JP4702198B2 - Alignment film, method for forming alignment film, substrate for electronic device, liquid crystal panel and electronic device - Google Patents

Description

  The present invention relates to an alignment film, a method for forming the alignment film, an electronic device substrate, a liquid crystal panel, and an electronic apparatus.

A projection display device that projects an image on a screen is known. In this projection display device, a liquid crystal panel is mainly used for image formation.
Such a liquid crystal panel usually has an alignment film set so as to develop a predetermined pretilt angle in order to align liquid crystal molecules in a certain direction. In order to manufacture these alignment films, a method of rubbing a thin film made of a polymer compound such as polyimide formed on a substrate with a cloth such as rayon in one direction is known (for example, , See Patent Document 1).

However, an alignment film formed of an organic material such as polyimide may cause photodegradation depending on the use environment, use time, and the like. When such photodegradation occurs, the forming materials such as the alignment film and the liquid crystal layer are decomposed, and the decomposition products may adversely affect the performance of the liquid crystal.
For the purpose of solving such problems, there is known one employing an alignment film (inorganic alignment film) formed of an inorganic material typified by SiO ₂ (see, for example, Patent Document 2). The inorganic alignment film is generally formed by oblique deposition.
JP-A-10-161133 (Claims) JP-A-5-203958

However, although the inorganic alignment film is superior in light resistance and heat resistance compared to an alignment film formed of an organic material, there is a problem that the ability to align liquid crystal molecules is low.
In addition, this inorganic alignment film is susceptible to moisture absorption during alignment due to silanol groups present on the film surface, and the moisture absorption results in poor alignment of the liquid crystal and deteriorates the display characteristics of the liquid crystal panel. There is also a problem that it is not secured.

  An object of the present invention is to provide an alignment film that is excellent in light resistance, excellent in alignment characteristics (function for regulating the alignment state of a liquid crystal material), and that can sufficiently ensure the long-term reliability of a liquid crystal panel. Another object of the present invention is to provide a method for forming an alignment film capable of efficiently producing a simple alignment film, and to provide an electronic device substrate, a liquid crystal panel, and an electronic apparatus provided with the alignment film.

  In order to achieve the above object, the alignment film of the present invention is an alignment film that controls the alignment of liquid crystal molecules, and is formed of at least an organosilicon material, and the organosilicon material has a cage structure or a partially-cleavage cage structure. The polysilsesquioxane comprises an affinity imparting group that improves the affinity with the liquid crystal molecules in the molecule, and an orientation imparting group that controls the orientation of the liquid crystal molecules. And hydrogen in the silanol group is substituted with a substituent to be inactivated.

  This alignment film has excellent light resistance and excellent alignment characteristics (function to regulate the alignment state of the liquid crystal material). Furthermore, since it has a cage structure or a partially cleaved cage structure and hydrogen in the silanol group is substituted by a substituent to be inactivated, this silanol is eliminated by eliminating the OH group that becomes a silanol group in the film. Moisture absorption by the base does not occur. Therefore, the display characteristics of the liquid crystal panel are not deteriorated due to moisture due to moisture absorption, and thereby long-term reliability of the liquid crystal panel using the alignment film is sufficiently ensured.

In the alignment film, the substituent is preferably a trimethylsilyl group.
In this way, since a trimethylsilyl group containing Si is introduced instead of hydrogen in the silanol group, the liquid crystal panel resulting from the OH group without greatly changing the properties of the alignment film made of polysilsesquioxane. The display characteristics can be reliably prevented from deteriorating.

In the alignment film, the affinity imparting group is preferably at least one of a vinyl group, an alkylene group, and a cyanoalkyl group.
In this way, since the affinity with the liquid crystal molecules can be more effectively improved, the liquid crystal molecules can be arranged in a more stable state, and the alignment characteristics are improved.

In the alignment film, the orientation-imparting group is at least one of a phenyl group, a substituted phenyl group, a phenylalkyl group, a substituted phenylalkyl group, and a branched alkyl group having 3 to 12 carbon atoms. Is preferred.
In this way, the desired pretilt angle of the liquid crystal molecules can be made more effective, and more excellent alignment characteristics can be exhibited.

In the alignment film, the organosilicon material preferably has a weight average molecular weight of 500 to 50,000.
In this way, the alignment film is stable both optically and physically.

In the alignment film, the average thickness of the alignment film is preferably 0.01 to 10 μm.
In this way, the orientation of the liquid crystal molecules can be more effectively regulated.

  The method for forming an alignment film of the present invention is a method for forming an alignment film for controlling the alignment of liquid crystal molecules, which has a cage structure or a partially cleaved cage structure by polycondensation of alkoxysilane, Synthesizing a polysilsesquioxane having an affinity imparting group for improving the affinity with the liquid crystal molecule in the molecule and an orientation imparting group for controlling the orientation of the liquid crystal molecule; and the polysilsesquioxane. Reacting sun with a compound having a substituent, and substituting the hydrogen in the silanol group in the polysilsesquioxane with the substituent to inactivate, and the inactivated polysilsesquioxane. And a step of forming an alignment film on the substrate using an alignment film forming liquid containing oxane.

According to this method for forming an alignment film, an alignment film having excellent light resistance and excellent alignment characteristics (function for regulating the alignment state of the liquid crystal material) can be efficiently formed.
Further, since the obtained alignment film has a cage structure or a partially cleaved cage structure and hydrogen in the silanol group is substituted with a substituent to be inactivated, an OH group that becomes a silanol group in the film By eliminating this, moisture absorption by this silanol group does not occur. Therefore, it is possible to eliminate the deterioration of the display characteristics of the liquid crystal panel due to moisture due to moisture absorption, and to sufficiently ensure the long-term reliability of the liquid crystal panel using this alignment film.

In the method for forming the alignment film, the substituent is preferably a trimethylsilyl group.
In this way, since a trimethylsilyl group containing Si is introduced instead of hydrogen in the silanol group, the liquid crystal panel resulting from the OH group without greatly changing the properties of the alignment film made of polysilsesquioxane. The display characteristics can be reliably prevented from deteriorating.

Further, in the method of forming the alignment film, a plurality of types of alkoxysilanes having different compositions are used, and a plurality of types of alkoxysilanes having different compositions are used as alkoxysilanes having an affinity-imparting group and alignment imparting. It is preferable to use an alkoxysilane having a group.
In this way, the abundance ratio of the affinity imparting group and the orientation imparting group in the organosilicon material forming the alignment film can be easily adjusted.

In the method for forming the alignment film, the alignment film is formed by curing the alignment film forming liquid, and the polysilsesquioxane is the alignment film forming liquid. It preferably has a curing reactive group that contributes to the curing reaction.
In this way, the film formability (moldability) of the alignment film forming liquid can be improved, and therefore a physically stable alignment film can be effectively formed.

In the method for forming the alignment film, the curing reactive group is at least one of a glycidoxyalkyl group, an alicyclic epoxyalkyl group, an acryloyl group, a methacryloyl group, a styryl group, and a styrylalkyl group. Preferably there is.
In this way, a stable alignment film can be formed more easily.

In the method for forming the alignment film, it is preferable that the alignment film-forming liquid is cured by performing a heat treatment and / or an energy ray irradiation treatment.
In this way, a stable alignment film can be formed more efficiently.

The electronic device substrate of the present invention is characterized in that an electrode and the alignment film are provided on the substrate.
According to this electronic device substrate, the alignment characteristics (function of regulating the alignment state of the liquid crystal material) are excellent, and the light resistance is excellent. Furthermore, it is possible to prevent the display characteristics of the liquid crystal panel from deteriorating due to moisture due to moisture absorption of the alignment film, and sufficiently ensure the long-term reliability of the liquid crystal panel using the electronic device substrate.

The liquid crystal panel of the present invention is characterized by comprising the alignment film and a liquid crystal layer.
If it does in this way, it will be excellent in the alignment characteristic (function which regulates the alignment state of liquid crystal material), and excellent in light resistance. Further, it is possible to prevent deterioration of the display characteristics of the liquid crystal panel due to moisture due to moisture absorption of the alignment film, and sufficiently ensure the long-term reliability of the liquid crystal panel.

An electronic apparatus according to the present invention includes the above-described liquid crystal panel.
In this way, a highly reliable electronic device can be provided.

DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
First, prior to the description of the alignment film of the present invention and the method for forming the alignment film, the liquid crystal panel according to the present invention will be described.
FIG. 1 is a schematic longitudinal sectional view showing a first embodiment of the liquid crystal panel of the present invention. In FIG. 1, reference numeral 1A denotes a liquid crystal panel. The liquid crystal panel 1A includes a liquid crystal layer 2, alignment films 3A and 4A, transparent conductive films 5 and 6, polarizing films 7A and 8A, and substrates 9 and 10. Have.

  The liquid crystal layer 2 is mainly formed of a liquid crystal material. As the liquid crystal material for forming such a liquid crystal layer 2, any liquid crystal material can be used as long as it can be aligned, such as a nematic liquid crystal or a smectic liquid crystal. For example, in the case of a TN type liquid crystal panel, one that forms a nematic liquid crystal is used. A phenylcyclohexane derivative liquid crystal, a biphenyl derivative liquid crystal, a biphenylcyclohexane derivative liquid crystal, a terphenyl derivative liquid crystal, a phenyl ether derivative liquid crystal, a phenyl ester derivative liquid crystal, a bicyclohexane A derivative liquid crystal, an azomethine derivative liquid crystal, an azoxy derivative liquid crystal, a pyrimidine derivative liquid crystal, a dioxane derivative liquid crystal, a cubane derivative liquid crystal, or the like is preferably used. Further, a liquid crystal molecule in which a fluorine-based substituent such as a monofluoro group, a difluoro group, a trifluoro group, a trifluoromethyl group, a trifluoromethoxy group, or a difluoromethoxy group is introduced into these nematic liquid crystal molecules is also used.

Alignment films 3A and 4A are arranged on both surfaces of the liquid crystal layer 2.
Further, the alignment film 3A is formed on a base material 100 composed of a transparent conductive film 5 and a substrate 9 as described later, and the alignment film 4A is composed of a transparent conductive film 6 and a substrate 10 as described later. It is formed on the substrate 101.
The alignment films 3A and 4A have a function of regulating the alignment state (when no voltage is applied) of the liquid crystal material (liquid crystal molecules) forming the liquid crystal layer 2.

Such alignment films 3A and 4A are formed by a method as described later (method for forming an alignment film of the present invention), and are formed of an organic silicon material.
The organosilicon material is made of polysilsesquioxane having a cage structure or a partially cleaved cage structure, and an organic functional group is added to a skeleton made of polysiloxane. With such a configuration, the alignment films 3A and 4A made of the organic silicon material have excellent chemical stability compared to the conventional organic materials such as polyimide, and therefore, compared with the alignment film made of the conventional organic material. Especially, it has excellent light resistance.

Moreover, in this invention, the organosilicon material which forms alignment film 3A, 4A has an affinity provision group which improves affinity with the liquid crystal material (liquid crystal molecule) mentioned above as an organic functional group in the molecule | numerator, and liquid crystal And an orientation-imparting group that controls the orientation state of the material.
Here, the alignment film formed of an inorganic material has excellent light resistance compared to an alignment film formed of a conventional organic material, but has a low affinity with liquid crystal molecules, and alignment of liquid crystal molecules. There is a problem that it is difficult to regulate the state and the ability to align liquid crystal molecules is low.

  Therefore, in the present invention, such a problem is solved by using an organosilicon material having an affinity imparting group and an orientation imparting group as a material for forming the alignment films 3A and 4A. That is, the affinity imparting group improves the affinity with the liquid crystal molecules, and attracts the liquid crystal molecules to the alignment film, thereby making it easy to regulate the alignment state of the liquid crystal molecules. In addition, the alignment state of the liquid crystal molecules is regulated by the orientation imparting group so that the liquid crystal molecules are aligned at a desired pretilt angle. As a result, the alignment films 3A and 4A have excellent light resistance and also have excellent alignment characteristics (function to regulate the alignment state of the liquid crystal material). Moreover, since the adhesiveness with the transparent conductive film which will be described later is improved, the reliability of the finally obtained electronic device is also improved.

Such an effect cannot be obtained when the organosilicon material has only one of an affinity imparting group and an orientation imparting group.
That is, when only the affinity imparting group is included, the liquid crystal molecules can be sufficiently attracted to the surfaces of the alignment films 3A and 4A, but it is difficult to align the liquid crystal molecules in a predetermined direction. Moreover, when it has only the orientation imparting group, since it has low affinity with the liquid crystal molecules, it becomes difficult to sufficiently attract the liquid crystal molecules to the surfaces of the alignment films 3A and 4A, and the alignment state of the liquid crystal molecules is restricted. Because it becomes difficult.

Examples of the affinity imparting group include a vinyl group, an alkylene group, a cyanoalkyl group, a phenyl group, a substituted phenyl group, and an alkylidene group.
The alignment films 3A and 4A are organosilicon materials having at least one or more of a vinyl group, an alkylene group, an alkylidene group, and a cyanoalkyl group, among the above-described affinity imparting groups. It is preferable that it is formed. Thereby, since affinity with a liquid crystal molecule can be improved more effectively, a liquid crystal molecule can be arranged in a more stable state, and alignment characteristics improve.

Examples of the orientation imparting group include a phenyl group, a substituted phenyl group, a phenylalkyl group, a substituted phenylalkyl group, and a branched alkyl group having 3 to 12 carbon atoms.
The alignment films 3A and 4A are, among the above-described orientation-imparting groups, in particular at least of a phenyl group, a substituted phenyl group, a phenylalkyl group, a substituted phenylalkyl group, and a branched alkyl group having 3 to 12 carbon atoms. It is preferably formed of an organic silicon material having one kind or two or more kinds. Thereby, the alignment direction of liquid crystal molecules becomes more uniform, and more excellent alignment characteristics are exhibited.

  Furthermore, among the orientation-imparting groups as described above, when an organosilicon material having a phenyl group, a substituted phenyl group, a phenylalkyl group, or a substituted phenylalkyl group is used, the affinity with liquid crystal molecules is also improved. The molecules are arranged in a stable state and have more excellent orientation characteristics.

The alignment films 3A and 4A are made of polysilsesquioxane having a cage structure or a partially-cleavage cage structure as described above, and hydrogen in the silanol group is substituted with a substituent to be inactivated, That is, it is formed of an end-capped organosilicon material.
FIG. 2A is a view showing an example of a polysilsesquioxane having a cage structure, where Si in FIG. 2A is silicon, O is oxygen, and R is an organic functional group. This polysilsesquioxane has, as the organic functional group (R), the above-described affinity-imparting group, orientation-imparting group, and further a curing reactive group described later. Moreover, when synthesizing this, it has a silanol group (Si-OH) that is inevitably formed, and this silanol group is not endcapped (inactivated). The hydroxyl group (OH group) in the silanol group has high hygroscopicity as described above, and therefore, moisture absorption causes liquid crystal alignment failure, resulting in deterioration of the display characteristics of the liquid crystal panel and loss of long-term reliability. End up.

Therefore, in the present invention, as described above, hydrogen in the silanol group is substituted with a substituent to perform end capping (inactivation). As such end capping, for example, a trialkylsilyl compound is preferably used as an endcapping material, and among them, a trimethylsilyl compound such as trimethylchlorosilane [(CH) ₃ SiCl] is more preferably used. By using this trimethylchlorosilane as an end-capping material and reacting with the silanol group in FIG. 2 (a), the hydrogen in the silanol group is converted to a trimethylsilyl group (Me ₃ Si—) as shown in FIG. 2 (b). Can be replaced and endcapped. That is, the trimethylsilyl group in the trimethylchlorosilane becomes a substituent that replaces the hydrogen in the silanol group.
As described above, since the hydrogen in the silanol group is replaced with the trimethylsilyl group, the alignment films 3A and 4A lose the hygroscopic property due to the hydroxyl group in the silanol group, thereby causing poor alignment of the liquid crystal due to the absorbed moisture. Disappears.

The weight average molecular weight of such an organosilicon material (polysilsesquioxane) is preferably 500 to 50,000, and more preferably 700 to 50,000. With such molecular weight, the alignment films 3A and 4A are stable both optically and physically.
Moreover, as such alignment film 3A, 4A, it is preferable that the average thickness is 0.01-10 micrometers, it is more preferable that it is 0.01-0.1 micrometer, and 0.02-0. More preferably, it is 05 μm. If the average thickness is less than 0.01 μm, the function as the alignment film may not be sufficiently exhibited depending on the composition of the organosilicon material. On the other hand, when the average thickness exceeds 10 μm, the driving voltage becomes high, and there is a possibility that the driving by the TFT becomes difficult. In addition, when the average thickness is in the range of 0.01 to 0.1 μm, and further 0.02 to 0.05 μm, the above-described fear is surely avoided, which is preferable.

A transparent conductive film 5 is disposed on the outer surface side of the alignment film 3A (the surface side opposite to the surface facing the liquid crystal layer 2). Similarly, the transparent conductive film 6 is disposed on the outer surface side of the alignment film 4A (the surface side opposite to the surface facing the liquid crystal layer 2).
The transparent conductive films 5 and 6 have a function of driving (changing the orientation of) the liquid crystal molecules of the liquid crystal layer 2 by energizing them.

Control of energization between the transparent conductive films 5 and 6 is performed by controlling a current supplied from a control circuit (not shown) connected to the transparent conductive film.
The transparent conductive films 5 and 6 have conductivity, and are made of, for example, indium tin oxide (ITO), tin oxide (SnO ₂ ), or the like.
On the outer surface side of the transparent conductive film 5 (surface side opposite to the surface facing the alignment film 3A), a substrate 9 is disposed. Similarly, the substrate 10 is disposed on the outer surface side of the transparent conductive film 6 (the surface side opposite to the surface facing the inorganic alignment film 4A).

  The substrates 9 and 10 have a function of supporting the liquid crystal layer 2, the alignment films 3A and 4A, the transparent conductive films 5 and 6, and the polarizing films 7A and 8A described later. The formation material of the substrates 9 and 10 is not particularly limited, and examples thereof include glass such as quartz glass and plastic material such as polyethylene terephthalate. Among these, it is particularly preferable that it is made of glass such as quartz glass. Thereby, it is possible to obtain a liquid crystal panel which is less likely to be warped or bent and which is more stable. In FIG. 1, the description of the sealing material, the wiring, and the like is omitted.

On the outer surface side of the substrate 9 (surface opposite to the surface facing the transparent conductive film 5), a polarizing film (polarizing plate, polarizing film) 7A is disposed. Similarly, a polarizing film (polarizing plate, polarizing film) 8A is disposed on the outer surface side of the substrate 10 (the side opposite to the side facing the transparent conductive film 6).
Examples of the material for forming the polarizing films 7A and 8A include polyvinyl alcohol (PVA). Moreover, as these polarizing films 7A and 8A, what doped the said material with iodine etc. can also be used, Furthermore, what extended | stretched the film formed with the said material to the uniaxial direction can be used.
By disposing the polarizing films 7A and 8A as described above, it is possible to more reliably control the light transmittance by adjusting the energization amount.
In addition, the direction of the polarization axis of these polarizing films 7A and 8A is normally determined appropriately according to the alignment direction of the alignment films 3A and 4A.

Next, a method for forming the alignment film of the present invention will be described.
The alignment film forming method of the present embodiment has a cage structure or a partially cleaved cage structure by polycondensing a plurality of types of alkoxysilanes having different compositions, and has affinity for the liquid crystal molecules in the molecule. A step of synthesizing a polysilsesquioxane having an affinity imparting group for improving the property and an orientation imparting group for controlling the orientation of the liquid crystal molecules [polysilsesquioxane synthesis step], and the obtained polysil A step of reacting sesquioxane with a compound having a substituent, substituting hydrogen in the silanol group in the polysilsesquioxane with the substituent, and performing end-capping (inactivation step); , A step of preparing an alignment film-forming liquid containing the above-mentioned end-capped polysilsesquioxane [an alignment film-forming liquid preparation step], and forming an alignment film obtained on the substrate The liquid was applied, and a step [Coating film formation step] for forming a coating film, and a step Curing Step] curing the formed coating film.

[Polysilsesquioxane synthesis process]
<1>
First, an alkoxysilane having an affinity imparting group at a ratio corresponding thereto so that the abundance ratio of the functional group such as the affinity imparting group and the orientation imparting group in the finally obtained alignment film becomes a desired one. And an alkoxysilane having an orientation-imparting group and a plurality of types of alkoxysilanes having an alkoxysilane having a curing reaction group that contributes to a curing reaction in forming a film, which will be described later.
As described above, by using a plurality of types of alkoxysilanes, it is possible to easily adjust the abundance ratio of the affinity imparting group and the orientation imparting group in the organic silicon material forming the alignment film.

  Examples of the alkoxysilane having an affinity-imparting group include vinyltrimethoxysilane, 3-cyanopropyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltriisopropoxysilane, butenyltrimethoxysilane, and butenyl. Triethoxysilane, butenylisopropoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltriisopropoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltriisopropoxysilane, ( Examples include 3-cyanobutyl) methyltrimethoxysilane, (3-cyanobutyl) ethyltrimethoxysilane, and (3-cyanobutyl) methyltriisopropoxysilane.

  Examples of the alkoxysilane having an orientation-imparting group include phenyltrimethoxysilane, isobutyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, isobutyltriethoxysilane, isobutyltriisopropoxysilane, and isopropyltrimethoxy. Examples thereof include silane, isopropyltriethoxysilane, isopropyltriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, and phenethyltriisopropoxysilane.

The curing reactive group is a functional group having a function of curing the coating film by reacting the curing reactive groups with each other under predetermined conditions. By using an alkoxysilane having such a curing reactive group, the film formability (moldability) of the alignment film forming liquid can be improved. As a result, a physically stable alignment film can be effectively formed.
Examples of such curing reactive groups include glycidoxyalkyl groups, alicyclic epoxyalkyl groups, acryloylalkyl groups, methacryloylalkyl groups, vinyl groups, alkylene groups, alkylidene groups, styryl groups, and styrylalkyl groups. It is done.

Among the foregoing, it is particularly preferable to use a glycidoxyalkyl group, an alicyclic epoxyalkyl group, or a methacryloylalkyl group. By having such a functional group, a stable alignment film can be formed more effectively.
Examples of the alkoxysilane having such a curing reaction group include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxysiloxyhexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Etc.

<2>
Next, a plurality of types of alkoxysilane as described above, water, and a diluting solvent used as necessary are mixed at a predetermined ratio to obtain a mixed solution. Here, as the diluting solvent, alcohols such as methanol, ethanol and isopropyl alcohol, ethers such as diethyl ether and tetrahydrofuran (THF), ketones such as acetone and methyl isobutyl ketone, hydrocarbons such as toluene and the like are appropriately used. Used for.

<3>
Next, while stirring the obtained mixed liquid, hydrolysis and polycondensation catalysts such as an acid catalyst and a base catalyst are added thereto. In addition, you may add these catalysts to the solvent or water used for reaction previously.
Examples of the acid catalyst (including a solid acid catalyst) include inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, and organic sulfonic acids (for example, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, ethane). And organic acids such as sulfonic acid. Examples of the base catalyst include inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, tertiary amines (trimethylamine, triethylamine, tributylamine, triethanolamine, pyridine, etc.), hydroxide And organic bases such as tetramethylammonium and choline. Of these basic catalysts, sodium hydroxide, potassium hydroxide, and tetraalkylammonium hydroxide, which have high activity as a base and are easily removed during post-treatment, are more preferable.

<4>
After adding the hydrolysis catalyst, the alkoxysilane is polycondensed by heating at a predetermined temperature while stirring.
The predetermined temperature (reaction temperature) is preferably 5 to 140 ° C, and more preferably 30 to 60 ° C. If the reaction temperature is too high, the reaction of the curing reactive group may occur. Conversely, if the reaction temperature is too low, the progress of the reaction is remarkably slowed.
The reaction time is preferably 1 to 48 hours, and more preferably 3 to 18 hours. If the reaction time is too long, the reaction of the curing reactive group may occur. Conversely, if the reaction time is too short, the reaction is not completed.

<5>
Next, treatments such as neutralization, removal of diluted solvent, and drying are performed. By performing such a treatment, it is possible to obtain (synthesize) a polysilsesquioxane having a cage structure (or a partially cleaved cage structure) as shown in FIG.

[End capping process]
Next, the polysilsesquioxane obtained in the above step is reacted with a compound having a substituent, and hydrogen in the silanol group in the polysilsesquioxane is substituted with the substituent to endcapping (non-capping). Activation).
In this step, first, the polysilsesquioxane obtained in the above step is dried using, for example, dry diethyl ether. Then, for example, trimethylchlorosilane is added as an end-capping material to the polysilsesquioxane after drying, and triethylamine is also added at the same time.
Next, a saturated aqueous sodium hydrogen carbonate solution is added, and further extraction treatment with ether, washing treatment with saturated brine, and drying treatment with anhydrous magnesium sulfate are sequentially performed.
Thereafter, the low boiling point portion was distilled off, and as shown in FIG. 2 (b), the hydrogen in the silanol group was replaced with a trimethylsilyl group (Me ₃ Si—), and the end-capped polysilsesquioxy having a cage structure was formed. Get sun.

[Liquid preparation step for alignment film formation]
Next, an alignment film forming liquid containing the above-mentioned end capping polysilsesquioxane is prepared.
In this preparation step, the polysilsesquioxane after the end-capping process obtained in the above step may be used as it is as an alignment film forming liquid, and a solvent or the like may be added as necessary. .
Moreover, about the liquid for alignment film formation to prepare, you may add a hardening | curing agent (polymerization initiator) as needed. Thereby, hardening of a coating film which is mentioned later can be performed easily.

Examples of such a curing agent include benzophenone, 1-hydroxycyclohexyl phenyl ketone, (thiophenoxyphenyl) diphenylsulfonium hexafluorophosphate, bis (diphenylsulfonium) diphenylthioether hexafluorophosphate, and the like. Examples include photopolymerization initiators, thermal polymerization initiators such as azobisisobutyronitrile, azobismethylbutyronitrile, and the like, and one or more of these can be used in combination.
Moreover, you may perform a filtration process with respect to the liquid for alignment film formation as needed. Thereby, impurities contained in the alignment film forming liquid can be removed, and an alignment film having a uniform thickness can be efficiently formed.

[Coating film forming process]
Next, the alignment film-forming liquid obtained in the above step is applied onto a substrate (base material 100, substrate 101) to form a coating film formed of the alignment film-forming liquid.
Examples of the method for applying the alignment film forming liquid include a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, and a die coating method.

[Curing process]
Next, the formed coating film is cured to form alignment films (alignment film 3A and alignment film 4A).
The coating film can be cured by, for example, heat treatment, energy ray irradiation treatment, or the like.
Examples of energy rays include visible light, ultraviolet light, radiation, infrared light, and the like.

By performing such treatment, the curing reaction groups as described above cause radical polymerization, cationic polymerization, polycondensation, etc. in the coating film, and the coating film is cured to form an alignment film. Thereby, the board | substrate (substrate for electronic devices of this invention) in which the oriented film was formed on the base material is obtained.
The coating film is particularly preferably cured after removing moisture, a solvent, and the like contained in the alignment film forming liquid for forming the coating film (after drying the coating film). Thereby, an alignment film having a stable film thickness can be efficiently formed.

Moreover, you may perform hardening of a coating film by irradiating an energy ray, for example, after hardening a coating film temporarily, and carrying out main curing by heat processing. That is, the coating film may be cured by temporarily curing the coating film with a relatively low energy once and then completely curing it. Thereby, an alignment film having a stable film thickness can be formed more efficiently.
After the curing, a rubbing treatment is performed in the same manner as a normal polyimide alignment film. Thereby, the alignment characteristic of the alignment film obtained can be made more excellent.

Next, a second embodiment of the liquid crystal panel of the present invention will be described.
FIG. 3 is a schematic longitudinal sectional view showing a second embodiment of the liquid crystal panel of the present invention. Hereinafter, the liquid crystal panel 1B shown in FIG. 3 will be described with a focus on differences from the first embodiment, and description of similar configurations will be omitted.
As shown in FIG. 3, a liquid crystal panel (TFT liquid crystal panel) 1B includes a TFT substrate (liquid crystal driving substrate) 17, an alignment film 3B bonded to the TFT substrate 17, a liquid crystal panel counter substrate 12, and a liquid crystal panel. The alignment film 4B bonded to the counter substrate 12, the liquid crystal layer 2 made of liquid crystal sealed in the gap between the alignment film 3B and the alignment film 4B, and the outer surface side (alignment film 4B) of the TFT substrate (liquid crystal driving substrate) 17 Polarized film 7B bonded to the surface opposite to the surface facing the liquid crystal) and polarized light bonded to the outer surface side of the liquid crystal panel counter substrate 12 (surface opposite to the surface facing the alignment film 4B). And a film 8B. The alignment films 3B and 4B are formed by the same method as the alignment films 3A and 4A described in the first embodiment (the method of forming the alignment film of the present invention), and the polarizing films 7B and 8B This is the same as the polarizing films 7A and 8A described in the first embodiment.

The counter substrate 12 for the liquid crystal panel is provided on the microlens substrate 11, the surface layer 114 of the microlens substrate 11, the black matrix 13 in which the opening 131 is formed, and the black matrix 13 on the surface layer 114 so as to cover the black matrix 13. A transparent conductive film (common electrode) 14.
The microlens substrate 11 includes a microlens concave substrate (first substrate) 111 provided with a plurality of (many) concave portions (microlens concave portions) 112 having a concave curved surface, and the microlens concave substrate 111. And a surface layer (second substrate) 114 joined via a resin layer (adhesive layer) 115 on the surface provided with the recess 112, and the resin layer 115 fills the recess 112. The microlens 113 is formed by the resin thus formed.

The substrate with concave portions for microlenses 111 is manufactured from a flat base material (transparent substrate), and a plurality of (many) concave portions 112 are formed on the surface thereof. The recess 112 can be formed by, for example, a dry etching method, a wet etching method, or the like using a mask.
The substrate with concave portions 111 for microlenses is made of, for example, glass.

The thermal expansion coefficient of the base material is preferably approximately the same as the thermal expansion coefficient of the glass substrate 171 (for example, the ratio of the thermal expansion coefficients of the two is about 1/10 to 10). As a result, in the obtained liquid crystal panel, warpage, deflection, peeling, and the like caused by differences in the thermal expansion coefficients of the two when the temperature changes are prevented.
From this point of view, it is preferable that the substrate with concave portions for microlenses 111 and the glass substrate 171 are formed of the same type of material. This effectively prevents warpage, deflection, peeling, and the like due to differences in the thermal expansion coefficient when the temperature changes.

  In particular, when the microlens substrate 11 is used in a high-temperature polysilicon TFT liquid crystal panel, the substrate 111 with concave portions for microlenses is preferably formed of quartz glass. The TFT liquid crystal panel has a TFT substrate as a liquid crystal driving substrate. For such a TFT substrate, quartz glass whose characteristics are unlikely to change depending on the manufacturing environment is preferably used. For this reason, by forming the microlens concave substrate 111 with quartz glass correspondingly, it is possible to obtain a TFT liquid crystal panel with excellent stability, which is less likely to be warped or bent.

A resin layer (adhesive layer) 115 that covers the recess 112 is provided on the upper surface of the substrate with recesses 111 for microlenses.
The concave portion 112 is filled with a material for forming the resin layer 115 to form the microlens 113.
The resin layer 115 can be formed of, for example, a resin (adhesive) having a refractive index higher than the refractive index of the material for forming the microlens recessed substrate 111. For example, an acrylic resin, an epoxy resin, or an acrylic epoxy is used. It can be suitably formed with an ultraviolet curable resin or the like such as a system.

A flat surface layer 114 is provided on the upper surface of the resin layer 115.
The surface layer (glass layer) 114 can be formed of glass, for example. In this case, it is preferable that the thermal expansion coefficient of the surface layer 114 is substantially equal to the thermal expansion coefficient of the substrate 111 with concave portions for microlenses (for example, the ratio of the thermal expansion coefficients of the two is about 1/10 to 10). As a result, warpage, deflection, peeling, and the like caused by the difference in thermal expansion coefficient between the substrate 111 with concave portions for microlenses and the surface layer 114 are prevented. Such an effect can be obtained more effectively when the substrate with concave portions for microlenses 111 and the surface layer 114 are formed of the same material.

When the microlens substrate 11 is used in a liquid crystal panel, the thickness of the surface layer 114 is usually about 5 to 1000 μm, more preferably about 10 to 150 μm, from the viewpoint of obtaining necessary optical characteristics.
The surface layer (barrier layer) 114 can also be formed of ceramics, for example. Examples of ceramics include nitride ceramics such as AlN, SiN, TiN, and BN, oxide ceramics such as Al ₂ O ₃ and TiO ₂ , and carbide ceramics such as WC, TiC, ZrC, and TaC. Can be mentioned. When the surface layer 114 is formed of ceramics, the thickness of the surface layer 114 is not particularly limited, but is preferably about 20 nm to 20 μm, and more preferably about 40 nm to 1 μm.
Such a surface layer 114 can be omitted if necessary.

The black matrix 13 has a light shielding function, and is formed of, for example, a metal such as Cr, Al, Al alloy, Ni, Zn, or Ti, a resin in which carbon, titanium, or the like is dispersed.
The transparent conductive film 14 has conductivity, and is formed of, for example, indium tin oxide (ITO), indium oxide (IO), tin oxide (SnO ₂ ), or the like.
The TFT substrate 17 is a substrate that drives the liquid crystal of the liquid crystal layer 2, and is a glass substrate 171 and a plurality (large number) of pixel electrodes 172 provided on the glass substrate 171 and arranged in a matrix (matrix). And a plurality of (many) thin film transistors (TFTs) 173 corresponding to the respective pixel electrodes 172. In FIG. 3, the description of the sealing material, the wiring, etc. is omitted.

The glass substrate 171 is preferably formed of quartz glass for the reasons described above.
The pixel electrode 172 drives the liquid crystal of the liquid crystal layer 2 by charging and discharging with the transparent conductive film (common electrode) 14. The pixel electrode 172 is made of the same material as that of the transparent conductive film 14 described above, for example.

The thin film transistor 173 is connected to the corresponding pixel electrode 172 in the vicinity. The thin film transistor 173 is connected to a control circuit (not shown) and controls a current supplied to the pixel electrode 172. Thereby, charging / discharging of the pixel electrode 172 is controlled.
The alignment film 3B is bonded to the pixel electrode 172 of the TFT substrate 17, and the alignment film 4B is bonded to the transparent conductive film 14 of the counter substrate 12 for the liquid crystal panel.

The liquid crystal layer 2 is formed of a liquid crystal material (liquid crystal molecules), and the alignment of the liquid crystal molecules, that is, the liquid crystal changes corresponding to the charge / discharge of the pixel electrode 172.
In such a liquid crystal panel 1B, normally, one micro lens 113, one opening 131 of the black matrix 13 corresponding to the optical axis Q of the micro lens 113, one pixel electrode 172, and such a pixel. One thin film transistor 173 connected to the electrode 172 corresponds to one pixel.

  Incident light L incident from the liquid crystal panel counter substrate 12 side passes through the microlens concave substrate 111 and is condensed when passing through the microlens 113, while opening the resin layer 115, the surface layer 114, and the black matrix 13. 131, the transparent conductive film 14, the liquid crystal layer 2, the pixel electrode 172, and the glass substrate 171 are transmitted. At this time, since the polarizing film 8B is provided on the incident side of the microlens substrate 11, when the incident light L passes through the liquid crystal layer 2, the incident light L is linearly polarized light. At this time, the polarization direction of the incident light L is controlled in accordance with the alignment state of the liquid crystal molecules in the liquid crystal layer 2. Therefore, the luminance of the emitted light can be controlled by transmitting the incident light L transmitted through the liquid crystal panel 1B to the polarizing film 7B.

  As described above, the liquid crystal panel 1 </ b> B has the microlens 113, and the incident light L that has passed through the microlens 113 is collected and passes through the openings 131 of the black matrix 13. On the other hand, the incident light L is shielded in a portion where the opening 131 of the black matrix 13 is not formed. Accordingly, in the liquid crystal panel 1B, unnecessary light is prevented from leaking from portions other than the pixels, and attenuation of the incident light L at the pixel portions is suppressed. For this reason, the liquid crystal panel 1B has a high light transmittance in the pixel portion.

  In the liquid crystal panel 1B, for example, alignment films 3B and 4B are formed on a TFT substrate 17 and a liquid crystal panel counter substrate 12 manufactured by a known method, respectively, and then a sealing material (not shown) is interposed therebetween. Then, the two can be joined together, and then liquid crystal can be injected into the gap from the gap sealing hole (not shown) formed thereby, and then the sealing hole is closed.

In the liquid crystal panel 1B, the TFT substrate is used as the liquid crystal drive substrate. However, a liquid crystal drive substrate other than the TFT substrate, for example, a TFD substrate or an STN substrate may be used as the liquid crystal drive substrate.
Moreover, the liquid crystal panel provided with the alignment film as described above can be suitably used for a strong light source or an outdoor one.

Next, an electronic apparatus (liquid crystal display device) of the present invention including the liquid crystal panel 1A as described above will be described based on the embodiments shown in FIGS.
FIG. 4 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 having a keyboard 1102 and a display unit 1106. The display unit 1106 is supported by the main body 1104 via a hinge structure so as to be rotatable. Yes.
In the personal computer 1100, the display unit 1106 includes the liquid crystal panel 1A described above and a backlight (not shown). An image (information) can be displayed by transmitting light from the backlight to the liquid crystal panel 1A.

FIG. 5 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 includes the above-described liquid crystal panel 1A and a backlight (not shown) as well as a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206.

FIG. 6 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.
The above-described liquid crystal panel 1A and a backlight (not shown) are provided on the back of the case (body) 1302 in the digital still camera 1300. The liquid crystal panel 1A is configured to perform display based on an imaging signal from the CCD. Functions as a finder that displays the subject as an electronic image.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the liquid crystal panel 1A and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the data communication input / output terminal 1314 as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

Next, as an example of the electronic apparatus of the present invention, an electronic apparatus (liquid crystal projector) using the liquid crystal panel 1B will be described.
FIG. 7 is a diagram schematically showing an optical system of the electronic apparatus (projection display device) of the present invention.
As shown in FIG. 7, the projection display apparatus 300 includes a light source 301, an illumination optical system including a plurality of integrator lenses, a color separation optical system (a light guide optical system) including a plurality of dichroic mirrors, and the like. A liquid crystal light valve (liquid crystal optical shutter array) 24 corresponding to red (liquid crystal optical shutter array) 24 corresponding to red, a liquid crystal light valve (liquid crystal optical shutter array) 25 corresponding to green (liquid crystal optical shutter array) 25, and a liquid crystal light valve corresponding to blue (for blue) ) A liquid crystal light valve (liquid crystal light shutter array) 26, a dichroic prism (color combining optical system) 21 formed with a dichroic mirror surface 211 reflecting only red light and a dichroic mirror surface 212 reflecting only blue light, and projection And a lens (projection optical system) 22.

The illumination optical system includes integrator lenses 302 and 303. The color separation optical system includes mirrors 304, 306, and 309, a dichroic mirror 305 that reflects blue light and green light (transmits only red light), a dichroic mirror 307 that reflects only green light, and a dichroic that reflects only blue light. A mirror (or a mirror that reflects blue light) 308 and condenser lenses 310, 311, 312, 313, and 314 are included.

The liquid crystal light valve 25 includes the liquid crystal panel 1B described above. The liquid crystal light valves 24 and 26 have the same configuration as the liquid crystal light valve 25. The liquid crystal panels 1B included in these liquid crystal light valves 24, 25 and 26 are connected to driving circuits (not shown).
In the projection display device 300, the dichroic prism 21 and the projection lens 22 constitute the optical block 20. The optical block 20 and liquid crystal light valves 24, 25 and 26 fixedly installed on the dichroic prism 21 constitute a display unit 23.

Hereinafter, the operation of the projection display apparatus 300 will be described.
White light (white light beam) emitted from the light source 301 passes through the integrator lenses 302 and 303. The light intensity (luminance distribution) of the white light is made uniform by the integrator lenses 302 and 303. The white light emitted from the light source 301 preferably has a relatively high light intensity. Thereby, the image formed on the screen 320 can be made clearer. In addition, since the projection display device 300 uses the liquid crystal panel 1B having excellent light resistance, excellent long-term stability can be obtained even when the intensity of light emitted from the light source 301 is large.

The white light transmitted through the integrator lenses 302 and 303 is reflected to the left side in FIG. 7 by the mirror 304, and blue light (B) and green light (G) of the reflected light are respectively reflected by the dichroic mirror 305 in FIG. The red light (R) is reflected downward and passes through the dichroic mirror 305.
The red light transmitted through the dichroic mirror 305 is reflected downward in FIG. 7 by the mirror 306, and the reflected light is shaped by the condenser lens 310 and enters the liquid crystal light valve 24 for red.

Green light out of blue light and green light reflected by the dichroic mirror 305 is reflected to the left side in FIG. 7 by the dichroic mirror 307, and the blue light passes through the dichroic mirror 307.
The green light reflected by the dichroic mirror 307 is shaped by the condenser lens 311 and enters the green liquid crystal light valve 25.

Further, the blue light transmitted through the dichroic mirror 307 is reflected on the left side in FIG. 7 by the dichroic mirror (or mirror) 308, and the reflected light is reflected on the upper side in FIG. 7 by the mirror 309. The blue light is shaped by the condenser lenses 312, 313, and 314, and enters the liquid crystal light valve 26 for blue.
As described above, the white light emitted from the light source 301 is separated into the three primary colors of red, green, and blue by the color separation optical system, and is guided to the corresponding liquid crystal light valve and enters.

At this time, each pixel (the thin film transistor 173 and the pixel electrode 172 connected thereto) of the liquid crystal panel 1B included in the liquid crystal light valve 24 is subjected to switching control by a drive circuit (drive means) that operates based on the image signal for red. (On / off), ie modulated.
Similarly, green light and blue light are incident on the liquid crystal light valves 25 and 26, respectively, and modulated by the respective liquid crystal panels 1B, thereby forming a green image and a blue image. At this time, each pixel of the liquid crystal panel 1B included in the liquid crystal light valve 25 is switching-controlled by a drive circuit that operates based on a green image signal, and each pixel of the liquid crystal panel 1B included in the liquid crystal light valve 26 is used for blue color. Switching control is performed by a drive circuit that operates based on the image signal.

As a result, red light, green light, and blue light are modulated by the liquid crystal light valves 24, 25, and 26, respectively, and a red image, a green image, and a blue image are formed, respectively.
The red image formed by the liquid crystal light valve 24, that is, the red light from the liquid crystal light valve 24, enters the dichroic prism 21 from the surface 213, is reflected by the dichroic mirror surface 211 to the left in FIG. The light passes through the surface 212 and exits from the exit surface 216.

Further, the green image formed by the liquid crystal light valve 25, that is, the green light from the liquid crystal light valve 25, enters the dichroic prism 21 from the surface 214, passes through the dichroic mirror surfaces 211 and 212, and exits. The light exits from the surface 216.
Further, the blue image formed by the liquid crystal light valve 26, that is, the blue light from the liquid crystal light valve 26 is incident on the dichroic prism 21 from the surface 215, and is reflected to the left side in FIG. 7 by the dichroic mirror surface 212. The light passes through the dichroic mirror surface 211 and exits from the exit surface 216.

  Thus, the light of each color from the liquid crystal light valves 24, 25 and 26, that is, the images formed by the liquid crystal light valves 24, 25 and 26 are synthesized by the dichroic prism 21, thereby forming a color image. Is done. This image is projected (enlarged projection) on the screen 320 installed at a predetermined position by the projection lens 22.

  In addition to the personal computer (mobile personal computer) of FIG. 4, the mobile phone of FIG. 5, the digital still camera of FIG. 6, and the projection display device of FIG. , Video camera, viewfinder type, monitor direct-view video tape recorder, car navigation device, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, video phone, crime prevention TV monitors, electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasonic diagnostic devices) , Endoscope display devices), fish detectors, various measuring instruments, instruments (for example, Two, aircraft, gauges of a ship), such as flight simulators, and the like. And it cannot be overemphasized that the liquid crystal panel of this invention mentioned above is applicable as a display part of these various electronic devices, and a monitor part.

As mentioned above, although this invention was demonstrated based on embodiment of illustration, this invention is not limited to this.
For example, in the method for forming an alignment film of the present invention, one or more arbitrary steps may be added. Further, for example, in the electronic device substrate, the liquid crystal panel, and the electronic apparatus of the present invention, the configuration of each part can be replaced with any configuration that exhibits the same function, and any configuration is added. You can also.

  In the above-described embodiment, the projection display device (electronic device) has three liquid crystal panels, and the liquid crystal panel of the present invention is applied to all of them, but at least these One of them may be the liquid crystal panel of the present invention. In this case, it is preferable to apply the present invention to at least a liquid crystal panel used for a liquid crystal light valve for blue.

In the above-described embodiment, the alkoxysilane having a curing reactive group is used. However, the alkoxysilane having a curing reactive group may not be used.
Moreover, in embodiment mentioned above, although demonstrated as what uses multiple types of alkoxysilane, it is not limited to this, For example, it has an affinity provision group, an orientation provision group, and a hardening reaction group in the same molecule | numerator. Alkoxysilane may be used.

[Manufacture of LCD panels]
A liquid crystal panel as shown in FIG. 3 was manufactured as follows.
(Example 1)
First, a microlens substrate was manufactured as follows.
Prepare a raw quartz glass substrate (transparent substrate) with a thickness of about 1.2 mm as a base material, and immerse it in a cleaning solution (mixed solution of sulfuric acid and hydrogen peroxide solution) at 85 ° C. to perform cleaning. The surface was cleaned.

Thereafter, a polycrystalline silicon film having a thickness of 0.4 μm was formed on the front and back surfaces of the quartz glass substrate by a CVD method.
Next, an opening corresponding to the recess to be formed was formed in the formed polycrystalline silicon film.
This was done as follows. First, a resist layer having a concave pattern to be formed was formed on the polycrystalline silicon film. Next, the polycrystalline silicon film was dry-etched with CF gas to form an opening. Next, the resist layer was removed.

Next, the quartz glass substrate was immersed in an etching solution (mixed aqueous solution of 10 wt% hydrofluoric acid + 10 wt% glycerin) for 120 minutes to perform wet etching (etching temperature 30 ° C.), thereby forming a recess on the quartz glass substrate.
Thereafter, the quartz glass substrate was immersed in a 15 wt% tetramethylammonium hydroxide aqueous solution for 5 minutes to remove the polycrystalline silicon film formed on the front and back surfaces, thereby obtaining a substrate with concave portions for microlenses.

Next, an ultraviolet (UV) curable acrylic optical adhesive (refractive index of 1.60) is applied without bubbles on the surface of the substrate with concave portions for microlenses, and then the optical adhesive is used. A cover glass (surface layer) made of quartz glass was bonded to the optical adhesive, and then the optical adhesive was cured by irradiating the optical adhesive with ultraviolet rays to obtain a laminate.
Thereafter, the cover glass was ground and polished to a thickness of 50 μm to obtain a microlens substrate. In the obtained microlens substrate, the thickness of the resin layer was 12 μm.

  With respect to the microlens substrate obtained as described above, a light shielding film (Cr film) having a thickness of 0.16 μm in which an opening is provided at a position corresponding to the microlens of the cover glass by using a sputtering method and a photolithography method. That is, a black matrix was formed. Further, an ITO film (transparent conductive film) having a thickness of 0.15 μm was formed on the black matrix by a sputtering method to manufacture a counter substrate for a liquid crystal panel.

On the transparent conductive film of the counter substrate for a liquid crystal panel thus obtained, an alignment film was formed as follows.
First, vinyl trimethoxysilane having a vinyl group as an affinity imparting group: 5.3 parts by weight, phenyltrimethoxysilane having a phenyl group as an orientation imparting group: 4.8 parts by weight, and a glycid as a curing reactive group A 3-glycidoxypropyltrimethoxysilane having a xyalkyl group: 14.2 parts by weight, tetrahydrofuran: 533 parts by weight, and 1N aqueous sodium hydroxide solution: 22.5 parts by weight were prepared.

Each of these components was put into a 1 L three-necked flask, heated to 60 ° C., and stirred for 3 hours.
Thereafter, the mixture was cooled to room temperature and neutralized by adding 22.5 parts by weight of 1N hydrochloric acid to obtain a mixed solution 1.
Next, tetrahydrofuran was distilled off from the mixed solution 1 by using an evaporator to obtain a mixed solution 2.

Next, from this mixed liquid 2, polysiloxane (polysilsesquioxane having a cage structure) contained in the mixed liquid 2 was extracted using 50 parts by weight of toluene to obtain an extract.
Next, the obtained extract was washed with 50 parts by weight of distilled water and 50 parts by weight of saturated saline, and then dried using anhydrous magnesium sulfate.
Next, toluene was removed from the washed and dried extract using an evaporator, and then low-boiling substances contained in the polysiloxane were removed under reduced pressure of 13.3 Pa.
Thereby, the polysilsesquioxane (polysiloxane) which has a cage | basket type structure before an end cap process was obtained.

Next, 15.5 g of the polysilsesquioxane obtained in the above step is put into a 200 ml three-necked flask, and 50 ml of dry diethyl ether is further added to the flask, and the water in the polysilsesquioxane is added to dry diethyl ether. It was moved to. Subsequently, while stirring the inside of the flask using a magnetic stirrer, the flask was immersed in ice water to cool the inside of the flask.
Next, 3.90 g (35.9 mmol) of trimethylchlorosilane as an end-capping material was added dropwise into the flask, and 4.04 g (40.0 mmol) of triethylamine was also added dropwise at the same time. In this state, stirring was continued for 1 hour.

Next, a saturated aqueous sodium hydrogen carbonate solution was added to the flask, and then the resulting mixture in the flask was extracted with ether. Subsequently, it was washed with saturated saline and further dried with anhydrous magnesium sulfate.
Thereafter, the low boiling point portion was distilled off, and as shown in FIG. 2 (b), the hydrogen in the silanol group was replaced with a trimethylsilyl group (Me ₃ Si—), and the end-capped polysilsesquioxy having a cage structure was formed. I got Sun.

The polysilsesquioxane thus obtained was mixed with a solvent (diethylene glycol ethyl ether acetate) to obtain a mixed solution 3.
Next, the mixed solution 3 was filtered using a filter having a pore size of 0.2 μm to remove impurities from the mixed solution 3.
A 50 wt% propylene carbonate solution of a mixture of (thiophenoxyphenyl) diphenylsulfonium hexafluorophosphate and bis (diphenylsulfonium) diphenylthioether hexafluorophosphate is added to the filtered mixture 3 as a curing agent, An alignment film-forming liquid was obtained.

Next, the obtained alignment film-forming liquid was applied onto the transparent conductive film of the counter substrate for a liquid crystal panel using a spin coater to form a coating film.
The obtained coating film was dried for 3 minutes using a hot plate heated to 150 ° C., and then light-irradiated for 5 minutes using a metal hydrate lamp to be temporarily cured.
Next, it was heated at 200 ° C. for 3 hours to be fully cured.

Thereafter, a rubbing treatment was performed to form an alignment film.
The formed alignment film had a thickness of 0.2 μm. The proportion of silicon units having an affinity imparting group in one molecule of the organic silicon material forming the alignment film was 29 mol%. Similarly, the abundance ratio of the orientation-imparting group was 21 mol%. These values were in good agreement with the raw material charge ratio when synthesizing the organosilicon material used for the preparation of the alignment film. The weight average molecular weight of the organosilicon material was 1800.

An alignment film was also formed on the surface of a separately prepared TFT substrate (made of quartz glass) in the same manner as described above.
The counter substrate for the liquid crystal panel on which the alignment film was formed and the TFT substrate on which the alignment film was formed were bonded together via a sealing material. This bonding was performed so that the alignment direction of the alignment film was shifted by 90 ° so that the liquid crystal molecules forming the liquid crystal layer were twisted to the left.
Next, liquid crystal (Merck Co., Ltd .: MJ99247) was injected into the gap from the gap hole formed between the alignment film and the alignment film, and then the gap was closed. The formed liquid crystal layer had a thickness of about 3 μm.

Thereafter, a polarizing film 8B and a polarizing film 7B are bonded to the outer surface side of the counter substrate for the liquid crystal panel and the outer surface side of the TFT substrate, respectively, thereby manufacturing a TFT liquid crystal panel having a structure as shown in FIG. did. As the polarizing film, a film formed of polyvinyl alcohol (PVA) and stretched in a uniaxial direction was used. The bonding directions of the polarizing film 7B and the polarizing film 8B were determined based on the alignment directions of the alignment film 3B and the alignment film 4B, respectively. That is, the polarizing film 7B and the polarizing film 8B are bonded so that the incident light is not transmitted when a voltage is applied and the incident light is transmitted when no voltage is applied.
The pretilt angle of the manufactured liquid crystal panel was in the range of 3 to 7 °.

The liquid crystal projector (electronic device) manufactured using the liquid crystal panel formed in this manner obtained a clear projected image even when it was continuously driven for a long time.
Moreover, when a personal computer, a cellular phone, and a digital still camera equipped with the liquid crystal panel of the present invention were manufactured and evaluated in the same manner, similar results were obtained.
From these results, it was found that the liquid crystal panel and the electronic device of the present invention are excellent in light resistance and can obtain stable characteristics even after long-term use.

It is a typical longitudinal section showing a 1st embodiment of a liquid crystal panel of the present invention. It is a figure which shows the polysilsesquioxane before and after an end cap process. It is a typical longitudinal cross-sectional view which shows 2nd Embodiment of the liquid crystal panel of this invention. It is a perspective view which shows the structure of a mobile type personal computer. It is a perspective view which shows the structure of a mobile telephone. It is a perspective view which shows the structure of a digital still camera. It is a figure which shows typically the optical system of a projection type display apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1A, 1B ... Liquid crystal panel, 2 ... Liquid crystal layer, 3A, 3B ... Orientation film, 4A, 4B ... Orientation film, 9 ... Substrate, 10 ... Substrate, 24-26 ... Liquid crystal light valve, 100 ... Base material, 101 ... Group 300, projection display device, 1100, personal computer, 1200, mobile phone, 1300, digital still camera

Claims (13)

An alignment film for controlling the alignment of liquid crystal molecules,
Formed of at least an organosilicon material,
The organosilicon material comprises a polysilsesquioxane having a cage structure or a partially cleaved cage structure, and the polysilsesquioxane imparts an affinity that improves the affinity with the liquid crystal molecules in the molecule. An alignment film having a group and an orientation-imparting group for controlling the alignment of the liquid crystal molecules, and wherein the hydrogen in the silanol group is substituted with a trimethylsilyl group to be inactivated. The alignment film according to claim 1, wherein the affinity imparting group is at least one of a vinyl group, an alkylene group, and a cyanoalkyl group. The orientation characteristic imparting group, claim 1, wherein a phenyl group, a substituted phenyl group, phenylalkyl group, a substituted phenylalkyl group, of the branched alkyl group having 3 to 12 carbon atoms, a is at least one Or the alignment film of 2 . The alignment film according to claim 1 , wherein the organosilicon material has a weight average molecular weight of 500 to 50,000. The average thickness of the alignment film, an alignment film according to claim 1, characterized in that a 0.01 to 10 [mu] m. A method of forming an alignment film that controls the alignment of liquid crystal molecules,
Condensation polymerization of alkoxysilane to control the orientation of the liquid crystal molecules and the affinity imparting group having a cage structure or a partially cleaved cage structure and improving the affinity with the liquid crystal molecules in the molecule A step of synthesizing a polysilsesquioxane having an orientation-imparting group.
A step of the compound having a polysilsesquioxane and trimethylsilyl groups are reacted to inactivate by replacing the trimethylsilyl group with hydrogen in the silanol groups of the polysilsesquioxane,
Forming an alignment film on a substrate using the liquid for forming an alignment film containing the inactivated polysilsesquioxane, and a method for forming the alignment film. As the alkoxysilane, a plurality of types having different compositions are used,
7. The method for forming an alignment film according to claim 6, wherein an alkoxysilane having an affinity imparting group and an alkoxysilane having an orientation imparting group are used as the plurality of types of alkoxysilanes having different compositions. The alignment film is formed by curing the alignment film forming liquid,
8. The method for forming an alignment film according to claim 6, wherein the polysilsesquioxane has a curing reactive group that contributes to a curing reaction of the alignment film forming liquid. The orientation according to claim 8 , wherein the curing reactive group is at least one of a glycidoxyalkyl group, an alicyclic epoxyalkyl group, an acryloyl group, a methacryloyl group, a styryl group, and a styrylalkyl group. Method for forming a film. 10. The method for forming an alignment film according to claim 8, wherein the alignment film-forming liquid is cured by performing a heat treatment and / or an energy ray irradiation treatment. An electrode on the substrate;
Substrate for an electronic device, characterized in that it comprises an alignment film according to any one of claims 1-5. And an alignment film according to any one of claims 1 to 5, a liquid crystal panel comprising the liquid crystal layer. An electronic apparatus comprising the liquid crystal panel according to claim 12 .

Images