JP2006124626A - Vertical orientation type composition containing low polar polyamic acid resin and liquid crystal oriented film using the same and liquid crystal cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: 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. <P>SOLUTION: 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 ≥89° and a voltage retention of ≥99%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a vertical alignment composition containing a low polar polyamic acid resin, a liquid crystal alignment film and a liquid crystal cell using the same, and more specifically, an acid dianhydride containing an alicyclic acid dianhydride and Low-polarity polyamic acid resin obtained by solution polymerization of aromatic diamines containing aromatic diamines having imide ring-containing side chain groups and polyamic acid derivatives are mixed at an appropriate ratio to achieve heat resistance, surface hardness, and transparency. And a novel polyamic acid mixed composition excellent in liquid crystal alignment, and a liquid crystal alignment film having excellent low surface roughness, printability, heat resistance and transparency using the polyamic acid composition, and 89 The present invention relates to a liquid crystal cell having a pretilt angle of more than 0 ° and a voltage holding ratio of more than 99%.

  In general, a polyimide resin refers to a high heat-resistant resin produced by condensation polymerization of an aromatic tetracarboxylic acid or derivative thereof and an aromatic diamine or aromatic diisocyanate, followed by imidization.

  The polyimide resin may have various molecular structures depending on the type of monomer used. As a general aromatic tetracarboxylic acid component, pyromellitic dianhydride (PMDA) or heavy phthalic dianhydride (BPDA) is used, and as an aromatic diamine component, para-phenylenediamine (p- PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2-bisaminophenylhexafluoropropane (HFDA), meta Bisaminophenoxydiphenylsulfone (m-BAPS), parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R) 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bis It is prepared by condensation polymerization of an aromatic diamine such as amino phenoxyphenyl hexafluoropropane (HFBAPP).

  Most polyimide resins are insoluble and infusible ultra-high heat resistant resins, (1) excellent thermal oxidation resistance, (2) high usable temperature, (3) long-term usable temperature of about 260 ° C and about It has excellent heat-resistant properties showing a short-term usable temperature of 480 ° C., (4) radiation resistance, (5) excellent low-temperature properties, and (6) excellent chemical resistance.

  However, in spite of such characteristics of polyimide resin, it is very difficult to apply to fields where transparency is required due to low light transmittance in the visible light region due to the formation of a charge transfer complex. There is a problem. Therefore, various types of main chain type aliphatic polyimide resins are manufactured and applied to fields requiring excellent light transmittance such as liquid crystal alignment films.

  Polyimide resins for liquid crystal alignment films with alicyclic groups introduced into the main chain, developed so far, have been used by introducing long alkyl chain groups into the side chain for the expression of the pretilt angle. Typical examples thereof include soluble polyimide resins and polyamic acid resins. However, in the case of a soluble polyimide resin, since the solubility of the solvent in a general organic solvent is poor, there is a problem that the printability is not good. In the case of a polyamic acid alignment film, the voltage holding ratio (VHR, There is a disadvantage that the voltage holding ratio decreases. In addition, control of the pretilt angle is required for application as an alignment film that can cope with various drive modes.

  Accordingly, the present inventors have made intensive research efforts to solve problems such as light transmittance, solubility, and a decrease in voltage holding ratio of a liquid crystal alignment film manufactured using a conventional polyimide resin. As a result, not only has an excellent solubility in an organic solvent, but also a composition in which a polyamic acid resin having a low-polar side chain and an aromatic or alicyclic polyamic acid derivative are mixed at a certain ratio in a solution state. It has been found that it has heat resistance, transparency, surface hardness, and vertical orientation, and the present invention has been completed.

Therefore, the object of the present invention is to provide a vertical alignment composition having excellent heat resistance, transparency, surface hardness and vertical alignment.
The present invention also provides a liquid crystal alignment film having low surface roughness, excellent printability, heat resistance and transparency, and a liquid crystal cell having an excellent pretilt angle and voltage holding ratio using the vertical alignment composition. There are other purposes in providing.

According to an embodiment of the present invention, in the present invention, a vertical alignment type in which a low-polar side chain-containing polyamic acid resin represented by the following formula (1) and a polyamic acid derivative represented by the following formula (2) are mixed. A composition is provided.


[Where,

1 type or 2 types or more of tetravalent groups selected from 1 and 2 types or more selected from structural formulas (a), (b), (c), (d) and (e). Including alicyclic tetravalent groups of

l and m each represent a natural number in the range of 1 to 300. ]
According to another embodiment of the present invention, the present invention provides a liquid crystal alignment film and a liquid crystal cell manufactured by coating the polyamic acid mixed composition.

  According to the present invention, polyamic acid having a low-polarity side chain with a novel structure having not only excellent optical transparency, heat resistance and mechanical properties but also excellent electro-optical properties and a high pretilt angle is contained. The polyamic acid mixed composition is provided and is useful as a liquid crystal alignment film for TFT-TN and STN LCDs and various point heat-resistant structural materials that require strict electro-optical properties.

Hereinafter, the present invention will be described in more detail.
The present invention relates to a vertical alignment composition in which a low-polarity side chain-containing polyamic acid resin represented by the formula (1) and a polyamic acid derivative represented by the formula (2) are mixed at an appropriate ratio. Furthermore, the present invention relates to a liquid crystal alignment film or a liquid crystal cell having characteristics such as excellent heat resistance, transparency, surface hardness, high voltage holding ratio and pretilt angle by coating the vertical alignment composition.

  The low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) are within a range of 1 to 99% by weight: 1 to 99% by weight. Used in.

  The low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) according to the present invention include an aromatic tetracarboxylic acid or a derivative thereof and an aromatic diamine or aromatic. It can be produced by polycondensation of a group diisocyanate and have various molecular structures depending on the type of monomer used. In general, aromatic tetracarboxylic acid monomers include pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, heavy phthalic dianhydride (BPDA), and hexafluoroisopropylate. It is selected from redene diphthalic dianhydride. As aromatic diamine monomers, generally, para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4-methylenedi Aniline (MDA), 2,2-bisaminophenyl hexafluoropropane (HFDA), metabisaminophenoxydiphenyl sulfone (m-BAPS), parabisaminophenoxydiphenyl sulfone (p-BAPS), 1,4-bisaminophenoxy From benzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafluoropropane (HFBAPP), etc. Select and use.

  In addition to the general aromatic monomer, the low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) according to the present invention have the structure described above. As an essential component, an aliphatic tetracarboxylic dianhydride monomer represented by the formulas (a) to (e) and an aromatic diamine substituted with the alkyl succinic imide group represented by the structural formula (f) are used. Manufactured using the included diamine monomer.

  That is, the low-polar side-chain-containing polyamic acid resin represented by the formula (1) is an acid dianhydride monomer, and an aliphatic tetracarboxylic acid dicarboxylic acid monomer in addition to a normal aromatic tetracarboxylic acid monomer. As anhydride monomers, 1,2,3,4-cyclobutanetetracarboxylic dianhydride [CBDA; (a)], 1,2,3,4-cyclopentanetetracarboxylic dianhydride [CPDA; b)], 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride [DOCDA; (c)], 4- (2,5-dioxotetrahydrofuryl) -3-yl) -tetralin-1,2-dicarboxylic dianhydride [DOTDA; (d)], and bicyclooctene-2,3,5,6-tetracarboxylic dianhydride [BODA; (e)] 1 selected from Or comprising two or more kinds of aliphatic tetracarboxylic dianhydride as an essential component. At this time, the aliphatic tetracarboxylic dianhydride represented by the structural formulas (a) to (e) is used in the range of 1 to 99 mol% based on the amount of the total acid dianhydride monomer used. .

  In the case of the low polarity side chain-containing polyamic acid resin represented by the formula (1), it has a structural feature in which an alkyl succinic imide group is simultaneously bonded together with an alicyclic group as a side chain group. As the diamine monomer, in addition to a normal aromatic diamine monomer, an aromatic diamine substituted with an alkyl succinic imide group represented by the structural formula (f) is contained as an essential component, and polymerization is performed. To manufacture. At this time, the aromatic diamine represented by the structural formula (f) is used in the range of 1 to 99 mol% with respect to the amount of all diamine monomers used.

   As a result, the novel mixture prepared using the aromatic diamine represented by (f) as an essential monomer component is a polyamic acid into which a succinic imide side group substituted with a low polar alkyl group is introduced. By mixing with a resin, transparency, printability, mechanical properties, and electro-optical properties of a liquid crystal cell produced using the composition are particularly improved.

   The low polar side chain-containing polyamic acid resin represented by the formula (1) as described above has a weight average molecular weight (Mw) in the range of 5,000 to 150,000 g / mol and an intrinsic viscosity of 0.1 to 1. It has characteristics of 5 dL / g range and glass transition temperature in the range of 150 to 300 ° C. The soluble polyimide resin represented by the formula (1) is aprotic polar such as dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetone, ethyl acetate. It has the property of being easily dissolved at room temperature in organic solvents such as solvents and meta-cresol.

  Furthermore, the polyamic acid derivative represented by the above formula (2) is an essential single amount of the aliphatic tetracarboxylic dianhydride represented by the structural formulas (a) to (e) as an acid dianhydride monomer. Since it is used as a body, it is possible to produce a polyamic acid derivative with improved mechanical properties and improved printability while minimizing a decrease in heat resistance. The polyamic acid derivative represented by the above formula (2) produced by solution polymerization with the monomer composition described above has a weight average molecular weight (Mw) in the range of 10,000 to 200,000 g / mol and an intrinsic viscosity. It has characteristics of 0.3 to 2.0 dL / g, glass transition temperature of 200 to 400 ° C, and imidization temperature of 200 to 300 ° C. The polyamic acid derivative represented by the formula (2) is aprotic polar such as dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetone, ethyl acetate. It has the property of being easily dissolved at room temperature in organic solvents such as meta-cresol, including solvents. In particular, it exhibits a high solubility of 10% by weight or more at room temperature even in low-boiling solvents such as tetrahydrofuran (THF) and chloroform and low-absorbing solvents such as γ-butyrolactone. Moreover, high solubility is shown also with respect to these mixed solvents.

  The low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) are coated by a usual method used in this field, and then a liquid crystal alignment film or a liquid crystal As a result of manufacturing the cell and evaluating the electro-optical characteristics, the pretilt angle is in the range of 87.0 to 89.9 °, and the voltage holding ratio is 98.0 to 99.9%. The residual voltage (residual-DC) was in the range of 100 to 400 mV. The above-mentioned characteristics are excellent in solubility and liquid crystal alignment characteristics while retaining the excellent characteristics of existing polyimide resins, so as a core heat-resistant material for various industries such as electrical, electronic, space, and aviation Can be used.

(Example)
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited thereto, and various modifications and corrections are possible within the scope of the technical idea of the present invention.

[Production Example 1] Production of 1- (3,5-dinitrophenyl) -3- (1-hexene) -succinic imide (DN-IM-6) Nitrogen gas in a 250 mL reactor equipped with a stirrer and a nitrogen injection device 9.2 g (0.05 mole) of 3,5-dinitroaniline was dissolved in 50 mL of acetic acid as a reaction solvent, and then 2-hexen-1-ylsuccinic anhydride 9. 1 g (0.05 mole) was added and refluxed for 24 hours. After cooling the reaction solution to room temperature, a precipitated solid was obtained.
The solid obtained above was recrystallized from methanol to produce 12.7 g of 1- (3,5-dinitrophenyl) -3- (1-hexene) -succinic imide (DN-IM-6). 73%).

[Production Example 2] Production of 1- (3,5-dinitrophenyl) -3- (1-octene) -succinicimide (DN-IM-8) Instead of 2-hexen-1-ylsuccinic anhydride, Except that 10.5 g (0.05 mole) of 2-octen-1-ylsuccinic anhydride was used, the same reaction as in Production Example 1 was performed to give 1- (3,5-dinitrophenyl) -3. -(1-Octene) -succinic imide (DN-IM-8) was obtained.
The solid obtained above was recrystallized from methanol to produce 13.1 g of 1- (3,5-dinitrophenyl) -3- (1-octene) -succinic imide (DN-IM-8). 70%).

[Production Example 3] Production of 1- (3,5-dinitrophenyl) -3- (1-decene) -succinic imide (DN-IM-10) Instead of 2-hexen-1-ylsuccinic anhydride, Except that 11.9 g (0.05 mole) of 2-decen-1-ylsuccinic anhydride was used, the same reaction as in Production Example 1 was performed to give 1- (3,5-dinitrophenyl) -3. -(1-Decene) -succinic imide (DN-IM-10) was obtained.
The solid obtained above was recrystallized from methanol to produce 14.5 g of 1- (3,5-dinitrophenyl) -3- (1-decene) -succinimide (DN-IM-10). 70%).

[Production Example 4] Production of 1- (3,5-dinitrophenyl) -3- (1-dodecene) -succinic imide (DN-IM-12) Instead of 2-hexen-1-ylsuccinic anhydride, Except for using 13.3 g (0.05 mole) of 2-dodecene-1-ylsuccinic anhydride, the same reaction as in Production Example 1 was performed to give 1- (3,5-dinitrophenyl) -3. -(1-Dodecene) -succinic imide (DN-IM-12) was obtained.
The solid obtained above was recrystallized from methanol to produce 14.0 g of 1- (3,5-dinitrophenyl) -3- (1-dodecene) -succinic imide (DN-IM-12). Rate 65%).

[Production Example 5] Production of 1- (3,5-dinitrophenyl) -3- (1-tetradecene) -succinicimide (DN-IM-14) Instead of 2-hexen-1-ylsuccinic anhydride, Except that 14.7 g (0.05 mole) of 2-tetradecen-1-ylsuccinic anhydride was used, the same reaction as in Production Example 1 was carried out to obtain 1- (3,5-dinitrophenyl)- 3- (1-tetradecene) -succinic imide (DN-IM-14) was obtained.
The solid obtained above was recrystallized from methanol to produce 14.9 g of 1- (3,5-dinitrophenyl) -3- (1-tetradecene) -succinic imide (DN-IM-14). Rate 65%).

[Production Example 6] Production of 1- (3,5-dinitrophenyl) -3- (1-hexadecene) -succinicimide (DN-IM-16) In place of 2-hexen-1-ylsuccinic anhydride, Except for using 16.1 g (0.05 mole) of 2-hexadecene-1-ylsuccinic anhydride, the same reaction as in Production Example 1 was carried out to obtain 1- (3,5-dinitrophenyl)- 3- (1-Hexadecene) -succinic imide (DN-IM-16) was obtained.
The solid obtained above was recrystallized from methanol to produce 15.4 g of 1- (3,5-dinitrophenyl) -3- (1-hexadecene) -succinic imide (DN-IM-16). Rate 63%).

[Production Example 7] Production of 1- (3,5-dinitrophenyl) -3- (1-octadecene) -succinic imide (DN-IM-18) Instead of 2-hexen-1-ylsuccinic anhydride, Except that 17.5 g (0.05 mole) of 2-octadecene-1-ylsuccinic anhydride was used, the same reaction as in Production Example 1 was performed to give 1- (3,5-dinitrophenyl)- 3- (1-Octadecene) -succinic imide (DN-IM-18) was obtained.
The solid obtained above was recrystallized from methanol to produce 16.2 g of 1- (3,5-dinitrophenyl) -3- (1-octadecene) -succinic imide (DN-IM-18). 63%).

[Production Example 8] Production of 1- (3,5-diaminophenyl) -3-hexyl-succinic imide (DA-IM-6) DN-IM-6 6 in 100 mL of NMP and ethanol (1/3 volume ratio) 0.9 g (0.02 mole) was dissolved, and then placed in a hydrogen reactor together with 0.5 g of a Pd / C (5%) catalyst (a catalyst in which 5% of metallic palladium was applied to the surface of carbon particles). The reduction reaction was performed at 60 ° C. for 2 hours. After filtering the reaction mixture, the reaction solvent was distilled under reduced pressure.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 3.18 g of 1- (3,5-diaminophenyl) -3-hexyl-succinic imide (DA-IM-6). (55% yield).

[Production Example 9] Production of 1- (3,5-diaminophenyl) -3-oxyl-succinic imide (DA-IM-8) 7.5 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-oxyl-succinic imide (DA-IM-8) was prepared in the same manner as in Production Example 8 except that -IM-8 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 3.68 g of 1- (3,5-diaminophenyl) -3-oxyl-succinic imide (DA-IM-8). (Yield 58%).

[Production Example 10] Production of 1- (3,5-diaminophenyl) -3-decyl-succinic imide (DA-IM-10) 8.1 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-decyl-succinic imide (DA-IM-10) was prepared in the same manner as in Production Example 8 except that -IM-10 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 4.15 g of 1- (3,5-diaminophenyl) -3-decyl-succinic imide (DA-IM-10). (Yield 60%).

[Production Example 11] Production of 1- (3,5-diaminophenyl) -3-dodecyl-succinic imide (DA-IM-12) 8.6 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-dodecyl-succinic imide (DA-IM-12) was prepared in the same manner as in Production Example 8 except that -IM-12 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 4.48 g of 1- (3,5-diaminophenyl) -3-dodecyl-succinic imide (DA-IM-12). (Yield 60%).

[Production Example 12] Production of 1- (3,5-diaminophenyl) -3-tetradecyl-succinic imide (DA-IM-14) 9.2 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-tetradecyl-succinic imide (DA-IM-14) was prepared in the same manner as in Production Example 8 except that -IM-14 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 5.6 g of 1- (3,5-diaminophenyl) -3-tetradecyl-succinic imide (DA-IM-14). (Yield 70%).

[Production Example 13] Production of 1- (3,5-diaminophenyl) -3-hexadecyl-succinic imide (DA-IM-16) 9.8 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-hexadecyl-succinic imide (DA-IM-16) was prepared in the same manner as in Production Example 8 except that -IM-16 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 6.01 g of 1- (3,5-diaminophenyl) -3-oxyl-succinimide (DA-IM-16). (Yield 70%).

[Production Example 14] Production of 1- (3,5-diaminophenyl) -3-octadecyl-succinic imide (DA-IM-18) 10.3 g (0.02 mole) of DN instead of DN-IM-6 1- (3,5-diaminophenyl) -3-octadecyl-succinic imide (DA-IM-18) was prepared in the same manner as in Production Example 8 except that -IM-18 was used. Got.
The solid obtained above was recrystallized in a co-solvent of hexane / ethyl acetate to produce 6.87 g of 1- (3,5-diaminophenyl) -3-octadecyl-succinic imide (DA-IM-18). (Yield 75%).
DA-IM-6-18 as a diamine monomer having a succinic imide side group substituted with a low polar alkyl group produced in Production Examples 8-14 has a yield after recrystallization of 50. %, It was confirmed that it could be produced in excess of%, and showed very excellent storage stability in air.

[Production Example 15] Production of low-polarity side chain-containing polyamic acid resin (PAA-1) While gradually passing nitrogen gas through a 250 mL reactor equipped with a stirrer, temperature control device, nitrogen injection device and cooler, 3.15 g (0.02 mole) of 3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) was dissolved in N-methyl-2-pyrrolidone as a reaction solvent, and then passed through nitrogen gas. Then, 5.28 g (0.02 mole) of solid 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride was gradually added. Under the present circumstances, solid content concentration (solid content) was fixed to 20 weight%, and it stirred for 24 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-1).

[Production Example 16] Production of low-polar side chain-containing polyamic acid resin (PAA-2) While gradually passing nitrogen gas through a 250 mL reactor equipped with a stirrer, temperature control device, nitrogen injection device and cooler, 1- ( 3.15 g (0.02 mole) of 3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) was dissolved in N-methyl-2-pyrrolidone as a reaction solvent, and then passed through nitrogen gas. Then, 3.92 g (0.02 mole) of solid 1,2,3,4-cyclobutanetetracarboxylic dianhydride was gradually added. Under the present circumstances, solid content concentration (solid content) was fixed to 20 weight%, and it stirred for 24 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-2).

[Production Example 17] Production of polyamic acid (PAA-3) 19.8 g (0.1 mole) of methylenedianiline was added as a reaction solvent N while gradually passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection device. -After dissolving in methyl-2-pyrrolidone, 19.6 g (0.1 mole) of solid 1,2,3,4-cyclobutanetetracarboxylic dianhydride was gradually added while passing nitrogen gas. Under the present circumstances, solid content concentration (solid content) was fixed to 15 weight%, and it stirred for 36 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-3).

[Production Example 18] Production of soluble polyimide resin (SPI) 1- (3,5-diaminophenyl) while gradually passing nitrogen gas through a 250 mL reactor equipped with a stirrer, temperature control device, nitrogen injection device and cooler After dissolving 9.15 g (0.02 mole) of -3-octadecyl-succinic imide (DA-IM-18) in N-methyl-2-pyrrolidone as a reaction solvent, solid 5- 5.28 g (0.02 mole) of (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride was gradually added. At this time, the solid content concentration 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.
Acetic anhydride (6.12 g, 0.06 mole) and pyridine (0.1 g, 0.1 mole) were added to the polyamic acid solution, stirred at room temperature for 24 hours, then stirred at 120 ° C. for 3 hours, and then several times with methanol. By washing, a soluble polyimide resin (SPI-1) was obtained.

[Example 1]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-2) Low-polar side-chain-containing polyamic of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 1.973 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 2]
Production of Low Polarity Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-3) The low polarity side chain containing polyamic of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and nitrogen injection device 4.166 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 3]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-4) Low-polar side chain-containing polyamic of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 16.073 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 4]
Production of low polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-5) Low polar side chain-containing polyamic of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and nitrogen injection device 37.503 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were placed in 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 5]
Production of low-polar side chain-containing polyamic acid and polyamic acid mixture (BPAA-6) Low-polar side-chain-containing polyamic acid of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 87.5 g of the resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 6]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-7) Low-polar side-chain-containing polyamic of Production Example 15 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 337.3 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 7]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-8) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device An acid resin solution (0.765 g) and the polyamic acid solution (50 g) of Production Example 17 were placed in N-methyl-2-pyrrolidone (80 g), γ-butyrolactone (120 g), and 2-n-butoxyethanol (60 g), and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 8]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-9) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 1.974 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were placed in 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 9]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-10) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 4.166 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 10]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-11) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 16.05 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 11]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-12) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 37.503 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were placed in 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 12]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-13) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and nitrogen injection device 87.5 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Example 13]
Production of low-polar side chain-containing polyamic acid resin and polyamic acid mixture (BPAA-14) Low-polar side-chain-containing polyamic of Production Example 16 while gradually passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device 337.3 g of the acid resin solution and 50 g of the polyamic acid solution of Production Example 17 were put into 75 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone and 60 g of 2-n-butoxyethanol as dilution solvents, and stirred for 24 hours. A solution having a viscosity of 25 cps was produced.

[Comparative Example 1] Production of low-polar side chain-containing polyamic acid resin (PAA-1) 1- () while gradually passing nitrogen gas through a 250 mL reactor equipped with a stirrer, temperature control device, nitrogen injection device and cooler 3.15 g (0.02 mole) of 3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) was dissolved in N-methyl-2-pyrrolidone as a reaction solvent, and then passed through nitrogen gas. Then, 5.28 g (0.02 mole) of solid 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride was gradually added. Under the present circumstances, solid content concentration (solid content) was fixed to 20 weight%, and it stirred for 24 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-1).

[Comparative Example 2] Production of low-polar side chain-containing polyamic acid resin (PAA-2) While gradually passing nitrogen gas through a 250 mL reactor equipped with a stirrer, temperature control device, nitrogen injection device, and cooler, 3.15 g (0.02 mole) of 3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) was dissolved in N-methyl-2-pyrrolidone as a reaction solvent, and then passed through nitrogen gas. Then, 3.92 g (0.02 mole) of solid 1,2,3,4-cyclobutanetetracarboxylic dianhydride was gradually added. Under the present circumstances, solid content concentration (solid content) was fixed to 20 weight%, and it stirred for 24 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-2).

[Comparative Example 3] Production of polyamic acid (PAA-3) 19.8 g (0.1 mole) of methylenedianiline was added as a reaction solvent N while gradually passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection device. -After dissolving in methyl-2-pyrrolidone, 19.6 g (0.1 mole) of solid 1,2,3,4-cyclobutanetetracarboxylic dianhydride was gradually added while passing nitrogen gas. Under the present circumstances, solid content concentration (solid content) was fixed to 15 weight%, and it stirred for 36 hours, keeping reaction temperature below 0 degreeC, and obtained the polyamic acid solution (PAA-3).

[Comparative Example 4] Production of soluble polyimide-containing polyamic acid (PAA-4) 50 g of the polyamic acid resin of Production Example 17 while gradually passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection device, and the production A solution having a viscosity of 25 cps was obtained by adding 0.395 g of the soluble polyimide solution of Example 18 to 80 g of N-methyl-2-pyrrolidone as a dilution solvent, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol and stirring for 24 hours. Manufactured.

[Experiment 1]
The solutions prepared according to Examples 1 to 13 and Comparative Examples 1 to 4 were spin-coated on an ITO glass plate to a thickness of 0.05 to 0.2 μm, and then thermally cured at 230 ° C. for 30 minutes. The physical properties of the obtained polyimide derivative thin film are shown in Table 1 below.

  As shown in Table 1, it is confirmed that the low polar side chain-containing polyamic acid resins according to the present invention are all bright pumpkin-colored transparent resins and have an intrinsic viscosity in the range of 0.49 to 1.38 dL / g. The resin was extremely excellent in film moldability and mechanical properties by a solvent mold.

  Moreover, the pencil hardness of the polyimide thin film according to the present invention was in the range of 1H to 5H and was uniform with an average of 3H or more, but in Comparative Examples 1, 2 and 4, it was significantly reduced. The surface tension of the thin film tended to decrease as the content of the diamine introduced with the succinic imide side group introduced with the imide ring-containing ring system side group was increased to 36.2-37.2 dyne / cm. A uniform value was shown.

[Experiment 2]
After the solution viscosity at room temperature of the solutions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was kept at 20 to 40 cp, thin film coating was performed (coating conditions; 400 to 4,000 rpm, 25 seconds). Manufactured. And after rubbing (0.25T) and manufacturing a liquid crystal cell, the characteristic of the manufactured liquid crystal cell was measured, and the result is shown in Table 2 below.
The alignment state of the liquid crystal is visually observed using a polarizing microscope, the pretilt angles of each liquid crystal cell are measured using the crystal rotation method, and the liquid crystal panel is electrically connected while changing the DC bias voltage. The residual voltage (residual DC) was measured by obtaining the voltage difference with the same capacitance with reference to the point where the capacitance change rate of the CV hysteresis curve where the capacitance was measured was 20%.

  As shown in Table 2, the liquid crystal cell manufactured using the polyamic acid mixed composition containing the polyamic acid having a low polarity side chain according to the present invention manufactured in Examples 1 to 13 is very It was found that a high pretilt angle and voltage holding ratio were exhibited, and an excellent residual voltage characteristic was exhibited.

  The pretilt angle is about 90 °, which is greatly increased as compared with Comparative Example 2 that does not contain low-polar side chain-containing polyamic acid, and retains a high pretilt angle of 89 ° or more on average even after rubbing. It turned out that a characteristic improves compared with the case of the comparative example 4 containing a polyimide resin. The voltage holding ratio at room temperature is in the range of 99.1 to 99.9%, and all are 99% or more, and it can be confirmed that it is superior to Comparative Examples 1 to 4, in particular, it contains soluble polyimide. As a result, the results increased compared to the case of Comparative Example 4 produced using the polyamic acid mixed composition. Moreover, the polyamic acid mixed composition containing the polyamic acid having a low-polar side chain showed a result that the residual voltage of the liquid crystal cell decreased to 89 to 395 mV. This shows a tendency to be remarkably lowered as compared with Comparative Examples 1 to 3, and it has been confirmed that the present invention is more excellent.

  Therefore, when the results of Experimental Example 1 and Experimental Example 2 are taken together, the low-polarity side chain-containing polyamic acid resin represented by Formula (1) of Examples 1 to 13 according to the present invention and the formula ( 2) It is confirmed that the polyamic acid mixed composition obtained by mixing the polyamic acid derivative represented by 2) exhibits very suitable characteristics for use in liquid crystal alignment films and liquid crystal cells for vertical alignment type TFT-TN and STN LCDs. did it.

¹ shows the ¹ H-NMR spectrum of 1- (3,5-diaminophenyl) -3-octadecyl-succinic imide (DA-IM-18) of the present invention. ¹ shows a ¹ H-NMR spectrum of PAA-1 produced according to Production Example 15 of the present invention. ¹ shows a ¹ H-NMR spectrum of PAA-3 produced according to Production Example 17 of the present invention. Figure 2 shows the UV spectra of BPAA-2 and BPAA-8-11 prepared according to Example 1 and Examples 7-10 of the present invention, and the PAA-2-3 and SPPA prepared according to Comparative Examples 2-4. .

Claims (13)

A vertically oriented composition comprising a mixture of a low polar side chain-containing polyamic acid resin represented by the following formula (1) and a polyamic acid derivative represented by the following formula (2).


[Where,

1 type or 2 types or more of tetravalent groups selected from 1 and 2 types or more selected from structural formulas (a), (b), (c), (d) and (e). Including alicyclic tetravalent groups of

l and m each represent a natural number in the range of 1 to 300. ]    The low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) are contained in a mixing ratio of 1 to 99% by weight: 1 to 99% by weight. The vertical alignment composition according to claim 1, wherein:   The low polar side chain-containing polyamic acid resin represented by the formula (1) has an intrinsic viscosity in the range of 0.1 to 1.5 dL / g and a weight average molecular weight in the range of 5,000 to 150,000 g / mol. The vertical alignment composition according to claim 1, wherein:    The polyamic acid derivative represented by the formula (2) has an intrinsic viscosity in the range of 0.3 to 2.0 dL / g and a weight average molecular weight in the range of 10,000 to 200,000 g / mol. The vertical alignment composition according to claim 1.   The vertical alignment composition according to claim 1, wherein the imidization temperature range of the polyamic acid derivative represented by the formula (2) is 200 to 300 ° C.   The low polar side chain-containing polyamic acid resin represented by the formula (1) is a solvent selected from dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, acetone, ethyl acetate and γ-butyrolactone The vertically-oriented composition according to claim 1, wherein the composition has solubility characteristics with respect to the composition.   A liquid crystal alignment film produced by coating any one composition selected from claims 1 to 6.   The liquid crystal alignment film according to claim 7, wherein the liquid crystal alignment film has a surface tension before rubbing in a range of 30 to 40 dyne / cm.   The liquid crystal alignment film according to claim 7, wherein the liquid crystal alignment film has a pencil hardness of 1H to 7H in the film surface.    A liquid crystal cell produced by coating any one composition selected from claims 1-6.   The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a pretilt angle in a range of 89 to 90 °.   The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a normal temperature voltage holding ratio in a range of 99 to 99.99%.   The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a room temperature residual voltage in a range of 100 to 400 mV.