KR20020031042A - Varnish for a liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

According to the present invention, an optically compensated birefringent (OCB) type liquid crystal display device is manufactured by using an alignment film formed from a liquid crystal aligning agent varnish containing solid fine particles or an alignment film in which solid fine particles are dispersed on a surface, thereby preventing from spray alignment at low voltage. It is possible to provide a liquid crystal display device which quickly and reliably transitions to a band alignment state.

Description

Varnish for a liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device for performing display by changing light transmittance using a band alignment state which may have a twist orientation, an alignment film for the liquid crystal display device, and a liquid crystal aligning agent varnish for forming the same.

Conventional liquid crystal display devices are mainly display devices using nematic liquid crystals, TN-type liquid crystal display devices twisted by 90 ^° , STN-type liquid crystal display devices usually twisted by 180 ^° or more, so-called TFT type liquid crystal display devices using thin film transistors. Has been put into practical use. However, these liquid crystal display devices have a drawback that the response speed is slow. In addition, there is a drawback that the viewing angle at which an image can be visually checked properly is narrow, and that the luminance or contrast decreases when viewed in the oblique direction, and that luminance inversion occurs in the meso phase. Among these, the problem of the latter viewing angle is a multi-domain vertical alignment using a technique of transverse electric field-type in-plane switching (hereinafter referred to as IPS) type liquid crystal display device, vertical alignment and projection structure ( Multi-domain Vertical Alignment (hereinafter referred to as MVA) type liquid crystal display device or a liquid crystal display device using an optical compensation film or the like has been improved and put into practical use. However, the problem of the former response speed is still not solved, and the development of the liquid crystal display element in which good visual confirmation is obtained even in the display of a high speed moving picture and in the inclination direction is actively performed.

For example, Japanese Patent Application Laid-Open No. 784254 discloses an optically compensated birefringence (hereinafter referred to as "optically compensated birefringence") that performs display by changing light transmittance using a metastable band alignment state which may have a twist orientation. An OCB) type liquid crystal display element is proposed. The OCB type liquid crystal display device is characterized by a very fast response speed and a relatively wide viewing angle, and is highly expected as a next generation liquid crystal display device.

One example of such an OCB type liquid crystal display is shown in FIG. 1. As in the conventional liquid crystal display device, the glass substrate 1 on which the transparent electrode 2 is formed, the glass substrate 8 on which the transparent electrode 7 is formed, and the substrate 1 and 8 are disposed It has the liquid crystal layer 4. In addition, the alignment films 3 and 6 are formed on the transparent electrodes 2 and 7, and the alignment film is subjected to an alignment process so that the liquid crystal molecules are aligned in parallel and in the same direction. The gap between the transparent electrodes 2 and 7 is kept constant by interposing a spacer 9 between the two. In addition, polarizing plates 10 and 12 are arranged in cross nicol on the outside of the substrates 1 and 8, and a phase compensating plate for optically compensating the transmitted light between the polarizing plates 10 and 12 and the substrates 1 and 8 ( 11 and 13).

The liquid crystal display of the above structure is characterized in that it causes a metastable band alignment state which may have a twisted orientation by applying voltage, and arranges phase compensation plates 11 and 13 for low voltage driving and viewing angle enlargement. In addition, in terms of performance, high-speed response can be achieved even in the intermediate image display area, and it has a wide viewing angle characteristic.

The OCB type liquid crystal display element requires an initialization process of changing from the spray alignment state 4 to the metastable band alignment state 5 before the display of the image. Such an initialization process can be performed in a relatively short time, for example, by applying a high voltage of 10 to 30V. However, when driving at a low voltage because an excessive load cannot be applied to the driving IC, there is a problem in that it does not transition to the band alignment state or even requires a minute time for the initialization process.

Various methods have been proposed to solve the above problems. For example, Japanese Unexamined Patent Application Publication No. Hei 9-96790 has a twisted alignment state similar to that of a TN type liquid crystal display device, and an alignment state rising in the normal direction of the substrate similarly to the OCB type liquid crystal display device. Techniques for combining are described. This technique avoids the above-mentioned problem by eliminating the need for the band alignment state to be formed, and at the same time forms the alignment state similar to the band alignment, thereby making the response speed faster than that of the TN type liquid crystal display element. In practice, however, even when the alignment state similar to the band alignment is formed, a high speed response speed is not necessarily obtained.

Further, Japanese Laid-Open Patent Publication No. Hei 11-7018 forms a high initial tilt angle region for giving an initial tilt angle larger than its surroundings on the surface of the alignment film, and then contains a chiral agent in the liquid crystal to twist angles of the liquid crystal molecules. The technique for setting the value to 160 to 200 degrees is described. This technique serves as a nucleus that forms a high initial tilt angle region to give an initial tilt angle larger than its surroundings on the surface of the alignment film and transitions it to a band alignment state. In practice, however, the alignment film having such a configuration is easily affected by the manufacturing process, and it is not easy to stably form a high initial tilt angle region. In addition, the larger the initial inclination angle, the larger the variation in the initial inclination angle in the reliability test or the like, which is also problematic.

In addition, a technique has been proposed in which a transition to a band alignment state is performed in a short time by providing a small projection structure on the electrode as in the case of an MVA type liquid crystal display device. There is a problem such that orientation defects are likely to occur in the protruding structure portion.

In addition, many techniques for containing solid fine particles in an alignment film have been proposed. However, these techniques are applied to general liquid crystal display devices or ferroelectric liquid crystal display devices, and are essentially different from those of the present invention described below which are applied to OCB type liquid crystal display devices which are a special driving mode. In addition, these prior arts do not refer to the OCB type liquid crystal display device, nor are they proposed. For example, the following is described as a technique of containing individual fine particles in a general liquid crystal display element. Japanese Unexamined Patent Publication (Kokai) No. 7-181499 discloses a liquid crystal display device characterized by dispersing electric field agent particles in an alignment film, but the effect partially changes the strength of the electric field applied to the liquid crystal. By improving the viewing angle. This technique is particularly effective for a TN type or STN type liquid crystal display device in which a viewing angle is a problem, and is essentially different from the technology for stabilizing the band alignment state of the OCB type liquid crystal display device of the present invention. In addition, JP-A-7-3018104, JP-A-8-54629, JP-A-8-54631, JP-A-8 Although the same technique is described in -114803 and the like, these are all techniques for improving the viewing angle to prevent display defects, to prevent ignition, to rub rubbing, and to stabilize the band alignment state of the OCB type liquid crystal display device of the present invention. And are essentially different.

On the other hand, as a technique for incorporating solid fine particles into a ferroelectric liquid crystal display device, Japanese Patent Application Laid-Open No. Hei 6-95122 discloses a liquid crystal optical element in which ultrafine particles having an average particle diameter of 30 to 300 kPa are dispersed in an alignment control layer. However, the effect is to improve the intermediate phase and the roughening characteristics, and to improve the orientation by completely embedding the naturally occurring irregularities on the surface of the electrode base body by minute irregularities according to the particle diameter. This technique is particularly effective for ferroelectric liquid crystal display devices in which orientation stability is a problem, and is essentially different from the technology for stabilizing the band alignment state of the OCB type liquid crystal display device of the present invention. In addition, Unexamined-Japanese-Patent No. 3-55518, Unexamined-Japanese-Patent No. 3-92824, Unexamined-Japanese-Patent No. 3-239221, Unexamined-Japanese-Patent No. 4-296821, Japanese Unexamined Patent Application Publication No. Hei 6-180455, etc., but all of these improve the bistable characteristic, the auxiliary properties, and the VT hysteresis, which are peculiar to ferroelectric liquid crystal display devices. It is essentially different from the technique of stabilizing the band alignment state of the OCB type liquid crystal display device. As described above, the conventional technique is a technique in which solid fine particles are contained in a general alignment layer for TN, STN, or ferroelectric liquid crystal display devices, and applied to an alignment film of an OCB type liquid crystal display device applied to a metastable band alignment state as in the present invention. It is essentially different from the technology involved.

The present invention provides a liquid crystal display device which quickly and reliably transitions from a spray alignment state to a band alignment state at low voltage in the above-described OCB type liquid crystal display device, an alignment film for the liquid crystal display device, and a liquid crystal aligning agent varnish for forming the same. The purpose.

1 is a longitudinal cross-sectional view showing the configuration of a conventional optically compensated birefringent (OCB) type liquid crystal display device.

Explanation of the sign

1, 8... … … Glass substrate

2, 7... … … Transparent electrode

3, 6... … … Alignment film

4 … … … Liquid crystal alignment (spray alignment state) when no voltage is applied

5... … … Liquid crystal orientation (band alignment state) when voltage is applied

9. … … Spacer

10, 12... … … Polarizer

11, 13... … … Phase compensation plate

14. … … Liquid crystal cell

As a result of earnestly examining in order to solve the problems described above, this problem can be solved by using an alignment film formed of a liquid crystal aligning agent varnish containing solid fine particles or an alignment film in which solid fine particles are dispersed on the surface of the OCB type liquid crystal display device. The present invention was completed based on the present finding.

The present invention is configured as follows.

The first aspect of the present invention is a liquid crystal aligning agent varnish for forming an alignment film for liquid crystal display device which performs display by changing light transmittance using a band alignment state which may have a twist orientation, wherein the varnish is at least one kind of solid fine particles. It is a liquid crystal aligning agent varnish characterized by containing.

A preferred embodiment thereof is a liquid crystal aligning varnish in which the solid fine particles are inorganic solid fine particles.

Another preferred embodiment is a liquid crystal aligner varnish in which the solid fine particles are metal fine particles or metal oxide fine particles.

In a more preferred embodiment, the solid fine particles are C, Mg, Al, Si, Ca, Ti, V, Fe, Co, Ni, Cu, Zn, As, Zr, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb It is a liquid crystal aligning agent varnish which is inorganic solid microparticles | fine-particles containing at least 1 type of element chosen from Ce, W, Os, Ir, Pt, and Au.

Another preferred embodiment is a liquid crystal aligner varnish in which the solid fine particles are organic solid fine particles.

Another preferred embodiment is a liquid crystal aligning varnish having an average particle diameter of the solid fine particles of 1 to 500 nm.

The 2nd of this invention is a liquid crystal aligning film obtained from said liquid crystal aligning agent varnish.

3rd of this invention is a liquid crystal aligning film in which solid microparticles | fine-particles are disperse | distributed to the surface.

A fourth aspect of the present invention is a liquid crystal display device using the liquid crystal alignment film described above, wherein the liquid crystal display device performs display by changing light transmittance using a band alignment state which may have a twisted alignment.

A preferred embodiment thereof is a liquid crystal display device in which the primary particle diameter or secondary particle diameter of the solid fine particles is 0.1 to 500 times the thickness of the alignment film.

Another preferred embodiment is a liquid crystal display device characterized by the absence of orientation defects around the solid fine particles when no voltage is applied.

Another preferred embodiment is a liquid crystal display device characterized in that, when voltage is applied, the solid fine particles become nuclei that transition from the spray alignment state to the band alignment state.

That is, by selecting the above-described configuration, when a voltage is applied between the transparent electrodes, the site where the solid fine particles on the surface of the alignment film are dispersed becomes a nucleus that transitions from the spray alignment state to the metastable band alignment state. Since the transition region grows extensively, the transition is reliably performed in a short time in all regions. In addition, since the electrical energy required for such a transition can be low, there is no load on the drive circuit. Therefore, it is possible to lower the minimum voltage required for maintaining the band alignment state, that is, the boundary voltage Vcr between the spray alignment state and the band alignment state.

Although the reason where the solid fine particles are dispersed on the surface of the alignment film is not clear, the anchoring strength of the liquid crystal molecules is weaker than the surroundings thereof, and therefore, it is expected to act physically as a nucleus that transitions from the spray alignment state to the band alignment state. In addition, when voltage is not applied, orientation defects do not occur in the vicinity of the solid fine particles, and act as transition nuclei to the initial band state due to electrical stimulation.

A preferred embodiment of the present invention is to use an alignment film formed of a liquid crystal aligning agent varnish containing solid fine particles or an alignment film in which solid fine particles are dispersed on the surface of the OCB type liquid crystal display device. Inorganic solid fine particles or organic solid fine particles such as metal oxide fine particles.

Since the solid fine particles used in the present invention are so large as not to cause orientation defects in the vicinity thereof when voltage is not applied, orientation defects do not occur in a portion where no voltage is applied between the electrodes. On the other hand, at the time of voltage application, the solid fine particles of the electrode portion act as nuclei that transition from the spray alignment state to the band alignment state.

Examples of the solid fine particles according to the present invention include inorganic solid fine particles and organic solid fine particles, but any solid fine particles may be used as long as the object of the present invention is achieved. As the inorganic solid fine particles that can be used in the present invention, for example, Li, Be, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga , As, Se, Rb, Sr, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Sb, Cs, Ba, Ta, W, Os, Ir, Pt, Au, Pb, Bi, Th And metal fine particles, partial oxides of metal fine particles or metal oxide fine particles containing an element selected from U. These fine particles may be a composite of two or more kinds of metals, and may be doped with inorganic elements such as P, B, and F. In addition, heteropolyacids such as molybdate and tungstic acid, metal sulfides, metal halides and inorganic solid fine particles such as carbon and graphite may be mentioned.

Although the organic solid microparticles | fine-particles which can be used by this invention are various organic compounds or a high molecular compound, Any organic solid microparticles | fine-particles may be sufficient as long as the objective of this invention is achieved. In addition, as long as the object of the present invention is achieved, there is no problem in using two or more solid fine particles together.

The average particle diameter of the solid fine particles which can be used in the present invention is 1 to 500 nm, preferably 5 to 200 nm. If the average particle diameter is too large, the eye becomes easy to be clogged in the filtration step of the liquid crystal aligning agent varnish. On the contrary, if the average particle diameter is too small, the solid fine particles tend to aggregate in the liquid crystal aligning agent varnish, which is a problem. In addition, when it disperse | distributes to the surface of an oriented film, the average particle diameter of the primary particle of solid microparticles | fine-particles or the secondary particle formed by aggregation of the said primary particle is 0.01-500 times the thickness of an oriented film, Preferably it is 0.1-200 times. . The solid fine particles are not a problem as long as either the primary particles or the secondary particles are particle diameters that do not impair the effects of the present invention. In addition, since the solid fine particles used in the present invention tend to spontaneously disperse on the surface when forming the alignment layer, even though the particles are smaller than the thickness of the alignment layer, the solid fine particles are hardly buried in the alignment layer. The effect as a nucleus to transition to less. On the contrary, when it is too large compared with the film thickness of the alignment film, it is difficult to stably maintain the solid fine particles on the surface of the alignment film, and the solid fine particles are scattered in the rubbing process or the like, or in extreme cases, the light utilization efficiency as the liquid crystal display device is deteriorated. It may cause.

The content of the solid fine particles used in the present invention is 0.1 to 90.0% by weight, preferably 0.1 to 70.0% by weight, more preferably 10.O to 0, based on the solids content (polymer component amount) after solvent drying of the alignment agent varnish. 50.O wt%. If the content of the solid fine particles is too small, the effect as a nucleus that transitions into the band alignment state is less. On the contrary, if the content is too large, the function of the alignment film may be hindered.

The solid fine particles used in the present invention are preferably contained and used in the liquid crystal aligning agent varnish for forming the alignment film, but may be used in any form as long as the object of the present invention is not impaired. Although it is preferable to disperse | distribute uniformly in the form of the primary particle of solid microparticles | fine-particles or the secondary particle formed by aggregation of the said primary particle in an alignment agent varnish, it is used as a liquid crystal aligning agent varnish even when a part aggregates or precipitates. If removed by a process such as filtration before, there is no problem. Furthermore, there are no problems as to the addition of various dispersants, surface treatment agents or other additives for the purpose of improving the dispersibility of the solid fine particles in the liquid crystal alignment agent varnish, unless the object of the present invention is suppressed.

The liquid crystal aligning agent varnish which concerns on this invention is a varnish composition in the state which melt | dissolved the polymer component in the solvent, apply | coats on a board | substrate, and then dries a solvent and forms an oriented film. The said polymer component may be copolymerized, such as random copolymerization and block copolymerization, and can use together various types of polymer components.

The polymer component in the liquid crystal aligning agent varnish of the present invention comprises a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine, a soluble polyimide obtained by a dehydration reaction of the polyamic acid, and a dicarboxylic acid or a dicarboxylic acid halide and a diamine. Polyamides obtained by the reaction are preferably used. In addition, the hydrogen atom of the amide bond (CONH) of the polyamide may be substituted with another group.

The following is mentioned as a specific example of the tetracarboxylic dianhydride which provides the polyamic acid or soluble polyimide of this invention.

Pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, naphthalene dianhydride (2,3,6 , 7-naphthalene anhydride, etc.), 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy Diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoropyridinediphthalic acid dianhydride, 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylsulpinoxide dianhydride, p-phenylenebis (triphenylphthalic acid) dianhydride, m-phenylenebis (triphenylphthalic acid) 2 Anhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride And so on.

Cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5, 6-tetracarboxylic dianhydride, 3,3'-bicyclohexyl-1,1 ', 2,2'-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2, 5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2, -c] -furan-1,3-dione, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3 Tetracarboxylic dianhydride in which a part of hydrogen atoms of 4,5-tetrahydrofuran tetracarboxylic acid dianhydride or these compounds is substituted with lower alkyl such as methyl, ethyl group,

Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, heptane tetracarboxylic dianhydride and the like.

The tetracarboxylic dianhydride according to the present invention is not limited thereto, and needless to say that various other forms exist within the scope of the object of the present invention. The above can be used in combination.

The following is mentioned as a specific example of the dicarboxylic acid or dicarboxylic acid halide which provides the polyamide of this invention.

Malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethyl in the form of dicarboxylic acid Glutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.

1,1-cyclopropanedicarboxylic acid,

1,2-cyclopropanedicarboxylic acid,

1,1-cyclobutanedicarboxylic acid,

1,2-cyclobutanedicarboxylic acid,

1,3-cyclobutanedicarboxylic acid,

3,4-diphenyl-1,2-cyclobutanedicarboxylic acid,

2,4-diphenyl-1,3-cyclobutanedicarboxylic acid,

3,4-bis (2-hydroxyphenyl) -1,2-cyclobutanedicarboxylic acid,

2,4-bis (2-hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid,

1-cyclobutene-1,2-dicarboxylic acid,

1-cyclobutene-3,4-dicarboxylic acid,

1,1-cyclopentanedicarboxylic acid,

1,2-cyclopentanedicarboxylic acid,

1,3-cyclopentanedicarboxylic acid,

1,1-cyclohexanedicarboxylic acid,

1,2-cyclohexanedicarboxylic acid,

1,3-cyclohexanedicarboxylic acid,

1,4-cyclohexanedicarboxylic acid,

1,4- (2-norbornene) dicarboxylic acid,

Norbornene-2,3-dicarboxylic acid,

Bicyclo [2.2.2] octane-1,4-dicarboxylic acid,

Bicyclo [2.2.2] octane-2,3-dicarboxylic acid,

2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid,

1,3-adamantanedicarboxylic acid,

4,8-dioxo-1,3-adamantanedicarboxylic acid,

2,6-spiro [3.3] heptanedicarboxylic acid,

1,3-adamantane diacetic acid,

Camphoric acid and the like.

o-phthalic acid,

Isophthalic Acid,

Terephthalic Acid,

5-methylisophthalic acid,

5-tert-butylisophthalic acid,

5-aminoisophthalic acid,

5-hydroxyisophthalic acid,

2,5-dimethylterephthalic acid,

Tetramethylterephthalic acid,

1,4-naphthalenedicarboxylic acid,

2,5-naphthalenedicarboxylic acid,

2,6-naphthalenedicarboxylic acid,

2,7-naphthalenedicarboxylic acid,

1,4-anthracenedicarboxylic acid,

1,4-anthraquinone dicarboxylic acid,

2,5-biphenyldicarboxylic acid,

4,4'-biphenyldicarboxylic acid,

1,5-biphenylenedicarboxylic acid,

4,4 "-terphenyldicarboxylic acid,

4,4'-diphenylmethanedicarboxylic acid,

4,4'-diphenylethanedicarboxylic acid,

4,4'-diphenylpropanedicarboxylic acid,

4,4'-diphenylhexafluoropropanedicarboxylic acid,

4,4'-diphenyl ether dicarboxylic acid,

4,4'-bibenzyldicarboxylic acid,

4,4'-steelbendicarboxylic acid,

4,4'-tolandicarboxylic acid,

4,4'-carbonyl ibenzoic acid,

4,4'-sulfonyl dibenzoic acid,

4,4'-dithio ibenzoic acid,

p-phenylene diacetic acid,

3,3'-p-phenylenedipropionic acid,

4-carboxycinnamic acid,

p-phenylenediacrylic acid,

3,3 '-[4,4'-(methylenedi-p-phenylene)] dipropionic acid,

4,4 '-[4,4'-(oxydi-p-phenylene)] dipropionic acid,

4,4 '-[4,4'-(oxydi-p-phenylene)] ibutyric acid,

(Isopropylidenedi-p-phenylenedioxy) ibutyric acid,

Bis (p-carboxyphenyl) dimethylsilane,

1,5- (9-oxofluorene) dicarboxylic acid,

3,4-furandicarboxylic acid,

4,5-thiazole dicarboxylic acid,

2-phenyl-4,5-thiazoledicarboxylic acid,

1,2,5-thiadiazole-3,4-dicarboxylic acid,

1,2,5-oxadiazole-3,4-dicarboxylic acid,

2,3-pyridinedicarboxylic acid,

2,4-pyridinedicarboxylic acid,

2,5-pyridinedicarboxylic acid,

2,6-pyridinedicarboxylic acid,

3,4-pyridinedicarboxylic acid,

3,5-pyridinedicarboxylic acid,

3,6-pyridinedicarboxylic acid and the like, but these dicarboxylic acids may be in the form of dicarboxylic acid halides.

The dicarboxylic acid or dicarboxylic acid halide according to the present invention is not limited to these, and needless to say that various other forms exist within the scope of the object of the present invention. In addition, these dicarboxylic acid or dicarboxylic acid halide can be used individually or in combination of 2 or more.

Specific examples of the diamine providing the polyamic acid, soluble polyimide and polyamide of the present invention include the following.

p-phenylenediamine,

m-phenylenediamine,

o-phenylenediamine,

p-xylenediamine,

m-xylenediamine,

p-xylylenediamine,

m-xylylenediamine,

2,4-diaminotoluene,

2,6-diaminotoluene,

2,3,5,6-tetramethyl-p-phenylenediamine,

2,5-dimethyl-p-phenylenediamine,

3,3'-diaminodiphenylmethane,

4,4'-diaminodiphenylmethane,

3,3'-diaminodiphenylethane,

4,4'-diaminodiphenylethane,

1,3-bis (4-aminophenyl) propane,

2,2-bis (4-aminophenyl) propane,

2,2-bis (3-aminophenyl) propane,

2,2-bis (4-aminophenyl) perfluoropropane,

2,2-bis (3-aminophenyl) perfluoropropane,

Bis (4-amino-3-methylphenyl) methane,

Bis (4-amino-2-methylphenyl) methane,

1,2-bis (4-amino-3-methylphenyl) ethane,

1,3-bis (4-amino-3-methylphenyl) propane,

1,2-bis (4-amino-2-methylphenyl) ethane,

1,3-bis (4-amino-2-methylphenyl) propane,

1,4-bis [(4-aminophenyl) methyl] benzene,

1,4-bis [(3-aminophenyl) methyl] benzene,

1,4-bis [(4-aminophenyl) ethyl] benzene,

1,4-bis [(3-aminophenyl) ethyl] benzene,

1,4-bis [(4-amino-3-methyl-phenyl) methyl] benzene,

1,4-bis [(4-amino-3-methyl-phenyl) ethyl] benzene,

Bis [(4- (4-aminophenylmethyl) phenyl] methane,

Bis [(4- (4-aminophenylmethyl) phenyl] ethane,

Bis [(4- (3-aminophenylmethyl) phenyl] methane,

Bis [(4- (3-aminophenylmethyl) phenyl] ethane,

2,2'-bis [(4- (4-aminophenylmethyl) phenyl] propane,

2,2'-bis [(4- (3-aminophenylmethyl) phenyl] propane,

2,2'-bis [(4- (3-aminophenylmethyl) phenyl] perfluoropropane,

1,4-bis (4-aminophenoxy) benzene,

1,3-bis (4-aminophenoxy) benzene,

2,2-bis (4-aminophenoxy) propane,

Bis [4- (4-aminophenoxy) phenyl] methane,

2,2-bis [4- (4-aminophenoxy) phenyl] ethane,

1,1-bis [4- (4-aminophenoxy) phenyl] propane,

2,2-bis [4- (4-aminophenoxy) phenyl] propane,

1,2-bis [4- (4-aminophenoxy) phenyl] propane,

2,2-bis [4- (2-aminophenoxy) phenyl] perfluoropropane,

2,2-bis [4- (3-aminophenoxy) phenyl] perfluoropropane,

2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane,

2,2-bis [4- (4-aminophenoxy) phenyl] butane,

4,4'-diaminobiphenyl,

3,3'-dimethylbenzidine,

3,3'-dimethoxybenzidine,

1,4-bis (4-aminophenyl) benzene,

4,4'-bis (4-aminophenyl) biphenyl,

4,4'-diaminoterphenyl,

3,3'-dimethyl-4,4'-diaminobiphenyl,

1,3-bis [4- (4-aminophenoxy) phenyl] benzene,

1,4-bis [4- (4-aminophenoxy) phenyl} benzene,

4,4-bis [4- (4-aminophenoxy) phenyl] biphenyl,

1,2-bis [4- (4-aminophenoxy) phenyl] cyclohexane,

1,3-bis [4- (4-aminophenoxy) phenyl] cyclohexane,

1,4-bis [4- (4-aminophenoxy) phenyl] cyclohexane,

1,5-diaminonaphthalene,

2,6-diaminonaphthalene,

2,7-diaminofluorene,

9,9-bis (4-aminophenyl) fluorene,

9,9-bis (4-aminophenyl) -10-anthracene,

4,4 '-(p-phenylenediisopropylidene) bisaniline,

4,4 '-(m-phenylenediisopropylidene) bisaniline,

4,4'-diaminobenzanilide,

3,3'-diaminobenzophenone,

3,4'-diaminobenzophenone,

4,4'-diaminobenzophenone,

3,3'-diaminodiphenylbenzophenone,

4,4'-bis (4-aminophenoxy) diphenyl ketone,

3,3'-diaminodiphenylsulfide,

4,4'-diaminodiphenylsulfide,

Bis [4- (4-aminophenoxy) phenyl] sulfide,

3,3'-diaminodiphenylsulfone,

4,4'-diaminodiphenylsulfone,

Bis [4- (4-aminophenoxy) phenyl] sulfone,

3,3'-diaminodiphenyl ether,

4,4'-diaminodiphenyl ether,

3,4'-diaminodiphenyl ether,

Bis (4-aminophenyl) diethylsilane,

Bis (4-aminophenyl) diphenylsilane,

Bis (4-aminophenyl) ethylphosphine oxide,

2,2-bis [4- (3-carbamoyl-4-aminophenoxy) phenyl] perfluoropropane,

2,2-bis- (3-sulfamoyl-4-aminophenyl) perfluoropropane,

2,2-bis- (3-carboxy-4-aminophenyl) perfluoropropane,

2,2-bis [4- (3-sulfamoyl-4-aminophenoxy) phenyl] perfluoropropane,

2,2-bis [4- (3-carboxy-4-aminophenoxy) phenyl] perfluoropropane,

1,3-bis [2- {4- (4-aminophenoxy) phenyl} perfluoroisopropyl] benzene,

2,4-bis (β-amino-t-butyl) toluene,

Bis (p-β-methyl-γ-aminopentyl) benzene,

Bis (p-1,1-dimethyl-5-aminopentyl) benzene,

Bis (p-β-amino-t-butylphenyl) ether,

Bis (4-aminobenzyloxy) methane,

Bis (4-aminobenzyloxy) ethane,

Bis (4-aminobenzyloxy) propane,

Bis (4-aminobenzyloxy) cyclohexane,

2,3-diaminopyridine,

2,6-diaminopyridine,

3,4-diaminopyridine,

2,4-diaminopyridine,

Diaminopyrimidine,

Diaminopiperazine,

Bis (4-aminophenyl) -N-butylamine,

N, N-bis (4-aminophenyl) -N-methylamine,

N- (3-aminophenyl) -4-aminobenzamide and the like.

1,4-diaminocyclohexane,

1,3-bis (aminomethyl) cyclohexane,

1,4-bis (aminomethyl) cyclohexane,

Isophorone diamine,

Norbornanediamine,

4,4'-diaminodicyclohexylmethane,

Bis (2-methyl-4-aminocyclohexyl) methane,

Tetrahydrodicyclopentadienylenediamine,

Hexahydro-4,7-methanoindanylenedimethylenediamine,

Tricyclo [6.2.1.O ^2,7 ] -undecylenedimethyldiamine,

4,4'-methylenebis (cyclohexylamine),

2,5-bis (aminomethyl) -bicycloheptane,

2,6-bisaminomethyl-bicycloheptane,

2,3-diaminobicyclo [2,2,1] heptane,

2,5-diaminobicyclo [2,2,1] heptane,

2,6-diaminobicyclo [2,2,1] heptane,

2,7-diaminobicyclo [2,2,1] heptane,

2,3-diamino-7-azabicyclo [2,2,1] heptane,

2,5-diamino-7-azabicyclo [2,2,1] heptane,

2,6-diamino-7-azabicyclo [2,2,1] heptane,

2,3-diamino-7-thiabicyclo [2,2,1] heptane,

2,5-diamino-7-thiabicyclo [2,2,1] heptane,

2,6-diamino-7-thiabicyclo [2,2,1] heptane,

2,3-diaminobicyclo [2,2,2] octane,

2,5-diaminobicyclo [2,2,2] octane,

2,6-diaminobicyclo [2,2,2] octane,

2,5-diaminobicyclo [2,2,2] octane-7-ene,

2,5-diamino-7-azabicyclo [2,2,2] octane,

2,5-diamino-7-oxabicyclo [2,2,2] octane,

2,5-diamino-7-thiabicyclo [2,2,2] octane,

2,6-diaminobicyclo [3,2,1] octane,

2,6-diaminoazabicyclo [3,2,1] octane,

2,6-diaminooxabicyclo [3,2,1] octane,

2,6-diaminothiabicyclo [3,2,1] octane,

2,6-diaminobicyclo [3,2,2] nonane,

2,6-diaminobicyclo [3,2,2] nonan-8-ene,

2,6-dimino-8-azabicyclo [3,2,2] nonane,

2,6-diamino-8-oxabicyclo [3,2,2] nonane,

2,6-diamino-8-thiabicyclo [3,2,2] nonane and the like.

Aliphatic diamine compounds and alkyls such as ethylenediamine, trimethylenediamine, propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine and alkyls Alkylene diamine etc. which have an oxygen atom in a len group.

1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-ethylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-propylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-butylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-pentylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-hexylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-heptylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-octylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-nonylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-decylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-undecylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-dodecylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-tridecylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-tetradecylcyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-pentadecylcyclohexane,

1,1-bis (4-aminophenyl) cyclohexane,

1,1-bis (4-aminophenyl) -4-methylcyclohexane,

1,1-bis (4-aminophenyl) -4-ethylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-propylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-butylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-pentylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-hexylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-heptylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-octylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-nonylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-decylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-undecylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-dodecylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-tridecylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-tetradecylcyclohexane,

1,1-bis (4-aminophenyl) -4-n-pentadecylcyclohexane,

1,1-bis (4-aminophenyl) -4-cyclohexylcyclohexane,

1,1-bis (4-aminophenyl) -4- (4-methyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-ethyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-propyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-butyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-pentyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-hexyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-heptyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-octyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-nonyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-decyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-undecyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-dodecyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-tridecyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-tetradecyl-trans-cyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (4-n-pentadecyl-trans-cyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (cyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-methylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-propylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-butylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-pentylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-hexylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-heptylcyclohexyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-octylcyclohexyl) cyclohexane,

1,1-bis (4-aminophenyl) -4- (cyclohexylmethyl) cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-methylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-ethylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-propylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-butylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-pentylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-hexylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-heptylcyclohexyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-octylcyclohexyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (phenylmethyl) cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-methylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-ethylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-propylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-butylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-pentylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-hexylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-heptylphenyl) methyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl) -4-[(4-octylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4- (phenylmethyl) cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-methylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-ethylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-propylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-butylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-pentylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-hexylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-heptylphenyl) methyl] cyclohexane,

1,1-bis (4-aminophenyl) -4-[(4-octylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- (phenylmethyl) cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-methylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-ethylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-propylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-butylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-pentylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-hexylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-heptylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-octylphenyl) methyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-methylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-ethylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-propylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-butylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-pentylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-hexylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-heptylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-octylcyclohexane.

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (cyclohexylethylcyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-methyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-ethyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-propyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-butyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-pentyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-amyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-hexyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-heptyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-octyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-nonyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-dodecyl-trans-cyclohexyl) ethyl] cyclohexane,

1,1-bis [4- (4-aminophenoxy) phenyl] pentane,

2,2-bis [4- (4-aminophenoxy) phenyl] pentane,

3,3-bis [4- (4-aminophenoxy) phenyl] pentane,

1,1-bis [4- (4-aminophenoxy) phenyl] hexane,

2,2-bis [4- (4-aminophenoxy) phenyl] hexane,

3,3-bis [4- (4-aminophenoxy) phenyl] hexane,

1,1-bis [4- (4-aminophenoxy) phenyl] heptane

2,2-bis [4- (4-aminophenoxy) phenyl] heptane,

3,3-bis [4- (4-aminophenoxy) phenyl] heptane,

4,4-bis [4- (4-aminophenoxy) phenyl] heptane

1,1-bis [4- (4-aminophenoxy) phenyl] octane,

2,2-bis [4- (4-aminophenoxy) phenyl] octane,

3,3-bis [4- (4-aminophenoxy) phenyl] octane,

4,4-bis [4- (4-aminophenoxy) phenyl] octane,

1,1-bis [4- (4-aminophenoxy) phenyl] nonane,

2,2-bis [4- (4-aminophenoxy) phenyl] nonane,

3,3-bis [4- (4-aminophenoxy) phenyl] nonane,

4,4-bis [4- (4-aminophenoxy) phenyl] nonane,

5,5-bis [4- (4-aminophenoxy) phenyl] nonane,

1,1-bis [4- (4-aminophenoxy) phenyl] decane,

2,2-bis [4- (4-aminophenoxy) phenyl] decane,

3,3-bis [4- (4-aminophenoxy) phenyl] decane,

4,4-bis [4- (4-aminophenoxy) phenyl] decane,

5,5-bis [4- (4-aminophenoxy) phenyl] decane,

2,2-bis [4- (4-aminophenoxy) phenyl] undecane,

2,2-bis [4- (4-aminophenoxy) phenyl] dodecane,

2,2-bis [4- (4-aminophenoxy) phenyl] tridecane,

2,2-bis [4- (4-aminophenoxy) phenyl] tetradecane,

2,2-bis [4- (4-aminophenoxy) phenyl] pentadecane,

2,2-bis [4- (4-aminophenoxy) phenyl] hexadecane,

2,2-bis [4- (4-aminophenoxy) phenyl] heptadecane,

2,2-bis [4- (4-aminophenoxy) phenyl] octadecane,

2,2-bis [4- (4-aminophenoxy) phenyl] nonadecan,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} pentane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} pentane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} pentane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} hexane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} hexane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} hexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} heptane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} heptane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} heptane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} heptane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} octane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} octane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} octane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} octane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} nonane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} nonane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} nonane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} nonane,

5,5-bis {4-[(4-aminophenyl) methyl] phenyl} nonane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} decane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} decane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} decane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} decane,

5,5-bis {4-[(4-aminophenyl) methyl] phenyl} decane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} undecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} dodecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} tridecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} tetradecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} pentadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} hexadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} heptadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} octadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} nonadecan,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorohexane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorohexane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorohexane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorooctane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorooctane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorooctane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorooctane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane,

5,5-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane,

1,1-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

3,3-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

4,4-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

5,5-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorododecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorotridecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorotetedecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorohexadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorooctadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononadecane and the like.

4- [3- (4-biphenyloxy) propoxy] -1,3-diamine,

4- [8- (4-biphenyloxy) octyloxy] -1,3-diaminobenzene,

4- [3- (4-cyanobiphenyl-4'-oxy) propoxy] -1,3-diaminobenzene,

4- [12- (4-cyanobiphenyl-4'-oxy) dodecyloxy] -1,3-diaminobenzene,

4- [6- (4-methoxybiphenyl-4'-oxy) hexyloxy] -1,3-diaminobenzene,

4- [3- (4-fluorobiphenyl-4'-oxy) propoxy] -1,3-diaminobenzene,

2,4-diaminobenzoic acid dodecyl,

Octyl 2,4-diaminobenzoate,

1,5-diamino-2-octyloxycarbonylaminobenzene,

1,4-diamino-3- [4- (4-alkylcyclohexyl) cyclohexyloxy] benzene,

1,4-diamino-3- [4- (4-alkylphenyl) cyclohexyloxy] benzene,

1,4-diamino-3-((4-alkylterphenyl) oxy) benzene,

1,4-diamino- (2-alkyl) benzene,

1,4-diamino- (2,5-dialkyl) benzene,

2-alkyloxy-1,4-diaminobenzene and the like.

1-cyclohexyl-4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-methylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-propylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-pentylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-octylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-decylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-dodecylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane,

1-cyclohexyl-4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-methylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-propylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-pentylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-octylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-decylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane,

1- (4-dodecylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane and the like.

In addition, cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranil And diamines having side chains of steroid skeletons such as methyl testosteryl, noretysteryl, pregnnonyl, β-sitosteryl, stigmasteril, testosteryl, and cholesterol esters.

The diamine according to the present invention is not limited to these, and needless to say that various other forms exist within the scope in which the object of the present invention is achieved. In addition, these diamines may be used alone or in combination of two or more.

In addition to these dicarboxylic acids, dicarboxylic acid halides, tetracarboxylic dianhydrides and diamines, a monoamine compound or / and a monocarboxylic acid anhydride forming the reaction terminal of the polyamic acid can be used in combination. An aminosilicone compound or a diaminosilicon compound may be introduced to improve the adhesion on the substrate.

Examples of the aminosilicone compounds include paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, and aminopropyltriethoxysilane. Etc. can be mentioned. Moreover, as a diamino silicone compound, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3- tetraphenyl disiloxane and 1, 3-bis (3-aminopropyl) -1, 1, 3 , 3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, and the like.

As for the density | concentration of the polymer component in the liquid crystal aligning agent varnish of this invention, 0.1-40 weight% is preferable. When the liquid crystal aligning agent varnish is applied to a substrate, an operation of diluting the containing polymer component with a solvent may be necessary beforehand to adjust the film thickness. Even if the solvent is increased, mixing with the liquid crystal aligning agent varnish may be deteriorated, which may cause deterioration such as a uniform solution not being obtained. In the case of the spinner method and the printing method, in order to keep film thickness favorable, it is usually made into 10 weight% or less in many cases. In other coating methods, for example, the immersion method may be lower than 10% by weight. On the other hand, when the concentration of the polymer component is less than 0.1% by weight, it is easy to cause a problem that the film thickness of the obtained alignment film becomes too thin. Therefore, the concentration of the polymer component is preferably 0.1% by weight or more, preferably 0.5 to 10% by weight in the usual spinner method, printing method and the like. However, depending on the coating method of the liquid crystal aligning agent varnish, it can be used in lower concentration.

The solvent used together with the above-mentioned polymer component in the liquid crystal aligning agent varnish of the present invention can be applied without particular limitation as long as it is a solvent capable of dissolving the polymer component. Such solvents include solvents that are commonly used in the manufacturing process or use of polyamic acid, soluble polyimide or polyamide, and a suitable solvent can be selected appropriately according to the purpose of use. Examples of these solvents include aprotic polar organic solvents such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, and N-methyl, which are good solvents for polyamic acid, soluble polyimide, and polyamide. Caprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide or γ-butyrolactone Other solvents for the purpose of improving applicability, for example, ethylene glycol such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ethyl, etc. Diethylene glycol monoalkyl ethers such as monoalkyl ether, diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monobutyl ether Ester compounds, such as dipropylene glycol monoalkyl ether, such as propylene glycol monoalkyl ether, such as propylene glycol monoalkyl ether, malonate dialkyl, dipropylene glycol monomethyl ether, or these acetate compounds, are mentioned.

When forming an oriented film, it carries out according to the process of apply | coating a liquid crystal aligning agent varnish on a board | substrate, the following drying process, and the process of heat processing required for dehydration and ring-closure reaction. Spinner methods, printing methods, immersion methods or dropping methods and the like are generally known as the coating methods carried out in these steps, but these methods can be equally applied in the present invention. In addition, as a heating method, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a heating plate, and the like are generally known, but these methods can be equally applied in the present invention.

It is preferable to perform a drying method at comparatively low temperature within the range which can evaporate a solvent, and it is preferable that heat processing temperature is about 150-300 degreeC generally.

The liquid crystal aligning agent varnish of this invention can contain various additives as needed. For example, when the coating property is desired, a surfactant according to this purpose, an antistatic agent when an antistatic improvement is required, and a silane coupling agent or a titanium-based coupling agent when an adhesiveness with the substrate is desired. It can be compounded.

It is not an essential condition to prepare the alignment film by dispersing the fine particles in the above-mentioned alignment agent varnish, and the alignment agent varnish and the fine particles may be separately prepared to disperse the fine particles on the surface thereof after varnish coating. For example, an alignment agent varnish containing no solid fine particles is spin-coated on a substrate, and then the solvent is dried to prepare a thin film. The fine particles dispersed in the dispersant are dispersed thereon, followed by heat treatment to prepare an alignment film. In addition, the same solid fine particles as those added to the alignment agent varnish may be used. Of course, the varnish of the present invention containing the solid fine particles can be applied, and then the solid fine particles can be dispersed again on this thin film.

The initial tilt angle of the alignment film that can be used in the present invention is preferably 3 to 20 degrees, more preferably 4 to 15 degrees. In the OCB type liquid crystal display device, the larger the initial inclination angle is preferable in that the band alignment state is stabilized when the initial inclination angle of the liquid crystal becomes larger.

Example

An example of an OCB type liquid crystal display device which quickly transitions from the spray alignment state to the band alignment state will be described.

Example 1

1) Synthesis of Liquid Crystal Alignment Varnish

In a 200 ml four-necked flask equipped with a thermometer, agitator, raw material inlet, and nitrogen gas inlet, 4,4'-diaminodiphenylethane O.8118g, 1,1-bis {4-[(4-aminophenoxy) Phenyl]}-4- [2- (4-heptyl-trans-cyclohexyl) ethyl] 2.5200 g of cyclohexane and 30.00 g of dehydrated N-methyl-2-pyrrolidone (NMP) were added thereto, followed by stirring under a dry nitrogen stream. Dissolve. While maintaining the temperature of the reaction system at 5 ° C., 1.6682 g of pyromellitic dianhydride was added and reacted for 30 hours. Then, 35.00 g of butyl cellosolve (BC) and 35.00 g of γ-butyrolactone were added to increase the concentration of the polymer component. The liquid crystal aligning agent varnish of polyamic acid which is 6 weight% is synthesize | combined. When the temperature rises by the reaction temperature during the reaction of the raw materials, the reaction temperature is suppressed to about 70 ° C. or lower and allowed to react. Furthermore, in the Example of this invention, reaction is performed, checking the viscosity during reaction, and the viscosity of the liquid crystal aligning agent varnish after adding butyl cellosolve is 55-65 mPa * s (using an E-type viscosity meter, 25 degreeC). At the point of time, the reaction is terminated and stored at low temperature.

10 wt% of indium tin oxide (hereinafter referred to as ITO) having an average particle diameter of 20 nm was mixed with the liquid crystal aligning agent varnish obtained as described above with respect to the amount of the polymer component, and the mixed system was mixed with 1: 1 of NMP and BC. Dilution with a mixed solvent is performed to adjust the concentration of the entire polymer component to 3% by weight, and is applied with a spinner on a substrate with a transparent electrode as a liquid crystal aligning agent varnish for application, and prebaked at 80 ° C. for about 5 minutes. Subsequently, heat treatment is performed at 210 ° C. for 30 minutes, and an alignment treatment is performed by forming an alignment film having a film thickness of 60 nm and rubbing its surface over the entire surface. Here, scanning electron microscope (SEM) observation confirmed that ITO microparticles | fine-particles with a secondary particle diameter of 600-180 Onm are disperse | distributed uniformly on the surface of the said oriented film.

2) Preparation of Cell for Electrical Characteristic Evaluation

The alignment film obtained as described above was ultrasonically cleaned in ethanol for 5 minutes, and then, the surface was washed with pron running water and then dried at 120 ° C. in an oven for 30 minutes. The gap material of 5 micrometers is spread | spreaded on the said board | substrate, it seals with the epoxy hardening | curing agent on the surface in which the oriented film was formed inward, and parallel cells of 5 micrometers of gaps are produced. A liquid crystal material is injected into the cell and the inlet is sealed with a photocuring agent. Subsequently, it heat-processes at 110 degreeC for 30 minutes, and it is set as the cell for electrical property evaluation. The composition of the liquid crystal composition used as the liquid crystal material is described next (% represents weight%).

A short-wave voltage of 7 V was applied to the obtained liquid crystal cell at a frequency of 30 Hz, and the number of nucleation transitions from the spray alignment state to the band alignment state per electrode front surface (1.0 cm ² ) was observed. The occurrence of the transition nucleus is confirmed, and the electrode entire surface reliably transitions from the spray alignment state to the band alignment state in about 5 seconds.

The voltage generated at the band transition nucleus was measured by applying a short-wave voltage of 0 to 5 V at a frequency of 30 Hz to the liquid crystal display device. In addition, the boundary voltage Vcr of spray orientation and band orientation state is 1.73V. Moreover, the orientation of a liquid crystal is also favorable.

3) Preparation of initial tilt angle measuring cell

A cell for initial inclination angle measurement is created in the same manner as the cell for electrical property evaluation, except that the gap material for 20 µm is manufactured and placed in a non-parallel state. In addition, the liquid crystal material in initial tilt angle measurement uses the same thing as the electrical property measurement. Using this cell, the initial tilt angle of the liquid crystal was measured by a crystal rotation method, which was 9.6 degrees.

Example 2

A cell was prepared in accordance with Example 1, except that 30 wt% of ITO was mixed with the liquid crystal aligning agent varnish, and the number of nucleation transitions from the spray alignment state to the band alignment state per electrode front surface (1.Ocm ² ) was observed. As a result, the occurrence of a myriad of transition nuclei is observed over almost the entire surface of the electrode, and in about 4 seconds, the entire surface of the electrode is reliably transitioned from the spray orientation state to the band alignment state.

When the short-wave voltage of 0 to 5V was applied to the liquid crystal display at a frequency of 30 Hz, the generated voltage of the band transition nucleus was measured. In addition, the boundary voltage Vcr of a spray orientation and a band orientation state is 1.70V. Moreover, the orientation of a liquid crystal is also favorable.

Moreover, the initial tilt angle of the liquid crystal was measured by the crystal rotation method by manufacturing the cell for initial tilt angle measurement based on Example 1, and it is 9.2 degrees.

Example 3

A cell was prepared according to Example 1 except that 50% by weight of ITO was mixed with the liquid crystal aligning agent varnish, and the number of nucleated cells transitioned from the spray orientation state to the band alignment state per electrode front surface (1.0 cm ² ) was observed. The occurrence of a myriad of transition nuclei is observed over almost the entire surface of the electrode, and the electrode entire surface reliably transitions from the spray orientation state to the band orientation state in about 1 second.

When the short-wave voltage of 0 to 5 V was applied to the liquid crystal display device at a frequency of 30 Hz, the generation voltage of the band transition nucleus was measured. In addition, the boundary voltage Vcr of spray orientation and band orientation state is 1.65V. Moreover, the orientation of a liquid crystal is also favorable.

Moreover, based on Example 1, the cell for initial inclination-angle measurement was manufactured and it was 8.8 degree when the initial inclination angle of the liquid crystal was measured by the crystal rotation method.

Example 4

A cell was prepared in accordance with Example 1 except that 10 nm by weight of 20 nm of antimony oxide was mixed with the liquid crystal aligning agent varnish in Example 1, and the band alignment state from the spray orientation state per electrode front surface (1.0 cm ² ) was obtained. When the number of nucleating cells to be transferred was observed, the occurrence of a myriad of transition nuclei was confirmed over almost the entire surface of the electrode, and in about 8 seconds, the entire surface of the electrode was reliably transitioned from the spray orientation state to the band alignment state.

When the short-wave voltage of 0 to 5V was applied to the liquid crystal display at a frequency of 30 Hz, the generated voltage of the band transition nucleus was measured to be 3.10V. In addition, the boundary voltage Vcr of a spray orientation and a band orientation state is 1.74V. Moreover, the orientation of a liquid crystal is also favorable.

Moreover, based on Example 1, when the cell for initial inclination angle measurement was manufactured and the initial inclination angle of the liquid crystal was measured by the crystal rotation method, it is 9.8 degrees.

Example 5

A cell was prepared in accordance with Example 1, except that 30 nm by weight of 20 nm of antimony oxide was mixed with the liquid crystal aligning agent varnish in Example 1, and then from the spray alignment state per electrode front surface (1.0 cm ² ) to the band alignment state. When the number of nucleating cells to be transferred was observed, the occurrence of a myriad of transition nuclei was confirmed over almost the entire surface of the electrode, and in about 6 seconds, the entire surface of the electrode was reliably transitioned from the spray orientation state to the band alignment state.

When the short-wave voltage of 0-5V was applied to the said liquid crystal display element at the frequency of 30Hz, the generation voltage of the band transition nucleus was measured and found to be 2.90V. In addition, the boundary voltage Vcr of spray orientation and band orientation state is 1.71V. Moreover, the orientation of a liquid crystal is also favorable.

Moreover, based on Example 1, the initial tilt angle measurement cell was produced and the initial tilt angle of the liquid crystal was measured by the crystal rotation method, and it is 9.4 degrees.

Example 6

A cell was prepared in accordance with Example 1 except that 10% by weight of silicon oxide was mixed in the liquid crystal aligning agent varnish in Example 1, and transitioned from the spray orientation state per electrode front surface (1.0 cm ² ) to the band alignment state. As a result of observing the number of nucleation cells, the occurrence of countless transition nuclei was confirmed over almost the entire surface of the electrode, and in about 7 seconds, the entire surface of the electrode was reliably transitioned from the spray orientation state to the band alignment state.

The voltage generated at the band transition nucleus was measured by applying a short wave voltage of 0 to 5 V at a frequency of 30 Hz to the liquid crystal display device. In addition, the boundary voltage Vcr of spray orientation and band orientation state is 1.73V. Moreover, liquid crystal orientation is also favorable.

Moreover, based on Example 1, the initial tilt angle measurement cell was produced and the initial tilt angle of the liquid crystal was measured by the crystal rotation method, and it was 9.7 degrees.

Example 7

A cell was prepared in accordance with Example 1 except that 30% by weight of silicon oxide was mixed with the liquid crystal aligning agent varnish in Example 1, and then transitioned from the spray orientation state per electrode front surface (1.0 cm ² ) to the band alignment state. As a result of observing the number of nucleation cells, countless transition nuclei were observed over almost the entire surface of the electrode, and in about 5 seconds, the entire surface of the electrode was reliably transitioned from the spray orientation state to the band alignment state.

When the short-wave voltage of 0-5V was applied to the said liquid crystal display element at the frequency of 30Hz, the generation voltage of band transition nucleus was measured and it is 2.85V. In addition, the boundary voltage Vcr of spray orientation and band orientation state is 1.71V. Moreover, the orientation of a liquid crystal is also favorable.

Moreover, the initial tilt angle of the liquid crystal was measured by the crystal rotation method by manufacturing the cell for initial tilt angle measurement based on Example 1, and it is 9.3 degrees.

Comparative Example 1

Except not adding solid fine particles to the liquid crystal aligning agent varnish in Example 1, the cell was produced in accordance with Example 1, and the number of nucleated cells transferred from the spray orientation state to the band alignment state per electrode front surface (1.0 cm ² ). Observation of the occurrence of about 20 transition nuclei is confirmed and the electrode front transitions from the spray orientation state to the band orientation state in about 15 seconds.

When the short-wave voltage of 0 to 5 V was applied to the liquid crystal display device at a frequency of 30 Hz, the generated voltage of the band transition nucleus was measured to be 3.74 V. In addition, the boundary voltage Vcr of a spray orientation and a band orientation state is 1.78V. Moreover, liquid crystal orientation is also favorable.

Moreover, based on Example 1, when the cell for initial inclination angle measurement was manufactured and the initial inclination angle of the liquid crystal was measured by the crystal rotation method, it is 10.7 degrees.

Table 1 shows the results of Examples 1 to 7 and Comparative Example 1.

Solid particulate % By weight of solid particulates relative to polymer component amount Number of band transfer nucleus outbreaks (pcs / ㎠) Transition time from spray orientation to band orientation in seconds Band transition nucleation voltage (V) Vcr (V) Initial tilt angle (°) Example One ITO 10 ∞ 5 3.02 1.73 9.6 2 ITO 30 ∞ 4 2.80 1.70 9.2 3 ITO 50 ∞ One 2.50 1.65 8.8 4 Antimony oxide 10 ∞ 8 3.10 1.74 9.8 5 Antimony oxide 30 ∞ 6 2.90 1.71 9.4 6 Silicon oxide 10 ∞ 7 3.05 1.73 9.7 7 Silicon oxide 30 ∞ 5 2.85 1.71 9.3 Comparative example One No addition - 20 15 3.74 1.78 10.7

As described above, in the liquid crystal display device to which the solid fine particles are added, nuclei that smoothly transition from the spray alignment state to the band alignment state are locally generated, and the transition is performed in a short time, and that the Vcr also decreases, that is, the vicinity of the solid fine particles in the alignment film. The voltage is increased locally, and as a result, it is considered that it is an opportunity for nucleation to transition from the spray orientation state to the band alignment state.

In general, the lower the initial tilt angle of the liquid crystal, the higher the transition voltage tends to be. However, in the liquid crystal display device to which the solid fine particles are added, it can be seen that the generation voltage of the band transition nucleus is lowered. The initial tilt angle of the liquid crystal of the alignment agent varnish to which the solid fine particles were added was found to be a value slightly lower than the initial tilt angle, 10.7 degrees, when all of the solid fine particles were not added.

According to the present invention, by using an alignment film formed of a liquid crystal aligning agent varnish containing solid fine particles or an alignment film in which solid fine particles are dispersed on the surface, OCB which quickly and reliably transitions from the spray alignment state to the band alignment state even at low electric energy. It is possible to provide a type liquid crystal display device.

Claims (13)

A liquid crystal aligning varnish for forming an alignment film for liquid crystal display elements that performs display by changing light transmittance by using a band alignment state which may have a twist orientation, characterized in that the varnish contains at least one kind of solid fine particles. Liquid crystal aligning agent varnish. The liquid crystal aligning agent varnish according to claim 1, wherein the solid fine particles are inorganic solid fine particles. The liquid crystal aligning varnish of claim 1, wherein the solid fine particles are metal fine particles or metal oxide fine particles. The method of claim 1, wherein the solid fine particles are C, Mg, Al, Si, Ca, Ti, V, Fe, Co, Ni, Cu, Zn, As, Zr, Ru, Rh, Pd, Ag, Cd, In, Sn A liquid crystal aligning agent varnish which is an inorganic solid fine particle containing at least one element selected from Sb, Ce, W, Os, Ir, Pt and Au. The liquid crystal aligning varnish of claim 1, wherein the solid fine particles are organic solid fine particles. The liquid crystal aligning agent varnish of Claim 1 whose average particle diameter of a solid fine particle is 1-500 nm. The liquid crystal aligning film obtained from the liquid crystal aligning agent varnish as described in any one of Claims 1-6. A liquid crystal aligning film in which solid fine particles are dispersed on the surface. A liquid crystal display device using the liquid crystal alignment film according to claim 7, wherein the liquid crystal display device performs display by changing light transmittance by using a band alignment state which may have a twist orientation. A liquid crystal display device using the liquid crystal alignment film according to claim 8, wherein the liquid crystal display device performs display by changing light transmittance by using a band alignment state which may have a twist orientation. The liquid crystal display device according to claim 9 or 10, wherein the primary particle diameter or secondary particle diameter of the solid fine particles is 0.1 to 500 times the thickness of the alignment film. The liquid crystal display device according to claim 9 or 10, wherein there is no orientation defect at the periphery of the solid fine particles when no voltage is applied. The liquid crystal display device according to claim 9 or 10, wherein the solid fine particles become nuclei that transition from the spray alignment state to the band alignment state when voltage is applied.