JPH09281506A - Liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the deterioration of the electrical property of a liquid crystal of its own by containing a resin coating film, which is obtained from a photosensitive resin composition using a photo-acid generating agent as an initiator and has liquid crystal resistance, as a spacer. SOLUTION: The resin coating film obtained from the photosensitive resin composition using the photo-acid generating agent as the initiator and having liquid crystal resistance is used as the spacer or a sealing material. The photosensitive resin composition consists essentially of a silicon-containing polyimide precursor and the photo-acid generating agent, is a solution obtained by dissolving the essential components in an organic solvent and contains no acrylic monomer. And the coating film of the photosensitive resin composition is formed on a substrate having a transparent electrode and a part of the coating film is exposed through a photomask. And one of the exposed region of the coating film or the unexposed region is developed to be removed. As a result, a liquid crystal layer having excellent liquid crystal orienting property, free from the deterioration of electrical property such as after-image phenomenon, excellent in opening ratio and contrast, high in mechanical strength and having uniform layer thickness is obtained.

Description

Detailed Description of the Invention

[0010]

TECHNICAL FIELD The present invention relates to a liquid crystal device.
More specifically, it relates to a liquid crystal element in which a resin film is incorporated into a liquid crystal element such as a TN type, an STN type, a ferroelectric type and an antiferroelectric type.

[0011]

2. Description of the Related Art In liquid crystal elements used in microcomputers, word processors, televisions, watches and calculators, nematic liquid crystal molecules are aligned at 90 degrees between a pair of upper and lower transparent electrode substrates. A twisted nematic (TN) mode with a twisted structure is adopted. In addition, a super twisted nematic (hereinafter abbreviated as STN) mode having a large twist angle of 180 to 300 degrees has been developed, and a liquid crystal element having a good display quality even on a large screen can be obtained. Furthermore, in recent years, since matrix display and color display have come to be performed, a large number of pixel electrodes and an MIM adopting an active TN mode capable of performing ON / OFF of these pixel electrodes are employed.
The development of (metal-insulating phase-metal) elements and TFT (field effect thin film transistor) elements has become active. Also,
A device using a ferroelectric liquid crystal capable of high-speed response or an antiferroelectric liquid crystal capable of high-definition display has also been developed.

As common to all of these modes, the liquid crystal layer has a layer thickness of several μm controlled by glass beads or divinylbenzene resin beads. Beads (spacers) have been devised as a material for controlling the layer thickness. That is, the spacers are generally spherical particles. The beads are sprayed on the substrate. As the spraying method, there are a dry method of spraying the beads in the atmosphere, a wet method of spraying a solution in which the beads are dispersed, and the like. However,
Since these beads are only scattered in the liquid crystal element,
Movement of beads, destruction of elements, and reduction in aperture ratio occur.
Therefore, for example, a method for manufacturing a liquid crystal display device using a photosensitive organic material is known from Japanese Patent Publication No. 7-56543, etc., but a photosensitive organic material is applied onto a substrate subjected to an alignment treatment to form a liquid crystal element. , The liquid crystal alignment failure occurs,
It was difficult to obtain a practical liquid crystal element because the deterioration of the electric characteristics was recognized. Photosensitive organic materials generally utilize the difference in solubility between irradiated and unirradiated areas by light irradiation, but when a compound having a polymerizable (crosslinkable) carbon-carbon double bond is contained and a photoinitiator, When a large amount of the sensitizer and the like are present, there is a problem that a practical liquid crystal element cannot be obtained due to the occurrence of alignment failure and deterioration of electric characteristics.

Further, conventionally, a sealant has been used as an adhesive for bonding liquid crystal elements and for sealing a liquid crystal compound (liquid crystal composition). Generally, an epoxy thermosetting resin is used as this sealing agent, but the problem of the occurrence of misalignment in the peripheral area of this sealing agent is caused by the epoxy curing accelerator and the resin itself. Is believed to be dissolved in the liquid crystal.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, having good liquid crystal orientation, and preventing deterioration of electric characteristics such as afterimage phenomenon and voltage holding ratio.
An object of the present invention is to provide a liquid crystal element having an excellent aperture ratio and contrast, a high mechanical strength, and a uniform liquid crystal layer thickness.

[0015]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems of the prior art. As a result, for example, Japanese Unexamined Patent Publication Nos. 6-298931 and 6
-308730, JP-A-6-308731, JP-A-6-348016, JP-A-7-361
No. 92, JP-A-7-228777, etc., containing a photosensitive resin, that is, a compound capable of generating an acid upon irradiation with light (hereinafter abbreviated as a photoacid generator), as an essential component, and an initiator thereof. It was found that the above-mentioned various problems can be solved by using a resin film obtained from the photosensitive resin composition described above, and the present invention has been completed.

The photosensitive resin composition used in the present invention is a solution obtained by dissolving a silicon-containing polyimide precursor and a photoacid generator as main components and dissolving them in an organic solvent. Therefore, it is characterized in that it does not contain any acrylic monomer contained in a usual photosensitive polyimide resin composition. The present invention has the following configurations. (1) A liquid crystal element comprising a resin film having liquid crystal resistance, which is obtained from a photosensitive resin composition having a photoacid generator as an initiator. (2) The liquid crystal device according to item (1), wherein the resin film is a spacer of the liquid crystal device. (3) The liquid crystal device according to item (2), wherein the resin film contains beads. (4) The resin film is a sealant for liquid crystal elements (1)
Alternatively, the liquid crystal element according to item (2). (5) A step of forming a film of a photosensitive resin composition having a photoacid generator as an initiator on a substrate having a transparent electrode, and a step of exposing a part of the film by irradiating with light through a photomask. The liquid crystal element according to item (1), which is manufactured through a step of developing and removing either an exposed region or an unexposed region of the film after the light irradiation.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A method for manufacturing a liquid crystal element of the present invention will be described below. The spacer controls the thickness of the liquid crystal layer, and can be produced by the following method. That is, inside the upper and lower substrates, transparent conductive electrodes (for example, indium tin oxide (ITO), tin oxide (Sn), etc.
O _x )) and the surface or the alignment film having the liquid crystal layer subjected to the alignment treatment are sequentially laminated. Further, a photosensitive resin composition is applied on one side or both sides of the upper side, the lower side, or both sides of the resin coating so as to have a desired thickness, and light irradiation is performed through a photomask, and then development and baking are performed, except for the opening. A columnar spacer is formed at the location (for example, between pixels). Here, the spacer may have a dot shape or a linear shape, but the latter is preferable from the viewpoint of preventing light leakage between pixels. Further, conventionally used beads can be dispersed and fixed in the resin film for use. Further, the photosensitive resin composition is applied onto a glass substrate, and the patterning is performed in the same manner to leave the composition only in the peripheral portion of the substrate, and a liquid crystal cell is assembled so as to face another substrate thereon, and pressure-bonded, The sealing material can be incorporated into the liquid crystal element by firing.
Further, the resin film can be used as an alignment treatment agent.

Here, as the liquid crystal compound and the composition,
A liquid crystal manufactured by Chisso Corporation is particularly preferable, but not limited thereto. That is, any liquid crystal compound and composition can be used. More specifically, the liquid crystal compounds are preferably compounds represented by the following general formulas (1) to (8).

[0019]

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In the formulas (1) to (3), R1 represents an alkyl group having 1 to 10 carbon atoms, Y1 represents a fluorine atom, a chlorine atom, OCF3, OCF2H, CF3, CF2H or CFH2, and L1, L2, L3 and L4 each independently represent a hydrogen atom or a fluorine atom, and Z1 and Z2
Are independently of each other a 1,2-ethylene group, -CH = CH-
Or a covalent bond, and a represents 1 or 2.

In the formula (4), R2 represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl group or alkenyl group may be substituted with an oxygen atom, but no two or more methylene groups are continuously substituted with an oxygen atom. Ring B is 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-
2,5-diyl, ring C represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring D represents 1,4-cyclohexylene or 1,4-phenylene. Z3 represents a 1,2-ethylene group, -COO- or a covalent bond, L5 and L6 each independently represent a hydrogen atom or a fluorine atom, and b and c each independently represent 0 or 1. Show.

In the formula (5), R3 has 1 to 10 carbon atoms.
Is an alkyl group, L7 is a hydrogen atom or a fluorine atom, and d is 0 or 1.

In the formula (6), R4 has 1 to 10 carbon atoms.
The alkyl group of, ring E and ring F are independently of each other 1,4-cyclohexylene or 1,4-phenylene, Z4 and Z5 are independently of each other -COO- or a covalent bond, Z6 represents -COO- or -C≡C-, L8 and L9 each independently represent a hydrogen atom or a fluorine atom, and Y2 represents a fluorine atom, OCF3, OCF.
2H, CF3, CF2H or CFH2, e, f
And g each independently represent 0 or 1.

In the formula (7), R5 and R6 are, independently of each other, an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms.
10 alkenyl groups are shown. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring G represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, Ring H represents 1,4-cyclohexylene or 1,4-phenylene, and Z7 is -C≡C. -, -CO
O-, 1,2-ethylene group, -CH = CH-C [identical to] C- or a covalent bond is shown, and Z8 is -COO- or a covalent bond.

In formula (8), R7 and R8 are independently of each other an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms.
10 alkenyl groups are shown. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring I is 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, Ring J is 1,4-cyclohexylene, and one or more hydrogen atoms on the ring are substituted with fluorine atoms. 1,4-phenylene or pyrimidine-2,5-diyl, which is optionally substituted, and ring K is 1,4-cyclohexylene or 1,4-cyclohexylene.
4-phenylene, Z9 and Z10 independently of each other represent -COO-, 1,2-ethylene group or a covalent bond, and Z11 represents -CH = CH-, -C≡C-, -COO-.
Alternatively, it represents a covalent bond, and h represents 0 or 1.

More specifically, the liquid crystal composition contains at least one compound selected from the group consisting of formulas (1), (2) and (3), or General formulas (4), (5), (6),
A liquid crystal composition comprising at least one compound selected from the group consisting of (7) and (8),
Alternatively, as the first component, at least one compound selected from the group consisting of formulas (1), (2) and (3) is used.
Containing a type, as the second component, the general formula (4), (5),
A liquid crystal composition or the like characterized by containing at least one compound selected from the group consisting of (6), (7) and (8) is preferable.

As the compounds of the general formulas (1) to (3), the compounds represented by the formulas (1-1) to (3-53) can be preferably mentioned.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

[Chemical 6]

[0033]

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[0034]

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[0035]

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[0036]

Embedded image (R1 has the same meaning as above)

The compounds of the general formulas (1) to (3) are compounds having a positive dielectric anisotropy value and are excellent in thermal stability and chemical stability, and particularly have a high voltage holding ratio or a specific resistance. It is an indispensable compound when preparing a liquid crystal composition for TFT, which requires high reliability such as a large value.

As the compounds of the general formulas (4) to (6), the compounds of the formulas (4-1) to (6-14) can be preferably mentioned.

[0039]

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[0040]

[Chemical 12]

[0041]

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(R2 to R4 have the same meanings as described above) The compounds of the general formulas (4) to (6) have a positive dielectric anisotropy value and a large value, and particularly the purpose of reducing the threshold voltage. Used in. It is also used for the purpose of adjusting the viscosity, adjusting the refractive index anisotropy value, and expanding the nematic range such as increasing the clearing point. Further, it is also used for the purpose of improving the steepness of the threshold voltage.

As the compounds of the general formulas (7) and (8),
Preferably, the compounds of formulas (7-1) to (8-12) can be mentioned.

[0044]

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[0045]

Embedded image (R5 to R8 have the same meanings as described above) The compounds of the general formulas (7) and (8) are compounds having a negative or weakly positive dielectric anisotropy value. The compound of the general formula (7) is mainly used for the purpose of decreasing the viscosity or adjusting the refractive index anisotropy value. Further, the compound of the general formula (8) is used for the purpose of broadening the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value.

The surface subjected to the alignment treatment and the aligning agent regulate the alignment of the liquid crystal molecules, and may be either an inorganic substance or an organic substance. Generally, polyimide-based and polyamide-based resins are often used, but as an example,
Chisso Orientation Agents are particularly preferred, but not limiting. That is, any of the aligning agents can be used.

More specifically, the aligning agent having a structure represented by the following general formula (9) is preferable.

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In the formula (9), X is a divalent aromatic group,
Y represents a tetravalent aromatic ring or an aliphatic ring having a 4-, 5- or 6-membered ring structure. Specific examples of X include formula (X1) to
The group shown by (X8) can be mentioned.

[0049]

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In the formula, R represents H or an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 3, and m represents 1 or 2. Specific examples of Y include formulas (Y1) to (Y11).
And the group represented by

[0051]

Embedded image In the formula, R represents H or an alkyl group having 1 to 10 carbon atoms, n represents an integer of 0 to 4, and m represents 0 or 1.

The substrate used as a liquid crystal element is usually one on which an electrode, specifically, a transparent electrode of ITO or SnO _x is formed. Further, between this electrode and the substrate,
An insulating film, an undercoat film such as a color filter or a color filter overcoat may be provided to prevent alkali elution from the substrate, and an overcoat film such as an insulating film or a color filter film may be provided on the electrode. The configuration of these electrodes, undercoat, and other liquid crystal elements is
Conventional liquid crystal element configurations can be used.

The resin film containing the photo-acid generator used in the present invention as an essential component is usually provided in the form of a solution. The resin film is applied on the substrate, and after the solvent is removed by heating, acid is generated when light irradiation is performed, and by using this as a catalyst, further heat treatment is performed, whereby the reactivity in the light irradiation portion and the non-irradiation portion is increased. Take advantage of the different. As a result, a difference in solubility occurs between the irradiated portion and the non-irradiated portion, and development can be performed by utilizing this difference. The reaction is completed by performing heat treatment again. From this, it becomes possible to form a patterned organic material layer at a desired location. The resin film has excellent adhesion to the substrate,
There is no need to add other photoreactive compositions such as carbon-carbon double bonds, photoinitiators, and sensitizers because the compound has sufficient photosensitivity by adding a small amount of a compound that generates an acid by light. Therefore, it is possible to prevent the occurrence of alignment failure of the liquid crystal element and the deterioration of electrical characteristics. Further, volume shrinkage during curing can be reduced.

Next, a method for forming a liquid crystal element having patterned columns using the resin film used in the present invention will be described. The resin film used in the present invention is applied onto a liquid crystal element substrate which has been subjected to an alignment treatment by a known method such as spin coating, dipping, printing, dispensing or a roll coater. Incidentally, it is also possible to carry out an orientation treatment such as a rubbing treatment after forming the columns of the resin film.

The obtained coating film was an electric furnace, a hot plate,
Most of the solvent in the coating film is removed by performing drying (prebaking) at a temperature of 30 to 150 ° C, more preferably 60 to 120 ° C for 1 to 90 minutes using a heating means such as an infrared heater. Next, a photomask is placed on this coating film and irradiated with actinic rays. Examples of the actinic rays include X-rays, electron rays, ultraviolet rays, visible rays and the like, but ultraviolet rays or electron rays are particularly preferable. Subsequently, if necessary, heating (post-exposure bake) is performed at 30 to 220 ° C., more preferably 60 to 200 ° C. for 30 seconds to 90 minutes by the above heating means, and the irradiated portion and unirradiated portion are subjected to a catalytic reaction by an acid generated by light irradiation. Promotes changes in the solubility of irradiated parts.

Next, a relief pattern is obtained by dissolving and removing the unreacted portion with a developing solution. The developing solution used here is N-methyl-2-pyrrolidone (hereinafter, abbreviated as NMP), N, N-dimethylacetamide (hereinafter, DMAc).
Abbreviated), N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridine, hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethano. -, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cresol, γ-butyrolactone, isophorone, N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylmethoxyacetamide, Tetrahydrofuran, N-methyl-ε-caprolactam, tetrahydrothiophene dioxide {sulfolane}, etc.,
Alternatively, a mixture of this with a poor solvent such as alcohol, xylene, or water, or a mixture with addition of a surfactant is used.
In addition to organic solvents, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n.
-Aqueous solutions of organic amines such as propylamine, triethylamine, methyldiethylamine, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and in some cases, solutions obtained by mixing alcohol with these aqueous solutions can be used.

Further, if necessary, it is rinsed in a poor solvent such as alcohol or water, and further dried at a temperature of 150 ° C. or lower.
The organic substance of the relief pattern formed by the development completes the reaction, so that the organic substance of 100-
1 minute ~ at a temperature of 500 ℃, preferably 150 ~ 400 ℃
By baking (post-baking) for 5 hours, a patterned organic film is formed. Further, it is possible to disperse and coat the conventional beads on the resin film and perform the above steps to fix the beads at a predetermined position. Furthermore, after applying the resin film, it is possible to spray conventional beads and place them on the liquid crystal element, and perform the above steps to fix the beads at predetermined positions.

The liquid crystal element substrate obtained in the above step is
The liquid crystal device is assembled by aligning the lower part and pressure-bonding, and then heat-treated to assemble the liquid crystal device substrates, injecting the liquid crystal, and sealing the injection port to manufacture the liquid crystal device. Alternatively, the liquid crystal element may be manufactured by spraying the liquid crystal on the liquid crystal element substrate, superposing the substrates, and sealing the liquid crystal so as not to leak. From these steps, a liquid crystal element in which a resin film having liquid crystal resistance is present in the liquid crystal element is manufactured. The liquid crystal element of the present invention has a good liquid crystal orientation, is excellent in electrical characteristics such as afterimage phenomenon and voltage holding ratio, is excellent in aperture ratio and contrast, is high in mechanical strength, and has a uniform liquid crystal layer thickness. The feature is that the device can be manufactured.

Evaluation Method In the examples and comparative examples shown below, the orientation was confirmed using a polarizing plate, and the voltage holding ratio was measured by a gate pulse width of 69 μs, a frequency of 60 Hz, and a wave height of ± 4.5 V.
It was performed by reading the drain which changed by applying the rectangular wave of 1 to the source with an oscilloscope. This was repeated four times, and the average value was used. When the voltage did not decrease at all, the relative value was defined as the voltage holding ratio, which was set to 100%. The larger the value of the voltage holding ratio, the smaller the current consumption of the liquid crystal element, which improves the durability and reliability of the entire liquid crystal element. The degree of the afterimage phenomenon (residual DC) was measured by the CV curve method. In the C-V curve method, an alternating current of 25 mV and 1 KHz is applied to the liquid crystal element, and the frequency of 0.
The voltage is -1 by overlapping the DC triangular wave of 0036Hz.
Capacitance C that changes by sweeping in the range of 0-10V
Is a method of recording. The value obtained here is a parameter for stabilizing the bias of electric charge when the thickness of the liquid crystal element and the thickness of the alignment agent are the same. That is, the after-image phenomenon can be alleviated as the liquid crystal element has smaller residual charges.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The photosensitive resin composition solution used in this example is a photosensitive resin composition containing a photo acid generator manufactured by Chisso Corporation as an essential component.
-298931, JP-A-6-308730, JP-A-6-308731, JP-A-6-348.
016, JP-A-7-36192, JP-A-7-
No. 228777. That is, LIXON coat PIP-8041 manufactured by Chisso Corporation
It is. The liquid crystal used in this example and the comparative example is LIXON5055XX manufactured by Chisso Corporation, and the alignment agent is LIXON aligner PIA-5004 manufactured by Chisso Corporation.
It is.

Example 1 LIXON aligner PIA-5004 was applied onto a 10 cm square transparent glass substrate having an ITO electrode on one side by a spin coating method, and after coating, the coating was dried at 100 ° C. for 10 minutes and then in an oven. Heat treatment at 250 ℃ for 90 minutes,
A substrate coated with an alignment film having a thickness of about 0.06 μm was obtained. The alignment film surfaces of the two substrates were each rubbed, LIXON coat PIP-8041 was applied to one substrate by spin coating, and prebaked at 90 ° C. for 30 minutes in an oven. At this time, the film thickness after drying is about 6.3.
The rotation at the time of application was adjusted so as to be μm. Then 10μ
Through a photomask with a line pattern of m width and 100 μm length, 150 with a high pressure mercury lamp (9 mW / cm ² ).
Exposure was performed at mJ / cm ² . After the exposure, post-exposure baking was performed in an oven at 120 ° C. for 30 minutes, development was performed with a mixed solution of 70 parts by weight of NMP and 30 parts by weight of isopropyl alcohol, rinsed with water, and then dried. Thus, a clear pattern having a width of 10 μm and a length of 100 μm was obtained between the electrodes (between the pixels). This is further 6 at 180 ℃
By performing post-baking for 0 minutes, a target columnar pattern having a thickness of 6 μm was obtained (spacer). The variation in the thickness of this pattern in the substrate is 6.00 ± 0.06.
μm (measurement at 40 points), and the in-plane uniformity was excellent. Next, a liquid crystal cell was assembled so that the rubbing directions of the above substrates were parallel and opposed to each other, and an epoxy-based sealant (Structbond XN-21 manufactured by Mitsui Toatsu Chemicals, Inc.) was used.
-F, the same below), using LIXON5
055XX was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

[0062]

[Table 1]

Example 2 A LIXON coat PIP-8041 was applied to a glass substrate and a substrate rubbed by the same method as in Example 1,
Development was performed. At this time, a pattern for bonding the liquid crystal cells and as a sealing material was also formed around the periphery of the substrate. Next, a liquid crystal cell is assembled so that the rubbing directions of the above substrates are parallel and face each other, and the substrates are pressure-bonded 180
Baking was performed at 60 ° C. for 60 minutes, and baking and bonding of the photosensitive resin were performed at the same time. When the cell thickness of this liquid crystal cell was measured, it was 6.0 μm. Here, the spacer and the sealing material were simultaneously formed. Next, LIXON5055XX
Was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Example 3 To 10 g of LIXON-coated PIP-8041, 1 g of beads (Micropearl PF-60 (average particle size 6.0 ± 0.3 μm) manufactured by Nippon Electric Glass Co., Ltd.) was added and dispersed. This dispersion was rubbed by the same glass substrate and method as in Example 1 to obtain a LIXON coat PIP-8 after firing.
Rotation speed was adjusted so that the thickness of 041 was 1 μm, and coating, pre-baking, exposure, post-exposure baking, development, 180 ° C.
Main firing was performed for 60 minutes. Micropearls (spacers) were adhered to the pattern obtained between the electrodes, and a substrate having no micropearl spacers on the electrodes was obtained. Next, a liquid crystal cell was assembled such that the rubbing directions were parallel to each other and opposed to each other, and the substrates were bonded together by using an epoxy-based sealing material. When the cell thickness was measured, it was 6.1 μm. Next, LIXON 505
After enclosing 5XX, an isotropic treatment was performed at 120 ° C. for 30 minutes after the encapsulation, and the liquid crystal element was obtained by gradually cooling to room temperature.
Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Example 4 LIXON coat PIP-8041 was baked on a glass substrate and a substrate which had been rubbed by the same method as in Example 1 and was then subjected to 1
The number of rotations was adjusted so that the thickness became μm, and coating was performed. Next, the micropearl used in Example 3 was dispersed on this coated substrate, and prebaking, exposure, post-exposure baking, development, and main baking at 180 ° C. for 60 minutes were performed in the same manner as in Example 1. Micropearls (spacers) were adhered to the pattern obtained between the electrodes, and a substrate having no micropearl spacers on the electrodes was obtained. Next, a liquid crystal cell was assembled such that the rubbing directions were parallel to each other and opposed to each other, and the substrates were bonded together by using an epoxy-based sealing material. The cell thickness of this liquid crystal cell was measured and found to be 6.1.
μm. Next, enclose LIXON 5055XX,
After encapsulation, an isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Example 5 A glass substrate and a method similar to those in Example 1 were used to apply LIXON aligner PIA-5004 to the substrate, followed by firing.
N coat PIP-8041 was applied and development was performed. At this time, a sealing pattern was also formed on the periphery of the substrate for sealing the liquid crystal cell. Here, the spacer and the sealing material were formed. Next, the above substrate and the substrate having only the alignment film are subjected to rubbing treatment to assemble the liquid crystal cells so that the rubbing directions are parallel and face each other, and pressure bonding is performed.
Baking was carried out at 0 ° C. for 60 minutes, and baking and bonding of the photosensitive resin were performed at the same time. When the cell thickness of this liquid crystal cell was measured, it was 6.0 μm. Next, LIXON5055
XX was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature.
Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Comparative Example 1 A 2 l flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen purging device was fixed in a constant temperature bath. 110 g of 4,4′-diaminodiphenyl ether was dissolved in 278 g of NMP to prepare an amine solution. Separately, 120 g of pyromellitic dianhydride was dispersed in 308 g of DMAc, and then 184 g of NMP was added and dissolved to obtain an acid solution. An acid solution was added to the amine solution at 60 ° C. and the mixture was reacted for 3 hours to obtain a solution of 6 Pa · s at 30 ° C.
30 g of 50 g of this solution and 1.15 g of 4,4′-dimethylaminobenzophenone (hereinafter abbreviated as Michler's ketone)
A solution prepared by dissolving 10.2 g of diethylaminoethyl methacrylate in 10 g of DMAc was mixed and filtered. The obtained solution was applied onto one of the rubbed substrates similar to that in Example 1, and the temperature was set to 100 ° C. for 5
After drying for 7 minutes, a coating film of 7.2 μm was obtained. Then, 800 mJ / cm ² exposure was performed through a photomask, and after the exposure, 71.4 parts by weight of DMAc and 28.
Development was performed with 6 parts by weight of the mixed solvent to obtain a relief pattern. In this way, 10 μm between the electrodes (pixels)
A clear pattern having a width of m and a length of 100 μm was obtained. By firing this at 180 ° C. for 60 minutes, the target 6
A columnar pattern having a thickness of μm was obtained. Next, a liquid crystal cell was assembled so that the rubbing directions were parallel to each other and opposed to each other, and the substrates were bonded together by using an epoxy-based sealing material, and then LIXON 5055XX was sealed.
After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. When the liquid crystal orientation was confirmed using a polarizing plate, no liquid crystal orientation was observed, and no liquid crystal switching was observed even when a voltage was applied. Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Comparative Example 2 In a 500 ml flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen purging device, 3, 3 ',
4,4'-benzophenonetetracarboxylic dianhydride 1
6.1 g, 30.9 g of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 27.0 g of 2-hydroxyethyl methacrylate and 67.8 g of γ-butyrolactone are added, and the mixture is stirred in an ice bath. While adding 17.0 g of pyridine. After stirring at room temperature for 16 hours,
A solution of 45.2 g of γ-butyrolactone containing 41.2 g of dicyclohexylcarbodiimide was added in an ice bath for 30 minutes, followed by addition of 35.0 g of 4,4′-bis (4-aminophenoxy) biphenyl to 79.1 g of γ-butyrolactone. The butyrolactone suspension was added over 60 minutes. Under ice bath, 3
After stirring for 3 hours, 3.97 g of ethyl alcohol was added, and the mixture was further stirred for 1 hour, and the solid produced in the above process was removed by filtration. The reaction solution was added to 7950 g of ethyl alcohol, the generated precipitate was filtered off, and then vacuum dried. 50 g of the obtained polyimide precursor, 2 g of benzophenone, 6 g of tetraethylene glycol dimethacrylate, 0.05 g of Michler's ketone, 1 g of N-phenyldiethanolamine, 1.5 g of 2-mercaptobenzimidazole, 1 g of γ-glycidoxypropylmethyldimethoxysilane, N -Nitrosodiphenylamine 0.0
5 g was dissolved in 75 g NMP and filtered.

The obtained solution was applied to one of the rubbed substrates similar to Example 1 and dried at 100 ° C. for 5 minutes,
A coating film having a thickness of 7.0 μm was obtained. Next, exposure was performed at 600 mJ / cm ² using a photomask, and after the exposure, development was performed with a mixed solvent of 50 parts by weight of γ-butyrolactone and 50 parts by weight of xylene to obtain a relief pattern. Thus, a clear pattern having a width of 10 μm and a length of 100 μm was obtained between the electrodes (between the pixels). This was baked at 180 ° C. for 60 minutes to obtain an intended columnar pattern having a thickness of 6 μm. Next, a liquid crystal cell is assembled so that the rubbing directions of the above substrates are parallel to each other and face each other,
LIXON, which is attached using an epoxy sealant
5055XX was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. When the liquid crystal orientation was confirmed using a polarizing plate,
No liquid crystal orientation was observed, and no liquid crystal switching was confirmed even when a voltage was applied. Table 1 shows the results of the liquid crystal orientation and the electrical characteristics.

Comparative Example 3 In a 2 l flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen purging device, 100 g of 4,4'-diaminodiphenyl ether was dissolved in 791 g of NMP to prepare an amine solution. Next, 109 g of pyromellitic anhydride was added to this solution while stirring, while keeping the solution temperature at about 15 ° C. by ice cooling. After the addition was completed, the mixture was further reacted at about 15 ° C. for 3 hours to obtain a solution. 10 g of this solution
2.34 g of 2- (N, N-dimethylamino) ethyl paraazide benzoate was dissolved in the resulting solution, followed by filtration. The obtained solution was applied to one of the rubbed substrates as in Example 1, and dried at 100 ° C. for 5 minutes to obtain a coating film of 6.5 μm. Then, using a photomask, 600 mJ / cm ²
After exposure, development was performed with a mixed solvent of 82.5 parts by weight of DMAc and 17.5 parts by weight of ethyl alcohol to obtain a relief pattern. Thus, a clear pattern having a width of 10 μm and a length of 100 μm was obtained between the electrodes (between the pixels). This was baked at 180 ° C. for 60 minutes to obtain an intended columnar pattern having a thickness of 6 μm. Next, a liquid crystal cell was assembled so that the rubbing directions were parallel to each other and opposed to each other, and the substrates were bonded together by using an epoxy-based sealing material, and LIXON5055XX.
Was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. When the liquid crystal orientation was confirmed using a polarizing plate, no liquid crystal orientation was observed, and no liquid crystal switching was observed even when a voltage was applied. The results of liquid crystal alignment and electrical properties are
The results are shown in Table 1.

Comparative Example 4 In a 500 ml flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen purging device, 51 g of silicon diamine (FM3311 manufactured by Chisso Corporation) and 4,4'- were added.
42 g of diaminodiphenyl ether was dissolved in 200 g of NMP to obtain an amine solution. Then, 3,3 ', 4
4'-benzophenonetetracarboxylic dianhydride 77g
Was added and reacted for 3 hours to obtain a polyamic acid solution. 2.297 g of 1,4-butanediol dimethacrylate and 0.138 g of Michler's ketone were dissolved in 10 g of the obtained polyamic acid solution by stirring at room temperature for 3 hours, and then filtered. The obtained solution was applied to one of the rubbed substrates as in Example 1, dried at 100 ° C. for 5 minutes, and 7.1 μm.
m was obtained. Then, using a photomask,
Exposure was performed at mJ / cm ² , and after exposure, development was performed with a mixed solvent of 60 parts by weight of NMP and 40 parts by weight of methyl alcohol to obtain a relief pattern. Thus, a clear pattern having a width of 10 μm and a length of 100 μm was obtained between the electrodes (between the pixels). This was baked at 180 ° C. for 60 minutes to obtain an intended columnar pattern having a thickness of 6 μm. Next, a liquid crystal cell was assembled so that the rubbing directions were parallel to each other and opposed to each other, and the substrates were bonded together by using an epoxy-based sealing material, and LIXON5055XX.
Was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. When the liquid crystal orientation was confirmed using a polarizing plate, no liquid crystal orientation was observed, and no liquid crystal switching was observed even when a voltage was applied. The results of liquid crystal alignment and electrical properties are
The results are shown in Table 1.

[0072]

The liquid crystal element using the resin film obtained by using the photo-acid generator used as an essential component in the present invention as a constituent material can be obtained by the conventional organic material without deteriorating the original electric characteristics of the liquid crystal. It has a practical orientation and electrical properties that were not available, and when the resin film is used as a spacer, the layer thickness of the liquid crystal layer is controlled uniformly, and the layer thickness is controlled in a columnar form to provide mechanical strength. It also has excellent adhesiveness when used as a sealant. According to the present invention, a liquid crystal element can be easily formed, its aperture ratio is improved, and its contrast is excellent.

[Brief description of drawings]

FIG. 1 is a drawing showing a structure of a liquid crystal element of the present invention.

[Explanation of symbols]

 1 Transparent Insulating Substrate (First Substrate) 2 Transparent Insulating Substrate (Second Substrate) 3 Transparent Conductive Electrode (First Electrode) 4 Transparent Conductive Electrode (Second Electrode) 5 Alignment Film 6 Liquid Crystal Layer 7 Columnar Resin Film

Claims (5)

[Claims] 1. A liquid crystal device comprising a resin film having liquid crystal resistance, which is obtained from a photosensitive resin composition containing a photo-acid generator as an initiator. 2. The liquid crystal element according to claim 1, wherein the resin film is a spacer of the liquid crystal element. 3. The liquid crystal device according to claim 2, wherein the resin film contains beads. 4. The liquid crystal element according to claim 1, wherein the resin film is a sealant for the liquid crystal element. 5. A step of forming a film of a photosensitive resin composition having a photoacid generator as an initiator on a substrate having a transparent electrode,
It is manufactured through a step of exposing a part of the film by light irradiation through a photomask and a step of developing and removing either an exposed region or an unexposed region of the film after the light irradiation. The liquid crystal element according to claim 1.