 4 BPAA-5 89.6 89.5 99.1 330 'Example 5 BPAA-6 89.6 89.5 99.1 325 'Example 6 BPAA-7 89.7 89.6 99.6 398 'Example 7 BPAA-8 89.6 79.6 99.1 136 ^ Example 8 BPAA-9 89.3 88.8 99.6 89 Example 9 BPAA- 1 0 89.8 90.0 99.5 134 ~ Example 10 BPAA- 1 1 89.4 89.5 9 9.4 170 'Example 11 BPAA- 1 2 89.6 89.3 9 9.4 213 ~ Example 12 BPAA- 1 3 89.5 89.4 99.2 3 67 ^' Example 13 BPAA-14 89.3 89.5 99.9 3 95 ^~ Comparative Example 1 PAA-1 89.7 89.6 98.5 547 'Comparative Example 2 PAA-2 89.2 89.4 98.8 5 16 ^' Comparative Example 3 PAA-3 7.3 4.9 97.1 65 8 ' Comparative Example 4 SPAA 90.0 70.3 97.5 260 ^' As shown in Table 2 above, it was found that the polyglycine mixed grade 21 1275630 containing the poly-proline (having the low-polarity side chain of the present invention) prepared in Examples 1 to 13 was obtained. The liquid crystal cell prepared by the object exhibits a very high pretilt angle and electroselective retention, and exhibits excellent residual voltage characteristics. The pretilt angle is about 90 degrees, and compared with Comparative Example 2 (not containing a structure having low polarity) The side chain poly-proline acid) is greatly increased in comparison, and maintains a high pretilt angle of an average of 89 degrees or more after rubbing, and can be improved when compared with Comparative Example 4 containing a soluble polyimine resin. . The voltage holding ratio at room temperature is in the range of 9 9 · 1 to 9 9 · 9 %, and all of them are above 9 %. When compared with Comparative Examples 1 to 4, it can be confirmed that it is excellent, in particular, and contains soluble poly When Comparative Example 4 produced by the amine polyamine amide mixture composition was compared, the results showed that the voltage holding ratio was increased. Further, a mixed composition containing polylysine (having a low-polarity side chain) showed that the residual voltage of the liquid crystal cell showed a decrease to 89 to 3 95 mV. When this was compared with Comparative Examples 1 to 3, the display was remarkably lowered, and it was confirmed that the residual voltage of the present invention was more excellent. Therefore, by combining the results of the above Experimental Example 1 and Experimental Example 2, it can be confirmed that the polyamic acid resin containing a low-polar side chain represented by the formula (1) of the present invention in relation to Examples 1 to 13 of the present invention contains the following formula (2) The polyglycine mixed composition obtained by mixing the poly-proline derivatives represented by the present invention is excellent in the properties of the liquid crystal alignment film for vertical alignment type TFT-TN and STN LCD, and liquid crystal. Unit cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H-NMR of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DN-IM-18) of the present invention. Spectrum. Fig. 2 is a 1H-NMR spectrum of PAA-1 obtained in Production Example 15 of the present invention. Fig. 3 is a 1H-NMR spectrum of PAA_3 prepared in accordance with Production Example 17 of the present invention. Fig. 4 is a UV spectrum of BPAA-2 and BPAA-8 to 11 prepared in accordance with Inventive Example 1 and Examples 7 to 10, and PAA-2 to 3 and SPPA prepared in accordance with Comparative Examples 2 to 4. UV spectrum. twenty two

Claims (1)

1275630 Pickup, patent application range: 1. The vertical alignment type composition represented by the formula (2) represented by the following formula (1), characterized in that a polyamic acid resin containing a low-polarity side chain is mixed and contains a polycondensation. Made from a proline derivative, [Chemical Formula 1] , in the formula 襄 is selected from ) 〇 C ) 〇Γ ° Ί〇 ( ) 〇 - 〇 (I > One or two or more kinds of tetravalent groups must contain one or two or more kinds of alicyclic rings selected from Structural Formula 23 1275630 (a), (b), (c), (d), and (e). Family 4 valent group; and One Pu d CH3i CF 3 In this case, η is one or two or more kinds of divalent groups in the natural number ranging from 1 to 30, and the above-mentioned ^*""" must contain the alkyl amber quinone imine side chain of the above structural formula (f). The aromatic divalent group; the 1 and m systems respectively represent natural numbers in the range of 1 to 300. The vertical alignment type composition according to claim 1, wherein the polyamic acid resin having a low polarity side chain represented by the formula (1) and the polyfluorene represented by the formula (2) The amino acid derivative contains a mixing ratio of 1 to 99% by weight and 1 to 99% by weight. 24 l27563〇3 jt Η γ|f / /, A vertical alignment type composition described in the first item of the patent range, wherein the poly-proline resin containing a low-polarity side chain represented by the formula (1) is inherent The & degree is in the range of 0.1 to 1.5 dL/g, and the weight average molecular weight is 〜l5 〇, 〇00 g/mole. The vertical alignment type composition according to claim 1, wherein the polyamic acid derivative represented by the formula (2) has an intrinsic viscosity of 0·3 to 2.0 dL/g, and a weight average The molecular weight is 1 〇, 〇〇〇~200,000 g / mole range. 5. The vertical alignment type composition according to claim 1, wherein the polyamido acid derivative represented by the formula (2) has a hydrazide temperature in the range of 200 to 300 〇C 〇 6 . The vertical alignment type composition according to claim 1, wherein the polyamic acid resin having a low polarity side chain represented by the formula (1) is selected from the group consisting of dimercaptoacetamide and dimethyl hydrazine. The solvent of decylamine, N-methyl-2-pyrrolidone, tetra- 2:chloroform, propylamine, acetic acid ethyl acetate, and 7-butyl vinegar has a liquid crystal alignment film, which is characterized by The coating according to any one of items 1 to 6 is selected from, for example, a patent application! Made of things. 8. The liquid crystal alignment film of the surface sheet before the rubbing of the crystal according to the seventh aspect of the patent application, wherein the liquid is in the range of 3 〇 4 〇 dyne/cm. 9. A liquid crystal alignment film having a pencil hardness of 1H to 7H as disclosed in claim 7 wherein the film surface 10 is a liquid crystal cell characterized by any of The cylinder described in the item + 'Coating is obtained as claimed in the patent scope 1st. 25 1275630 11 A liquid crystal cell as described in claim 10, wherein the pretilt angle is in the range of 89 to 90 degrees. 1 2 The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a normal temperature voltage retention ratio of 99 to 99.99%. The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a residual temperature at room temperature of 100 to 400 mV. 26