JPH03200218A - Function member having intra-surface oriented and polymerized thin film and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a functional member having a polymeric thin film with excellent in-plane orientation and a method for manufacturing the same, and more specifically relates to a functional member having a polymeric thin film with excellent in-plane orientation, and more specifically relates to a polarizer, ferroelectric material, nonlinear optical material, etc. The present invention relates to a functional component having a homogeneous polymeric thin film with excellent in-plane orientation for use in bodies, etc., and a method for producing the same.

[Prior art and its problems]

Conventionally, various organic thin film formation methods have been studied for the purpose of producing insulating films and dielectric films. One method is to simultaneously vacuum evaporate two types of monomers that cause condensation polymerization or polyaddition reactions and polymerize them on a solid surface (hereinafter referred to as evaporation polymerization) in order to form a polymerized thin film with high heat resistance and insulation properties. There are (JP-A-61-78463, JP-A-63-
No. 62869, JP-A-63-166962). This method allows the chemical structure to be controlled in the same way as polymers produced using normal chemical methods, and since polymerization is performed in a gas phase system, there are no problems such as contamination with impurities or waste liquid treatment that occur with wet methods. There is a characteristic that

On the other hand, in addition to applications in simple insulating films and dielectric films, functional organic thin films such as nonlinear optical films and ferroelectric films are being actively developed. In order to obtain this functional organic thin film, it is important to control not only the chemical structure but also the higher order structure such as orientation and crystallinity. In particular, regarding orientation, it is essential to be able to control not only the orientation in the film thickness direction but also the in-plane orientation in order to realize three-dimensional orientation control. However, in the conventional method, although the chemical structure is controlled, the higher-order structure related to orientation cannot be controlled.
Even if it were possible to do so, there would only be an example of orientation in the film thickness direction, and therefore a functional organic thin film with higher functionality could not be produced. In addition, there are many other known methods for controlling orientation in the film thickness direction, including the LB method, cluster method, and vacuum evaporation method.
There have been no examples of achieving in-plane orientation using these methods, and the development of functional organic thin films with higher functionality has been delayed.

Therefore, in order to obtain a highly functional thin film with three-dimensional orientation, methods are being developed to achieve this in-plane orientation. One of these is a method that develops the method of rubbing a polyimide film and orienting liquid crystal molecules along the scratches in the rubbing direction into a film formation method. An example of achieving in-plane orientation by vapor deposition of -(p-)unisinsulfide) (Proceedings of the Japan Society of Applied Physics 1989 Autumn Conference, P, P, 996-9
97). In addition, as another method to achieve in-plane orientation, after stretching a polytetrafluoroethylene, mylar, or polyethylene sheet, 82N
Example (A,
A, Bright et al., Appl, Phys, L
ett.

26, 612 (1975)). However, these methods use a polymer film as a substrate, and in the latter case in particular, although an example using a glass substrate has been shown, a uniform alignment film cannot be produced. In other words, in these methods, crystal nuclei are generated along the scratches on the polymer surface, and the vapor-deposited molecules are oriented to create a film with in-plane orientation. Therefore, these methods have the problem that it is difficult to produce an in-plane alignment film on an inorganic substrate.

In addition, as an example of forming an in-plane alignment film on an inorganic substrate,
After rubbing the (SN)X thin film prepared by vapor deposition,
Method of forming (SN)x film again (T, \(itani
et al., J, Phy, Soc, Jap, 47.
679 (1979)), and a method for producing in-plane alignment films of diacetylene compounds by a similar method (T, Kane
take et al., Appl, Phys, Lett,
51. 1957 (1987)). However, these methods have the disadvantage that vacuum deposition must be performed twice. This also shows that it is difficult to produce an in-plane alignment film on an inorganic substrate in one step.

By the way, when considering coating an organic alignment film, it is often necessary to form the film on an inorganic substrate, such as directly on an electrode, so it is important to establish a method for producing an in-plane alignment film on an inorganic substrate. be.

Furthermore, in the conventional in-plane alignment film forming method described above, the applicable substances are limited to highly crystalline conductive substances or their monomers. Some of these methods ultimately yield polymers, but these take advantage of the property of monomers to undergo solid phase polymerization, which can be seen in general polymers, for example in the present invention. The mechanism is completely different from condensation polymerization and polyaddition polymerization.

Normally, when crystals are grown by the sublimation method, individual crystals become crystals in which the molecular directionality is aligned, that is, in an oriented state, but when viewed as a whole, the orientation of each crystal is random. In the conventional in-plane oriented film formation method, crystals in the desired direction that remain after rubbing scratches on a polymer film or the same substance that has already been deposited are used as nuclei to grow crystals by sublimation to form an in-plane oriented film. Deposit a film. Therefore, at present, the applicable materials are limited to a single highly crystalline conductive material, and with the exception of special cases such as charge transfer complexes, two or more materials can be simultaneously deposited and It is considered difficult to control the orientation in a state where the substances are mixed together because the crystal types of each substance are different. In particular, when forming a film of a polymeric material, the difficulty is expected to be even greater because the crystallinity is often absent or low, and the crystalline type is usually significantly different from that of the monomer. For this reason, an insulating polymer film with in-plane orientation that is directly formed on an inorganic substrate has not yet been produced.

Therefore, the present inventors conducted intensive research to solve the problems of the prior art as described above, and as a result of conducting various systematic experiments, they came up with the present invention.

[Purpose of the invention]

An object of the present invention is to provide a functional member having a polymeric thin film that is homogeneous and has excellent in-plane orientation, and a method for manufacturing the same.

The present inventors have focused on the following regarding the problems of the prior art described above.

That is, if a polymeric film (especially an insulating polymeric film) having in-plane orientation can be formed directly on a substrate, especially an inorganic substrate,
For example, it can be used as a liquid crystal alignment film. In addition, if an in-plane alignment film can be realized using polycondensation or polyaddition polymers, which are known to have high heat resistance and insulation resistance, it would be ideal for the above applications, and could also be used to supplement areas that could not be achieved with conventional technology. I thought it would be.

More specifically, at least two types of monomers that cause condensation polymerization or polyaddition reactions are deposited on a substrate that has been given anisotropy, and each monomer can be adsorbed in a manner that reflects the information of the substrate, and the monomers can be polymerized. If the object is a rigid molecule, it is possible to achieve in-plane orientation at least according to the information of the substrate at the initial stage of vapor deposition, and subsequently, even on a polymer with in-plane anisotropy, a polymer with similar anisotropy can be formed. was thought to be generated. If this is possible, it will be possible to provide a polymeric thin film with in-plane orientation.

[Description of the first invention] Structure of the first invention The functional member having the in-plane oriented polymeric thin film of the first invention comprises a substrate having in-plane anisotropy at least on the surface, and an in-plane anisotropy portion of the substrate. Information on the in-plane anisotropy formed directly on the substrate and in the in-plane anisotropic portion of the substrate is transmitted to the film surface in a form in which the orientation of the polymer main chain or functional group is in-plane anisotropy. was formed. It is characterized by consisting of a polymer film consisting of a polyaddition polymer film or a condensation polymer film excluding a ring-opening polymer.

Functions and Effects of the First Invention The functional member having an in-plane oriented polymeric thin film according to the first invention has a homogeneous polymeric film with excellent in-plane orientation.

The mechanism by which the in-plane oriented polymeric thin film of the first invention exhibits the above-mentioned effects is not necessarily clear yet, but it is thought to be as follows.

In other words, in the conventional vapor deposition polymerization method, polymerization is thought to proceed due to the adsorbed monomers, but since the direction of adsorption is isotropic within the substrate plane, a polymer film with in-plane anisotropy is not formed. do not have. In contrast, the present invention has a structure in which a polymeric thin film is directly formed on a substrate provided with in-plane anisotropy so that the in-plane directionality of adsorbed molecules can be controlled. The direction of the monomer directly adsorbed on the substrate, that is, the directionality of the functional groups involved in polymerization, is determined by the in-plane anisotropy imparted to the substrate. In-plane anisotropy of thin films has been achieved. Furthermore, since the polymer film directly formed on the substrate surface has anisotropy, the polymer film accumulated on the surface of the polymer film formed directly on the substrate has an adsorbed and polymerized structure that reflects that information. Therefore, the polymer film is formed with orientation up to the film surface.

Moreover, in the present invention, the polymer film is composed of a polyaddition polymer film or a condensation polymer film excluding a ring-opening polymer, and the polycondensation or polyaddition polymer has polar groups such as carbonyl groups, amino groups, and amide groups. Because it is a monomer and a polymer, it has hydrogen bonding ability and is a rigid polymer, resulting in a polymer film with excellent in-plane anisotropy.

Furthermore, since rigidity is required to achieve in-plane orientation, when producing a polymer film with the above-mentioned vapor-deposited in-plane orientation, the target object is a π-conjugated polymer, that is, a so-called conductive polymer. It must be. In contrast, in the present invention, the polymer film made of a polycondensation or polyaddition polymer is insulative, making it possible to provide an alignment film with properties completely different from those of conventional methods.

The functional component having the in-plane oriented polymeric thin film of the present invention is a very useful polymeric material.

In conventional methods, complex techniques such as liquid crystal spinning and stretching were used to ensure orientation and to develop high-strength fibers. However, these materials often have very high melting points or are insoluble in solvents, making it difficult to make them into thin films. On the other hand, although vapor deposition polymerization can easily form a thin film, it cannot impart in-plane orientation. Therefore, the conventional in-plane alignment method is limited to special cases such as conductive materials, and the method of the present invention is limited to special cases such as conductive materials. There are no known examples of orientation control. From the above, it is clear that the present invention has made possible for the first time a functional member having an in-plane alignment film with a novel higher-order structure, chemical structure, and physical properties.

In addition, in a structure in which this in-plane alignment film is directly formed on an inorganic substrate, it can be used as a protective film or an insulating film for electrodes, and since it has alignment properties, it can be used as a liquid crystal alignment film that requires an electrode system.
It is expected to be applied to optical devices, etc.

[Description of other inventions of the first invention] Other inventions of the first invention will be described below.

In the in-plane oriented polymer thin film of the first invention, the substrate has in-plane orientation information imparted with in-plane anisotropy, which is information for controlling and determining the in-plane directionality of the oriented polymer thin film. It is a holding/transmission means, and any material that satisfies this is not particularly limited. Specific examples include various crystals, insulators such as glass and quartz, semiconductors such as silicon, transparent electrodes such as indium tin oxide and tin oxide, and inorganic materials made of inorganic substances such as metals such as aluminum and gold. It will be done. Although a polymeric material can be similarly used as the organic material for the substrate, one that is resistant to scratches and has a critical surface tension that is significantly different from the critical surface tension of the polymer film formed on the substrate surface is used. The structure of the substrate is not particularly limited, and may be a single structure or a laminated structure in which electrodes and insulating layers are coated on an organic or inorganic support material by vapor deposition, sputtering, wet film formation, etc. But that's fine.

Further, the shape of the substrate is usually flat, but is not limited to this, and may be cylindrical, spherical, or wavy. Further, the smoothness of the substrate may be such that in-plane anisotropy can be imparted to the entire surface. Regarding the thickness, the surface condition is important and is not limited. Regarding the surface condition of the substrate, it is necessary to impart in-plane anisotropy, and special materials such as single crystals can be used. Preferably, it is attached. Further, a substrate having fine grooves or a composition distribution formed in one direction on the substrate surface by oblique vapor deposition or the like can be used.

Further, the in-plane oriented polymer film is a polyaddition polymer film or a condensation polymer film excluding ring-opening polymerization. Examples of the former polyaddition polymer include polyurea and polyurethane, and examples of the latter condensation polymer include polyamide, polyazomethine, and polyester. Each polymer is produced by reacting a difunctional isocyanate, an acid chloride, an aldehyde with a diamine, or a difunctional alcohol. The most preferred among them is polyamide. This is considered to be due to the hydrogen bonding between the polymer and the monomer.

It should be noted that in the vapor deposition polymerization method, polyimide films have been produced most frequently (it has been reported that polyamide alignment films have been produced according to the method of the present invention, and that at least the surface of the polyamide alignment film has a thickness of several thousand Å or more). It does not have internal orientation. This also makes it clear that the present invention is not a mere diversion of vapor deposition polymerization.

This polyimide is produced by ring-opening polymerization by converting an amine into an acid anhydride to produce a polyamic acid as a precursor, followed by thermal dehydration ring-closure and imidization. Even in the polyamic acid state, it does not have in-plane orientation, so the reason why an in-plane orientation film cannot be created with polyimide is because the precursor polyamic acid has a polar group called a carboxyl group in its side chain. It is speculated that this is because the influence is strong and the information on the main chain is erased, or because the information is erased due to movement of the main chain during partial ring imidization.

In addition, in-plane orientation as used in the present invention refers to information imparted to the substrate when viewed from above, such as the fact that main chains or functional groups such as carbonyl groups are arranged parallel to or perpendicular to the rubbing direction. Refers to the state of being.

Therefore, it is not necessary that the main chain and the functional groups are all parallel to the substrate, but it is also possible for the main chain and the functional group to be tilted in a certain direction while maintaining a certain angle with the substrate.

In addition, when considering applications such as liquid crystal alignment, it is not necessary for all molecules to be oriented in a fixed direction, and even if individual molecules are to some extent random, they are oriented in an anisotropic direction as a whole. Also. Therefore, the in-plane orientation here is
Infrared spectroscopy was used to obtain substrate information, such as dichroism in the absorption of functional groups, which was detected by observing the difference spectrum between the transmission spectra measured by irradiating and transmitting polarized light parallel and perpendicular to the rubbing direction perpendicularly to the substrate. In this case, a film is placed between crossed Nicol polarizers, and birefringence is confirmed by rotating the film so that the rubbing direction is parallel to the polarizer and at an angle of 45°, and The orientation of the film can be determined by injecting two films of guest-host type liquid crystal into a cell fixed at regular intervals so that the substrate information, for example, the rubbing directions are parallel to each other, and checking the orientation of the liquid crystal. This refers to cases where it is possible to indirectly confirm that

The in-plane oriented polymer film only needs to have orientation up to the surface, and the film thickness is not particularly limited, but as a functional member, it is preferably 10 Å or more and 100 μm or less, and more preferably 100 Å or more and 10 μm or less. More suitable.

Next, a specific example of the method for producing an in-plane oriented polymer film of the present invention will be briefly described below.

That is, first, a silicon wafer, glass, glass coated with an indium tin oxide transparent electrode, etc. is used as a substrate, and its surface is unidirectionally coated with a polymeric material such as cotton, polyacrylonitrile, polyacrylic acid, hydroxyethyl polymethacrylate. , rubbed with polytetrafluoroethylene fibers or sheets. This substrate is placed in a vacuum chamber and maintained at a predetermined temperature as necessary. Two types of monomers that cause polycondensation and polyaddition reactions are placed opposite the substrate.
Examples include terephthalic acid chloride, sebacic acid dichloride, methylene diphenyl isocyanate, terephthalaldehyde, etc., fatty acid diamines such as decamethylene diamine and hexamenediamine, aromatic diamines such as paraphenylene diamine, 4,4'-diaminodiphenyl ether, and ethylene glycol. , difunctional alcohols such as rose hydroxyphenol are placed in separate containers. The temperature of each container can be adjusted by a heater, and the opening of the container, that is, the spout of monomer vapor, has a mechanism in which the degree of opening and closing can be adjusted by a shutter as necessary. Inside the vacuum chamber, use an oil diffusion pump, etc.
After exhausting to a temperature below X 10-5 Torr, each monomer container is heated to a predetermined temperature, and the shutter is opened to blow out both monomers. At this time, the degree of opening and closing of the shutter or the temperature of each monomer container is finely adjusted so that the amounts of the two monomers do not differ significantly. The pressure during vapor deposition is lXl0-5~1
×1O-3 Torr. If you want to strictly control the spouting amount of each monomer, you can do so by installing a film thickness monitor using a crystal oscillator near each monomer spout, and for monomers with relatively high volatility, With the spout of the monomer container containing the smaller amount, that is, the one with the lower vapor pressure at the monomer temperature, fully open, finely adjust the opening/closing degree of the shutter of the other monomer container spout, so that the pressure measured with the ion gauge is It may be set to the lowest value. This is because as the polymerization reaction progresses, the pressure in the system decreases due to a decrease in volatility, and the relative sensitivity of the low molecular weight gas produced by the condensation reaction to the monomer on the ion gauge is low. Since the pressure measured by the gauge decreases, the lowest pressure indicates an approximately 1:1 ratio of both monomers. In addition, if one monomer is extremely volatile, the less volatile monomer is fully opened in the same manner as above, and the pressure is slightly higher than the minimum, and the highly volatile monomer is supplied in excess. You can keep it in the same condition as it is. This state can be confirmed by the fact that when the supply of the monomer with low volatility is stopped, the pressure monotonically increases, and when the monomer is supplied, the pressure monotonically decreases. By performing open film formation at predetermined times in this manner, an in-plane alignment film can be obtained. Naturally, the time will vary depending on the polymerization rate, substrate temperature, system pressure, and desired film thickness. Evaluation of in-plane orientation is confirmed by infrared spectroscopy, measurement of birefringence, and liquid crystal alignment ability as described above. In particular, whether or not the material has in-plane orientation up to the surface can be confirmed by the liquid crystal orientation ability.

The field of application of the in-plane alignment film of the present invention is not particularly limited as long as it is a product that can utilize the above properties, but examples include liquid crystal alignment films, functional organic alignment films, nonlinear optical materials,
Suitable applications include:

Furthermore, the functional member having the in-plane oriented polymeric thin film of the present invention is
Compared to the conventional method of producing an in-plane alignment film on an inorganic substrate, not only are the film materials and properties different, but the method also simplifies the process by requiring only one deposition, whereas the conventional method required two depositions. be.

Furthermore, when an organic substrate is rubbed, scratches are inevitably generated due to its softness, and if the alignment film is thin, the surface of the alignment film becomes rough. In this regard, the method of the present invention is characterized in that an alignment film with a smooth surface can be obtained since it can be produced on an inorganic substrate.

Furthermore, although the present invention was carried out using basic monomers, if a functional substituent, such as a dye or a polar group, is introduced into the monomer and a polymer film is prepared, polarizers, ferroelectric materials, and nonlinear photon materials can be used. It is thought that molecular alignment films can also be realized.

[Description of the Second Invention] The second invention is a method suitable for producing a functional member having the in-plane oriented polymeric thin film of the first invention.

Tamanushi R plate 0 times roasted In addition to the above objects, the invention has the following objects.

Another object of the second invention is to provide a method for easily obtaining a functional member having a polymeric thin film that is homogeneous and has excellent in-plane orientation.

Constitution of the Second Invention The method for manufacturing a functional member having an in-plane oriented polymeric thin film according to the second invention includes a step of rubbing the surface of a substrate to impart in-plane anisotropy to the surface layer of the substrate; A substrate imparted with internal anisotropy is placed in a vacuum evaporation apparatus, and two or more types of monomers that cause a polyaddition reaction or a polycondensation reaction excluding ring-opening polymerization are simultaneously vapor-deposited on the surface of the substrate to form a surface layer of the substrate. The method is characterized by comprising a polymeric thin film forming step of forming an in-plane oriented polymeric film by transmitting information on in-plane anisotropy formed in the deposited film to the surface of the vapor-deposited film.

! The mechanism by which the method for manufacturing a functional member having an in-plane oriented polymeric thin film of the second invention produces the effects is not necessarily clear yet, but it is thought to be as follows.

Since a substrate usually does not have in-plane orientation, the surface of the substrate is subjected to a rubbing treatment in order to achieve in-plane anisotropy, particularly anisotropy in the direction of organic substance adsorption.

This makes it possible to impart anisotropy to virtually all types of substrates, preferably inorganic substrates. The substrate is placed in a vacuum device so that organic gas can be easily adsorbed and desorbed. When two or more types of monomers that cause polyaddition reactions or condensation reactions other than ring-opening polymerization are deposited under vacuum, a polymer film in which each monomer is alternately bonded can be formed on the solid surface. At this time, since the substrate has in-plane anisotropy, anisotropy occurs in the direction of monomer adsorption, and the anisotropically adsorbed monomer reacts and polymerizes with another type of monomer, resulting in in-plane anisotropy. A polymer having orientation will be produced. In this way, the substrate surface is directly covered with a polymer having in-plane orientation.

Next, since the polymer film has anisotropy that reflects the information of the substrate, the monomer is adsorbed in a manner that reflects that anisotropy.
It is possible to form a polymer thin film in a state in which information about the substrate is transmitted to the film surface through polymerization, that is, in a state in which the entire polymer film has in-plane orientation.

At this time, if the polymer is not a rigid molecule but has high flexibility, the orientation will be disturbed until it reaches the membrane surface, resulting in a random structure. In addition, in the process of adsorption of monomers onto polymers and polymerization, hydrogen bonds are formed with polymer chains, etc.
It is also necessary that the interaction between the polymer and the monomer be large so that the directionality of adsorption can be determined. In this respect, condensation polymerization,
Polyaddition polymers have polar groups such as carbonyl groups, amino groups, and amide groups in monomers and polymers, so they have hydrogen bonding ability and are rigid polymers, so they can be polymerized with in-plane anisotropy. This means that a membrane can be produced. Polymer reactions include polycondensation, polyaddition, ring-opening polymerization, and high polymerization. Normally, activation is required to cause a polymerization reaction, so
Except for cases where solid phase polymerization occurs as in the conventional vapor deposition in-plane orientation method, condensation polymerization and polyaddition reactions, which are highly reactive and do not require initiators such as radicals and ionic species, are the main methods that can be polymerized by vapor deposition. This is a reaction. Since rigidity is required to achieve in-plane orientation, when producing a polymer film using vapor deposition in-plane orientation using the conventional technique, the target object is a π-conjugated polymer, that is, a so-called conductive polymer. It must be. On the other hand, polycondensation and polyaddition polymers are insulative and can provide alignment films with properties completely different from those of conventional methods.

Effects of the Second Invention By the method for manufacturing a functional member having an in-plane oriented polymeric thin film according to the second invention, a functional member having a homogeneous polymeric thin film with excellent in-plane orientation can be easily obtained.

Further, by the method of the second invention, a film having in-plane anisotropy formed directly on a substrate can be provided.

In the conventional method, there was no technology to directly form an alignment film of polycondensation or polyaddition polymer having high strength, high heat resistance, and high insulation property on a substrate, but it is now possible with the method of the second invention. became.

Furthermore, since the method of the second invention enables the production of an in-plane alignment film directly on an inorganic substrate, a single vapor deposition process is required, thereby simplifying the process. In other words, in order to produce an alignment film using conventional methods, two methods are used: one is to rub an organic substrate, and the other is to rub a substrate that has been vapor-deposited to leave crystals with uniform orientation, and then vapor-deposit them again. However, the former method is not an inorganic substrate and is scratched by rubbing, so there is a risk that the surface of the alignment film may become rough, and the latter method requires vapor deposition twice, resulting in poor workability. In contrast, the method of the second invention eliminates these drawbacks of the prior art by making it possible to produce an in-plane alignment film by directly forming it on an inorganic substrate.

Further, by the method of the second invention, the processing area of the substrate is wide, and a uniform large-area polymer film can be produced.

Therefore, the present invention can be said to be an excellent method in that it can take advantage of this advantage and provide in-plane orientation.

[Description of other inventions of the second invention] Below, other inventions of the second invention will be described.

In the method of manufacturing a functional member having an in-plane oriented polymeric thin film according to the present invention, first, the surface of a substrate is subjected to a rubbing treatment to impart in-plane anisotropy to the surface layer of the substrate (in-plane anisotropy imparting step).

The substrate is a means for holding/transmitting in-plane orientation information imparted with in-plane anisotropy, which is information for controlling and determining the in-plane orientation of a functional member having an oriented polymeric thin film. There are no particular limitations as long as the material satisfies the following. Specific examples include various crystals, insulators such as glass and quartz, semiconductors such as silicon, transparent electrodes such as indium tin oxide and tin oxide, and inorganic materials made of inorganic substances such as metals such as aluminum and gold. It will be done. Among these, those that are not damaged in the step of imparting in-plane anisotropy are preferred. A polymer material can be used similarly as an organic material made of an organic substance, but in this case, it is necessary to use a material that is difficult to scratch when imparting in-plane anisotropy, and the critical surface tension of the polymer material to impart anisotropy. It is necessary that the critical surface tension of the material is significantly different from the critical surface tension of the material.

The structure of the substrate is not particularly limited, and may be a single structure or a laminated structure in which an electrode or an insulating layer is coated on an organic or inorganic support material by vapor deposition, sputtering, wet film formation, etc. .

The shape of the substrate is usually flat, but is not limited to this, and may be cylindrical, spherical, or wavy.

The smoothness of the substrate may be such that in-plane anisotropy can be imparted to the entire surface. Regarding thickness, surface condition is important;
It is not limited. Regarding the surface condition of the substrate,
It is necessary to have in-plane anisotropy, and special materials such as single crystals can be used, but it is preferable to rub the substrate in one direction with a polymer material and partially adhere the polymer. .

Further, a substrate having fine grooves or a composition distribution formed in one direction on the substrate surface by oblique vapor deposition or the like can be used.

The material of the rubbing material used in the rubbing process is preferably an organic material because the rubbing material needs to slightly adhere to the substrate surface. In particular, it is more desirable to use a polymeric material because anisotropy will not be imparted substantially if it volatilizes or melts under the film forming conditions. Among polymer materials, it depends on the combination with the substrate and the affinity with the monomer. Although it is difficult to generalize, hydrophilic polymer materials that are expected to have high monomer adsorption ability or adsorption with the substrate Hydrophobic polymeric materials with large differences in performance can be used. In particular, a hydrophilic polymer material with a critical surface tension of 356 dyn/am or more or a hydrophobic polymer material with a critical surface tension of 20 dyn/am or less is suitable. Specifically, hydrophilic polymer materials include polyacrylonitrile, cotton, polyacrylic acid, hydroxymethyl methacrylic acid, polyvinyl alcohol, polyamide, polyacrylamide, etc., and hydrophobic polymer materials include polytetrafluoroethylene. . In addition, even in the middle, although the orientation is inferior to the above hydrophilic polymer materials and hydrophobic polymer materials,
It may exhibit some degree of orientation, and can be selected as appropriate depending on the required properties.

Further, the rubbing treatment does not need to be performed on the entire surface of the substrate, and may be performed only on the portion where the alignment film is desired to be formed. Moreover, the shape of the rubbing material may be any shape, such as fibrous, film, or block.

It is thought that by rubbing with a polymeric material, the polymeric material is partially attached to the substrate surface in a linear manner.

Based on this information, an oriented polymer film is formed on the entire surface of the substrate, so the entire surface of the substrate is not covered with a polymer rubbing material. Therefore, the polymer film is formed in close contact with the substrate. Further, the number of times of rubbing is not limited, and it is usually sufficient to perform the rubbing several times to several thousand times. Furthermore, the direction of rubbing must always be parallel, and any deviation will naturally disrupt the orientation of the polymer film. In addition to rubbing the entire substrate in the same direction, we can also change the rubbing direction of only a part of the substrate, change the orientation of the polymer film, or rub it in a curved shape.
It is also possible to obtain an alignment film that conforms to this.

Next, the substrate imparted with the in-plane anisotropy is placed in a vacuum evaporation apparatus, and two or more types of monomers that cause a polyaddition reaction or a polycondensation reaction excluding ring-opening polymerization are simultaneously evaporated onto the surface of the substrate. Then, information about the in-plane anisotropy formed on the surface layer of the substrate is transmitted to the surface of the deposited film, thereby forming an in-plane oriented polymer film (polymerized thin film forming step).

The monomers used here are two or more types of monomers that cause polyaddition or polycondensation reactions other than ring-opening polymerization. Specifically, difunctional acid chlorides such as terephthalic acid chloride and sebacic acid chloride, diisocyanate compounds such as phenyl diisocyanate and methylene diisocyanate, dialdehyde compounds such as terephthalaldehyde, and decamethylene diamine, hexamenediamine, etc. fatty acid diamine, paraphenylenediamine, 4゜4
゛-One type of aromatic diamine such as diaminodiphenyl ether is used. In addition, when producing polyurethane, diisocyanate and parahydroxyphenol,
Examples include ethylene glycol-based difunctional alcohols, and in the case of producing polyester, difunctional acid chlorides and difunctional alcohols. Furthermore, in addition to the above-mentioned monomers, derivatives obtained by substituting polar groups such as nitro groups or functional groups such as dyes on these monomers may be used within the range that does not inhibit the polymerization reaction.

Note that the directionality of monomer adsorption must be determined according to the in-plane anisotropy imparted to the substrate at the initial stage of polymerization, and according to the anisotropy of the polymerized film thereafter.

Therefore, when the polymerization rate is high, molecules adsorbed in random directions may be involved in the polymerization.

In this case, the monomer supply determines the polymerization rate. In order to develop in-plane anisotropy, it is necessary to conduct polymerization in a state where monomer adsorption and desorption are occurring vigorously, rather than being rate-limited by monomer supply. This is because monomers that are adsorbed in a more stable state have a longer adsorption lifetime (adsorption time) and are more likely to participate in the polymerization reaction, whereas monomers that are adsorbed in an unstable direction have a longer lifetime. This is because it is short and cannot participate in the polymerization reaction. Therefore, the molecules adsorbed in a stable state, that is, in this case, in a state according to the anisotropy of the substrate and the anisotropy of the polymeric film, participate in the reaction and can achieve in-plane orientation. Methods for reducing the amount of monomer adsorption include increasing the substrate temperature or decreasing the partial pressure.

In this polymerized thin film forming step, in order to obtain an in-plane oriented film, the substrate temperature may be raised and the polymerization rate may be made slower than the rate-determining rate of monomer supply. However, if the temperature is too high, the polymerization rate will drop significantly, which is not practical. Its temperature range is
Since it cannot be determined based on polymerization and adsorption properties, we measured the relationship between the polymerization rate and substrate temperature for each monomer series, and determined the temperature above which the polymerization rate does not change much even if the substrate temperature is lowered (monomer supply). It is necessary to determine the rate-determining temperature), and it is preferable to set the substrate temperature higher than the monomer supply rate-determining temperature.

On the other hand, under certain monomer supply conditions, even at the temperature that determines the monomer supply rate, when monomer supply I is reduced, that is, when the monomer partial pressure of the system is lowered, the amount of monomer adsorption decreases.
Since adsorption and desorption occur vigorously, this temperature can be suitable.

In this case as well, conditions cannot be specified depending on polymerization and adsorption properties. Therefore, similarly to the above, the temperature range that determines the rate of monomer supply must be determined for each supply condition, and the temperature must be determined. However, the trend is that when it is desired to lower the substrate temperature and produce an alignment film, it is necessary to lower the monomer supply, that is, the monomer partial pressure. In addition, if one of the monomers has poor volatility, it is necessary to determine the substrate temperature and monomer supply amount while increasing the amount of the highly volatile monomer and decreasing the amount of the less volatile monomer. If the volatility of both monomers is poor, the adsorptivity will increase, so naturally it is necessary to raise the substrate temperature or reduce the monomer supply amount to satisfy the above conditions.

The polymer film produced as described above is a polymer film that transmits substrate information to the film surface. In addition, it is also possible to simultaneously vapor-deposit other molecules, such as a dye, separately from the monomer to achieve both the dye orientation and the orientation of the polymer film, or to use two or more types of monomers and It is also possible to fabricate an alignment film in which each of these is contained in a polymer molecule.

〔Example〕

The present invention will be explained in detail below.

A silicon wafer, indium tin oxide transparent electrode coated glass, and glass are used as a substrate on a large dust tray, and after a rubbing process is performed, a polymer film is formed on the treated surface of the substrate by vapor deposition process. A functional component having an oriented polymerized thin film was produced, and a performance evaluation test of the functional component was conducted.

First, a 2 cm x 2, 5 cm silicon wafer, indium tin oxide transparent electrode coated glass (hereinafter referred to as ITO), and glass were prepared as substrates, and one side of the substrate was coated with a polytetrafluoroethylene plate (critical surface tension 18 .5 dyn/cm ) was rubbed 50 times in one direction to impart in-plane anisotropy. At this time, blow on the part of the substrate to which in-plane anisotropy has been imparted, and confirm that in-plane anisotropy has been imparted to the rubbed surface of the substrate by checking that there is anisotropy in the way the substrate is clouded. did.

Next, these substrates are placed in a vacuum device, and a heater is used to heat them.
While heating and maintaining at 2 to 65°C, heat at 1×1°5 Torr (
(measured using an ion gauge).

Next, with the shutters closed, the two monomer containers containing terephthalic acid chloride and decamethylene diamine, which were installed in a position facing the substrate arranged in the vacuum device, were placed in a position facing the substrate, and the terephthalic acid chloride container was 45
The containers of decamethylene diamine were heated to 55-75°C, respectively.

Next, while keeping the substrate and monomer container temperatures at the above temperatures, the shutter of the decamethylene diamine container was fully opened, and the terephthalic acid chloride container was partially opened.
The degree of opening and closing of the shutter of the terephthalic acid chloride container was finely adjusted so that the pressure inside the vacuum device was 5×1 O −5 Torr or less. Note that no matter which shutter was closed, an increase in pressure was observed when one of the shutters was open. Since the pressure fluctuates over time, the shutter of the terephthalic acid chloride container was finely adjusted every 10 to 30 minutes so that the pressure was at its lowest level (below 5 x 10" Torr at the beginning of film formation, and below 2 x 10" Torr thereafter). . In this state, 2-hour open film formation was performed to form a polymer film having a thickness of approximately 6000 on the substrate, thereby obtaining the functional member of this example.

A performance evaluation test of this functional member was conducted by measuring transmission IR spectrum and evaluating in-plane orientation.

The transmission IR spectrum of a polymer film formed on a silicon wafer was measured using polarized light parallel and perpendicular to the rubbing direction under conditions of normal incidence on the substrate. The result is
Shown in Figure 1. In the figure, "ll" and "12" are the polarized IR spectra of the polymer film, "ll" is the spectrum obtained with polarized light perpendicular to the rubbing direction, "12" is the spectrum obtained with polarized light parallel to the rubbing direction, and "13" is the spectrum obtained with polarized light parallel to the rubbing direction. The difference spectra, that is, (polarized IR spectrum perpendicular to the rubbing direction) - (polarized IR spectrum parallel to the rubbing direction) are shown, respectively. From FIG. 1, it was found from these spectra that the polymer film had the structure of a polyamide film. Furthermore, as is clear from this difference spectrum, dichroism is observed, and the absorption of the carbonyl group in the direction perpendicular to the rubbing direction (1635 cm-') is strong, so the main chain of the polyamide polymer is parallel to the rubbing direction. It was found that it was oriented. From this, it was confirmed that an in-plane oriented polyamide film that reflected the rubbing information of the substrate could be produced.

In addition, for those using ITO and glass as substrates, the in-plane orientation of the polymerized film, particularly the in-plane orientation of the film surface, was evaluated based on the presence or absence of liquid crystal alignment ability.

Two substrates each having a polymeric film formed thereon were stacked one on top of the other with the polymeric film facing the inner surface and the rubbing directions parallel to each other to produce a liquid crystal cell with an interval between the polymeric films of 10 μm. This cell is kept at a temperature above the clear point (1008C), and a guest-host type liquid crystal (host liquid crystal: Merck ZLI-
1840, Dye 2 Mitsubishi Kasei (black dichroic dye, which is a mixture of several anthraquinone-based azo-based dyes) was sealed. After cooling to room temperature, the alignment of the liquid crystal was observed using a polarizer.

As a result, it was found that the orientation was parallel to the rubbing direction of the substrate, and it was found that an in-plane oriented polyamide film in which substrate information was transmitted to the surface of the polymerized film had been produced.

Polyacrylonitrile (critical surface tension 44 dyn
/cm ), and absorbent cotton (critical surface tension 44 dy
n/am), and other conditions were the same as in Example 1, a polyamide film was formed on the substrate to obtain the functional member of this example.

The polarized IR spectrum of the obtained functional member polymer film was measured in the same manner as in Example 1. The difference spectrum obtained as a result is shown in FIG. In the figure, "21" indicates the results when polyacrylonitrile was used as the rubbing material (Example 2), and "31" indicates the results when absorbent cotton was used as the rubbing material (Example 3). Second
As is clear from the figure, it was found that when polyacrylonitrile was used as the rubbing material, an in-plane oriented polyamide film in which the polyamide polymer chains were oriented parallel to the rubbing direction was obtained as in Example 1. In addition, when absorbent cotton is used as a rubbing material, dichroism is observed, contrary to polyacrylonitrile, so it is possible to obtain an in-plane oriented polyamide film in which polyamide polymer chains are oriented perpendicular to the rubbing direction. I found out that there is.

Next, the liquid crystal alignment ability was measured in the same manner as in Example 1, and it was found that in the case of polyacrylonitrile, the liquid crystal was aligned parallel to the rubbing direction, and in the case of absorbent cotton, the liquid crystal was aligned perpendicular to the rubbing direction.

From the above, it was found that although the orientation direction differs depending on the rubbing material, a polymer film with in-plane anisotropy that transmitted the information of in-plane anisotropy imparted to the substrate to the polymer film surface was fabricated. .

Examples 4 to 6 As a rubbing material, instead of polytetrafluoroethylene, polyhydroxyethyl methacrylate plate (critical surface tension: 40 dyn/cm or more: Example 4), polyvinyl alcohol sheet (critical surface tension: 37 dyn/cm: Example) 5) and filamentous polyacrylic acid (critical surface tension 35 dyn/cm: Example 6), and a polyamide film was formed on the substrate in the same manner as in Example 1, except that only a glass substrate was used as the substrate. was formed to obtain the functional member of this example.

Regarding the obtained functional member, in the same manner as in Example 1, the in-plane orientation of the polymer film, particularly the in-plane orientation of the film surface, was evaluated based on the presence or absence of liquid crystal alignment ability. As a result, it was found that when a polyhydroxyethyl methacrylate plate and a polyvinyl alcohol sheet were used as the rubbing material, the liquid crystal was oriented parallel to the rubbing direction, and when polyacrylic acid was used, the liquid crystal was oriented perpendicular to the rubbing direction.

From the above, it was found that although the orientation direction differs depending on the rubbing material, a polyamide polymer film with in-plane anisotropy was obtained that transmitted information on the in-plane anisotropy imparted to the substrate to the polymer film surface. Ta.

Comparative Examples 1 to 4 As a rubbing material, polypropylene thread (critical surface tension 29 dyn/c) was used instead of polytetrafluoroethylene.
m: Comparative Example 1), 5-polyvinylidene fluoride plate (critical surface tension 25 dyn/am: Comparative Example-2), and polystyrene plate (critical surface tension 33 dyn/Cm: Comparative Example 3), or rubbing treatment. I didn't do it (
Comparative Example 4) A polyamide film was formed on a substrate under the same conditions as in Example 1 except for Comparative Example 4) to obtain a comparative member as this comparative example.

The polarized IR spectrum of the obtained comparative member was measured in the same manner as in Example 1. As a result, no dichroism was observed in the difference spectrum of the polarized IR spectra for each film, and when the liquid crystal alignment ability was measured in the same manner as in Example 1, no liquid crystal alignment ability was observed.

From Examples 1 to 6 and Comparative Examples 1 to 4, orientation cannot be obtained without using a rubbing material, and the rubbing material used is either hydrophilic (high critical surface tension) or hydrophobic (critical surface tension tJ It can be seen that a rubbing material with strong resistance is suitable for imparting in-plane anisotropy to the substrate.

Comparative Examples 5 to 7 Using the same rubbing material and substrate as in Examples 1 to 3, the substrate was coated in the same manner as in Example 1 except that the substrate temperature was room temperature (25°C) and the vapor deposition time was 30 minutes. A polyamide film was formed to obtain a comparative member as this comparative example. The thickness of the polyamide polymer film formed on the surface of the obtained comparison member was about 5,000. No dichroism was observed in the difference spectra of the polarized IR spectra of these polymer films, and no liquid crystal alignment ability was observed. From this, it was found that an in-plane oriented film could not be obtained when the polymerization rate was high, that is, under conditions where the substrate temperature was low and monomer supply was rate-limiting.

Comparative Example 8 Results of attempting to fabricate a polyamide film on a substrate in the same manner as in Example 1, using the same rubbing material and substrate as in Example 1, except that the substrate temperature was 80°C and the vapor deposition time was 4 hours. It was found that no polymeric film was formed on the substrate.

From the results of Comparative Examples 5 to 8, it was found that there is an appropriate range of substrate temperature, and that it is necessary to set the substrate temperature higher than the monomer supply rate-limiting conditions and within a temperature range in which polymerization proceeds.

Comparative Example 9 Using a polyimide film formed by a wet method as a substrate,
A polyamide film was formed on a substrate under the same conditions as in Example 1, except that the polyimide film was rubbed with a nylon brush, and a comparative member as this comparative example was obtained. The polymer film on the surface of this comparative member did not exhibit liquid crystal alignment ability. From this, it was found that an inorganic substrate is suitable for the substrate.

Example 7 Using paraphenylene diamine instead of decamethylene diamine as a monomer, the substrate temperature was varied from 50°C to 35°C.
While cooling the temperature to ℃ over 1 hour and keeping it at that temperature for 2 hours,
The temperature of the paraphenylene diamine container is 758C to 85C.
By adjusting the shutter of the terephthalic acid chloride container with the shutter of the para-phenylenediamine container fully open, the amount of terephthalic acid chloride supplied is in excess of the amount of para-phenylenediamine supplied. The pressure during membrane polymerization was 5 to 10 x 1O-5 Torr.
The functional member of this example was produced in the same manner as in Example 3 except that the capping process was carried out for 3 hours while maintaining the temperature at r. In addition,
Excess supply of terephthalyl chloride means that
It was confirmed that when the supply amount was reduced at an appropriate time, that is, when the shutter was slightly closed, the pressure decreased, and when the shutter of the paraphenylenediamine container was closed, the pressure monotonically increased, and when it was opened again, the pressure decreased monotonically.

When the performance evaluation test of the polymer film formed on the surface of this functional member was carried out by IR spectrum measurement in the same manner as in Example 1, it was found that the polymer film was an aromatic polyamide film. Furthermore, the polarized IR spectrum was measured in the same manner as in Example 1. The results are shown in FIG. In the same figure, "71"
and “72” is the polarized IR spectrum of the polymer film, “
71'' indicates a spectrum obtained by polarization perpendicular to the rubbing direction, ``72'' indicates a spectrum obtained by polarization parallel to the rubbing direction, and ``73'' indicates a difference spectrum thereof. Carbonyl group absorption (1650 cm''-') is not observed at all in the polarized spectrum parallel to the rubbing direction, but is observed in the vertically polarized spectrum and the difference spectrum, indicating almost perfect in-plane orientation. It was also confirmed that the in-plane orientation of the aromatic polyamide film was such that even when absorbent cotton was used as the rubbing material, the polymer chains were oriented parallel to the rubbing direction.

In addition, the birefringence of polymer films prepared on ITO substrates and glass substrates was measured by sandwiching the substrate between polarizers made of orthogonal Nicols and rotating the substrate. As a result, it was very dark when the rubbing direction was parallel to one of the polarizers, and became brightest when the rubbing direction was at an angle of 45 degrees, confirming birefringence. From this, the aromatic polyamide membrane is
It can be seen that it is very highly oriented in the rubbing direction.

Further, as in Example 1, the in-plane orientation of the polymerized film, particularly the in-plane orientation of the film surface, was evaluated based on the presence or absence of liquid crystal alignment ability. As a result, it was found that the liquid crystal was oriented parallel to the rubbing direction.

From the above, it has been found that a highly oriented aromatic polyamide film that transmits information from the substrate to the film surface can be obtained on a substrate that has been rubbed with absorbent cotton to impart in-plane anisotropy.

Example 8 Example 7 except that the substrate temperature is room temperature (25°C)
In the same manner as above, an aromatic polyamide film was produced by vapor deposition for 1 hour. The results of polarized IR spectrum measurement of the obtained polymer film are shown in FIG.

In the figure, "81" and "82" indicate the polarized IR of the polymer film.
In the spectrum, "81" is polarized light perpendicular to the rubbing direction, "
82'' is a spectrum obtained by polarization parallel to the rubbing direction, and ``83'' is a difference spectrum thereof. Since absorption of carbonyl groups (1650 cm-') is slightly observed even in the polarized light spectrum parallel to the rubbing direction, although it has high orientation, it is found that the orientation is slightly inferior compared to Example 7. I understand. From this, it can be seen that the higher the substrate temperature, the better. Furthermore, when the liquid crystal orientation was measured in the same manner as in Example 1, it was found that the liquid crystal was oriented parallel to the rubbing direction, and a highly oriented aromatic polyamide film was obtained that transmitted information from the substrate to the film surface. Ta. Note that when the substrate temperature is 50° C. or higher, no polymer film is formed. Further, in the polyamide films of Comparative Examples 5 to 7, no alignment film was obtained at room temperature. In the case of monomers with low reactivity such as para-phenylene diamine in this example, the adsorption time for adsorbed species is long (otherwise they cannot participate in the polymerization reaction, so the temperature that determines the rate of monomer supply is low, below room temperature, and However, it is thought that an in-plane oriented film can be obtained.

Example 9 A polyamide polymer membrane was produced in the same manner as in Example 7 except that polyacrylonitrile thread was used instead of absorbent cotton as the rubbing material. The difference spectrum of the polarized IR spectrum of the obtained polymer film is shown in FIG. 5 ("91"). As a result, IR dichroism was confirmed. Furthermore, as a result of a birefringence measurement test, birefringence was confirmed, although it was somewhat uneven, and it was found that there was in-plane orientation (the main chain is parallel to the rubbing direction). Furthermore, as a result of measuring the liquid crystal alignment ability in the same manner as in Example 1, it was found that the liquid crystal was aligned parallel to the rubbing direction. From these results, it was found that an in-plane oriented film was obtained in which information on in-plane anisotropy due to substrate rubbing was transmitted to the film surface.

Examples 1O and 11 Polyamide polymer membranes were produced in the same manner as in Example 7 except that polyacrylic acid (Example 10) and polytetrafluoroethylene (Example 11) were used as rubbing materials instead of absorbent cotton. A performance evaluation test of the obtained polymeric film was conducted by a birefringence measurement test and a liquid crystal alignment ability measurement test. The results of the birefringence measurement test showed that there was in-plane orientation, and the results of the liquid crystal alignment ability measurement test showed that the liquid crystal was aligned parallel to the rubbing direction. From this, it was found that an aromatic polyamide film was obtained in which information on in-plane anisotropy due to rubbing of the substrate was transmitted to the film surface.

Examples 12 and 13 Polyacrylonitrile as rubbing material (Example 12)
and polyvinylidene fluoride (Example 13), and under the same conditions as in Example 8 above, a polymer film was produced by vapor deposition polymerization for 1 hour on a silicone wafer. The polarized IR spectrum of the obtained polymer film was measured, and the difference spectrum was obtained, and the results are shown in FIG. In the same figure, r
121'' shows the results using polyacrylonitrile as the rubbing material, and r131'' shows the results using polyvinylidene fluoride as the rubbing material. Since dichroism was confirmed, it was found that an aromatic polyamide film in which the main chains were oriented parallel to the rubbing direction was obtained. An oriented film could not be obtained with the polyamide film of Comparative Example 2 (using polyvinylidene fluoride), whereas an aromatic polyamide film had a surface with a high degree of orientation even with polyvinylidene fluoride, although the degree of orientation was inferior to that of polyacrylonitrile. It can be seen that an internally oriented film can be obtained.

Comparative Examples 9 and 10 Aromatic polyamide films were produced on silicone wafers under the same conditions as in Example 8, except that polystyrene plates and polypropylene threads were used as rubbing materials (Comparative Examples 9 and 10).
. FIG. 6 shows the difference spectrum as a result of measuring the polarized IR spectrum of the obtained polymer film. In the same figure, "C91J indicates Comparative Example 9, and rclolJ indicates Comparative Example 10. From the test results of this Comparative Example, the dichroism is small compared to the polymerized films of Examples 12 and 13, and the orientation is considerably It was found that Comparative Example 1 was inferior.
The polyamide films of Comparative Examples 9 and 3 did not show any in-plane orientation, whereas Comparative Examples 9 and IO slightly showed in-plane orientation, so depending on the monomer, the rubbing material may be hydrophilic. Those with intermediate hydrophobic properties (critical surface tension 35 dyn/cm >> 20 dyn
It can be seen that a certain degree of orientation can be achieved even by using ./cm). However, the degree of orientation is higher when a rubbing material with high hydrophilicity or hydrophobicity is used, and slightly inferior when a rubbing material with high hydrophilicity or hydrophobicity is used.

An aromatic polyamide membrane was produced in the same manner as in Example 8, except that rubbing with the soil on the plate was not performed. As a result of measuring the polarized IR spectrum of this film, no dichroism was observed and it was found that there was no orientation.

Set the temperature of the upper substrate of Satoaki Plate Doshuji 1 to 73 to 77°C, use pyromellitic dianhydride instead of terephthalic acid chloride, keep the container of pyromellitic dianhydride at 200 to 220°C, and vacuum The pressure during vapor deposition inside the container is 4 to 20 x 10-5 Torr.
A polymer film was produced on a substrate under the same conditions as Examples 1 to 6 and Comparative Examples 1 to 4 except that r was used. From the IR measurement results of the obtained films, it was found that all of these films were made of polyamic acid (polyimide precursor). Furthermore, as a result of measuring the liquid crystal alignment ability of these films by polarized light IR measurement, it was found that none of them had in-plane alignment.

Furthermore, these films were kept at 200° C. for 30 minutes to imidize them. From the IR measurement results of the obtained films, it was confirmed that all of these films had an imide structure. Furthermore, as a result of measuring the liquid crystal alignment ability of the polyimide film using polarized light IR measurement, it was found that the polyimide film did not have in-plane alignment in any case.

Comparative Examples 22 to 31 The substrate temperature was set to 35 to 36°C, paraphenylenediamine was used instead of decamethylene diamine, the paraphenylenediamine container was kept at 70 to 80°C, and the temperature of the pyromellitic dianhydride container was A polymer film was produced on the substrate in the same manner as Comparative Examples 12 to 21 by fully opening the shutter and finely adjusting the degree of opening and closing of the shutter of the paraphenylenediamine container.

From the IR measurement results of the obtained films, it was found that all of these films were made of polyamic acid (polyimide precursor). Furthermore, as a result of measuring the liquid crystal alignment ability of these films by polarized light IR measurement, it was found that none of them had in-plane alignment.

Furthermore, these films were kept at 200° C. for 30 minutes to imidize them. From the IR measurement results of the obtained films, it was confirmed that all of these films had an imide structure. Furthermore, as a result of measuring the liquid crystal alignment ability of the polyimide film using polarized light IR measurement, it was found that the polyimide film did not have in-plane alignment in any case.

As mentioned above, from the comparative test results of Comparative Examples 12 to 31, it was found that even in a polyaddition reaction, an in-plane oriented film could not be obtained with a ring-opening polymer accompanied by a ring-opening reaction of an acid-inorganic substance.

[Brief explanation of drawings]

Figure 1 shows the polarized IR of the in-plane oriented polymer film obtained in Example 1.
A diagram showing a spectrum and its difference spectrum (polarized spectrum perpendicular to the rubbing direction - polarized spectrum parallel to the rubbing direction),
FIG. 2 is a diagram showing the difference spectrum of the polarized IR spectra of the in-plane oriented polymer films obtained in Example 2 and Example 3;
Figure 3 shows the polarized IR of the in-plane oriented polymer film obtained in Example 7.
4 is a diagram showing the polarized IR spectrum and the difference spectrum of the in-plane oriented polymer film obtained in Example 8. FIG. 5 is a diagram showing the spectrum and the difference spectrum. A diagram showing the difference spectrum of polarized IR spectra of in-plane oriented polymer films, FIG. 6 is for Examples 12 and 1.
3. Polarized light I of polymer films obtained in Comparative Examples C9 and C1O
FIG. 3 is a diagram showing a difference spectrum of R spectra. 1 2 7.7 8.8 21 31 91 l01 2.13 ...Example 1 ...Example 2 ...Example 3 2.73 ...Example 7 2.83 ...Example 8...Example 9...Example 12...Example 13...Comparative example C9...Comparative example CIO

Claims (2)

[Claims] (1) A substrate having in-plane anisotropy at least on the surface, and information on the in-plane anisotropy formed directly on the in-plane anisotropic part of the substrate, and formed in the in-plane anisotropic part of the substrate. A polymer film consisting of a polyaddition polymer film or a condensation polymer film, excluding ring-opening polymers, which is formed by transferring the polymer main chain or functional group to the film surface with in-plane anisotropy. A functional component having an in-plane oriented polymeric thin film, comprising: (2) a step of rubbing the surface of the substrate to impart in-plane anisotropy to the surface layer of the substrate; placing the substrate imparted with the in-plane anisotropy in a vacuum evaporation device; By simultaneously depositing two or more monomers that cause polyaddition reactions or condensation polymerization reactions excluding ring-opening polymerization,
an in-plane polymer film forming step of forming a polymer film oriented in-plane by transmitting information about the in-plane anisotropy formed on the surface layer of the substrate to the surface of the deposited film; A method for producing a functional component having an oriented polymerized thin film.