JP4701888B2 - Substrates for electronic devices, liquid crystal panels, and electronic equipment - Google Patents

Description

  The present invention relates to an electronic device substrate, a liquid crystal panel, and an electronic apparatus.

In recent years, vertical alignment type liquid crystal display elements (liquid crystal panels) have been put into practical use in liquid crystal televisions (direct view display devices), liquid crystal projectors (projection display devices), and the like.
As a vertical alignment film used for these vertical alignment type liquid crystal display elements, for example, an organic alignment film such as polyimide is used in a liquid crystal television. In addition, oblique deposition films (inorganic alignment films) such as SiO ₂ are frequently used in liquid crystal projectors (see, for example, Patent Document 1).
This obliquely deposited film has a plurality of uniaxially oriented pores and high structural regularity. Due to this structural regularity, the liquid crystal molecules of the liquid crystal layer provided thereon are easily aligned vertically.
At present, various studies have been made with the aim of developing an obliquely deposited film with better alignment of liquid crystal molecules.

JP 2003-186018 A

  An object of the present invention is to provide an electronic device substrate, a highly reliable liquid crystal panel, and an electronic apparatus that are excellent in orientation of liquid crystal molecules and the like.

Such an object is achieved by the present invention described below.
The substrate for electronic devices of the present invention is a substrate for electronic devices comprising a substrate and an alignment film formed on one surface of the substrate by oblique vapor deposition and including an inorganic oxide film having a plurality of pores. The inorganic oxide film is subjected to a hydroxyl group reduction treatment for reducing the number of hydroxyl groups present on at least the surface of the inorganic oxide film by a chemical bond of at least one alcohol to the hydroxyl group, and a BET method. The surface area of one surface of the substrate measured in step S1 is S1 [nm2], the surface area of the inorganic oxide film measured by the BET method is S2 [nm2], and the average thickness of the inorganic oxide film is t When [nm] is set, the relationship of 0.55 log ≦ S2 / S1 ≦ 0.55 log + 4.4 is satisfied.
Thereby, it is excellent in orientation of a liquid crystal molecule etc., and it can make it difficult for the orientation to fall over time. In addition, when a hydroxyl group reduction treatment for reducing the number of hydroxyl groups present on the surface of the inorganic oxide film and the inner surface of the pores is performed, the number of hydroxyl groups can be reliably and sufficiently reduced.

In the electronic device substrate of the present invention, the BET method is preferably a BET multipoint method.
According to the BET multipoint method, the surface area of the inorganic oxide film can be measured more accurately.
In the electronic device substrate of the present invention, the BET method preferably uses krypton gas as an adsorbed gas.
According to the BET method using krypton gas, the surface area can be measured with good reproducibility.

In the electronic device substrate of the present invention, it is preferable that the alignment film is subjected to a hydroxyl group reduction treatment that reduces the number of hydroxyl groups present on at least the surface of the inorganic oxide film.
As a result, the number of active hydroxyl groups present in the inorganic oxide film can be reduced, and various impurities adhere to the inorganic oxide film, and the inorganic oxide film reacts with liquid crystal molecules. Can be prevented. For this reason, for example, it is possible to prevent a decrease in the vertical anchoring force of the alignment film with respect to the liquid crystal molecules, and as a result, it is possible to prevent alignment abnormality from occurring in the liquid crystal molecules.

In the substrate for an electronic device of the present invention, the alignment film is formed by reducing the number of hydroxyl groups present on the inner surfaces of the pores of the inorganic oxide film by a treatment treatment in which at least one alcohol is chemically bonded to the hydroxyl groups. Preferably it is.
Thereby, it is possible to more reliably prevent the occurrence of alignment abnormality in the liquid crystal molecules .

The liquid crystal panel of the present invention includes an electronic device substrate of the present invention,
And a liquid crystal layer provided on the opposite side of the alignment film from the substrate.
Thereby, a highly reliable liquid crystal panel is obtained.
The liquid crystal panel of the present invention includes a first electronic device substrate including a first alignment film,
A second substrate for an electronic device comprising a second alignment film;
A liquid crystal panel having a liquid crystal layer interposed between the first alignment film and the second alignment film,
The first electronic device substrate and the second electronic device substrate are each composed of the electronic device substrate of the present invention.
Thereby, a highly reliable liquid crystal panel is obtained.

In the liquid crystal panel of the present invention, it is preferable that the average molecular weight of the alcohol of the first alignment film is different from the average molecular weight of the alcohol of the second alignment film.
Thereby, it is excellent in light resistance and becomes difficult to be seized.
In the liquid crystal panel of the present invention, the first electronic device substrate includes a driving element,
It is preferable that the average molecular weight of the alcohol of the first alignment film is larger than the average molecular weight of the alcohol of the second alignment film.
Thereby, it is excellent in light resistance and becomes difficult to be seized.

In the liquid crystal panel of the present invention, the average molecular weight of the alcohol of the first alignment film is preferably 100 to 400.
Thereby, it is possible to extend the time required for the occurrence of the alignment abnormality more reliably, that is, to improve the durability (light resistance) more reliably.
In the liquid crystal panel of the present invention, the alcohol of the first alignment film preferably has mainly 6 to 30 carbon atoms.
Thereby, the effect of durability improvement becomes more remarkable.

In the liquid crystal panel of the present invention, the average molecular weight of the alcohol in the second alignment film is preferably 32 to 70.
Thereby, image sticking can be prevented more reliably.
In the liquid crystal panel of the present invention, the alcohol of the second alignment film is preferably mainly having 1 to 4 carbon atoms.
Thereby, the burn-in prevention effect becomes more remarkable.

In the liquid crystal panel of the present invention, it is preferable that at least one of the alcohol of the first alignment film and the alcohol of the second alignment film includes a plurality of types of alcohols.
For example, when a high molecular weight alcohol and a low molecular weight alcohol are used in combination, the alcohol can be chemically bonded to the hydroxyl groups between the high molecular weight alcohols or to the hydroxyl groups existing in the back of the pores. There is an advantage that the hydroxyl groups remaining in the material film can be more reliably reduced.

In the liquid crystal panel of the present invention, one of the alcohol of the first alignment film and the alcohol of the second alignment film includes a plurality of types of alcohol, and the other is composed of one type of alcohol. And
The alcohol of the one alignment film preferably contains the same kind of alcohol as the alcohol of the other alignment film.
This has the advantage that the vertical anchoring force for the liquid crystal molecules can be easily adjusted.

In the liquid crystal panel of the present invention, both the alcohol of the first alignment film and the alcohol of the second alignment film comprise a plurality of types of alcohols,
The alcohol of the first alignment film and the alcohol of the second alignment film preferably contain the same kind of alcohol.
This has the advantage that the vertical anchoring force for the liquid crystal molecules can be easily adjusted.
An electronic apparatus according to the present invention includes the liquid crystal panel according to the present invention.
As a result, a highly reliable electronic device can be obtained.

Hereinafter, a substrate for an electronic device, a liquid crystal panel, and an electronic apparatus according to the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a longitudinal sectional view schematically showing an embodiment of a liquid crystal panel to which an electronic device substrate of the present invention is applied, and FIG. 2 is an enlarged longitudinal sectional view showing an alignment film provided in the liquid crystal panel shown in FIG. It is. In FIG. 1, the description of the sealing material, the wiring, etc. is omitted. In the following description, the upper side in FIGS. 1 and 2 is referred to as “upper” and the lower side is referred to as “lower”.

  A liquid crystal panel (TFT liquid crystal panel) 1 shown in FIG. 1 includes a TFT substrate (liquid crystal drive substrate) 17, an alignment film 3 bonded to the TFT substrate 17, a liquid crystal panel counter substrate 12, and a liquid crystal panel counter substrate 12. Bonding to the outer surface (upper surface) side of the TFT substrate (liquid crystal driving substrate) 17 and the liquid crystal layer 2 containing liquid crystal molecules sealed in the gap between the alignment film 3 and the alignment film 4. And the polarizing film 8 bonded to the outer surface (lower surface) side of the counter substrate 12 for liquid crystal panel.

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 substrate 111 with a microlens recess provided with a plurality of (many) recesses (microlens recesses) 112 having a concave curved surface, and a recess 112 of the substrate 111 with a microlens recess. And a surface layer 114 bonded to the other surface via a resin layer (adhesive layer) 115.
In the resin layer 115, the microlens 113 is formed of a resin filled in the recess 112.

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 glass, for example.

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 liquid crystal panel 1 obtained, warpage, deflection, peeling, and the like caused by the difference in thermal expansion coefficient between the two when the temperature changes are prevented.
From this point of view, it is preferable that the substrate 111 with concave portions for microlenses and the glass substrate 171 are made 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, for the TFT substrate 17 to be described later, quartz glass whose characteristics are not easily changed by the environment during manufacture is preferably used. For this reason, it is preferable that the substrate 111 with concave portions for microlenses is made of quartz glass correspondingly. As a result, it is possible to obtain the liquid crystal panel 1 that is less likely to be warped or bent and has excellent stability.
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 the constituent material of the resin layer 115 to form the microlens 113.
The resin layer 115 can be made of, for example, a resin (adhesive) having a refractive index higher than the refractive index of the constituent material of the substrate 111 with concave portions for microlenses. For example, acrylic resin, epoxy resin, acrylic epoxy It can be suitably configured with an ultraviolet curable resin or the like.
A flat surface layer 114 is provided on the upper surface of the resin layer 115.

  The surface layer (glass layer) 114 can be made 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, etc. 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 more effectively obtained when the substrate with concave portions for microlenses 111 and the surface layer 114 are made of the same material.

The average thickness of the surface layer 114 is generally about 5 to 1000 μm, more preferably about 10 to 150 μm, from the viewpoint of obtaining necessary optical characteristics.
In addition, the surface layer (barrier layer) 114 can also be comprised, for example with ceramics. 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 made of ceramics, the average 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 blocking function and is made of, for example, a metal such as Cr, Al, Al alloy, Ni, Zn, Ti, or a resin in which carbon, titanium, or the like is dispersed.

The transparent conductive film 14 has conductivity and is made 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 (alignment control) the liquid crystal molecules contained in the liquid crystal layer 2. The TFT substrate 17 is provided on the glass substrate 171 and the glass substrate 171, and is arranged in a matrix (matrix). It has (many) pixel electrodes 172 and a plurality (many) thin film transistors (TFTs) 173 corresponding to the pixel electrodes 172.

The glass substrate 171 is preferably made of quartz glass for the reasons described above.
The pixel electrode 172 drives the liquid crystal molecules 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, for example, the same material as that of the transparent conductive film 14 described above.

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.
A polarizing film (polarizing plate, polarizing film) 7 is disposed on the outer surface (upper surface in FIG. 1) side of the TFT substrate 17. Similarly, a polarizing film (polarizing plate, polarizing film) 8 is disposed on the outer surface (lower surface in FIG. 1) side of the counter substrate 12 for liquid crystal panel.

Examples of the constituent material of the polarizing films 7 and 8 include polyvinyl alcohol (PVA). Moreover, as a polarizing film, you may use what doped the said material with iodine.
As a polarizing film, what extended | stretched the film comprised with the said material to the uniaxial direction can be used, for example.
By disposing the polarizing films 7 and 8 as described above, it is possible to more reliably control the light transmittance by adjusting the energization amount.
The direction of the polarization axis of the polarizing films 7 and 8 is usually determined according to the alignment direction of the alignment films 3 and 4 (in this embodiment, when a voltage is applied).

The TFT substrate 17 is provided with the alignment film 3 bonded to the pixel electrode 172, and the liquid crystal panel counter substrate 12 is provided with the alignment film 4 bonded to the transparent conductive film 14.
In the present embodiment, the TFT substrate 17 and the alignment film 3 constitute a first electronic device substrate, and the liquid crystal panel counter substrate 12 and the alignment film 4 constitute a second electronic device substrate.
The liquid crystal layer 2 is interposed between the alignment film 3 and the alignment film 4. The liquid crystal layer 2 contains liquid crystal molecules (liquid crystal material), and the alignment of the liquid crystal molecules changes in accordance with charge / discharge of the pixel electrode 172.

Examples of liquid crystal molecules include phenylcyclohexane derivatives, biphenyl derivatives, biphenylcyclohexane derivatives, terphenyl derivatives, phenyl ether derivatives, phenyl ester derivatives, bicyclohexane derivatives, azomethine derivatives, azoxy derivatives, pyrimidine derivatives, dioxane derivatives, cubane derivatives, and more. These derivatives include those obtained by introducing a fluorine-based substituent such as a fluoro group, a trifluoromethyl group, a trifluoromethoxy group, and a difluoromethoxy group.
As will be described later, when the alignment films 3 and 4 are used, the liquid crystal molecules are easily aligned vertically. Examples of the liquid crystal molecules suitable for the vertical alignment include compounds represented by the following chemical formulas 1 to 3. Is mentioned.

［式中、環Ａ〜Ｉは、それぞれ独立して、シクロヘキサン環またはベンゼン環を示し、Ｒ^１〜Ｒ^６は、それぞれ独立して、アルキル基、アルコキシ基またはフッ素原子のいずれかを示し、Ｘ^１〜Ｘ^１８は、それぞれ独立して、水素原子またはフッ素原子を示す。］

[Wherein, Rings A to I each independently represent a cyclohexane ring or a benzene ring, R ^{1 to} R ⁶ each independently represent an alkyl group, an alkoxy group or a fluorine atom, and X ^{1 to} X ¹⁸ each independently represent a hydrogen atom or a fluorine atom. ]

The alignment films (vertical alignment films) 3 and 4 have a function of regulating the alignment state (when no voltage is applied) of the liquid crystal molecules contained in the liquid crystal layer 2.
The configuration of the alignment films 3 and 4 will be described in detail later.
In such a liquid crystal panel 1, normally, one microlens 113, one opening 131 of the black matrix 13 corresponding to the optical axis Q of the microlens 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 8 is provided on the incident side of the microlens substrate 11, the incident light L is linearly polarized when the incident light L passes through the liquid crystal layer 2.

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, by transmitting the incident light L transmitted through the liquid crystal panel 1 to the polarizing film 7, the luminance of the emitted light can be controlled.
As described above, the liquid crystal panel 1 includes 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. Therefore, in the liquid crystal panel 1, 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 1 has a high light transmittance in the pixel portion.
As shown in FIG. 2, each of the alignment films 3 (4) includes an inorganic oxide film 31 (41) formed by oblique vapor deposition. In this embodiment, this inorganic oxide film The film 31 (41) is subjected to a treatment (hydroxyl reduction treatment) by a method as described later, thereby forming a film 32 (42).

Since the inorganic oxide film 31 (41) is formed by oblique vapor deposition, as shown in FIG. 2, it has a structure having a plurality of pores 30 (40), and the axis of each pore 30 (40). Are uniaxially oriented in an inclined state with respect to the upper surface (the surface on which the alignment film 3 (4) is formed) of the TFT substrate 17 (liquid crystal panel counter substrate 12).
Here, the axis of each pore 30 (40) being uniaxially oriented means that the majority of the pores 30 (40) are oriented in substantially the same direction (the axis of the pore 30 (40). The plurality of pores 30 (40) include pores 30 (40) whose axial directions are different from the majority of the pores 30 (40). It may be.

As described above, since the pores 30 (40) are regularly arranged, the inorganic oxide film 31 (41) has high structural regularity.
With such a configuration, the liquid crystal molecules contained in the liquid crystal layer 2 can be easily vertically aligned (homeotropic alignment). Therefore, the alignment film 3 (4) having such a configuration is useful for the construction of a VA (Vertical Alignment) type liquid crystal panel.

In addition, since the alignment film 3 (4) has high structural regularity, the alignment direction of the liquid crystal molecules is more accurately aligned in a certain direction (vertical direction). As a result, the performance (characteristics) of the liquid crystal panel 1 can be improved.
The angle (angle θ in FIG. 2) formed between the pore 30 (40) and the upper surface of the TFT substrate 17 (liquid crystal panel counter substrate 12) is not particularly limited, but is preferably about 45 to 85 °. More preferably, it is about 55 to 75 °. Thereby, the liquid crystal molecules can be vertically aligned more reliably.

The inorganic oxide film 31 (41) is a film composed of an inorganic oxide as a main material. In general, inorganic materials have superior chemical stability (light stability) compared to organic materials. Therefore, the inorganic oxide film 31 (41) has particularly excellent light resistance as compared with the alignment film made of an organic material.
Further, the inorganic oxide constituting the inorganic oxide film 31 (41) preferably has a relatively low dielectric constant. Thereby, image sticking etc. in liquid crystal panel 1 can be prevented more effectively.

Examples of such inorganic oxides include silicon oxide such as SiO ₂ and SiO, Al ₂ O ₃ , MgO _, TiO ₂ , TiO ₂ , In ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , and Y. Examples include metal oxides such as ₂ O ₃ , CeO ₂ , WO ₃ , CrO ₃ , GaO ₃ , HfO ₂ , Ti ₃ O ₅ , NiO, ZnO, Nb ₂ O ₅ , ZrO ₂ , Ta ₂ O _5. Of these, one or a combination of two or more thereof can be used, and those containing SiO ₂ or Al ₂ O ₃ as the main component are particularly preferred. SiO ₂ and Al ₂ O ₃ have a particularly low dielectric constant and high light stability.

  In such an inorganic oxide film 31 (41), as the proportion of the pores 30 (40) increases, that is, as the regularly arranged pores 30 (40) exist at a higher density, the liquid crystal layer 2 tends to increase the orientation with respect to the liquid crystal molecules contained therein (orientation depending on the shape of the inorganic oxide film). On the other hand, if the proportion of the pores 30 (40) is too large, the inorganic oxide The number of active hydroxyl groups exposed on the surface of the membrane 31 and the inner surface of the pores 30 is increased, the adhesion of various impurities and the reaction with liquid crystal molecules occur over time, and the vertical anchoring force decreases, It shows a tendency to easily cause orientation abnormality.

Therefore, in the inorganic oxide film 31 (41), by setting the ratio of the pores 30 (40) to an appropriate range, excellent orientation with respect to liquid crystal molecules can be exhibited over a long period of time. .
Examples of the impurities include impurities and unreacted components in the sealing material that seals the liquid crystal layer 2, impurities and moisture in the liquid crystal layer, and dirt adhered in the manufacturing process.

Here, the ratio of the fine pores 30 (40) in the inorganic oxide film 31 (41) is the upper surface of the TFT substrate 17 (liquid crystal panel counter substrate 12), that is, the substrate on which the alignment film 3 (4) is formed. The ratio of the surface area of the inorganic oxide film 31 (41) to the surface area of one of the surfaces can be used as an index. In addition, the value of the surface area of the inorganic oxide film 31 (41) is a total value of the surface area of the inorganic oxide film 31 (41) and the area of the inner surface of the pore 30 (40).
The larger the surface area ratio value, the greater the proportion of the pores 30 (40) in the inorganic oxide film 31 (41).

  The BET (Brunauer-Emmett-Teller) method is used for each surface area measurement method. As a method for measuring the surface area, there are a gas adsorption method (BET method, Harkins-Jura relative method), a liquid phase adsorption method, a soaking heat method, a permeation method, and the like. The surface area of the oxide film 31 (41), that is, the total area of the surface of the inorganic oxide film 31 (41) and the inner surface of the pore 30 (40) can be accurately measured.

The value of the surface area ratio varies depending on (depends on) the film thickness of the inorganic oxide film 31 (41).
In view of the above, the present inventor has made extensive studies and as a result, when the inorganic oxide film 31 (41) satisfies the following relationship, the orientation of the liquid crystal molecules is extremely good. As a result, the present invention has been completed.

That is, in the present invention, the inorganic oxide film 31 (41) is measured by the BET method with the surface area of the upper surface of the TFT substrate 17 (liquid crystal panel counter substrate 12) measured by the BET method being S ₁ [nm ² ]. is an inorganic oxide film 31 surface area (41) and _S ² [nm 2] is, when the average thickness of the inorganic oxide film 31 (41) was _{t [nm], 0.55log e t} ≦ S 2 / _S has a feature in ₁ ≦ _{0.55log e} t + 4.4 becomes possible to satisfy the relationship.

When the area ratio S ₂ / S ₁ is less than the lower limit, the proportion of the pores 30 (40) in the inorganic oxide film 31 (41) is too small, and the orientation of the liquid crystal molecules in the initial stage is significantly reduced. Or, liquid crystal molecules are not aligned. On the other hand, when the area ratio S ₂ / S ₁ exceeds the upper limit, the number of active hydroxyl groups present in the inorganic oxide film 31 (41) becomes too large, and a hydroxyl group reduction process as described later is performed. However, it is difficult to sufficiently reduce the number of hydroxyl groups, and it is difficult to prevent deterioration in the orientation of liquid crystal molecules over time.

The BET method used in the present invention may be either the BET multipoint method or the BET single point method, but it is preferable to use the BET multipoint method. According to the BET multipoint method, the surface area of the inorganic oxide film 31 (41) can be measured more accurately.
Further, examples of the adsorbed gas used in the BET method include noble gases such as krypton gas and neon gas, nitrogen gas, and the like, but it is preferable to use noble gases, particularly krypton gas. According to the BET method using krypton gas, the surface area can be measured particularly accurately and with good reproducibility.

Further, the area ratio _S 2 / _{S 1} and the average thickness t, it is sufficient to satisfy the _{0.55log e t ≦ S 2 / S} 1 ≦ 0.55log e t + 4.4 the _{relationship,} 0.55log e t it is more preferred that they satisfy the _{≦ S 2 / S 1 ≦ 0.55log} e t + 3.5 the relationship, more to satisfy the _{0.55log e t + 0.5 ≦ S 2} / S 1 ≦ 0.55log e t + 2 the relationship preferable.
The surface area of the inorganic oxide film 31 (41) can be adjusted, for example, by appropriately setting various conditions such as the degree of vacuum in the vapor deposition apparatus and vapor deposition rate during oblique vapor deposition as described later. .

  The specific value of the average thickness t is preferably about 20 to 300 nm, more preferably about 20 to 150 nm, and still more preferably about 40 to 80 nm. If the thickness of the inorganic oxide film 31 (41) is too thin, it may not be possible to sufficiently prevent the liquid crystal molecules from directly contacting the pixel electrode 172 (transparent conductive film 14) and short-circuiting. On the other hand, if the thickness of the inorganic oxide film 31 (41) is too thick, the driving voltage of the liquid crystal panel 1 becomes high and the power consumption may increase.

In addition, the specific value of the area ratio S ₂ / S ₁ is preferably about 2 to 5, and more preferably about 2.5 to 4. Thereby, the orientation of liquid crystal molecules can be further improved.
A coating 32 (42) is formed along at least the surface of the inorganic oxide film 31 (41) (in this embodiment, the surface and the inner surface of the pore 30 (40)).

  The coating film 32 (42) of the present embodiment is a film formed by applying a treatment (hydroxyl group reduction treatment) to the inorganic oxide film 31 (41) using a treatment liquid described later, that is, an inorganic oxide film. A film formed by a chemical reaction (dehydration condensation reaction) between an active hydroxyl group present on the surface of 31 (41) and the inner surface of the pore 30 (40) and a hydroxyl group of the alcohol, and the main skeleton portion of the alcohol Is a film mainly composed of

  By forming the film 32 (42), the number of active hydroxyl groups present in the inorganic oxide film 31 (41) can be reduced, and various impurities adhere to the inorganic oxide film 31 (41). In addition, it is possible to prevent the inorganic oxide film 31 (41) from reacting with liquid crystal molecules. For this reason, for example, it is possible to prevent a decrease in the vertical anchoring force of the alignment film 3 (4) with respect to the liquid crystal molecules, and as a result, it is possible to more reliably prevent the occurrence of alignment abnormality in the liquid crystal molecules.

In particular, in the present embodiment, since the alcohol is chemically bonded to the hydroxyl group present on the inner surface of the pore 30 (40), the effect becomes more remarkable.
In the present invention, since the inorganic oxide film 31 (41) satisfies the above-described relationship, it exists not only on the surface of the inorganic oxide film 31 (41) but also on the inner surface of the pore 30 (40). Alcohol can be reliably chemically bonded to the hydroxyl group.
In addition, the inorganic oxide films 31 and 41 are treated with an alcohol having the same composition (same type), and the average molecular weights of the alcohol chemically bonded to the inorganic oxide films 31 and 41 are equal in the alignment film 3 and the alignment film 4. However, the average molecular weight of the alcohol chemically bonded to each of the films 31 and 41 is preferably different.

In this embodiment, the average molecular weight of the alcohol in the alignment film (first alignment film) 3 provided on the TFT substrate 17 side is equal to the alignment film (second alignment film) 4 provided on the liquid crystal panel counter substrate 12 side. It is larger than the average molecular weight of alcohol. That is, more alcohol having a larger molecular weight (having a larger number of carbon atoms) is chemically bonded to the inorganic oxide film 31 than to the inorganic oxide film 41. Thereby, the characteristic of the liquid crystal panel 1 can be improved.
In general, from the viewpoint of preventing image sticking of the liquid crystal panel 1, if the force for aligning liquid crystal molecules is too strong than necessary, the tendency for image sticking to occur increases, so the intermolecular force between the liquid crystal molecules and the alignment film is reduced to some extent. Therefore, it is preferable to select alcohol having a relatively small molecular weight (with a relatively small number of carbon atoms) as the alcohol chemically bonded to the inorganic oxide film 31 (41).

  On the other hand, from the viewpoint of preventing the occurrence of abnormal alignment of the liquid crystal panel 1 due to the reaction between the hydroxyl groups present in the inorganic oxide film 31 (41) and liquid crystal molecules (improving light resistance and durability), the inorganic oxide film In order to keep the liquid crystal molecules as far as possible from the hydroxyl groups remaining on the surface of 31 (41), the alcohol that is chemically bonded to the inorganic oxide film 31 (41) is one having a relatively large molecular weight (with a relatively large number of carbon atoms). It is preferable to select.

  By the way, since the TFT substrate 17 includes the TFT 173, the temperature tends to be higher than the counter substrate 12 for the liquid crystal panel, and the activity of the hydroxyl group remaining in the inorganic oxide film 31 is further increased by heating. For this reason, at the interface between the alignment film 3 and the liquid crystal layer 2, the liquid crystal molecules are in a state of being easily altered or deteriorated by reacting with active hydroxyl groups. Therefore, in the alignment film 3 on the TFT substrate 17 side, it is particularly effective to chemically bond alcohol having a higher molecular weight and reliably prevent the liquid crystal molecules from coming into contact with the inorganic oxide film 31.

On the other hand, in the alignment film 4 on the counter substrate 12 side for the liquid crystal panel, it is only necessary to focus on preventing burn-in, so it is preferable to actively select alcohol having a low molecular weight.
In this case, the alcohols of the alignment films 3 and 4 only have to have a difference in average molecular weight. As the alcohol, a high molecular weight alcohol and a low molecular weight alcohol may be appropriately combined.

In particular, when the low molecular weight alcohol is used in combination in the alignment film 3 that should use a high molecular weight alcohol, the alcohol is chemically bonded to the hydroxyl group between the high molecular weight alcohols and the hydroxyl group existing in the back of the pores 30. There is also an advantage that the number of hydroxyl groups remaining in the inorganic oxide film 31 can be more reliably reduced.
For this reason, in this embodiment, the average molecular weight of the alcohol in the alignment film 3 provided on the TFT substrate 17 side is larger than the average molecular weight of the alcohol in the alignment film 4 provided on the liquid crystal panel counter substrate 12 side. Thus, the alcohol used for the treatment of the inorganic oxide films 31 and 41 is selected.

Here, when the molecular weight is alcohol X> alcohol Y> alcohol Z, examples of combinations in which the average molecular weight of the alcohol in the alignment film 3 is greater than the average molecular weight of the alcohol in the alignment film 4 include the following combinations: Can be mentioned.
I: Alignment film 3: X, Alignment film 4: Y or Z
II: Alignment film 3: X + Y, Alignment film 4: X + Y (where X / Y: Alignment film 3> Alignment film 4)
III: Alignment film 3: X + Y, Alignment film 4: Y + Z
IV: Alignment film 3: X, Alignment film 4: X + Z

In addition, when one of the alcohol of the alignment film 3 and the alcohol of the alignment film 4 includes a plurality of types of alcohol, and the other includes one type of alcohol, The alcohol preferably contains the same kind of alcohol as that of the other alignment film (see IV above).
In addition, when both the alcohol of the alignment film 3 and the alcohol of the alignment film 4 include a plurality of types of alcohol, the alcohol of the alignment film 3 and the alcohol of the alignment film 4 include the same type of alcohol. Are preferred (see III above).

  As described above, when the alcohol of the alignment film 3 and the alcohol of the alignment film 4 contain the same kind of alcohol, when the vertical anchoring force for the liquid crystal molecules is adjusted, there is a large difference in the vertical anchoring force in the alignment films 3 and 4. In other words, it is possible to easily control the difference in minute force. That is, there is an advantage that the vertical anchoring force for the liquid crystal molecules can be easily adjusted.

The average molecular weight of the alcohol in the alignment film 3 is preferably about 100 to 400, and more preferably about 120 to 400. Thereby, in the liquid crystal panel 1, it is possible to extend the time required for the occurrence of the alignment abnormality more reliably, that is, to improve the durability (light resistance) more reliably.
Further, the alcohol of the alignment film 3 is preferably one having a main component mainly having 6 to 30 carbon atoms (particularly, having 8 to 30 carbon atoms). Thereby, the effect becomes more remarkable.

  Further, such an alcohol having a carbon number is liquid at room temperature, or can be liquid at a relatively low temperature even if it is semi-solid (solid). For this reason, the handling at the time of processing the inorganic oxide film 31 (41) with the process liquid mentioned later is easy. Further, since the affinity for the liquid crystal molecules is higher, the vertical anchoring force for the liquid crystal molecules can be reliably increased.

Examples of such alcohols include aliphatic alcohols, aromatic alcohols, alicyclic alcohols, heterocyclic alcohols, polyhydric alcohols, and halogen-substituted products thereof (particularly, fluorine-substituted products). Alcohol, alicyclic alcohol or a fluorine-substituted product thereof (fluoroalcohol) is preferred. By using an aliphatic alcohol, an alicyclic alcohol, or a fluorine-substituted product thereof, the vertical anchoring force for the liquid crystal molecules is further increased, and the liquid crystal molecules can be more reliably vertically aligned.
The alicyclic alcohol or its fluorine-substituted product is more preferably one having a steroid skeleton. Since the alicyclic alcohol having a steroid skeleton or a fluorine-substituted product thereof has a highly planar structure, it is particularly excellent in the function of controlling the alignment of liquid crystal molecules.

  For these reasons, the alcohol of the alignment film 3 includes octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, eicosanol, heneicosa. Ol, docosanol, tricosanol, tetracosanol, and other aliphatic alcohols, cholesterol, epicholesterol, cholestanol, epicholestanol, ergostanol, epiergostanol, copressanol, epicoprestanol, α-ergosterol, β-sitosterol In particular, those mainly composed of alicyclic alcohols such as stigmasterol and campesterol or fluorine-substituted products thereof are suitable.

Further, the aliphatic alcohol or the fluorine-substituted product thereof may be either one in which the hydrocarbon portion or the fluorocarbon portion (main skeleton portion) is linear or branched.
On the other hand, the average molecular weight of the alcohol in the alignment film 4 is preferably about 32 to 70, and more preferably about 32 to 60. Thereby, the burn-in of the liquid crystal panel 1 can be prevented more reliably.

Further, the alcohol of the alignment film 4 is preferably one having a main component mainly having 1 to 4 carbon atoms (particularly one having 1 to 3 carbon atoms). Thereby, the effect becomes more remarkable.
Further, since the first alcohol having such a carbon number has a small molecular size, it can be surely penetrated deeply into the pores 40. Moreover, since it is liquefied at normal temperature, the handling at the time of processing the inorganic oxide film 31 (41) with the process liquid mentioned later is easy.

Examples of such alcohols include aliphatic alcohols, polyhydric alcohols, and halogen-substituted products thereof (particularly fluorine-substituted products). Among these, aliphatic alcohols or fluorine-substituted products thereof (fluoroalcohols) are preferable. .
For this reason, as the alcohol of the alignment film 4, those mainly composed of methanol, ethanol, propanol, or a fluorine-substituted product thereof are suitable.
Since many liquid crystal molecules are fluorinated, the use of a fluorine-substituted product improves the affinity with the liquid crystal molecules and further enhances the effect of vertically aligning the liquid crystal molecules.

  In the present embodiment, the case where the average molecular weight of the alcohol in the alignment film 3 on the TFT substrate 17 side that is at a high temperature is made larger than the average molecular weight of the alcohol in the alignment film 4 on the counter substrate 12 side for the liquid crystal panel has been described. In the case of a liquid crystal panel having a configuration in which the electronic device substrate is higher in temperature than the first electronic device substrate side, the average molecular weight of the alcohol in the alignment film on the second electronic device substrate side is preferably It is set to be larger than the average molecular weight of alcohol in the alignment film on the substrate side for electronic devices.

Further, in order to change the average molecular weight of the alcohol in the alignment films 3 and 4, for example, to eliminate the electrical variation in the pair of alignment films, in addition to preventing the occurrence of abnormal alignment and the occurrence of burn-in, etc. Is mentioned.
In addition to the process of chemically bonding alcohol, the hydroxyl group reducing process includes a process of chemically bonding various coupling agents such as a silane coupling agent having a hydrocarbon moiety of alcohol as described above. Even when a treatment for chemically bonding such a coupling agent is used, the same effect as described above can be obtained.
In addition, it is preferable to use an alcohol treatment for the hydroxyl group reduction treatment because alcohol is easily and inexpensively obtained and the alcohol is particularly easy to handle.
In addition, you may abbreviate | omit a hydroxyl group reduction process as needed.

Such a liquid crystal panel 1 can be manufactured as follows, for example.
[1] First, a TFT substrate 17 manufactured by a known method and a counter substrate 12 for a liquid crystal panel are prepared.
[2] Next, the alignment film 3 is formed on the TFT substrate 17 so as to cover the pixel electrode 172 and the TFT 173, while the alignment film 4 is formed on the transparent conductive film 14 of the counter substrate 12 for the liquid crystal panel.

Since the formation method (formation process) of the alignment films 3 and 4 is the same, the formation method of the alignment film 3 will be described below as a representative.
In steps [22] to [24], for example, a processing apparatus 900 as shown in FIG. 3 is used.
A processing apparatus 900 shown in FIG. 3 includes a chamber 910, a stage 950 provided in the chamber 910, a container 920 disposed on the stage 950, and a liquid supply unit 960 that supplies the processing liquid S into the container 920. , A drainage means 940 for draining the processing liquid S in the container 920 and an exhaust means 930 for exhausting the chamber 910.

The stage 950 is provided with heating means (not shown) such as a heater.
The exhaust means 930 includes a pump 932, an exhaust line 931 that communicates the pump 932 and the chamber 910, and a valve 933 provided in the middle of the exhaust line 931.

The drainage means 940 includes a recovery tank 944 that recovers the processing liquid S, a drainage line 941 that connects the recovery tank 944 and the container 920, and a pump 942 and a valve 943 provided in the middle of the drainage line 941. It consists of and.
The liquid supply means 960 includes a storage tank 964 that stores the processing liquid S, a liquid supply line 961 that guides the processing liquid S from the storage tank 964 to the container 920, a pump 962 provided in the middle of the liquid supply line 961, and And a valve 963.
Further, each of the drainage means 940 and the liquid supply means 960 is provided with a heating means (for example, a heater) (not shown) so as to heat the processing liquid S.

[21] First, the inorganic oxide film 31 is formed on the TFT substrate 17 by oblique vapor deposition.
Specifically, in the oblique deposition method, as shown in FIG. 4, a deposition source 810 containing an inorganic oxide (raw material) 800 and a TFT substrate 17 are installed in a chamber (not shown), A slit plate 820 in which a slit 821 is formed is disposed between them.

The TFT substrate 17 is fixed to the driving device 830, and can be translated in a state where a vapor deposition angle (angle θ _{2 in} FIG. 4) described later is maintained. The TFT substrate 17 can be heated by a heating means (not shown).
In this state, the inorganic oxide 800 is heated and evaporated (vaporized) by a heating means (not shown) provided in the vapor deposition source 810. Then, the evaporated particles of the inorganic oxide 800 are allowed to reach the upper surface (the surface on which the inorganic oxide film 31 is formed) of the TFT substrate 17 through the slits 821 of the slit plate 820.

At this time, the TFT substrate 17 is heated to a predetermined temperature by the heating means described above, and is translated by the driving device 830 at a predetermined speed.
Thereby, an inorganic oxide film 31 having a plurality of pores 30 is obtained on the TFT substrate 17.
Here, the TFT substrate of the pores 30 is appropriately set by appropriately setting the deposition angle (angle θ _{2 in} FIG. 4) at which the inorganic oxide (evaporated particles) 800 evaporated from the evaporation source reaches the upper surface of the TFT substrate 17. The angle with respect to the upper surface of 17 can be adjusted.

Further, the surface area S ₂ of the inorganic oxide film 31 is vaporized inorganic oxide 800 is highly dependent on the state of the structure (column structure) that is formed when arriving at the substrate, the vacuum in the chamber during deposition It can be adjusted by appropriately setting various conditions such as the temperature, the deposition rate, the temperature of the TFT substrate 17 (substrate temperature), and the deposition angle θ ₂ .
The degree of vacuum in the chamber (evaporation apparatus) is preferably about 1 × 10 ⁻⁵ to 1 × 10 ⁻² Pa, and more preferably about 5 × 10 ^{−5 to} 5 × 10 ⁻³ Pa.

Moreover, it is preferable that the substrate temperature at the time of vapor deposition is about 20-150 degreeC, and it is more preferable that it is about 50-120 degreeC.
The deposition rate is preferably about 2.5 to 25 liters / second, more preferably about 4 to 20 liters / second.
In addition, the vapor deposition angle θ ₂ is preferably about 45 to 85 °, and more preferably about 50 to 75 °.

By setting the various conditions within the above ranges, the inorganic oxide film 31 having the target area ratio S ₂ / S ₁ can be formed with high accuracy.
For example, when the degree of vacuum is set high, the surface area S ₂ tends to decrease, and when the substrate temperature is set high, the surface area S ₂ tends to decrease. When the deposition angle θ ₂ is set large, self-shadowing (self shadow pickled) shows a tendency to surface area S ₂ is increased due to the effect.
Further, the azimuth angle between the deposition source 810 and the TFT substrate 17 (angle θ _{1 in} FIG. 4), the separation distance between the TFT substrate 17 and the deposition source 810 (L in FIG. 4), the thickness of the slit plate 820 (FIG. (T in 4), the width of the slit 821 (W in FIG. 4), and the like are appropriately set to control the direction uniformity of the column structure, that is, to control the orientation of the inorganic oxide film 31. .

[22] Next, the TFT substrate 17 on which the inorganic oxide film 31 is formed is immersed in the treatment liquid S containing alcohol as described above.
Specifically, the chamber 910 is opened, and the TFT substrate 17 on which the inorganic oxide film 31 is formed is loaded and installed in the container 920.
Next, the chamber 910 is sealed, and the pump 962 is operated. In this state, the valve 963 is opened to supply the processing liquid S from the storage tank 964 into the container 920 through the liquid supply line 961. .

Then, when a predetermined amount of the processing liquid S, that is, an amount of the processing liquid S in which the TFT substrate 17 is completely immersed is supplied into the container 920, the pump 962 is stopped and the valve 963 is closed.
Here, the alcohol may be liquid at normal temperature, or solid or semi-solid at normal temperature.
In the case of using liquid alcohol at room temperature, the treatment liquid S can be the alcohol itself (alcohol content is almost 100%) or can be used by mixing the alcohol with an appropriate solvent. .

In addition, when using a solid or semi-solid alcohol at room temperature, the treatment liquid S can be a liquid obtained by heating the alcohol, or can be used by dissolving the alcohol in a suitable solvent. it can.
When the alcohol is mixed or dissolved in the solvent, a solvent that can mix or dissolve the alcohol and is less polar than the alcohol is selected. This can prevent the solvent from interfering with the reaction between the hydroxyl group of the inorganic oxide film 31 and the alcohol in the post-process [24], and can surely cause a chemical reaction.

[23] Next, the processing liquid S is permeated into the pores 30 of the inorganic oxide film 31 by reducing the pressure in the chamber 910 (the space in which the processing liquid S is installed).
Specifically, the chamber 910 is sealed, the pump 932 is operated, and the valve 933 is opened in this state, whereby the gas in the chamber 910 is discharged out of the processing apparatus 900 through the exhaust line 931. .
As the pressure in the chamber 910 gradually decreases, the gas (for example, air) in the treatment liquid S and in the pores 30 of the inorganic oxide film 31 is removed, and the treatment liquid S permeates into the pores 30. To go.

When the inside of the chamber 910 reaches a predetermined pressure, the pump 932 is stopped and the valve 933 is closed.
The predetermined pressure in the chamber 910 (space), that is, the degree of vacuum in the chamber 910 is preferably about 1 × 10 ⁻⁴ to 1 × 10 ⁴ Pa, and preferably 1 × 10 ⁻² to 1 × 10 ^3. More preferably, it is about Pa. Thereby, air is sufficiently removed from the pores 30 of the inorganic oxide film 31, and the treatment liquid S can be sufficiently permeated into the pores 30.
Next, the pump 942 is operated, and in this state, the valve 943 is opened, whereby the excess processing liquid S in the container 920 is recovered in the recovery tank 944 via the drain line 941.
When almost all of the processing liquid S is collected from the container 920, the pump 942 is stopped and the valve 943 is closed.

[24] Next, alcohol is chemically bonded to the surface of the inorganic oxide film 31 and the inner surfaces of the pores 30.
Specifically, the TFT substrate 17 on which the inorganic oxide film 31 is formed is heated by operating a heating means provided on the stage 950.
As a result, a dehydration condensation reaction occurs between the hydroxyl group present on the surface of the inorganic oxide film 31 and the inner surface of the pore 30 and the hydroxyl group possessed by the alcohol, and on the surface of the inorganic oxide film 31 and the inner surface of the pore 30. , Alcohol is chemically bonded.
As a result, a coating 32 mainly comprising a main skeleton portion of alcohol is formed along the surface of the inorganic oxide film 31 and the inner surface of the pores 30, and the alignment film 3 is obtained.
Prior to this heating, the inside of the chamber 910 may be decompressed again as necessary.

  The heating temperature of the TFT substrate 17 is not particularly limited, but is preferably about 80 to 250 ° C., and more preferably about 100 to 200 ° C. If the heating temperature is too low, the alcohol may not be sufficiently chemically bonded to the inorganic oxide film 31 depending on the type of alcohol, the type of inorganic oxide, and the like. Even if it exceeds this value, no further increase in effect can be expected.

  The heating time of the TFT substrate 17 is not particularly limited, but is preferably about 20 to 180 minutes, and more preferably about 40 to 100 minutes. If the heating time is too short, alcohol may not be sufficiently chemically bonded to the inorganic oxide film 31 depending on other conditions such as the heating temperature. On the other hand, the heating temperature is set higher than the upper limit. However, no further increase in effect can be expected.

As described above, as a method of reacting a hydroxyl group present on the surface of the inorganic oxide film 31 and the inner surface of the pore 30 with the alcohol, the reaction is performed relatively easily and reliably by using a method using heating. be able to.
In addition, the said reaction is not limited to the method by heating, For example, it can also carry out by irradiation of an ultraviolet-ray, infrared irradiation, etc. In these cases, a mechanism (means) necessary for performing each process is provided in the processing apparatus 900.
Note that when a plurality of alcohols are used, a plurality of alcohols may be mixed in the treatment liquid S at the same time. In this case, the ratio of the plurality of types of alcohols chemically bonded to the inorganic oxide film 31 is adjusted by appropriately setting, for example, the blending ratio, type, molecular weight, processing conditions, and the like of the plurality of types of alcohols in the processing solution. Can do.

  Alternatively, a plurality of processing solutions each containing each alcohol may be prepared, and the TFT substrate 17 may be processed as described above using each processing solution in turn. In this case, it is preferable to process the TFT substrate 17 by sequentially changing the treatment liquid containing the alcohol having the smallest molecular weight to the treatment liquid containing the alcohol having the higher molecular weight. Thereby, the low molecular weight alcohol can be more securely chemically bonded to the back of the pores 30.

Furthermore, when it is sufficient that alcohol is selectively chemically bonded in the vicinity of the surface of the inorganic oxide film 31, the treatment liquid S may be simply brought into contact with the surface of the inorganic oxide film 31. Thereby, the use of the processing apparatus 900 as described above can be omitted, and the manufacturing process of the liquid crystal panel 1 can be simplified and the manufacturing cost can be reduced.
As a method of bringing the treatment liquid S into contact with the inorganic oxide film 31, for example, a method of applying the treatment liquid S to the inorganic oxide film 31 (coating method), or treating the TFT substrate 17 on which the inorganic oxide film 31 is formed is treated. Examples include a method of immersing in the liquid S (immersion method), a method of exposing the inorganic oxide film 31 to the vapor of the processing liquid S, and the like, and one or more of these can be used in combination.
Examples of the coating method include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, A flexographic printing method, an offset printing method, an inkjet printing method, or the like can be used.

[3] Next, the alignment films 3 and 4 are opposed to each other, and the TFT substrate 17 and the liquid crystal panel counter substrate 12 are bonded to each other through a sealing material (not shown), and the void enclosing hole formed thereby After injecting liquid crystal (liquid crystal composition) from the gap (not shown) into the gap, the sealing hole is closed.
In the liquid crystal panel 1, a TFT substrate is used as the liquid crystal drive substrate. However, a liquid crystal drive substrate other than the TFT substrate, such as a TFD substrate or an STN substrate, may be used as the liquid crystal drive substrate.

Next, an electronic apparatus (liquid crystal projector) using the liquid crystal panel 1 will be described as an example of the electronic apparatus of the present invention.
FIG. 5 is a diagram schematically showing an optical system of the electronic apparatus (projection display device) of the present invention.
As shown in the figure, 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 (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 1 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 1 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 1 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. 5 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. 5 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 of blue light and green light reflected by the dichroic mirror 305 is reflected to the left side in FIG. 5 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. 5 by the dichroic mirror (or mirror) 308, and the reflected light is reflected on the upper side in FIG. 5 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 1 included in the liquid crystal light valve 24 is subjected to switching control by a driving circuit (driving means) that operates based on a red image signal. (On / off), ie modulated.

  Similarly, green light and blue light enter the liquid crystal light valves 25 and 26, respectively, and are modulated by the respective liquid crystal panels 1, thereby forming a green image and a blue image. At this time, each pixel of the liquid crystal panel 1 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 1 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, red light from the liquid crystal light valve 24, enters the dichroic prism 21 from the surface 213, is reflected to the left side in FIG. 5 by the dichroic mirror surface 211, and is dichroic mirrored. 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 by the dichroic mirror surface 212 to the left in FIG. 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.

The projection display device 300 of the present embodiment has three liquid crystal panels, and the liquid crystal panel 1 is applied to all of them, but at least one of them is the liquid crystal panel 1. I just need it. In this case, it is preferable to apply the liquid crystal panel 1 to at least a liquid crystal light valve for blue.
In addition to the projection display device of FIG. 5, the electronic device of the present invention includes, for example, a personal computer (mobile personal computer), a mobile phone (including PHS), a digital still camera, a television, a video camera, a view Finder type, monitor direct-view type video tape recorder, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, video phone, TV monitor for crime prevention, electronic Devices equipped with binoculars, POS terminals, 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, endoscopes) Display device), fish finder, various measuring instruments, instruments (eg, vehicle) Aircraft, gauges of a ship), such as flight simulators, and the like. Needless to say, the present invention can be applied to a liquid crystal panel included in the display unit and the monitor unit of these various electronic devices.

As mentioned above, although the board | substrate for electronic devices, the liquid crystal panel, and electronic device of this invention were demonstrated based on embodiment of illustration, this invention is not limited to this.
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 an arbitrary configuration that exhibits the same function, and an arbitrary configuration can be added. it can.

The electronic device substrate of the present invention is not limited to application to the liquid crystal panel having the configuration described in the above embodiment. For example, a configuration in which a pair of electrodes for applying a voltage to the liquid crystal layer is provided on the same substrate. It can be applied to LCD panels.
Furthermore, the electronic device substrate of the present invention is not limited to application to a liquid crystal panel, and may be applied to, for example, an organic transistor. In this case, by using such an electronic device substrate, the orientation direction of the organic semiconductor layer can be regulated to improve carrier mobility.
In addition, when it is not necessary to use a pair of electronic device substrates, that is, when one electronic device substrate is used, the inorganic oxide film has a hydroxyl group reduction treatment such as the alcohol or the coupling agent described above. What is necessary is just to make it use in combination of 1 type, or 2 or more types for an appropriate thing among various processing agents.

Next, specific examples of the present invention will be described.
1. Preparation of TFT substrate with alignment film In the following, each sample No. A plurality of TFT substrates with alignment films were prepared.
(Sample No. A1)
<1A> First, the TFT substrate shown in FIG. 1 was prepared, and the substrate surface was set in the chamber of the vacuum evaporation apparatus so that the angle θ ₁ was 50 ° with respect to the evaporation source. The thickness of the slit plate is 1.5 cm, the width of the slit is 2.0 cm, the vapor deposition angle θ ₂ is 60 °, the vapor deposition distance is 1.5 m, and the substrate operating speed (moving speed) is 2.5 cm / min. It was.

Then, the inside of the chamber is depressurized (1 × 10 ⁻⁴ Pa), the substrate temperature is 110 ° C., the deposition rate is 10 秒 / sec, and the SiO ₂ is obliquely deposited, and the TFT substrate with the obliquely deposited film (inorganic oxide film) Was made.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 45 nm.

<2A> Next, the TFT substrate with the obliquely deposited film was heated in a clean oven at 200 ° C. for 90 minutes, and immediately after the heating was completed, the TFT substrate was moved into a dry nitrogen atmosphere and left as it was.
<3A> Next, 2-propanol (molecular weight: 60) was prepared, and after removing ionic impurities using a filtration filter, a trace amount of water was removed by nitrogen bubbling to prepare a treatment liquid.

<4A> Next, the TFT substrate with the obliquely deposited film was carried into the processing apparatus shown in FIG. 3, and the obliquely deposited film was placed in the container (made of polytetrafluoroethylene).
Then, after the chamber was sealed, the prepared processing liquid was supplied into the container, and the TFT substrate with the oblique deposition film was immersed in the processing liquid.
<5A> Next, the pressure in the chamber was reduced to 100 Pa in the state of the step <4A>.
As a result, the gas in the pores of the oblique deposition film was replaced with the treatment liquid. That is, the treatment liquid was permeated into the pores.

<6A> Next, after the excess processing liquid was discharged from the container, the inside of the chamber was again decompressed to 133 Pa (1 Torr), and the substrate was heated at 150 ° C. for 1 hour.
Thereby, 2-propanol was chemically bonded to the surface of the oblique deposition film and the inner surface of the pores.
<7A> After completion of heating, the mixture was allowed to cool while maintaining a reduced pressure state.
As described above, a TFT substrate with an alignment film was obtained.

(Sample No. A2)
In the step <1A>, the sample No. 1 was changed except that the inside of the chamber was depressurized (3 × 10 ⁻³ Pa). A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 50 nm.

(Sample No. A3)
In the above step <1A>, except that the inside of the chamber was depressurized (5 × 10 ⁻⁴ Pa), the sample No. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 40 nm.

(Sample No. A4)
In the above step <1A>, the sample No. was changed except that the vapor deposition rate was 20 liters / second. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 110 nm.

(Sample No. A5)
In the above step <1A>, the sample No. was changed except that the vapor deposition rate was 4 liters / second. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 35 nm.

(Sample No. A6)
In the step <1A>, the sample No. 1 was changed except that the chamber was depressurized (5 × 10 ⁻² Pa). A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 150 nm.

(Sample No. A7)
In the above step <1A>, the sample No. was changed except that the vapor deposition rate was 2 liters / second. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 35 nm.

(Sample No. A8)
In the step <1A>, sets the deposition angle theta ₂ so that the 30 °, except that the deposition rate was 5 Å / sec, the sample No. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained deposited film had an angle θ of about 90 ° with respect to the upper surface of the TFT substrate and an average thickness of 50 nm.

(Sample No. A9)
A mixed liquid (weight ratio = 95: 5) of 1-octanol (molecular weight: 130) and 2-propanol (molecular weight: 60) is prepared, and after removing ionic impurities using a filtration filter, a small amount is obtained by nitrogen bubbling. Except that the moisture contained was removed and the treatment liquid was prepared and used, the sample No. A TFT substrate with an alignment film was produced in the same manner as A1.

Three of the prepared TFT substrates with alignment films were each heated to 200 ° C., and the generated gas was analyzed by GC-MS (manufactured by Shimadzu Corporation, “GC-MS QP5050A”).
Then, from the obtained GC-MS chart, the areas of peaks derived from propylene and octene were integrated over time to determine the amount of propylene and octene generated (the same applies hereinafter).
As a result, propylene: octene = 90: 10.
The amounts of propylene and octene generated are proportional to the amounts of 2-propanol and 1-octanol chemically bonded to the oblique deposition film, respectively.
Therefore, the average molecular weight of the alcohol chemically bonded to the inorganic oxide film is 123.

(Sample No. A10)
1-octanol was prepared, and after removing ionic impurities using a filtration filter, a trace amount of water was removed by nitrogen bubbling to prepare a treatment solution. A TFT substrate with an alignment film was produced in the same manner as A1.
(Sample No. A11)
In the above step <1A>, the sample No. was changed except that the substrate temperature was set to 200 ° C. A TFT substrate with an alignment film was produced in the same manner as A1.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the TFT substrate and an average thickness of 45 nm.

2. Production of counter substrate for liquid crystal panel with alignment film A plurality of counter substrates for liquid crystal panels with alignment films were prepared.
(Sample No. B1)
<1B> First, the counter substrate for a liquid crystal panel shown in FIG. 1 was prepared, and the substrate surface was set in the chamber of the vacuum vapor deposition apparatus so that the angle θ ₁ was 50 ° with respect to the vapor deposition source. The thickness of the slit plate is 1.5 cm, the width of the slit is 2.0 cm, the vapor deposition angle θ ₂ is 60 °, the vapor deposition distance is 1.5 m, and the substrate operating speed (moving speed) is 2.5 cm / min. It was.

Then, the inside of the chamber is decompressed (1 × 10 ⁻⁴ Pa), SiO ₂ is obliquely vapor-deposited at a substrate temperature of 110 ° C. and a vapor deposition rate of 10 Å / second, and a liquid crystal panel with an oblique vapor deposition film (inorganic oxide film) A counter substrate was prepared.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 45 nm.

<2B> Next, the counter substrate for an oblique vapor deposition film-equipped liquid crystal panel was heated in a clean oven at 200 ° C. for 90 minutes, and immediately after completion of the heating, moved to a dry nitrogen atmosphere and left as it was.
<3B> Next, 2-propanol (molecular weight: 60) was prepared, and after removing ionic impurities using a filtration filter, a trace amount of water was removed by nitrogen bubbling to prepare a treatment liquid.

<4B> Next, the counter substrate for the liquid crystal panel with the oblique vapor deposition film was carried into the processing apparatus shown in FIG. 3, and the oblique vapor deposition film was placed in the container (made of polytetrafluoroethylene). .
Then, after the chamber was sealed, the prepared processing liquid was supplied into the container, and the counter substrate for a liquid crystal panel with an oblique deposition film was immersed in the processing liquid.
<5B> Next, the pressure in the chamber was reduced to 100 Pa in the state of the step <4B>.
As a result, the gas in the pores of the oblique deposition film was replaced with the treatment liquid. That is, the treatment liquid was permeated into the pores.

<6B> Next, after excess processing liquid was discharged from the container, the inside of the chamber was again depressurized to 133 Pa (1 Torr), and the substrate was heated at 150 ° C. for 1 hour.
Thereby, 2-propanol was chemically bonded to the surface of the oblique deposition film and the inner surface of the pores.
<7B> After completion of heating, the mixture was allowed to cool while maintaining a reduced pressure state.
In this manner, a counter substrate for a liquid crystal panel with an alignment film was obtained.

(Sample No. B2)
In the step <1B>, the sample No. 1 was changed except that the inside of the chamber was depressurized (3 × 10 ⁻³ Pa). In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 50 nm.

(Sample No. B3)
In the step <1B>, the sample No. 1 was changed except that the inside of the chamber was depressurized (5 × 10 ⁻⁴ Pa). In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
In addition, the obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 40 nm.

(Sample No. B4)
In the above step <1B>, the sample No. was changed except that the vapor deposition rate was 20 liters / second. In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 110 nm.

(Sample No. B5)
In the above step <1B>, the sample No. was changed except that the vapor deposition rate was 4 liters / second. In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 35 nm.

(Sample No. B6)
In the step <1B>, the sample No. 1 was changed except that the pressure in the chamber was reduced (5 × 10 ⁻² Pa). In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 150 nm.

(Sample No. B7)
In the above step <1B>, the sample No. was changed except that the vapor deposition rate was 2 liters / second. In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the counter substrate for a liquid crystal panel and an average thickness of 35 nm.

(Sample No. B8)
In the step <1B>, except that the counter substrate for a liquid crystal panel was set so that the deposition angle theta ₂ and 30 °, and the evaporation rate and 5 Å / sec, the sample No. In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
The obtained deposited film had an angle θ of about 90 ° with respect to the upper surface of the counter substrate for a liquid crystal panel, and an average thickness of 50 nm.

(Sample No. B9)
A mixed liquid (weight ratio = 75: 25) of 2-propanol (molecular weight: 60) and ethanol (molecular weight: 46) is prepared, and after removing ionic impurities using a filtration filter, a trace amount of water is contained by nitrogen bubbling. The sample No. was prepared except that the treatment liquid was adjusted and this was used. In the same manner as in B1, a counter substrate for a liquid crystal panel with an alignment film was produced.
As a result of GC-MS analysis, propylene: ethylene = 75: 25.
Therefore, the average molecular weight of the alcohol chemically bonded to the inorganic oxide film is 57.

(Sample No. B10)
In the step <1B>, the sample No. was changed except that the substrate temperature was set to 200 ° C. In the same manner as in B1, a liquid crystal panel substrate with an alignment film was produced.
The obtained obliquely deposited film had an angle of about 70 ° with respect to the upper surface of the liquid crystal panel substrate and an average thickness of 45 nm.

3. Each sample before calculating the alcohol treatment of the area ratio _S 2 / _{S 1} No. The substrate is cut into a predetermined size (1.5 cm × 1.8 cm), and five pieces of each of these sections are sealed in a test tube. A high-precision fully automatic gas adsorption device (“BELSORP 36” manufactured by Bell Japan Co., Ltd.) Was used to measure the surface area.
Specifically, the inside of the test tube in which each section was sealed was replaced with helium gas, followed by vacuum degassing at 100 ° C. Then, krypton gas was adsorbed at the adsorption temperature of 77 K (liquid nitrogen temperature) over the entire slice including the inorganic oxide film. The measurement range was relative pressure (P / P0) = 0.0 to 0.4, and the equilibrium time was 180 seconds for each equilibrium relative pressure. The BET theory was applied to the surface area measurement. Such inorganic oxide film from the surface area S of each whole sections were measured by subtracting the geometric surface area s of the portion not formed, were calculated surface area S ₂ of an inorganic oxide film.
Further, even in the same manner with respect to each substrate before the inorganic oxide film formed was measured surface area S _1.
Based on the measured values of _{S 1} and _{S 2,} to calculate the area ratio _S 2 / _{S 1.}

4). Manufacture of a liquid crystal panel In the following, the liquid crystal panel of each Example and each comparative example was manufactured, respectively.
(Example 1)
First, sample no. A thermosetting adhesive (manufactured by Nippon Kayaku Co., Ltd., “ML3804P”) is left on the TFT substrate with an alignment film A1 along the outer periphery of the surface on which the alignment film is formed, leaving a portion that becomes a liquid crystal injection port The solvent was removed by printing and heating at 80 ° C. for 10 minutes.

The thermosetting adhesive is an epoxy resin in which silica spheres having a diameter of about 3 μm are mixed.
Next, sample no. The two substrates were bonded together by heating at 140 ° C. for 1 hour with the surface on which the alignment film of the counter substrate for the liquid crystal panel with alignment film B1 was formed facing inward.
Note that the two substrates were arranged so that the alignment films were aligned at 180 °.

Next, fluorine-based negative dielectric anisotropic liquid crystal (“MLC-6610”, manufactured by Merck & Co., Inc.) is injected from the liquid crystal injection port into the inner space formed by bonding the two substrates by vacuum injection. Injected.
Next, the liquid crystal injection port is cured by irradiating 3000 mJ / cm ² of UV having a wavelength of 365 nm with an acrylic UV adhesive (manufactured by Henkel Japan, “LPD-204”) to seal the liquid crystal injection port did.
A liquid crystal panel was manufactured as described above.

(Example 2)
Sample No. TFT substrate with alignment film of A2 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B2 was used.
(Example 3)
Sample No. TFT substrate with alignment film of A3 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for the liquid crystal panel with alignment film B3 was used.

Example 4
Sample No. TFT substrate with alignment film of A4 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B4 was used.
(Example 5)
Sample No. TFT substrate with alignment film of A5 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B5 was used.

(Example 6)
Sample No. TFT substrate with alignment film of A9 and sample no. A liquid crystal panel was manufactured in the same manner as in Example 1 except that the counter substrate for the liquid crystal panel with alignment film B1 was used.
(Example 7)
Sample No. TFT substrate with alignment film of A10 and Sample No. A liquid crystal panel was manufactured in the same manner as in Example 1 except that the counter substrate for the liquid crystal panel with alignment film B1 was used.
(Example 8)
Sample No. TFT substrate with alignment film of A9 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B9 was used.

(Comparative Example 1)
Sample No. TFT substrate with alignment film of A6 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B6 was used.
(Comparative Example 2)
Sample No. TFT substrate with alignment film of A7 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B7 was used.

(Comparative Example 3)
Sample No. TFT substrate with alignment film of A8 and sample No. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B8 was used.
(Comparative Example 4)
Sample No. TFT substrate with alignment film of A11 and sample no. A liquid crystal panel was produced in the same manner as in Example 1 except that the counter substrate for a liquid crystal panel with alignment film B10 was used.

5. Light Resistance Test of Liquid Crystal Panel The light resistance test is performed by setting the liquid crystal panels manufactured in each of the examples and comparative examples as the blue liquid crystal light valve of the projection display device shown in FIG. While maintaining the surface temperature at 55 ° C., the light source was continuously turned on, and the time until display abnormality occurred was measured.
A 130 WUHP lamp (manufactured by Philips) was used as the light source.
The results are shown in Table 1 below.

Table 1 summarizes the alignment films of the liquid crystal panels produced in each example and each comparative example.
Table 1 shows that the time until a display abnormality occurs in the liquid crystal panel of Comparative Example 1 is set to “1.0”, and the display abnormality occurs in the liquid crystal panels of Examples 1 to 8 and Comparative Example 2. Each time was expressed as a relative value.

As shown in Table 1, it has been clarified that each of the liquid crystal panels of each example has a longer time until a display abnormality occurs than the liquid crystal panels of Comparative Examples 1 and 2.
In the liquid crystal panel of Comparative Example 3, the liquid crystal was not aligned at all. Further, in the liquid crystal panel of Comparative Example 4, the initial display abnormality occurred before the light resistance test apparatus was introduced due to the weak alignment regulating force of the liquid crystal.

Further, in place of SiO ₂ , a liquid crystal panel is produced using a TFT substrate with an alignment film in which an inorganic oxide film is formed of Al ₂ O ₃ and a counter substrate for a liquid crystal panel with an alignment film in the same manner as described above. When the evaluation was performed in the same manner as described above, the same result as described above was obtained.
In addition, the same result as described above was obtained when a silane coupling agent treatment using an alkylalkoxysilane was performed instead of the alcohol treatment.

It is a longitudinal cross-sectional view which shows typically embodiment of the liquid crystal panel to which the board | substrate for electronic devices of this invention is applied. It is a longitudinal cross-sectional view which shows typically the structure of the alignment film with which the liquid crystal panel shown in FIG. 1 is provided. It is a schematic diagram which shows the structure of the processing apparatus used for the manufacturing method of the board | substrate for electronic devices of this invention. It is a schematic diagram which shows the structure of a vacuum evaporation system. It is a figure which shows typically the optical system of the projection type display apparatus to which the electronic device of this invention is applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Liquid crystal panel 2 ... Liquid crystal layer 3, 4 ... Orientation film 30, 40 ... Pore 31, 41 ... Inorganic oxide film 32, 42 ... Coating 11 ... Microlens substrate 111 ... Microlens Substrate with concave portion 112 …… Recess portion 113 …… Micro lens 114 …… Surface layer 115 …… Resin layer 12 …… Counter substrate for liquid crystal panel 13 …… Black matrix 131 …… Opening 14 …… Transparent conductive film 17 …… TFT substrate 171: Glass substrate 172: Pixel electrode 173: Thin film transistor 800 ... Inorganic oxide (raw material) 810 ... Deposition source 820 ... Slit plate 821 ... Slit 830 ... Drive device 900 ... Processing device 910 ... Chamber 920 ... Container 930 ... Exhaust means 931 ... Exhaust line 932 ... Pump 933 ... Valve 940 ... Drained hand 941 …… Discharge line 942 …… Pump 943 …… Valve 944 …… Collection tank 950 …… Stage 960 …… Liquid supply means 961 …… Liquid supply line 962 …… Pump 963 …… Valve 964 …… Storage tank S… ... Processing solution 300 ... Projection type display device 301 ... Light source 302, 303 ... Integrator lens 304, 306, 309 ... Mirror 305, 307, 308 ... Dichroic mirror 310-314 ... Condensing lens 320 ... Screen 20 …… Optical block 21 …… Dichroic prism 211, 212 …… Dichroic mirror surface 213 to 215 …… Surface 216 …… Exit surface 22 …… Projection lens 23 …… Display unit 24 to 26 …… Liquid crystal light valve

Claims (13)

A substrate for an electronic device having a substrate and an alignment film including an inorganic oxide film having a plurality of pores formed on one surface of the substrate by oblique vapor deposition,
The inorganic oxide film is subjected to a hydroxyl group reduction treatment for reducing the number of hydroxyl groups present on at least the surface of the inorganic oxide film by a chemical bond of at least one alcohol to the hydroxyl group,
The surface area of one surface of the substrate measured by the BET method is S1 [nm2], the surface area of the inorganic oxide film measured by the BET method is S2 [nm2], and the average thickness of the inorganic oxide film An electronic device substrate characterized by satisfying a relationship of 0.55 log ≦ S2 / S1 ≦ 0.55 log + 4.4, where t is [nm].   The electronic device substrate according to claim 1, wherein the BET method is a BET multipoint method.   The electronic device substrate according to claim 1, wherein the BET method uses krypton gas as an adsorption gas. 2. The electronic device according to claim 1 , wherein the alignment film also reduces the number of hydroxyl groups present on the inner surfaces of the pores of the inorganic oxide film by a process of chemically bonding at least one alcohol to the hydroxyl group. substrate. An electronic device substrate according to any one of claims 1 to 4 ,
A liquid crystal panel comprising: a liquid crystal layer provided on a side opposite to the substrate of the alignment film. A first electronic device substrate comprising a first alignment film;
A second substrate for an electronic device comprising a second alignment film;
A liquid crystal panel having a liquid crystal layer interposed between the first alignment film and the second alignment film,
The liquid crystal panel in which the first electronic device substrate and the second electronic device substrate, respectively, characterized in that it consists of an electronic device substrate according to any one of claims 1 to 4. The liquid crystal panel according to claim 6 , wherein an average molecular weight of the alcohol of the first alignment film is different from an average molecular weight of the alcohol of the second alignment film. The first electronic device substrate includes a driving element;
The liquid crystal panel according to claim 7 , wherein an average molecular weight of the alcohol of the first alignment film is larger than an average molecular weight of the alcohol of the second alignment film. The liquid crystal panel according to claim 8 , wherein an average molecular weight of the alcohol of the first alignment film is 100 to 400. 10. The liquid crystal panel according to claim 9 , wherein the alcohol of the first alignment film is mainly composed of 6 to 30 carbon atoms. The average molecular weight of the alcohol of the second alignment film, a liquid crystal panel according to any one of the which claims 8 to 10 32 to 70. It said alcohol of the second alignment film, a liquid crystal panel according to claim 1 1, the main ones having 1 to 4 carbon atoms. An electronic apparatus comprising the liquid crystal panel according to any one of claims 5 to 12.

Images