TWI326699B - Polyimide based varnish liquid-crystal oriented film, orienteded film using said varnish, and liquid-crystal display device using said oriened film - Google Patents

Description

[Technical Field] The present invention relates to a polyimide film varnish for forming an alignment film for a liquid crystal display element, an alignment film, and a liquid crystal display element having the alignment film, wherein The polyamidamine-based varnish can form an alignment film having a refractive index Δ of 1.3 or more after liquid crystal treatment represented by a specific formula, and particularly relates to a lateral display by forming a main parallel electric field on the surface of the substrate. An electric field type, that is, a polyimine-based varnish for a liquid crystal display element of an IPS (In Plane Switching) type, an alignment film formed using the varnish, and an IPS type liquid crystal display element having the alignment film. [Prior Art] The liquid crystal display element was originally used as a monitor for a notebook type personal computer and a desktop personal computer, and has various liquid crystals such as a view hiider for a camera, a display type display, and the like. It has been on the display device and has recently been used on TV sets. Moreover, optoelectronics-related components such as a printer head, a Fourier transform element, and a light valve are also utilized. In the past, a liquid crystal display element was mainly a display element using a nematic liquid crystal, and a TN (Twisted Nematic) liquid crystal display element of a 90 degree twist was used, and a STN of a 180 degree twist was usually used. Super Twisted Nematic) The so-called TFT (Thin-film transistor) type liquid crystal display device of the "Transistor" is becoming practical. However, it is suitable for viewing these. The viewing angle of the image of the liquid crystal display element is equivalent to 1326699 14414pif.doc, and when viewed from the oblique side, there are disadvantages such as brightness reduction or contrast reduction and halftone brightness inversion. In recent years, regarding the viewing angle, a MVA (Multi-domain Vertical Alignment) type liquid crystal display element using a TN type liquid crystal display element using an optical compensation film, a vertical alignment and protrusion structure technique, or a lateral direction The IPS (Intra-Plane Switching) type liquid crystal display element of the electric field type (see, for example, Japanese Patent Laid-Open Publication No. Hei. No. 3) is being improved and put into practical use. Relative to the black display brightness, the comparison of the ratio of the white display brightness is currently used as one of the performance indexes of the liquid crystal display element. In general, since the white display brightness does not become large, the contrast is severely affected by the black display brightness of the denominator. Therefore, to enhance the contrast, the black display brightness must be reduced. A method for reducing the brightness of black display, such as a TN type liquid crystal display of an optical mode, includes the first Δη (double refraction) of the liquid crystal and the cell gap. A method of optimizing the minimum minimum conditions (for example, refer to Non-Patent Document 1), etc., but if the uniaxial alignment of the alignment film is insufficient, the alignment direction of the liquid crystal expressed by the order parameter is indicated. The light leak caused by the distribution's black display characteristics deteriorate.

In particular, an IPS type liquid crystal display device generally has a black display for black display when no voltage is applied by making the alignment direction of the liquid crystal coincide with the direction of the polarizing plate of one side under crossed nic〇1. (normal black) Shows no. When the tracking element is formed, the light leakage phenomenon due to the division of the liquid crystal alignment direction is remarkable, and the black display characteristic is liable to be deteriorated. Further, in the IPS 7 14414 pif.doc type liquid crystal display element, the alignment film is given uniaxial alignment by rubbing treatment. However, since the electrode disposed in the shape of a dent is in a range in the vicinity of the level diffrance, it is particularly difficult to perform the rubbing treatment, so that the uniaxial alignment property of the alignment film is incomplete. In this range, since the alignment is a disordered direction, light leakage occurs and the contrast deteriorates. Based on the above, in order to improve the contrast of the liquid crystal display elements, it is extremely important to control the uniaxial alignment of the alignment film. There are currently two proposals for the liquid crystal alignment mechanism on the rubbed alignment film. (1) The surface shape effect of the micro group which occurs due to the rubbing treatment. (2) The interaction between the alignment film and the liquid crystal molecules which are uniaxially aligned by the rubbing treatment. In recent years, it has been confirmed that the surface shape effect of (1) contributes relatively little, and the intermolecular interaction of (2) is the main cause. Therefore, by controlling the uniaxial alignment of the alignment film, it is desirable to improve the alignment state of the liquid crystal to which the alignment film is attached, and it is even possible to improve the performance with respect to the liquid crystal display element. For example, an alignment film is generally composed of a polymer compound, and an infrared absorption spectroscopic method using polarized infrared rays is widely used for a method of directly evaluating its molecular alignment. In this method, the infrared absorption of two linearly polarized infrared rays incident on the sample is detected, and the so-called erroneous infrared dichroic is detected by the molecular alignment direction to evaluate the molecular alignment. The scope of application of this method is limited to films made of silicon or calcium fluoride (fluorite: CaF2) and the like, which are formed on a substrate transparent to infrared light. Since the infrared light 14414pif.doc cannot pass through the glass substrate, this method cannot measure the molecular alignment of the alignment film formed on the glass substrate. Regarding the evaluation method of the infrared dichroism of the alignment film, there are currently proposed (1) methods for evaluating the infrared dichroic ratio (for example, refer to Patent Document 4, Non-Patent Document 2), and (2) methods for evaluating dichromatic aberration (for example, reference) Patent Document 3, Non-Patent Document 4) and the like. The infrared dichroism of the alignment film is obtained from two kinds of absorbances, one is the absorbance when the infrared ray having the polarized component parallel to the alignment treatment direction is incident on the alignment film, and the other is the incident on the alignment film perpendicular to the alignment processing direction. The absorbance of the polarized component in the infrared. Further, a method of measuring the infrared dichroic ratio is described in Non-Patent Document 2. That is, a polarizer is disposed between a light source of an infrared spectrophotometer (which is preferably Fourier infrared spectroscopy (FT-IR)) and a sample holder that supports the alignment film sample, and the rubbing treatment direction of the alignment film is made. The sample was fixed to the sample holder in parallel with the polarization direction of the polarizer, and the infrared absorbance was measured. Then, the sample holding material is rotated by 90 degrees while the alignment film is fixed to the sample holder, and the infrared ray absorbance is measured by causing the polarized infrared rays passing through the polarizer to enter the alignment film perpendicular to the rubbing alignment direction. In the infrared absorbance thus obtained, from the wavelength showing a strong absorption (peak), the dichroic ratio is calculated based on the enthalpy. Patent Document 1: Japanese Patent Laid-Open Publication No. SHO 63-21907. Patent Document 2: Japanese Patent Laid-Open No. Hei 6-160878. 1326699 14414pif.doc Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 9-15650. Patent Document 4: Japanese Patent Laid-Open Publication No. SHO 64-35419 Sulphur. Non-Patent Document 1: Yoshino Satoshi and Ozaki Masa Co., the foundation of liquid crystal and display applications, Corona Publishing Co. Ltd., 107-109 pages. Non-Patent Document 2: S. Ishibaslii et al., Liquid Crystals, No. 4, p. 669, 1989. Non-Patent Document 3: R. Hasegawa et al., Molecular Crystals and Liquid Crystals, vol. 262, p. 7, 1998. Non-Patent Document 4: Hasegawa et al., Liquid Crystal Symposium, 21st, 1A07, 14~157. SUMMARY OF THE INVENTION The present invention provides a polyamidamine-based varnish which can form an alignment film of high uniaxial alignment, an alignment film using the varnish, and a liquid crystal display element having the alignment film and having good black display characteristics. In order to solve the above problems, the present inventors have intensively reviewed the results, and found a polyamido varnish for forming an alignment film for a liquid crystal display element, and found that liquid crystal treatment represented by the formula (1) can be formed by using the liquid crystal display. The polyamidamine-based varnish having an alignment film having an index of alignment A of 1.3 or more can greatly improve the black display characteristics of the liquid crystal display element, and the present invention has been completed based on such knowledge. 1326699 14414pif.doc Δ

|a II -A A || +A

(1) where A|| is the incident infrared light incident on the alignment film having a polarization component parallel to the alignment treatment direction, the absorbance of the carbon (C)-nitrogen (N) stretching vibration of the melamine ring, A丄 is incident When the infrared light having the polarizing component perpendicular to the alignment treatment direction is in the alignment film, d is the film thickness of the alignment film (unit: nanometer) due to the absorbance of the CN stretching vibration of the melamine ring. The present invention consists of the following. [1] An object of the present invention is to provide a polyimide film varnish for forming an alignment film of a liquid crystal display element. The polyamidamine varnish can be formed by a liquid crystal treatment after the alignment index Δ Is an alignment film Δ A -A 丄A +A 丄X d (1) of the formula L3 or more, wherein A|| is infrared light incident on the alignment film having a polarization component parallel to the alignment treatment direction, and is caused by the CN of the melamine ring The absorbance of the telescopic vibration, A 丄 is the infrared light incident on the alignment film when the infrared light having the polarization component perpendicular to the alignment treatment direction is incident on the film. The d is the film thickness of the alignment film (unit: nanometer) [2] The polyamidamine-based varnish according to the above [1], wherein the liquid crystal display element is a lateral electric field type liquid crystal display element which is formed by forming a main parallel electric field on the surface of the substrate. [3] The polyamidamine-based varnish according to the above [1] or [2], wherein the alignment index Δ of the liquid crystal at 11 1326699 14414pif.doc is 1.5 to 10.0, wherein the alignment index Δ after the liquid crystal treatment is as follows. The above formula (1). [4] as described above [1] ~ [3 The polyamidamine-based varnish according to any one of the above, wherein the polymer component is obtained from at least one of the following tetracarboxylic dianhydrides and at least one of the diamines represented by the following: The soluble polyamidamine or polyainic acid which is a precursor thereof. Here, η is an integer of 1 to 20, and R is a hydrogen atom or a carbon number of 1 to 20 Any of these alkyl groups, any of -CH2 may be substituted by a hydrazine - '-CH=CH- or a CeC-, a cyclohexane or any hydrogen atom in the benzene ring, or a halogen or a carbon number. 1 to 5 alkyl substituted. 12 1326699 14414pif.doc

13 1326699 14414pif.doc 1-13 1-15 1-17

1-14

1-19 1-21

1-16 1-18 1-20 1-22

14 1326699 14414pif.doc

2 secret

1-30

1-32

1-35 1-37

1-34 1-36 1-38

15 1326699 14414pif.doc 2-1

2-3

2-6 2-5

2-7

2-8

2-9

H2N

2-13 — _^NH2 0^ch2^0 h2n 2-12

H2N 16 1326699 14414pif.doc

2-19 2-20 H2N^D^〇如如==\^NH〇^"°~^ch2V0-O h2n^^"^ NH2 2

2-22 y^=y /==\ 2-23 /=\

HzN S〇2~^J^NHz h2n-^Q^-s-Q^nh2 O 9.9« 2-26 2-28

NH, NH 2 2-24 2-29

17 1326699 14414pif.doc

2-30 2-31 _ 乂)"O〇^s〇2^cy.乂)~nh2 2-32 F, C CF-,

2-33

2-34

H2N

2-35 2-37 2-36

,-〇".

18 1326699 14414pif.doc

2-44

H2N 2-45

19 1326699 14414pif.doc 2-46

H2N

2-48

2-50

2-51

20 1326699 14414pif.doc 2-52

XX>R ο h2n nh2

Nh2 2-53 2-54 2-55 2-56

H2N

R

H2N

21 1326699 14414pif.doc [5] The polyamidamine varnish described in [4], wherein the tetracarboxylic dianhydride is from the formula 1-1, the formula 1-2, and the formula 1-13 'form i_i7 At least one selected from the group consisting of the formula i_i8, the formula ι·ΐ9, and the formula 1-20 of the formula 1-27, the formula 1_28, and the formula 1_29. [6] The polyamido varnish according to the above [4], wherein the diamine is from the formula 2-5, the formula 2-6, the formula 2-9, the formula 2-10, the formula 2-U, the formula. 2-12, Formula 2-13, Formula 2-14, Formula 2-15, Formula 2-16, Formula 2-17, Formula 2-18 'Formula 2-19, Formula 2·20, Formula 2-30, Formula At least one of the diamines represented by the respective formulae 2-35, 2-39, 2-40, 2-4-1, 2-4-2, 2-4-3, and 2-56 is selected. Here, in the formula, η is an integer of 2 to 10, and any hydrogen atom in the benzene ring may be substituted by halogen or an alkyl group having 1 to 5 carbon atoms. [7] The polyamido varnish according to [4], wherein the diamine is from the formula 2-12, the formula 2-13', the formula 2-14, the formula 2-15, the formula 2-16, and the formula At least one of the diamines represented by the formulas 2-17, 2-18, 2-19, 2-20, and 2_39 is selected. Here, in the formula, η is an integer of 2 to 1 Å, and any hydrogen atom in the benzene ring may be substituted by halogen or an alkyl group having 1 to 5 carbon atoms. [8] An alignment film formed using the polyamidamine-based varnish according to any one of the above [1] to [7]. [9] The alignment film according to the above [8], wherein the alignment treatment is performed with a hair tip of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm/sec, and a roller rotation speed. The rubbing treatment was carried out under conditions of 500 to 2,000 revolutions per minute (rpm). [10] A liquid crystal display element having the alignment film according to the above [8] or [9]. 22 1326699 14414pif.doc [11] A transverse electric field type liquid crystal display element having the alignment film according to the above [8] or [9]. According to the present invention, a liquid crystal display element, an alignment film, and a polyimide film varnish which can form the alignment film can be provided. The above and other objects, features, and advantages of the present invention will become more apparent <RTIgt; The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] The present invention realizes a liquid crystal display element having excellent black display characteristics by using a particularly high uniaxial alignment film, that is, an alignment film having an alignment index Δ of 1.3 or more after liquid crystal treatment. In the present invention, the uniaxial alignment of the alignment film is evaluated by the alignment index Δ of the alignment film. The alignment index Δ is represented by the formula (1), and the alignment film is subjected to alignment treatment and subsequent liquid crystal treatment. A —A 丄(1) Δ = —π——:−X d A +A 丄 where A |丨 is the infrared light incident on the alignment film having a polarization component parallel to the alignment treatment direction, due to the imipenem ring The absorbance of carbon (C)-nitrogen (N) stretching vibration, and A丄 is the infrared light that is incident on the alignment film with a polarizing component perpendicular to the alignment treatment direction. 23 1326699 14414pif. Doc absorbance. d is the film thickness of the alignment film (unit: nanometer (nm)). When a polyiminamide-based alignment film is used, the peak of the strong infrared absorption spectrum of polyiminamide appears in the vicinity of 1380 cm·1 (CN stretching vibration of the melamine ring) and around 1510 cm·1. (C_C stretching vibration of phenyl) and the vicinity of lUOcnT1 (0-9 stretching vibration of the sulfhydryl group). Originally, no matter what kind of infrared absorption spectrum is used, the direction of the polarization generated by molecular vibration is along the direction of the polyamine chain, and the change of the peak 値 of the infrared absorption spectrum composed of polyamidamine is relatively small. It is especially useful in the vicinity of 1380 CDT1 (CN stretching vibration of the melamine ring). In addition, the infrared dichroic ratio differs depending on the film thickness of the alignment film, and it is preferable to remove the influence of the film thickness by the infrared dichroism to evaluate the uniaxial alignment property. From the above, in the present invention, the infrared dichroism of the C-N stretching vibration of the melamine ring near nSOciif1 was evaluated as the uniaxial alignment of the alignment film. Further, in the present invention, the absorbance in the vicinity of 1380 CIXT1 shows the maximum peak height of the absorption spectrum in the range of 1330 to 1430 cnT1. In addition, the film thickness (in nm) for compensating for the influence of the film thickness was also measured. Originally, the liquid crystal display element is driven by the state in which the alignment film is in contact with the liquid crystal. Since the uniaxial alignment of the alignment film changes due to the contact between the alignment film and the liquid crystal, the alignment index Δ is evaluated by contact with the liquid crystal. The uniaxial alignment of the alignment film is necessary. In the liquid crystal treatment of the present invention, after the liquid crystal is dropped onto the surface of the alignment film after the treatment, the heat treatment is performed, and the temperature of the heat treatment is preferably 60 to 140 ° C, more preferably 80 to 120 ° C, and the heat treatment time is 5 ~600 minutes is better, 10~180 minutes is better. In the present invention, after the liquid crystal treatment, the liquid crystal is removed by a suitable solvent of 24 1326699 14414 pif.doc, and the alignment film is dried at room temperature (22 to 24 ° C), and then the alignment index Δ is measured. The solvent for removing the liquid crystals is not particularly limited as long as it does not impair the purpose of the present invention, and it is preferable that the solvent to be used is *Jinjiyuan. The alignment film for a liquid crystal display element used in the present invention has a distribution index Δ of 1.3 or more after liquid crystal treatment as shown in the above formula (1). The upper limit of the alignment index Δ after the liquid crystal treatment is not particularly limited, and it is considered that the scraping of the alignment film by rubbing treatment is practically limited to 10.0. The alignment film index Δ after liquid crystal treatment is preferably 1.5 to 10.0, more preferably 2_0 to 8_0. When the alignment index Δ after the liquid crystal treatment is 丨3 or more, the uniaxial alignment property is sufficient, and the obtained liquid crystal display element has good black display characteristics. The film thickness of the alignment film for a liquid crystal display device of the present invention is usually 10 to 500 nm, preferably 30 to 200 nm. The film polyimide varnish having the alignment of the above-mentioned alignment index after the liquid crystal treatment of the present invention can be formed into a polyamic acid or a p〇lyainic ester. A varnish composition in which a polymer component such as soluble polyamidamine or polyamide-imide is dissolved in a solvent. After the varnish composition is applied to the substrate, the alignment film is formed after the solvent is dried. The polymer component may be a random copolymer, a block polymer, or the like, or a plurality of polymer components may be used to form a polyimide film varnish for forming an alignment film. Any polymer compound having a sulfene bond can also be used. Soluble polyamidoline obtained by reacting tetracarboxylic dianhydride or the like with diamine 25 1326699 14414pif.doc (diamine) to obtain polylysine, followed by dehydration reaction of polylysine or the like is particularly preferable. A polymer compound bonded by a melamine. The tetracarboxylic dianhydride to which the polyamic acid 'soluble polyamidamine is given, which belongs to the aromatic ring (including heterocyclic aromatic) which is directly bonded to the dicarboxylic anhydride on the aromatic ring A compound of any of the aliphatic systems (including a heterocyclic ring) which does not directly bind a dicarboxylic acid anhydride is also preferable. The soluble polyamidene obtained by using the polylysine, the dehydration reaction of the polyamic acid, or the like is preferably a structure containing no oxygen or sulfur such as an ester or ether bond, and the structure is easy to make. The electrical characteristics of the liquid crystal display element are degraded. However, even with such a structure, if the amount of use does not affect the range of these characteristics, no problem occurs. Specific examples of the tetracarboxylic dianhydride which can be used in the present invention are, for example, the above 1-1 to 1-38. The tetracarboxylic dianhydride which can be used in the present invention is not limited to such a compound, and other various types of compounds may be present within the scope of the object of the invention. Further, these tetracarboxylic dianhydrides may be used singly or in combination of two or more. Among these compounds, preferred are formula 1-1, formula 1-2, formula 1-13, formula 1-17, and formula. 1-18, Formula 1-19, Formula 1-20 'Formula 1-27, Formula 1-28, and Formula 1-29. More preferably, it is a tetracarboxylic dianhydride represented by any one of Formula 1-1, Formula 1-13, Formula 1-17, Formula 1-19, Formula 1-20, and Formula 1-29. The aliphatic tetracarboxylic dianhydride is superior to the electrical properties of the voltage holding ratio of 26 1326699 14414pif.doc. However, the orientation characteristics of the aliphatic tetracarboxylic acid diterpenes and the like are slightly inferior, especially when the temperature is less than 180 ° C, and the alignment tends to collapse. On the other hand, although the aromatic tetracarboxylic dianhydride has excellent alignment properties, it is preferable to use an aliphatic tetracarboxylic dianhydride as a function related to electricity. In the polymer component of the polyamidoamine-based varnish of the present invention, a diamine which gives polylysine or a soluble polyamidamine, for example, specifically, the above formula 2-1 to 2-56 °, and further includes: a gallbladder Cholesteryl, androsteryl 'A-cholesteryl, epiandrosteryl, ergosteryl, estoryl, 11 a-hydroxymethylsteryl, 11 α -progesteryl, lanosteryl, Methyltestosteryl, Norethisteryl 'pregnenonyl, Θ-sitosteryl, stigmasteryl, Testosteryl, cholesteryl citrate, and the like having a branched steroid of a steroid structure. As the other diamine which can be used with the above-mentioned diamine oxime used in the present invention, it includes a sand oxide system diamine which is combined with siloxan. The molybdenum diamine is not particularly limited, and a naphthenic diamine represented by the formula (2) can be preferably used in the present invention. H2n—〇)y~sj&quot;tR4&quot;hrNH2 (2) R3 R3 where R2 and R3 are independently alkyl or phenyl groups having a carbon number of 1 to 3, and 1 is methylene and phenylene. Or an alkyl substituted ethylene 27 1326699 I4414pif.doc support. X is an integer of 1 to 6, and y is an integer of 1 to 10. The diamine which can be used in the present invention is not limited to these compounds, and other various types of compounds may be used within the scope of the object of the invention. Further, these diamines may be used singly or in combination of two or more. Among these compounds, preferred are Formula 2-5, Formula 2-6, Formula 2-9, Formula 2-10, Formula 2-11, Formula 2-12, Formula 2-13, Formula 2-14, and Formula. 2-15, Formula 2-16, Formula 2-17, Formula 2-18, Formula 2-19, Formula 2-20, Formula 2-30, Formula 2-35, Formula 2-39, Formula 2-40, Formula Diamine represented by 2-41, Formula 2-42, Formula 2-43, and Formula 2-56. More preferably, it has a linear alkylene having the formula 2-12, the formula 2-13, the formula 2-14, the formula 2-15, the formula 2-16, the formula 2-17, and the formula 2-18' In the aromatic diamine represented by Formula 2-19, Formula 2-20, and Formula 2-39, η is a diamine of 2 to 10, and Formula 2-13 of an benzene ring having an amine at a 3,3'-position. The diamine represented by Formula 2-16 and Formula 2-20, and the diamine represented by Formula 2-14 of the amine at the 3,4' position. A higher alignment index Δ can be easily obtained by using these diamines. On the other hand, the diamine which can be used in the present invention, like the above-mentioned tetracarboxylic dianhydride, belongs to an aromatic system (including a heterocyclic aromatic group) in which an amine group is directly bonded to an aromatic ring, and there is no direct bond on the aromatic ring. A compound of any one of the aliphatic groups (including heterocyclic groups) of the diamine is also preferable. Among them, the aromatic diamine having a cyclic structure and the aliphatic diamine having a cyclic structure can maintain good liquid crystal alignment. Further, it is preferable that the structure of oxygen or sulfur which does not contain an ester or an ether bond or the like is preferable. This structure tends to lower the electrical characteristics of the liquid crystal display element. However, even with such a structure, no problem occurs if the amount used is within the range of 28 1326699 14414pi. Further, the reaction terminal of the polycarboxylic acid and the soluble polyamidamine other than the tetracarboxylic dianhydride and the diamine may be formed, and a monoamine compound or/and a monocarboxylic anhydrase may be used. ). In order to improve the adhesion to the substrate, an aminoguanidine (aminoguanidine) compound can also be introduced. Examples of the aminoguanidine compound include para-aminophenyltrimethoxysilane, para-aminophenyltriethoxysilane, and m-aminotoluene trimethoxysilane ( Meta-aminophenyltrimethoxysilane) 'meta-aminophenyltriethoxysilane, aminopropyltrimethoxysilane, arri propyl triethoxysilane, etc. The molecular weight of the polyamic acid or the soluble polyamidamine used in the present invention is, for example, a polystyrene-based weight average molecular weight (Mw) in terms of gel permeation chromatography (GPC). It is preferably 10,000 to 50,000, more preferably 20,000 to 200,000. The concentration of the polymer component in the polyamido varnish of the present invention is preferably 0.1 to 40% by mass (%), although it is not particularly limited. When the varnish is coated on a substrate, it is necessary to dilute the polymer component contained in advance by using a solvent in order to adjust the film thickness. When the concentration of the polymer component is 4% by weight or less, the viscosity of the varnish is most suitable, and when it is necessary to dilute the varnish in order to adjust the film thickness, it is preferred to use a solvent which is easily mixed with the varnish. When a coating method such as a spirmer method or a printing method is used, in order to maintain the film 29 1326699 14414 pif.doc - . . . , the thickness is generally adjusted to 10% by weight or less. Other coating methods such as a dipping method or an ink-jet method may also use a lower concentration. On the other hand, when the concentration of the polymer component is at least 5% by weight, the film thickness of the obtained alignment film tends to be an optimum thickness. Therefore, in a general coating method such as a spin coating method or a printing method, the concentration of the polymer component is 〇 J by weight or more, preferably 0.5 to 10% by weight. However, depending on the coating method of the varnish, a more dilute concentration can also be used. In the polyamidamine-based varnish of the present invention, the solvent which can be used together with the polymer component is not particularly limited, and any solvent having a polymer component can be used. The related solvent widely includes a solvent which is often used in the manufacturing engineering or use of a molecular component such as polyamine, soluble polyamidamine or the like, and can be appropriately selected depending on the purpose of use. These solvents include all of the solvents listed below. As a solvophilic proton polar organic solvent for polylysine or soluble polyamidamine, including N-methyl-2-pyrrolidone, dimethyl Dimethylimidazolidinone 'N-methylcaprolactam, N-methylpropionamide, Ν, Ν-dimethylacetamide (N, N-dimethylacetamide) ), dimethylsulfo.xied, N,N-dimethylformamide, N,N-diethylformamide,diethyl Diethylacetamide, 7-butyl acrylate (butyrolactone) and the like. Other solvents for the purpose of improving coating properties and the like include: alkyl lactic acid 30 1326699 I4414 pif. doc (alkyl lactic acid), 3-methyl-3-methoxybutanol , tetralin, isophorone, ethylene glycol monobutyl ether, etc. ethylene glycol monoalkyl ether, diethylene glycol monoacetic acid (diethylene) Glycol monoethyl ether), etc. Diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenylacetate, triethylene glycol monoalkyl Ether), propylene glycol monobutyl ether, etc., propolene glycol monoalkyl ether, diethyl malonate, etc. Dialkyl glycol monoalkyl ether, dipropylene glycol monomethyl ether, etc., esters of these acetates, etc. . Wherein, N-methyl-2-pyrrolidone, dimethylimidazolidinone, 7-butyl acrylate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, diglycerin single Methyl ether and the like are particularly good. In the present invention, the polyamido varnish may contain various additives as needed. For example, when it is desired to improve the coating property, it is possible to match a surfactant which meets the relevant purpose, and it is necessary to improve the prevention of charging, to prevent the charging agent from being added, or to improve the adhesion of the substrate, and to use a silane coupling. Or a mixture of ingredients. The liquid crystal display device of the present invention usually contains a liquid crystal sandwiched between two substrates having a transparent electrode. The liquid crystal, TN type liquid crystal display has a 90 degree twist in the 14414pif.doc element, and a 180 degree twist in the STN type liquid crystal display element. In particular, in a TFT-type liquid crystal display device using a color display of a thin film transistor, a thin film transistor, an insulating film, a protective film, a pixel electrode, and the like are formed on the first transparent substrate, and the second transparent substrate is interrupted. Black matrixs of light other than pixels, color filters, flattening films, and pixel electrodes. Further, the IPS type liquid crystal display device according to the present invention is constituted by a first transparent substrate on which a thin film transistor is formed, a second transparent substrate on the opposite side, and a liquid crystal interposed between the substrates. The first transparent substrate has a pixel electrode formed as a molar extending tooth and a common electrode. The second transparent substrate, which is the same as the conventional liquid crystal display element, has a black matrix, a color filter, and a planarization film that block light other than the pixels. The dentate electrode is formed on a transparent substrate such as glass, and a metal such as chromium (Cr) is deposited by a sputtering method, and a resist pattern of a predetermined shape is used as a mask. And formed by etching. Then, a step of applying a varnish to the obtained two transparent substrates, a subsequent drying step, and a heat treatment step necessary for the dehydration and ring closure reaction are carried out, and a coating method of the varnish coating step is performed, and a generally known method includes Spin coating method, printing method, dipping method, dropping method 'inkjet method, and the like. These methods are equally applicable to the present invention. Further, in terms of the drying step and the heat treatment method necessary for the dehydration and the ring closure reaction, generally known methods include a method of heat treatment in an oven or an infrared furnace, and heating on a hot plate. Method and so on. These methods are equally applicable 32 1326699 14414pif.doc Evaporation of the solvent in the drying step of the invention ** is preferably carried out at a lower temperature in the range possible. The heat treatment step is preferably carried out at a temperature in the range of from 150 ° C to 300 ° C. Then, a liquid crystal display element is produced by a step of performing an alignment treatment on the obtained alignment film, a step of assembling the substrate by a spacer, a step of sealing the liquid crystal material, and a step of adhering the polarizing film. For the treatment method in the alignment treatment, generally known methods include a rubbing method, a photo-alignment method, a transcription method, and the like, and these methods are equally applicable to the present invention as long as they are within the scope of the present invention. A particularly preferred alignment treatment method in the present invention is a rubbing method. Any rubbing treatment conditions are possible as long as the scope of the invention is reached. However, particularly preferred conditions are: hair tip insertion amount of 0.2 to 0.8 mm (mm), stage movement speed of 5 to 250 mm/sec (mm/s), and rotor rotation speed of 500 to 2 〇. 00 rpm (rpm). A better condition is that the platform moves at a speed of 31 to 250 mm/s. Increasing the amount of hair pushing, reducing the speed of the platform, or speeding up the rotation speed of the rotor 'enhanced friction treatment conditions, a higher alignment index Δ u can be obtained after liquid crystal treatment. However, if the condition of the friction treatment is excessively enhanced, an alignment film will occur. Film cutting. The alignment film platform of the present invention can move at a speed of 31 mm/sec or more, and there is still room for increasing the production speed. The liquid crystal display element of the present invention can be subjected to a cleaning treatment with a cleaning liquid before and after the alignment treatment. As far as the washing method is concerned, it includes brushing, jet spraying, steam washing or ultrasonic cleaning. These washing methods can be carried out separately or used. In the case of the washing liquid, various alcohols such as pure water, methyl alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like, benzene, toluene (peptone) can be used. Toluene), xylene, and other aromatic hydrocarbons, such as chloride methylene, etc., ketone solvents such as acetone, methyl-ethyl-ketone, etc. There are no solvents defined here. Of course, these cleaning solutions must use a solvent that is sufficiently refined and has little impurities. Among the liquid crystal display elements which can be used in the present invention, the suitable pretilt angle varies depending on the type of the liquid crystal display element. The small pretilt angle is suitable for the IPS type liquid crystal display element, and the pretilt angle of 3 to 8 degrees is suitable for the TN type liquid crystal display element. Further, there is a case where a larger pretilt angle is required for the STN type liquid crystal display element and the VA (Vertical Alignment) type liquid crystal display element. In particular, the IPS type liquid crystal display device of the present invention has a suitable pretilt angle of 0.1 to 5.0 degrees, more preferably 0.2 to 3.0 degrees. In the IPS type liquid crystal display element, a large liquid crystal pretilt angle is not required in the driving principle. The IPS type liquid crystal display element can obtain good viewing angle characteristics in a range of a pretilt angle of 0.1 to 5.0 degrees. The liquid crystal composition used in the liquid crystal display device of the present invention is not particularly limited, and various liquid crystal compositions having a dielectric anisotropy of positive can be used. Examples of the preferred liquid crystal composition include: Japanese Patent Publication No. 3086228, No. 2635435, Japanese Patent Laid-Open Publication No. Hei No. 5-501735, No. Hei 8-15782, No. Japanese Patent Laid-Open No. Hei 9-241644 (EP885272A1), JP-A-H9-302346 (EP806466A1), and JP-A-34-132269 14414pif.doc 8-199168 (EP722998A1) : 9-255956, JP-A-9-241643 (EP885271A1), Special Kaiping. 10-204016? 844,229,1), JP-A-H10-204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like. Various liquid crystal compositions having negative dielectric anisotropy can be used. Examples of the preferred liquid crystal composition include: JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, JP-A-8-104869 Japanese Patent Laid-Open No. Hei 10-168076, No. Hei 10-168453, No. 10-236989, No. 10-236990, No. 10-236992, No. 10-236993, and No. 10-236994. Japanese Patent Laid-Open No. 10-237000, No. 10-237004, No. 10-237024, No. 10-237035, No. 10-237075, No. 10-237076, and No. 10-237448 (EP967261A1). Japanese Patent Laid-Open No. Hei 10-287874, No. 10-287875, JP-A No. 10-291945, No. 11-029581, No. 11-080049, No. 2000-256307, and No. 2001-019965. It is disclosed in No. 2001-072626, JP-A-2001-192657, and the like. The use of the above optically active compound in the liquid crystal composition having positive or negative dielectric anisotropy is also not inhibited. [Examples] Hereinafter, the present invention will be described by way of Experimental Examples and Comparative Examples, but the present invention is not limited to these examples. Further, the names of the dicarboxylic acid diterpenoids, diamines and solvents used in the experimental examples and the comparative examples are indicated by the abbreviation for 35 1326699 14414 pif.doc. The following is a description of the abbreviations used. • tetracarboxylic dianhydride PMDA · pyromellitic dianhydride CBDA : 1,2,3,4-cyclobutanetetracarbyl dianhydrde (1,2,3,4-cyclobutanetetracarbxylic dianhydrde) TDA : l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy)-3-furanyl)-naphtho[l,2-c]furan-1,3 - Dione (1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo)-3-furanyl )-naphth[l,2-c]furan-l ,3-dione • Diamine BZ3: 1,3-bis(4-(4-aminobenzyl)phenyl)propane) DDE : 4,4'- 4,4-diamino-diphenyl-ethane • Solvent composition NMP : N-methyl-2-pyrrolidone GBL·: 7- Butyl lactone (r-butyroiactone) BC : butyl cellulose (butyl cellosolve) Experimental Example 1 (1) Polyimide-based varnish A1 was prepared by using a thermometer, a stirrer, a raw material inlet, and a nitrogen introduction port of 200 ml (ml). In a four-necked flask, 2.7760 g (g) of BZ3, 0.3624 of DDE, and 30.00 g of dehydrated NMP were added, and stirred in a dry nitrogen stream to dissolve 36 1326699 14414 pif.doc solution. While maintaining the temperature of the reaction system at 5 ° C, 1.8616 g of PMDA 1.8616 g was added, and after reacting for 30 hours, 35.00 g of BC and 30.00 g of GBL were added to prepare a polymer having a concentration of the polymer component of 5% by weight. Proline. When the temperature is raised by the reaction temperature in the reaction of the raw material, the reaction temperature is suppressed to 70 ° C or lower to carry out the reaction. Further, in the experimental example of the present invention, it is necessary to carry out an experiment while confirming the viscosity in the reaction, and the viscosity of the varnish after the addition of BC is changed to 30 to 35 milliPascals per second (mPa · s) (using an E-type viscometer, At 25 ° C), it is regarded as the end point of the reaction and is kept at a low temperature. The polyamine acid obtained had a weight average molecular weight of 70,000. Further, the weight molecular weight was measured at a column temperature of 50 ° C by a Shimadzu GPC measuring device (chromatography pack C-R7A). The varnish A1 obtained by the above method was diluted with a 1:1 mixed solvent of NMP and BC to adjust a coating varnish having a total polymer component concentration of 3% by weight. (2) Measurement of film thickness of infrared light absorbance alignment film and calculation of distribution index Δ The obtained coating varnish was applied onto a ruthenium substrate by spin coating. The coating conditions were 2,300 rpm and 15 seconds. After coating, the film was dried at 80 ° C for about 5 minutes, and then subjected to a heat baking treatment at 210 ° C for 30 minutes to form an alignment film of about 80 nm. The obtained polyamidamine alignment film was subjected to rubbing treatment under the following conditions in a rubbing treatment apparatus of a rice garden measuring apparatus: rubbing cloth (fleece length: 1.9 mm: rayon), the amount of fluffing was 0_4 mm, and the platform was moved. The speed is 60 nm/sec, and the rotor rotation speed is l rpm. The obtained alignment film (about 13 mm angle) was placed in the center of a 30 mm diameter dial 37 1326699 144l4pif.doc and covered with liquid crystal (4-cyano-4-pentylbiphenyl) 4-cyano-4-pentylbiphenyl On the surface of the polyimide film. This was placed in an oven at 110 ° C for 30 minutes, and then taken out and allowed to cool to room temperature (22 to 24 ° C). Then, the polyiminamide film was gently loaded into a beaker containing 20 ml of n-hexan (n-hexan), immersed for a few minutes and stirred frequently, and the used n-hexane was discarded, and 20 ml of new n-hexane was charged. Dip for another 15 minutes. Then, the polyimide film was taken out from n-hexane, and the surface of n-hexane was dried at room temperature, and then placed in a desiccator for 12 hours or more. Further, regarding the infrared absorption spectrum measurement of the alignment film of the liquid crystal (4-cyano-4-pentylbiphenyl)' which is removed from the polyamidamine film, the peak of the cyano group has been confirmed. Not detected. The infrared absorption spectrum of the obtained alignment film was measured using a FT-IR apparatus (Paragon 100) manufactured by Perkin Elmer, and the measurement was carried out under the conditions of a decomposition energy of 4 cm·1 and a score of 144 times. Further, dry nitrogen or air (dew point - 60 ° C or lower) was used to remove the noise of water vapor, and the sample chamber and the spectroscope were washed at a flow rate of 10 liters/min (L/min) and 5 L/min, respectively. The infrared rays transmitted through the polarizer are incident perpendicularly from the alignment film to the alignment film. The absorbance measured when the rubbing direction (alignment processing direction) of the sample is parallel to the polarizing direction is A||, and the absorbance measured in the vertical direction is A丄. The spectral difference between the parallel and vertical measured infrared spectra is calculated by absorbance, and the peak height corresponding to the C-N stretching vibration is set to (A|| - A丄). Further, a sum (A|| + A 丄) corresponding to the peak height of the C-N stretching vibration of the parallel and vertical spectrums expressed by the absorbance is calculated. 38 1326699 14414pif.doc The film thickness (d) of the alignment film was 82,2 nm as measured by an Ellipsometer (DVA-FLG) manufactured by Gully Optical Industries. Then, according to the formula (1), the obtained (All - A 丄), (All + A 丄), and the film thickness (d) are substituted into the calculation, and the alignment index Δ of the alignment film obtained after the liquid crystal treatment is 2.62. » (1) X d A |丨一 A 丄△-- A +A 丄(3) Production of liquid crystal cell (cell) for measuring black display characteristics and voltage retention rate. Use 栉 with IPS In addition to the glass substrate of the electrode and the two non-electrode glass substrates, an alignment film is formed in accordance with the method of using the ruthenium substrate. The alignment film obtained by the above method was ultrasonically washed in ethanol for 5 minutes, and then the surface was washed with pure water, and then placed in an oven and dried at 120 ° C for 30 minutes. A 4 μm (gap) material is spread on the glass substrate of the electrode, and the surface on which the alignment film is formed is used as an inner surface to face the non-electrode glass substrate, and then sealed with an epoxy hardener. (seal), a parallel liquid crystal cell (parellel cell) with a gap of 4/zm is completed. The liquid crystal composition A was injected into the above liquid crystal cell, and the injection port was sealed with a light hardener. Then, heat treatment at 110 ° C for 30 minutes was carried out to obtain a liquid crystal cell for measuring black display characteristics and voltage holding ratio. Further, the glass substrates and the non-electrode glass substrates with the IPS pin electrodes are opposed to each other in the same direction of rubbing. The composition of the liquid crystal composition A used as a liquid crystal material is expressed as follows. Neighbors of these compositions (NI) 39 1326699 14414pif.doc

The point is 100.0 ° C, and the birefringence is 0.093 〇 liquid crystal composition A

F ; L7wt. % ' 16wt. % lQwt:.:;9〇 10.wt.,% ;|wt:: %. .l:3wt;i%: p

P

Then, using the liquid crystal characteristic evaluation device 40 14414pif.doc. (0MS-CA3) of Central Precision Machinery Co., Ltd., under the crossed nicol, the alignment direction of the liquid crystal is aligned with the direction of the polarizer, and the light transmittance is measured. The result was 0.022%, which was used as an evaluation of blackness and non-characteristics. Further, in the state where the liquid crystal cell for characteristic measurement is not displayed in black, the light amount when the polarizer is arranged in parallel with the analyzer is taken as 1 〇 0%, and the light transmittance is calculated. Moreover, it was found that there was no alignment spot or alignment defect like the alignment rib, and a very uniform display was obtained. In addition, the voltage holding ratio of this voltage was determined to be 98.3% by the existing method (refer to Minamata, the fourteenth liquid crystal seminar draft set, page 78). The measurement conditions of the voltage holding ratio were a gate width of 69 μsec (s), a frequency of 60 Hz, a wave height of ±4.5 volts (v), and a measurement temperature of 60 °C. (4) Production of liquid crystal cell for pretilt angle measurement A glass substrate with a pair of indium tin oxide (IT0) transparent electrodes was used, and was made of a gap material of 20, except that the rubbing method was antiparallel bonding (antiparallel). A liquid crystal cell for measuring a pretilt angle was produced by the same method as the liquid crystal cell for measuring the black display characteristics and the voltage holding ratio. Further, the liquid crystal material used in the measurement of the pretilt angle was also the same as that used in the black display measurement. Using this cell, the pretilt angle of the liquid crystal was measured by a crystal rotation method, and as a result, it was 1.7 degrees. Experimental Examples 2 to 6 'Comparative Examples 1 to 3 The varnishes A2 to A6 and the varnishes B1 to B3 were prepared according to the raw material composition of the following Table 1', and the varnish A1 in Experimental Example 1 was replaced with the same as in Experimental Example 1. Evaluation of the alignment index Δ, black display characteristics, voltage holding ratio, and pretilt angle. 1326699 14414pif.doc IPS type liquid crystal display element with excellent black display characteristics. Further, it was found that the alignment films of Experimental Examples 1 to 6 exhibited excellent voltage holding ratio and pretilt angle as IPS type liquid crystal display elements. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a structural view of a dentate electrode for IPS. 44

Claims (1)

1326699 Revision date: November 12, 1998 x jjt jr 14414pif.doc Public f No. 93123201 Chinese patent scope without slash correction Patent scope of this application · v〇书丨月丨!·日修正1· A polya An amine-based varnish for forming an alignment film of a liquid crystal display element. The polyamidamine-based varnish can form an alignment film having a distribution index A of 1.3 or more after liquid crystal treatment represented by the formula (1), A-A丄A + A丄X d Δ Wherein A || is the incident infrared light incident on the alignment film having a polarization component parallel to the alignment treatment direction, and the absorbance of the carbon-nitrogen stretching vibration of the imipenem ring, A 丄 is incident perpendicular to the alignment treatment direction. When the infrared light of the polarizing component is in the alignment film, the absorbance of the carbon-nitrogen stretching vibration of the melamine ring, d is the film thickness of the alignment film (unit: nanometer), The polymer component of the polyamidamine-based varnish includes at least one selected from the formula 4-12 and the tetracarboxylic dianhydride represented by each of the formulas 1-1 to 1-12 using 30 mol% or more. The soluble polyamidamine obtained by the diamine represented by the formula 2-39 or the poly-proline which is a precursor thereof, wherein η in the following formula is an integer of 1 to 20. 45 1326699 14414pif.doc 2. The polyamido varnish according to claim 1, wherein the polymer component of the polyamido varnish further comprises at least one of the following tetracarboxylic dianhydrides and at least one of the following The soluble polyimine obtained by the diamine or the poly-proline which is its precursor, here, in the following 46 1326699 14414 pif. doc, η is an integer of 1 to 20, and R is a hydrogen atom. Or a hospital with a carbon number of 1 to 20, and any of the thiol groups may be substituted with -0-, -CH=CH- or a C^C-, any of cyclohexane and benzene rings. The hydrogen atom may also be substituted by halogen or an alkyl group having 1 to 5 carbon atoms. 47 1326699 14414pif.doc 1-23 1-24 1-27 1-28 1-29 1-31 1-33 1-30 1-32 48 1326699 14414pif.doc 49 1326699 14414pif.doc 2-19 2-20 f^mmSmSllSlr^ ^mmSSSS!^ 2-22 Δ〇2~Λ i—NH2 2-23 50 1326699 14414pif.doc 2-31 51 1326699 14414pif.doc 2-41 52 1326699 14414pif.doc 2-49 2-50 2-51 53 1326699 14414pif.doc 2-53 3. The polyaminin-based varnish according to claim 1, wherein the liquid crystal display element is a lateral electric field type liquid crystal display element which is displayed by forming a main parallel electric field on a surface of the substrate. 4. The polyamido varnish according to claim 2, wherein the alignment index Δ after the liquid crystal treatment is 1.5 to 10.0, wherein the alignment index Δ after the liquid crystal treatment is as in the first item of the patent application. The formula (1) is described. 5. The polyamido varnish according to claim 2, wherein the tetracarboxylic dianhydride is from the formula 1-13, the formula 1-17, the formula 1-18, the formula 1-19, and the formula 1- 20. At least one of the tetracarboxylic dianhydrides represented by the formulae 1-27, 1-28, and 1-29 is selected. 54 1326699 14414pif.doc 6. The polyamido varnish according to claim 2, wherein the diamine is from the formula 2-5, the formula 2-6, the formula 2-9, the formula 2-10, 2-U, Formula 2_13, Formula 2-14, Formula 2-15, Formula 2-16, Formula 2-17, Formula 2-18, Formula 2-19, Formula 2-20, Formula 2-30, Formula 2 35. At least one of the diamines represented by the formulas of Formula 2-40, Formula 2-41, Formula 2-42, Formula 2_43, and Formula 2-56, wherein η of these formulas is 2 to 10 An integer of any hydrogen atom in the benzene ring may be substituted by halogen or an alkyl group having 2 to 5 carbon atoms. 7. The polyamido varnish according to claim 1, wherein the diamine is from the formula 2-13, the formula 2-14, the formula 2-15, the formula 2-16, and the formula 2-17' 2-18, at least two species of the diamines represented by the formulae 2-19 and 2-20, wherein η in the formula is an integer of 2 to 10, and any hydrogen atom in the benzene ring is also It may be substituted by halogen or an alkyl group having 1 to 5 carbon atoms. 8. An alignment film formed by using the polyamidamine-based varnish according to any one of claims 1 to 7, wherein the alignment film has a thickness of 10 to 500 nm 〇9. The alignment film according to item 8 is characterized in that the alignment treatment is carried out under the conditions of a fluffing amount of 0.2 to 0.8 mm, a platform moving speed of 5 to 250 mm/sec, and a rotor rotation speed of 500 to 2,000 rPm. The electric field type liquid crystal display device includes: a first transparent substrate on which a thin film transistor is formed; a second transparent substrate on the opposite side; and a liquid crystal interposed between the first transparent substrate and the second transparent substrate, wherein the first The transparent substrate has a pixel electrode formed by mutually extending molars and a common electrode, and the second transparent substrate has a black matrix, a color filter, and a planarizing film that block the pixels from the light of 55 1326699 14414 pif.doc. An alignment film according to item 8 of the patent application is provided on a surface of the first transparent substrate that is in contact with the liquid crystal on the second transparent substrate. 11. A lateral electric field type liquid crystal display device comprising: &gt; a first transparent substrate forming a thin film transistor; a second transparent substrate opposite; a liquid crystal sandwiched between the first transparent substrate and the second transparent substrate, wherein the first transparent substrate has a pixel electrode and a common electrode formed by mutually extending teeth, and the second transparent substrate has an occlusion The black matrix, the color filter, and the flattening film of the light other than the pixel, and the alignment film according to claim 9 of the invention, wherein the first transparent substrate and the second transparent substrate are in contact with the liquid crystal. 56