CN103959152B - Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention provides a method for manufacturing a liquid crystal alignment film capable of efficiently introducing anisotropy into a film without rubbing, and provides a liquid crystal alignment film and a liquid crystal display element. The manufacturing method of the liquid crystal aligning film comprises: [I] the operation of forming on the substrate the photosensitive side chain type polymer film that embodies liquid crystallinity in the specified temperature range; A step of irradiating polarized ultraviolet rays; and [III] a step of heating the side chain type polymer film irradiated by said ultraviolet rays; it is characterized in that the ultraviolet irradiation amount of the [II] step reaches 1% of the maximum ultraviolet irradiation amount at ΔA In the range of ~70%, ΔA is the difference between the ultraviolet absorbance of the side chain type polymer film in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays .

Description

Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element

technical field

The present invention relates to a method for manufacturing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element, in particular to a method for manufacturing a liquid crystal alignment film used in a liquid crystal display element, a liquid crystal alignment film obtained by the manufacturing method, and a liquid crystal alignment film using the liquid crystal alignment film. Film liquid crystal display element.

Background technique

Liquid crystal display elements are well known as light-weight, thin, and low-power-consumption display devices, and in recent years they have been used in large-scale television sets and the like, and have achieved remarkable development. The liquid crystal display element is constituted, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates having electrodes. Then, in a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal aligning film in order to make a liquid crystal in a desired alignment state between substrates.

That is, the liquid crystal aligning film is a constituent member of the liquid crystal display element, and is formed on the surfaces of the substrates sandwiching the liquid crystal that are in contact with the liquid crystal, and functions to align the liquid crystal in a certain direction between the substrates. Therefore, in addition to the function of orienting the liquid crystal in a certain direction such as a direction parallel to the substrate, the liquid crystal aligning film may also require the function of controlling the pretilt angle of the liquid crystal. The ability (henceforth orientation control ability) of such a liquid crystal aligning film to control the liquid crystal orientation is provided by performing an orientation process to the organic film which comprises a liquid crystal aligning film.

Conventionally, a rubbing method is known as an orientation processing method for the liquid crystal aligning film for providing orientation control ability. The rubbing method refers to the following method: For organic films such as polyvinyl alcohol, polyamide, and polyimide on the substrate, wipe (rub) the surface with cotton, nylon, polyester, etc. in a certain direction, so that the liquid crystal faces The direction of wiping (rubbing direction) is oriented. This rubbing method can easily realize a relatively stable liquid crystal alignment state, so it has always been used in the existing manufacturing process of liquid crystal display elements. Then, as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and electric characteristic is conventionally mainly selected.

However, in the rubbing method which rubs the liquid crystal aligning film surface which consists of polyimide etc., generation|occurrence|production of dust and static electricity may become a problem. In addition, due to the high-definition of liquid crystal display elements in recent years, the unevenness caused by the electrodes on the corresponding substrate or the switching active elements for liquid crystal driving, it is sometimes impossible to rub the surface of the liquid crystal alignment film uniformly with a cloth, and it is impossible to Achieve uniform liquid crystal alignment.

Then, as another orientation treatment method of the liquid crystal aligning film which does not perform rubbing, many studies have been conducted on the photo-alignment method.

There are various photo-alignment methods, but all of them use linearly polarized light or collimated light to form anisotropy in the organic film constituting the liquid crystal alignment film, and align the liquid crystal along the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays to cause anisotropic decomposition using the polarization direction dependence of ultraviolet absorption of molecular structure. Then, the liquid crystal is aligned by the polyimide which remains without decomposing (refer patent document 1).

In addition, photo-crosslinking-type or photo-isomerization-type photo-alignment methods are also known. For example, when polarized ultraviolet rays are irradiated using polyvinyl cinnamate, a dimerization reaction (crosslinking reaction) occurs at double bond portions of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see Non-Patent Document 1). In addition, in the case of using a side-chain type polymer having azobenzene in the side chain, when polarized ultraviolet rays are irradiated, an isomerization reaction occurs in the azobenzene part of the side chain parallel to the polarized light, and the liquid crystal is oriented perpendicular to the polarization direction. orientation (see Non-Patent Document 2).

As described in the above example, in the alignment treatment method of the liquid crystal alignment film using the photo-alignment method, no rubbing is required, and there is no need to worry about the generation of dust and static electricity. Therefore, alignment treatment can be performed even on a substrate of a liquid crystal display element having irregularities on the surface, and it is an alignment treatment method of a liquid crystal alignment film suitable for a production process in the industrial field.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3893659

non-patent literature

Non-Patent Document 1: M.Shadt et al., Jpn.J.Appl.Phys.31, 2155 (1992)

Non-Patent Document 2: K. Ichimura et al., Chem. Rev. 100, 1847 (2000)

Contents of the invention

The technical problem to be solved by the invention

As described above, the photo-alignment method has a great advantage in that it does not require the rubbing process itself, compared with the rubbing method conventionally used in the industrial field as an alignment treatment method for liquid crystal display elements. Furthermore, compared with the rubbing method in which the orientation control ability by rubbing is substantially constant, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, in order to realize the same degree of alignment control ability as when using the rubbing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be achieved.

For example, in the decomposition-type photo-alignment method described in the above-mentioned Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, which requires a long time and a large amount of ultraviolet irradiation. In addition, in the case of a dimerization-type or photo-isomerization-type photo-alignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. In addition, in the case of photo-crosslinking or photo-isomerization photo-alignment methods, the alignment of liquid crystals has poor thermal stability and photostability, and thus there is a problem of poor alignment or display burn-in when manufactured into a liquid crystal display element.

Therefore, in the photo-alignment method, high-efficiency alignment treatment and stable liquid crystal alignment are required, and development of a liquid crystal alignment film manufacturing method capable of efficiently imparting high alignment control ability to the liquid crystal alignment film is required.

Then, the object of this invention is to provide the manufacturing method of the liquid crystal aligning film which can perform favorable liquid-crystal orientation control efficiently with light.

Moreover, the object of this invention is to provide the liquid crystal aligning film which realized the efficient orientation process using light using the manufacturing method of this liquid crystal aligning film.

Another object of the present invention is to provide a liquid crystal display element having a liquid crystal aligning film produced by realizing efficient orientation treatment using light.

Technical solutions adopted to solve technical problems

The inventors of the present invention have conducted earnest studies, and as a result, have obtained the following findings, thereby completing the present invention.

The manufacturing method of the liquid crystal aligning film of this invention employ|adopts the method of using the photosensitive side chain type polymer film which can express liquid crystallinity, and performing an orientation process by polarized light irradiation, without performing a rubbing process. Then, after polarized light irradiation, the process of heating this side chain type polymer film is provided, and a liquid crystal aligning film is manufactured. At this time, by optimizing the irradiation amount of polarized light and the heating temperature in the heating step after polarized light irradiation, efficient alignment treatment can be realized by the liquid crystal alignment film, and good alignment control ability can be imparted with high efficiency.

The present invention has the following technical content.

(1) a manufacture method of liquid crystal alignment film, it comprises:

[1] A step of forming a photosensitive side chain type polymer film that exhibits liquid crystallinity within a predetermined temperature range on a substrate;

[II] a step of irradiating polarized ultraviolet rays to the side chain type polymer film; and

[III] A step of heating the side-chain type polymer film irradiated with the ultraviolet rays;

It is characterized in that the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount at which ΔA reaches the maximum, and ΔA is the polarization direction of the side chain type polymer film relative to the polarized ultraviolet rays. The difference between the ultraviolet absorbance in the parallel direction and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.

(2) The manufacturing method of the liquid crystal aligning film as described in said (1) whose ultraviolet-ray irradiation amount of [II] process exists in the range of 1% - 50% of the ultraviolet-ray irradiation amount at which the said ΔA becomes a maximum.

(3) The method for producing a liquid crystal aligning film as described in (1) or (2) above, wherein the heating temperature in the step [III] is higher than the lower limit of the temperature range in which the side chain type polymer film exhibits liquid crystallinity The temperature within the range of the temperature of 10 degreeC - the temperature 10 degreeC lower than the upper limit of this temperature range.

(4) The method for producing a liquid crystal aligning film according to any one of the above (1) to (3), wherein the photosensitive group contained in the photosensitive side chain type polymer exhibiting liquid crystallinity It is azobenzene, stilbene, cinnamic acid, cinnamate, chalcone, coumarin, tolan, phenyl benzoate or its derivatives.

(5) a manufacture method of liquid crystal alignment film, it comprises:

[1] A step of forming a photocrosslinkable side-chain polymer film that exhibits liquid crystallinity within a predetermined temperature range on a substrate;

[II] a step of irradiating polarized ultraviolet rays to the photocrosslinkable side chain type polymer film; and

[III] A step of heating the side-chain type polymer film irradiated with the ultraviolet rays;

[IV] A step of irradiating a non-polarized ultraviolet ray to the side chain type polymer film irradiated with the ultraviolet ray and then heated;

It is characterized in that the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount at which ΔA reaches the maximum, and ΔA is the polarization direction of the side chain type polymer film relative to the polarized ultraviolet rays. The difference between the ultraviolet absorbance in the parallel direction and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.

(6) The manufacturing method of the liquid crystal aligning film as described in said (5) whose ultraviolet-ray irradiation amount of [II] process exists in the range of 1% - 50% of the ultraviolet-ray irradiation amount which becomes the maximum of the said ΔA.

(7) The method for producing a liquid crystal aligning film as described in (5) or (6) above, wherein the heating temperature in the step [III] is higher than the lower limit of the temperature range in which the side chain type polymer film exhibits liquid crystallinity The temperature within the range of the temperature of 10 degreeC - the temperature 10 degreeC lower than the upper limit of this temperature range.

(8) The method for producing a liquid crystal aligning film according to any one of the above (5) to (7), wherein the photo-crosslinking of the side chain type polymer film by the ultraviolet irradiation in the step [IV] More than 20 mol% of the active groups react.

(9) The method for producing a liquid crystal aligning film according to any one of (5) to (8) above, wherein the photosensitivity contained in the photocrosslinkable side chain type polymer exhibiting liquid crystallinity The group is cinnamic acid, cinnamate, chalcone, coumarin, tolan or derivatives thereof.

(10) The method for producing a liquid crystal aligning film according to any one of the above (1) to (9), wherein the side chain type polymer film has a structure including a main chain and a side chain, and the main chain consists of At least one composition selected from hydrocarbons, acrylates and methacrylates, the side chains are represented by at least one of the following formulas (1) to (7);

[chemical 1]

In formula (1), A ₁ and B ₁ independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO-, and Y ₁ is selected from benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and at least one group of cyclic hydrocarbons with 5 to 8 carbons, and the hydrogen atoms bonded to these groups can be independently replaced by -NO ₂ , - CN, -C=C(CN) ₂ , -C=CH-CN, halogen group, alkyl or alkoxy substitution; X ₁ represents a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C- or C ₆ H ₄ -, l1 (also known as l ₁ ) represents an integer from 1 to 12, m1 represents an integer from 1 to 3, and n1 represents an integer from 1 to 12; the formula ( In 2), A ₂ , B ₂ , and D ₁ independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO-, and Y ₂ is selected from At least one group of benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and cyclic hydrocarbons with 5 to 8 carbons, the hydrogen atoms bonded to these groups can be independently replaced by -NO ₂ , -CN, -C=C(CN) ₂ , -C=CH-CN, halogen group, alkyl or alkoxy substitution; X ₂ represents a single bond, -COO-, -OCO-, -N=N- , -C=C-, -C≡C- or C ₆ H ₄ -, R ₁ represents a hydrogen atom or an alkyl group with 1 to 6 carbons; l2 (also called l ₂ ) represents an integer of 1 to 12, and m2 represents An integer of 1 to 3, n2 represents an integer of 1 to 12; in formula (3), A ₃ represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO -, X ₃ represents a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C- or C ₆ H ₄ -, R ₂ represents a hydrogen atom or a carbon number from 1 to 6 alkyl; l3 (also known as l ₃ ) represents an integer of 1 to 12, m3 represents an integer of 1 to 3; in formula (4), l4 (also known as l ₄ ) represents an integer of 1 to 12; formula (5 ), A ₄ represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO-, X ₄ represents -COO-, Y ₃ is selected from benzene ring, At least one group of naphthalene ring and biphenyl ring, the hydrogen atoms bonded to these groups can be independently represented by -NO ₂ , -CN, -C=C(CN) ₂ , -C=CH-CN, Halogen group, alkyl or alkoxy substitution; l5 (also known as l ₅ ) represents an integer of 1 to 12, m4 represents an integer of 1 to 3; in formula (6), A ₅ represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO-, R ₃ is selected from hydrogen atom, -NO ₂ , -CN, -C=C(CN) ₂ , -C=CH -CN, halogen group, carbon number At least one group of an alkyl group of 1 to 6 and an alkoxy group with a carbon number of 1 to 6; l6 (also called l ₆ ) represents an integer of 1 to 12; the hydrogen bonded to the benzene ring in formula (6) Atoms can be independently substituted by -NO ₂ , -CN, -C=C(CN) ₂ , -C=CH-CN, halogen groups, alkyl groups or alkoxy groups; in formula (7), A ₆ represents Single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH- or NH-CO-, _B3 represents single bond, -COO-, -OCO-, -N=N-, - C=C-, -C≡C- or C ₆ H ₄ -; W ₁ is at least one member selected from benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and cyclic hydrocarbons with 5 to 8 carbon atoms groups, the hydrogen atoms bonded to these groups can be independently replaced by -NO ₂ , -CN, -C=C(CN) ₂ , -C=CH-CN, halogen groups, alkyl groups or alkoxy groups substituent; l7 represents an integer of 1 to 12, and m5 and m6 represent an integer of 1 to 3, respectively.

(11) A liquid crystal aligning film produced by the manufacturing method of the liquid crystal aligning film in any one of said (1)-(10).

(12) A liquid crystal display element having the liquid crystal aligning film as described in said (11).

The effect of the invention

According to this invention, the manufacturing method of the liquid crystal aligning film which can realize efficient orientation process can be provided.

Moreover, according to the manufacturing method of this liquid crystal aligning film, the liquid crystal aligning film which can realize efficient orientation process can be provided. According to this liquid crystal aligning film, the liquid crystal display element which has a liquid crystal aligning film produced by realizing the orientation process of high efficiency can also be provided.

Description of drawings

FIG. 1 is a diagram schematically illustrating an example of an anisotropic introduction process in the method for producing a liquid crystal aligning film according to the first aspect of the present invention. (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, especially the case where the introduced anisotropy is small, that is, the liquid crystal including the above steps [I] to [IV] of the present invention A schematic diagram of a case where the ultraviolet irradiation amount in the [II] step in the manufacturing method of the alignment film is in the range of 1% to 15% of the ultraviolet irradiation amount at which ΔA becomes the maximum. (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, (c) is a diagram schematically showing the state of the side chain type polymer film after heating, and (d) is a schematic diagram A diagram showing the state of the side chain type polymer film irradiated with non-polarized light after heating. The above-mentioned first form will be described later.

2 is a diagram schematically illustrating an example of an anisotropy introduction process in the method for producing a liquid crystal alignment film of the first aspect of the present invention, especially when the anisotropy introduced is large, that is, the present invention includes the above-mentioned Schematic diagram of the case where the ultraviolet irradiation amount in the [II] step in the manufacturing method of the liquid crystal aligning film of the [I] to [IV] steps is in the range of 15% to 70% of the ultraviolet irradiation amount at which ΔA becomes the maximum. (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, and (c) is The figure schematically shows the state of the side-chain type polymer film after heating, and (d) is a view schematically showing the state of the side-chain type polymer film irradiated with non-polarized light after heating.

3 is a diagram schematically illustrating an example of an anisotropic introduction process in a method for producing a liquid crystal aligning film according to a second aspect of the present invention. In particular, the side chain type polymer has a structure represented by the above formula (6). In the case, that is, in the production method including the steps [I] to [III] of the present invention, when using a side chain type polymer film having a structure represented by formula (6), the amount of ultraviolet irradiation in the step [II] reaches the maximum at ΔA A schematic diagram of the situation in the range of 1% to 70% of the ultraviolet radiation dose. (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, and (c) is A diagram schematically showing the state of a side chain type polymer film after heating. The above-mentioned second form will be described later.

Fig. 4 is a diagram schematically illustrating an example of an anisotropic introduction process in a method for producing a liquid crystal aligning film according to a second aspect of the present invention, especially a side chain type polymer having a structure represented by the above formula (7). In the case, that is, in the production method including the steps [I] to [III] of the present invention, when a side chain type polymer having a structure represented by formula (7) is used, the amount of ultraviolet irradiation in the step [II] reaches the maximum at ΔA Schematic diagram of the situation in the range of 1% to 70% of the ultraviolet radiation dose. (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, and (c) is A diagram schematically showing the state of a side chain type polymer film after heating.

detailed description

The photosensitive side chain type polymer film capable of expressing liquid crystallinity used in the manufacturing method of the liquid crystal aligning film of the present invention is a photosensitive side chain type polymer film expressing liquid crystallinity in a predetermined temperature range. Moreover, the side chains bonded to the main chain are photosensitive, and can sense light to undergo cross-linking reactions, isomerization reactions or photo-Friesian rearrangements. The photosensitive group bonded to the main chain is not particularly limited, but a structure in which a crosslinking reaction or photo-Friesian rearrangement occurs in response to light is preferred. In this case, even when exposed to external pressure such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies this property, but a rigid unit component (Japanese: メソゲン component) in the side chain structure is preferable.

At this time, when the side chain type polymer is used as a liquid crystal aligning film, stable liquid crystal orientation can be obtained. The structure of the polymer can include, for example, a main chain and a side chain bonded to it, and the side chain has basic units such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, and azophenyl The structure of the component and the photosensitive group that is bonded to the front end and undergoes a crosslinking reaction or isomerization reaction in response to light, or may include a main chain and a side chain bonded to it, and the side chain is also a basic component , and has the structure of a phenylbenzoate group undergoing a photofries rearrangement reaction.

As a more specific example of the structure of the photosensitive side chain type polymer film that can exhibit liquid crystallinity, it is preferable to include at least A main chain composed of one type and a side chain composed of at least one of the following formulas (1) to (7).

[Chem 2]

(A ₁ , B ₁ , X ₁ , Y ₁ , l1, m1, n1 in formula (1) are as defined above, A ₂ , B ₂ , D ₁ , X ₂ , Y ₂ , R in formula (2) ₁ , l2, m2, n2 are as defined above, A ₃ , X ₃ , R ₂ , l3, m3 in formula (3) are as defined above, l4 in formula (4) is as defined above, and in formula (5) A ₄ , X ₄ , Y ₃ , I5, and m4 are as defined above, and A ₅ , R ₃ , and I6 in formula (6) are as defined above. A ₆ , B ₃ , W ₁ , l7, m5, m6 are as defined above.)

The side chains represented by the above formulas (1) to (7) include structures having groups such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, and azobenzene as basic components. Moreover, its front end has at least any one of the following structures, that is, it has a photosensitive group that responds to light and undergoes a dimerization reaction or a crosslinking reaction, or includes a main chain and a side chain bonded thereto. , This side chain is also a basic component, and has a phenylbenzoate group that undergoes a photofries rearrangement reaction.

In the present invention, the side chain type polymer film may be used in combination with a side chain structure not having photoreactivity as long as the liquid crystallinity and photoreactivity are not lost. If one wants to give an example, the structure of the following formula (8) can be given as an example.

[Chem 3]

In the above formula (8), E ₁ represents a single bond, -O-, -CH ₂ -, -COO, -OCO-, -CONH-, -NH-CO-, Z represents a single bond, -COO, -OCO- , -N=N-, -C=C-, -C≡C- or C ₆ H ₄ -, k1 represents an integer of 1 to 12, p1 and q1 independently represent an integer of 0 to 3, R ₄ represents hydrogen Atom, -NO ₂ , -CN, -C═C(CN) ₂ , -C═CH-CN, halogen group, alkoxy group having 1 to 6 carbons, carboxyl group or a combination thereof.

Hereinafter, the photosensitive side chain type polymer film which can express liquid crystallinity used for the manufacturing method of the liquid crystal aligning film of this invention is abbreviated as the side chain type polymer film of this invention.

In the manufacturing method of the liquid crystal aligning film of this invention, polarized ultraviolet-ray is irradiated after forming a coating film on a board|substrate using the side chain type polymer of this invention. Next, anisotropy is efficiently introduced into the side chain type polymer film by heating, and the liquid crystal aligning film which has the orientation control ability of a liquid crystal is produced. In the manufacturing method of the liquid crystal aligning film of the present invention, the photoreaction of the side chain type polymer film of the present invention and the principle of molecular reorientation induced by self-assembly based on liquid crystallinity are used to efficiently align the side chain type polymer film. Introducing anisotropy. In addition, in the production method of the liquid crystal aligning film of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group, after forming a coating film on the substrate with the side chain type polymer of the present invention, , by irradiating polarized ultraviolet rays, followed by heating, and then irradiating non-polarized ultraviolet rays, the anisotropy introduced into the polymer film can be fixed.

Fig. 1 is a schematic diagram of the anisotropy in the production method of the liquid crystal alignment film using a side chain type polymer having a photocrosslinkable group as a photoreactive group in the production method of the liquid crystal alignment film of the present invention. A diagram illustrating an example of import processing. Fig. 1 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 1 (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, Fig. 1 (c) is a diagram schematically showing the state of the side chain type polymer film after heating, and Fig. 1 (d) is a diagram schematically showing the state of the side chain type polymer film after unpolarized light irradiation, particularly In the case where the introduced anisotropy is small, that is, in the method for producing a liquid crystal aligning film including the above-mentioned [I] to [IV] steps of the present invention, the ultraviolet irradiation amount in the [II] step reaches the maximum ultraviolet irradiation amount at ΔA A schematic diagram of the case in the range of 1% to 15%.

Fig. 2 is a schematic diagram of the anisotropy in the method for producing a liquid crystal aligning film of the present invention, using a side chain type polymer having a photocrosslinkable group as a structure of a photoreactive group A diagram illustrating an example of import processing. Fig. 2 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 2 (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, Fig. 2 (c) is a diagram schematically showing the state of the side chain type polymer film after heating, and Fig. 2 (d) is a diagram schematically showing the state of the side chain type polymer film after unpolarized light irradiation, particularly In the case where the introduced anisotropy is large, that is, in the method for producing a liquid crystal aligning film including the above-mentioned [I] to [IV] steps of the present invention, the ultraviolet irradiation amount in the [II] step reaches the maximum ultraviolet irradiation amount at ΔA A schematic diagram of the case in the range of 15% to 70%.

Fig. 3 schematically shows the liquid crystal alignment of the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (6) as the photoreactive group in the manufacturing method of the liquid crystal alignment film of the present invention. A diagram illustrating an example of an anisotropy introduction process in a film production method. Fig. 3 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 3 (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, Fig. 3(c) is a diagram schematically showing the state of the side chain type polymer film after heating, especially the case where the introduced anisotropy is small, that is, the production including the above-mentioned steps [I] to [III] of the present invention. A schematic diagram of the case where the ultraviolet irradiation dose in the [II] step in the method is in the range of 1% to 70% of the ultraviolet irradiation dose at which ΔA becomes the maximum.

Fig. 4 schematically shows the liquid crystal alignment of a side-chain polymer having a photoreactive group represented by the photofries rearrangement group represented by the above formula (7) in the method for producing a liquid crystal alignment film of the present invention. A diagram illustrating an example of an anisotropy introduction process in a film production method. Fig. 4 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 4 (b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, Fig. 4(c) is a diagram schematically showing the state of the side chain type polymer film after heating, especially the case where the introduced anisotropy is large, that is, the production including the above-mentioned steps [I] to [III] of the present invention. A schematic diagram of the case where the ultraviolet irradiation dose in the [II] step in the method is in the range of 1% to 70% of the ultraviolet irradiation dose at which ΔA becomes the maximum.

Hereinafter, the embodiment using a side chain type polymer having a photocrosslinkable group as a photoreactive group will be referred to as the first aspect, and the use of a photofries rearrangement group as a photoreactive group will be referred to as the first embodiment. An embodiment of a side chain type polymer having a group structure is referred to as the second embodiment and will be described.

By introducing anisotropy into the side chain type polymer film in the method for producing a liquid crystal aligning film according to the first aspect of the present invention, the amount of ultraviolet irradiation in the step [II] reaches 1% of the maximum ultraviolet irradiation amount at ΔA In the case of a range of -15%, first, the side chain type polymer film 1 of the present invention is formed on a substrate. As shown in FIG. 1( a ), the side chain type polymer film 1 of the present invention formed on a substrate has a structure in which side chains 2 are randomly arranged. Along with the random arrangement of the side chains 2 of the side chain type polymer film 1, the elementary components of the side chain 2 and the photosensitive groups are also randomly oriented, and the side chain type polymer film 1 is isotropic.

By introducing anisotropy into the side chain type polymer film in the method for producing a liquid crystal aligning film according to the first aspect of the present invention, the amount of ultraviolet irradiation in the step [II] reaches 15% of the maximum ultraviolet irradiation amount at ΔA In the case of the range of -70%, first, the side chain type polymer film 3 of the present embodiment is formed on the substrate. As shown in FIG. 2( a ), the side chain type polymer film 3 of the present invention formed on a substrate has a structure in which side chains 4 are randomly arranged. Along with the random arrangement of the side chains 4 of the side chain type polymer film 3, the elementary components and photosensitive groups of the side chain type 4 are also randomly oriented, and the side chain type polymer film 2 is isotropic.

Through the introduction treatment of anisotropy in the side chain type polymer film in the manufacturing method of the liquid crystal aligning film of the second aspect of the present invention, the method using the photofries rearrangement group represented by the above formula (6) is adopted. In the case of a liquid crystal aligning film of a side-chain type polymer having a structure, when the ultraviolet irradiation dose in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation dose at which ΔA reaches the maximum, first form this film on the substrate. Invented side chain type polymer membrane 5. As shown in FIG. 3( a ), the side chain type polymer film 5 of the present invention formed on a substrate has a structure in which side chains 6 are randomly arranged. Along with the random arrangement of the side chains 6 of the side chain type polymer film 5, the elementary components of the side chain 6 and the photosensitive groups are also randomly oriented, and the side chain type polymer film 5 is isotropic.

Through the introduction treatment of anisotropy in the side chain type polymer film in the manufacturing method of the liquid crystal aligning film of the second aspect of the present invention, adopt the photofries rearrangement group represented by the above formula (7) as In the case of a liquid crystal aligning film of a side-chain type polymer having a structure of , when the ultraviolet irradiation amount in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation amount at which ΔA reaches the maximum, first form a The side chain type polymer membrane 7 of the present invention. As shown in FIG. 4( a ), the side chain type polymer film 7 of the present invention formed on a substrate has a structure in which side chains 8 are randomly arranged. Along with the random arrangement of the side chains 8 of the side chain type polymer film 7, the elementary components and photosensitive groups of the side chain type 8 are also randomly oriented, and the side chain type polymer film 7 is isotropic.

In the first aspect of the present invention, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount at which ΔA reaches the maximum, the isotropic side chain type of the present invention is highly effective. The molecular film 1 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 1(b), the photosensitive group of the side chain 2a having a photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes light such as a dimerization reaction. reaction. As a result, the density of the photoreacted side chains 2a slightly increases in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the side chain type polymer film 1 of the present invention.

In the first aspect of the present invention, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount at which ΔA reaches the maximum, the isotropic side chain type of the present invention is highly effective. The molecular film 3 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 2(b), the photosensitive group of the side chain 4a having a photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially undergoes light such as a dimerization reaction. reaction. As a result, the density of the photoreacted side chains 4a increases in the polarization direction of the irradiated ultraviolet rays, and as a result, the side chain type polymer film 3 of the present invention is given a small anisotropy.

In the second aspect of the present invention, in the case of using a liquid crystal aligning film using a side chain polymer having a structure represented by the above formula (6) of the photofries rearrangement group, the amount of ultraviolet irradiation in the step [II] When ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic side chain type polymer film 5 of the present invention is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 3( b), the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes photo-Fries rearrangement. Wait for the light reaction. As a result, the density of side chains 6a after the photoreaction slightly increases in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the side chain type polymer film 5 of the present invention.

In the second aspect of the present invention, in the case of using a liquid crystal aligning film using a side chain type polymer having a structure represented by the photo-Friesian rearrangement group represented by the above formula (7), the amount of ultraviolet irradiation in the step [II] When ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic side chain type polymer film 7 of the present invention is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 4( b), the photosensitive group of the side chain 8a having a photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially undergoes photo-Fries rearrangement. Wait for the light reaction. As a result, the density of side chains 8a after the photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the side chain type polymer film 7 of the present invention.

Next, in the first aspect of the present invention, when the ultraviolet irradiation dose in the [II] step is within the range of 1% to 15% of the ultraviolet irradiation dose at which ΔA becomes the maximum, the side chain of the present invention after irradiation with polarized light Type polymer film 1 is heated to make it in a liquid crystal state. Then, as shown in FIG. 1( c ), in the side chain type polymer film 1 , the amount of crosslinking reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to it. At this time, the amount of crosslinking reaction occurring in a direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, so the crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is higher than that in the parallel direction, self-assembles in the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains 2 including the elementary components are reoriented. As a result, the very small anisotropy of the side chain type polymer film 1 of the present invention induced by the photocrosslinking reaction is amplified under the effect of heat, thereby giving the side chain type polymer film 1 of the present invention more large anisotropy.

Similarly, in the first aspect of the present invention, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount at which ΔA reaches the maximum, the side of the present invention after polarized light irradiation The chain polymer film 3 is heated to make it into a liquid crystal state. Then, as shown in FIG. 2( c ), in the side chain type polymer film 3 , the amount of crosslinking reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to it. Therefore, self-assembly occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains 4 including the elementary components are reorientated. As a result, the less anisotropy of the side chain type polymer film 3 of the present invention induced by the photocrosslinking reaction is amplified under the effect of heat, thereby giving the side chain type polymer film 3 of the present invention more large anisotropy.

Similarly, in the second aspect of the present invention, when a liquid crystal aligning film using a side chain type polymer having a structure of the photofries rearrangement group represented by the above formula (6) is used, the step of [II] When the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount at which ΔA becomes the maximum, the side chain type polymer film 5 of the present invention after polarized light irradiation is heated to make it into a liquid crystal state. Then, as shown in FIG. 3(c), in the side chain type polymer film 5, the amount of photo-Fries rearrangement reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to it. of. At this time, the liquid crystal alignment force of the optical Fries rearrangement body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than that of the side chain before the reaction, so in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays Self-assembly, reorientation of the side chains 6 comprising the primitive components occurs. As a result, the very small anisotropy of the side chain type polymer film 5 of the present invention induced by the photo-Friesian rearrangement reaction is amplified under the action of heat, thereby giving the side chain type polymer film of the present invention 5 with greater anisotropy.

Similarly, in the second aspect of the present invention, when a liquid crystal aligning film using a side chain type polymer having a structure of the photofries rearrangement group represented by the above formula (7) is used, the step of [II] When the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount at which ΔA becomes the maximum, the side chain type polymer film 7 of the present invention after polarized light irradiation is heated to make it into a liquid crystal state. Then, as shown in FIG. 4(c), in the side chain type polymer film 7, the amount of the photo-Fries rearrangement reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to it. of. The photo-Fries rearrangement body 8 (a) has stronger anchoring force than the side chain 8 before rearrangement, so if a certain amount or more of the photo-Fries rearrangement body is produced, it will be in a direction parallel to the polarization direction of the irradiated ultraviolet rays. Direction self-assembly, reorientation of the side chain 8 containing the primitive components occurs. As a result, the small anisotropy of the side chain type polymer film 7 of the present invention induced by the photo-Friesian rearrangement reaction is amplified under the action of heat, thereby giving the side chain type polymer film of the present invention 7 with greater anisotropy.

In addition, in the first aspect of the present invention, as shown in Fig. 1(d) and Fig. 2(d), when the photoreactive group of the side chain type polymer of the present invention is a photocrosslinkable group , as shown in Figure 1(c) and Figure 2(c), after the anisotropy is induced in the polymer film of the side chain through the self-assembly of the primitives, non-polarized light irradiation is performed, whereby a large degree of Anisotropic immobilization.

Therefore, in the manufacturing method of the liquid crystal aligning film of the present invention, by sequentially performing polarized ultraviolet ray irradiation and heat treatment on the side chain type polymer film of the present invention, and non-polarization after the heat treatment in the case of the first aspect of the present invention, light exposure. An anisotropic liquid crystal aligning film can be efficiently obtained.

And in the manufacturing method of the liquid crystal aligning film of this invention, the irradiation amount of the polarized ultraviolet-ray with respect to the side chain type polymer film of this invention, and the heating temperature in heat processing are optimized. Thereby, anisotropy can be efficiently introduced into the side chain type polymer film.

After earnest research, the inventor has obtained the following knowledge. That is, the irradiation amount of the optimal polarized ultraviolet ray that efficiently introduces anisotropy to the side chain type polymer film of the present invention and makes the photosensitive group in the side chain type polymer film carry out photocrosslinking reaction, photoisomerization The amount of chemical reaction or photofries rearrangement reaction corresponds to the amount of optimally polarized ultraviolet radiation. As a result of irradiating polarized ultraviolet rays to the side chain type polymer film of the present invention, if there are few photosensitive groups in the side chains that undergo photocrosslinking reaction, photoisomerization reaction or photofries rearrangement reaction, it will not reach Sufficient amount of photoreaction. In this case, sufficient self-assembly cannot be performed even if subsequent heating is performed.

On the other hand, in the side chain type polymer film of the present invention, as a result of irradiating polarized ultraviolet rays to a structure having a photocrosslinkable group, if the photosensitive group of the side chain undergoing a crosslinking reaction is excessive, the side chain The cross-linking reaction on the In this case, the obtained film is rigid, which may hinder the subsequent self-assembly by heating. In addition, in the side chain type polymer film of the present invention, as a result of irradiating polarized ultraviolet rays to the structure having the photo-Fries rearrangement group, if the photosensitive group of the side chain that undergoes the photo-Fries rearrangement reaction is excessive , the liquid crystallinity of the side chain type polymer film decreases excessively. In this case, the liquid crystallinity of the obtained film is also lowered, which may hinder the subsequent self-assembly by heating. Furthermore, when irradiating polarized ultraviolet rays to a structure having a photo-Friesian rearrangement group, if the irradiation amount of ultraviolet rays is too high, the side chain type polymer of the present invention may be photolyzed, which may hinder subsequent subsequent heating. Self-assembly proceeds.

Therefore, in the side chain type polymer film of the present invention, the photosensitive group of the side chain undergoes photocrosslinking reaction, photoisomerization reaction or photofries rearrangement reaction by irradiation of polarized ultraviolet rays. Preferably it is 0.1 mol% - 40 mol% of the photosensitive group which this side chain type polymer film has, More preferably, it is 0.1 mol% - 20 mol%. In the present invention, by setting the amount of the photosensitive group of the side chain that undergoes photoreaction within this range, self-assembly by the subsequent heat treatment proceeds efficiently, and anisotropy can be efficiently formed in the film.

In the manufacture method of the liquid crystal aligning film of the present invention, optimize the photocrosslinking reaction, photoisomerization reaction or photosensitive group on the side chain of the side chain type polymer film by optimizing the irradiation amount of the polarized ultraviolet ray. The amount of the Fries rearrangement reaction. Thus, together with subsequent heat treatment, anisotropy can be efficiently introduced into the side chain type polymer film. At this time, the amount of suitable polarized ultraviolet rays can be determined based on the evaluation of the ultraviolet absorption of the side chain type polymer film of the present invention.

That is, for the side chain type polymer film of the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet rays after irradiation with polarized ultraviolet rays were measured. ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, of the side chain type polymer film, was evaluated from the measurement results of ultraviolet absorption. Next, the maximum value (ΔAmax) of ΔA realized in the side chain type polymer film of the present invention and the irradiation amount of polarized ultraviolet rays to realize the maximum value were obtained. In the manufacturing method of the liquid crystal aligning film of this invention, the preferable amount of polarized ultraviolet rays irradiated in the manufacturing process of a liquid crystal aligning film can be determined based on the irradiation amount of polarized ultraviolet rays which realizes this ΔAmax.

In the manufacturing method of the liquid crystal aligning film of the present invention, the amount of irradiation of polarized ultraviolet rays to the side chain type polymer film of the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ΔAmax, more preferably 1%. ~50% range. In the side chain type polymer film of the present invention, the amount of irradiation of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ΔAmax is equivalent to making all the photosensitive groups that the side chain type polymer film has. 0.1 mol% to 20 mol% of the group undergoes the amount of polarized ultraviolet light for photocrosslinking reaction.

Next, in the manufacturing method of the liquid crystal aligning film of this invention, after irradiating polarized ultraviolet-ray to the side chain type polymer film of this invention, heating of this side chain type polymer film is performed. The side chain type polymer film of the present invention is a polymer film capable of exhibiting liquid crystallinity within a predetermined temperature range. The heat treatment after polarized ultraviolet irradiation can be determined based on the temperature at which the liquid crystallinity of the side chain type polymer film is exhibited. That is, the heating temperature after polarized ultraviolet irradiation is preferably 10°C higher than the lower limit of the temperature range in which the side chain type polymer film of the present invention exhibits liquid crystallinity (hereinafter referred to as the liquid crystal temperature range) to a temperature lower than the upper limit of the liquid crystal temperature range. temperature within the temperature range of 10°C.

The side chain type polymer film of the present invention is heated after being irradiated with polarized ultraviolet rays, becomes a liquid crystal state, self-assembles in a direction parallel to the polarization direction, and undergoes reorientation. As a result, the small anisotropy of the side chain type polymer film of the present invention induced by photocrosslinking reaction, photoisomerization reaction and photofries rearrangement reaction is amplified by heat. However, even when the side chain type polymer film of the present invention is heated to a liquid crystal state, if the heating temperature is low, the viscosity of the side chain type polymer film in the liquid crystal state is high, and reorientation by self-assembly becomes difficult. For example, when the heating temperature is within the range of a temperature that is 10° C. higher than the lower limit of the liquid crystal temperature range of the side chain type polymer film of the present invention, it is not possible to generate sufficient heat in the side chain type polymer film of the present invention. The anisotropic amplification effect caused by heat.

In addition, even if the side chain type polymer film of the present invention is in a liquid crystal state by heating, if the heating temperature is high, the state of the side chain type polymer film is close to an isotropic liquid state, and it is difficult to self-assemble in one direction. Reorientation. For example, when the heating temperature is higher than the temperature 10° C. lower than the upper limit of the liquid crystal temperature range of the side chain type polymer film of the present invention, a sufficient amount of the side chain type polymer film of the present invention cannot be produced. Amplifying effects of heat-induced anisotropy in .

As mentioned above, in the manufacturing method of the liquid crystal aligning film of the present invention, in order to efficiently introduce anisotropy into the side chain type polymer film, the liquid crystal temperature range of the side chain type polymer film is used as a reference to determine the appropriate heating temperature. And as mentioned above, the temperature of the heating after the polarized ultraviolet irradiation is set to a temperature that is 10° C. higher than the lower limit of the liquid crystal temperature range of the side chain type polymer film as the lower limit and 10° C. lower than the upper limit of the liquid crystal temperature range. The temperature is a temperature within the range of the upper limit. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer film of the present invention is 100°C to 200°C, the heating temperature after polarized ultraviolet irradiation is preferably 110°C to 190°C. Thereby, greater anisotropy can be imparted to the side chain type polymer film of the present invention.

The orientation process in the manufacturing method of the liquid crystal aligning film of this invention was demonstrated above, and the manufacturing method of the liquid crystal aligning film of this invention is demonstrated next.

The manufacturing method of the liquid crystal aligning film of this invention contains the process of following [I]-[III] or the process of following [I]-[IV] in the following order. The liquid crystal aligning film which introduced anisotropy efficiently can be manufactured.

[1] A step of forming a photosensitive side chain type polymer film capable of exhibiting liquid crystallinity on a substrate;

[II] A step of irradiating polarized ultraviolet rays to the side chain type polymer film obtained in the step [I];

[III] A step of heating the side chain type polymer film irradiated with polarized ultraviolet rays in the step [II];

[IV] A step of irradiating a non-polarized ultraviolet ray to the side chain type polymer film irradiated with the ultraviolet ray and then heated.

Hereinafter, each process of the process of [I]-[III] contained in the manufacturing method of the liquid crystal aligning film of this invention or the process of following [1]-[IV] is demonstrated.

In step [I], the side chain type polymer film of the present invention is formed on a substrate. The substrate is not particularly limited. For example, transparent substrates such as plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates. In consideration of the application of the obtained liquid crystal aligning film, from the viewpoint of simplification of the manufacturing process of the liquid crystal display element, a substrate on which an ITO (Indium Tin Oxide: indium tin oxide) electrode for liquid crystal driving, etc. is formed can also be used. In addition, considering the application in reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used, and the electrodes at this time can also use light-reflecting materials such as aluminum.

When the side chain type polymer film of the present invention is in the form of a solution dissolved in a desired solvent, film formation on the substrate is performed by coating the solution form of the side chain type polymer film. The coating method is not particularly limited, and the industrial field generally adopts a method of coating by screen printing, offset printing, flexographic printing, or an inkjet method. As other coating methods, there are dip coating method, roll coating method, slit coating method, spin coating method (spin coating method), spray coating method, etc., and these methods can be used according to the purpose.

After coating the solution-like side chain type polymer film of the present invention on the substrate, it can be heated at 20°C to 180°C, preferably at 40°C to The solvent was evaporated at 150° C. to obtain the side chain type polymer film of the present invention. If the thickness of the side chain type polymer film is too thick, then it is disadvantageous in the power consumption of the liquid crystal display element using the liquid crystal alignment film; 10nm ~ 100nm.

In addition, after the [I] step and before the subsequent [II] step, a step of cooling the substrate on which the side chain type polymer film is formed to room temperature may be provided.

In step [II], polarized ultraviolet rays are irradiated to the side chain type polymer film obtained in step [I]. In the case of irradiating polarized ultraviolet rays to the film surface of the side chain type polymer film, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays within a wavelength range of 100 nm to 400 nm can be used. It is preferable to select an appropriate wavelength through a filter or the like according to the type of side chain type polymer film to be used. For example, in order to selectively induce a photocrosslinking reaction, ultraviolet light within a wavelength range of 250 nm to 400 nm can be selected and used. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

Regarding the amount of irradiation of polarized ultraviolet rays, as described above, it is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realize ΔAmax of the side chain type polymer film of the present invention used, more preferably 1% to 50%. %In the range.

In step [III], the side chain type polymer film irradiated with polarized ultraviolet rays in step [II] is heated. For heating, a heating device such as a heating plate, a thermal circulation furnace or an IR (infrared ray) furnace is used. The heating temperature can be determined in consideration of the temperature at which the side chain type polymer film of the present invention to be used exhibits liquid crystallinity as described above. That is, the heating temperature after polarized ultraviolet ray irradiation is preferably a temperature that is 10° C. higher than the lower limit of the liquid crystal temperature range in which the side chain type polymer film of the present invention used exhibits liquid crystallinity, and is lower than the upper limit of the liquid crystal temperature range. The temperature of 10° C. is a temperature within the range of the upper limit.

By including the above process, anisotropy can be efficiently introduced into a side chain type polymer film by the manufacturing method of the liquid crystal aligning film of this invention. And the liquid crystal aligning film of this invention can be manufactured efficiently.

In the step [IV], the side chain type polymer film irradiated with the above-mentioned ultraviolet rays and then heated is irradiated with non-polarized ultraviolet rays. Through this step, the side chain type polymer film of the present invention that remains unreacted in the step [II] and has been reoriented in the step [III] undergoes a crosslinking reaction, thereby stabilizing the orientation.

Preferably, 20 mol% or more of the photocrosslinkable groups contained in the side chain type polymer film are reacted by the ultraviolet irradiation in the step [IV]. In other words, unless 20 mol% or more of photocrosslinkable groups remain in the step [II], it will be difficult to achieve sufficient orientation stabilization in this step. The reason for this is that it is difficult for a re-aligned photoreactive group to be immobilized while maintaining its aligned state. In the case of the above formulas (6) and (7), if this step is carried out, the effect of the present invention will not be easily exerted on the contrary.

Example

Embodiments of the present invention will be described in more detail with examples given. However, the present invention should not be construed as being limited thereto.

<Synthesis Example 1>

4'-(6-bromohexyloxy)biphenyl-4-ol was synthesized by heating 4,4'-biphenyldiphenol and 1,6-dibromohexane under alkaline conditions. This product was reacted with lithium methacrylate to obtain 2-(4'-hydroxybiphenyl-4-yloxy)hexyloxymethacrylate. Next, 4-methoxycinnamoyl chloride was added under basic conditions to synthesize a compound represented by the following formula (9).

<Synthesis Example 2>

4-(6-hydroxyhexyloxy)cinnamic acid was synthesized by heating 1-hydroxycinnamic acid and 1-hydroxy-6-hexanol under alkaline conditions. This product is reacted with methacryloyl chloride under basic conditions to obtain a compound represented by the following formula (10).

<Synthesis Example 3>

4-(6-hydroxyhexyloxy)benzoic acid was synthesized by heating 1-hydroxybenzoic acid and 1-hydroxy-6-hexanol under basic conditions. This product is reacted with methacryloyl chloride under basic conditions to obtain a compound represented by the following formula (11).

<Synthesis Example 4>

4-iodophenol and 6-chloro-1-hexanol are heated under basic conditions to synthesize 4-(6-hydroxyhexyloxy)iodophenol. This product was reacted with 2-methyl-3-butyn-2-ol, and then heated under basic conditions to obtain 4-(6-hydroxyhexyloxy)ethynylbenzene (compound A). Furthermore, 4-iodophenyl-3-(4-methoxyphenyl)acrylate (compound B) was synthesized by reacting 4-methoxycinnamoyl chloride and 4-iodophenol by another route. Next, compound A and compound B are reacted under basic conditions to obtain a compound represented by the following formula (12).

<Synthesis Example 5>

1-hydroxybenzoic acid and 1-hydroxy-6-hexanol were heated under basic conditions to synthesize 4-(6-hydroxyhexyloxy)benzoic acid, and thionyl chloride was added to obtain 4-(6- hydroxyhexyloxy)benzoyl chloride. This product was reacted with p-methoxyphenol under basic conditions to obtain a compound represented by the following formula (13).

<Synthesis Example 6>

Polymer 1 was obtained by dissolving the methacrylate represented by the above formula (9) in tetrahydrofuran, adding azobisisobutyronitrile (AIBN) as a reaction initiator, and polymerizing. This polymer 1 exhibited liquid crystallinity in the temperature range of 116°C to 315°C.

<Synthesis Example 7>

Polymer 2 was obtained by dissolving the methacrylate represented by the above formula (10) in tetrahydrofuran, adding azobisisobutyronitrile (AIBN) as a reaction initiator, and polymerizing. This polymer 2 exhibits liquid crystallinity in the temperature range of 135°C to 187°C.

<Synthesis Example 8>

Dissolve the methacrylate represented by the above formula (10) and the methacrylate represented by the above formula (11) in tetrahydrofuran at a ratio of 25 to 75, and add azobisisobutyronitrile (AIBN) as a reaction initiator The agent was polymerized to obtain polymer 3. This polymer 3 exhibited liquid crystallinity in the temperature range of 146°C to 183°C.

<Synthesis Example 9>

Polymer 4 was obtained by dissolving the methacrylate represented by the above formula (12) in tetrahydrofuran, adding azobisisobutyronitrile (AIBN) as a reaction initiator, and polymerizing. This polymer 4 showed liquid crystallinity in the temperature range of 66°C to 320°C.

<Synthesis Example 10>

Polymer 5 was obtained by dissolving the methacrylate represented by the above formula (13) in tetrahydrofuran, adding azobisisobutyronitrile (AIBN) as a reaction initiator, and polymerizing. This polymer 5 exhibited liquid crystallinity in the temperature range of 143°C to 283°C.

[chemical 4]

<Preparation of anisotropy-introduced liquid crystal alignment film>

<Example 1>

Polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride and spin-coated to a thickness of about 190 nm on an optically isotropic substrate to form a side chain type polymer film on the substrate. The ultraviolet absorption spectrum was measured using this substrate, and the maximum absorbance was 0.89 at 314 nm. The side-chain type polymer film on the obtained substrate was irradiated with ultraviolet rays converted into linearly polarized light by a Glan-Taylor prism.

Using the side chain type polymer film on the substrate obtained as described above, the ultraviolet absorption spectrum was measured to evaluate ΔA, which is the sum of the ultraviolet absorbance in the direction parallel to the polarization direction of the irradiated polarized ultraviolet light of the side chain type polymer film The difference in ultraviolet absorbance in the direction perpendicular to the polarization direction of the irradiated polarized ultraviolet rays. When 4500mJ of polarized ultraviolet light is irradiated in terms of wavelength 365nm, ΔA reaches a maximum of 0.2 at 314nm, and 650mJ of polarized ultraviolet light is irradiated so that ΔA reaches 0.065 (a difference of 32% from the maximum value), and then the substrate is heated to 155°C , to make the side chain type polymer film into a liquid crystal phase, and maintain this state for 5 minutes. Then, it was cooled to room temperature to obtain a substrate having a side chain type polymer film with anisotropy introduced into the film. At this time, ΔA is enlarged to 1.8, and the degree of orientation is 0.73. Next, a substrate having a liquid crystal aligning film was obtained by irradiating the substrate having the anisotropic side chain type polymer film with 1500 mJ of non-polarized ultraviolet rays in terms of wavelength 365 nm.

<Example 2>

Polarized ultraviolet irradiation and subsequent heat treatment were carried out in the same manner as in Example 1 except that the polymer 1 obtained in Synthesis Example 6 was used and the irradiation dose of polarized ultraviolet rays was 500 mJ (irradiation dose at which ΔA reaches 25% of the maximum value of ΔA). As a result, ΔA before and after heat treatment was enlarged from 0.05 to 1.85, and the degree of orientation at this time was 0.74 at 314 nm. Then, it irradiated the non-polarized ultraviolet-ray similarly to Example 1, and obtained the board|substrate which has a liquid crystal aligning film.

<Example 3>

Except that the polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran, spin-coated on an optically isotropic substrate with a thickness of about 150 nm, and the irradiation amount of polarized ultraviolet rays was 5 mJ (the irradiation amount at which ΔA reached 10% of the maximum value of ΔA ), the subsequent heat treatment was performed at 165° C. for 5 minutes, and polarized ultraviolet irradiation and subsequent heat treatment were performed in the same manner as in Example 1. As a result, ΔA before and after heat treatment was enlarged from 0.03 to 1.6, and the degree of orientation at this time was 0.72 at 314 nm. Then, it irradiated 1000 mJ of non-polarized ultraviolet rays similarly to Example 1, and obtained the board|substrate which has a liquid crystal aligning film.

<Example 4>

Polarized ultraviolet irradiation and subsequent heat treatment were carried out in the same manner as in Example 3, except that the polymer 3 obtained in Synthesis Example 8 was used and the irradiation dose of polarized ultraviolet rays was 20 mJ (the irradiation dose at which ΔA reaches 40% of the maximum value of ΔA). As a result, ΔA before and after heat treatment was enlarged from 0.12 to 1.6, and the degree of orientation at this time was 0.62 at 314 nm. Then, it irradiated 1000 mJ of non-polarized ultraviolet rays similarly to Example 1, and obtained the board|substrate which has a liquid crystal aligning film.

<Example 5>

In addition to dissolving the polymer 4 obtained in Synthesis Example 9 in dichloromethane and spin-coating it on an optically isotropic substrate with a thickness of about 220 nm to form a side chain type polymer film on the substrate, the irradiation amount of polarized ultraviolet rays was Except for 300 mJ (irradiation dose at which ΔA reaches 29% of the maximum value of ΔA) and subsequent heat treatment at 200° C. for 5 minutes, polarized ultraviolet irradiation and subsequent heat treatment were carried out in the same manner as in Example 1. As a result, ΔA before and after heat treatment was enlarged from 0.04 to 1.4, and the degree of orientation at this time was 0.62 at 294 nm. Then, it irradiated 5000 mJ of non-polarized ultraviolet rays similarly to Example 1, and obtained the board|substrate which has a liquid crystal aligning film.

<Example 6>

In addition to dissolving the polymer 5 obtained in Synthesis Example 10 in dichloromethane and spin-coating it on an optically isotropic substrate with a thickness of about 220 nm to form a side chain type polymer film on the substrate, the irradiation amount of polarized ultraviolet rays was Except for 1000 mJ (irradiation dose at which ΔA reaches 49% of the maximum value of ΔA) and subsequent heat treatment at 180° C. for 5 minutes, polarized ultraviolet irradiation and subsequent heat treatment were carried out in the same manner as in Example 1. As a result, ΔA before and after the heat treatment was enlarged from 0.07 to 1.7, and the orientation degree at this time was obtained as a substrate having a liquid crystal aligning film of 0.72 at 262 nm.

<Comparative example 1>

Polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride and spin-coated to a thickness of about 190 nm on an optically isotropic substrate to form a side chain type polymer film on the substrate. The ultraviolet absorption spectrum was measured using this substrate, and the maximum absorbance was 0.89 at 314 nm. The side-chain type polymer film on the obtained substrate was irradiated with ultraviolet rays converted into linearly polarized light by a Glan-Taylor prism.

Using the side chain type polymer film on the substrate obtained as described above, the ultraviolet absorption spectrum was measured to evaluate ΔA, which is the sum of the ultraviolet absorbance in the direction parallel to the polarization direction of the irradiated polarized ultraviolet light of the side chain type polymer film The difference in ultraviolet absorbance in the direction perpendicular to the polarization direction of the irradiated polarized ultraviolet rays. When 4500mJ of polarized ultraviolet light is irradiated in terms of wavelength 365nm, ΔA reaches a maximum of 0.2 at 314nm, and 650mJ of polarized ultraviolet light is irradiated so that ΔA reaches 0.065 (a difference of 32% from the maximum value), and then the substrate is heated to 155°C , to make the side chain type polymer film into a liquid crystal phase, and maintain this state for 5 minutes. Then, it cooled to room temperature, and the board|substrate which has the liquid crystal aligning film which introduced anisotropy into a film was obtained. At this time, ΔA is enlarged to 1.8, and the degree of orientation is 0.73.

<Comparative example 2>

In addition to dissolving the polymer 1 obtained in Synthesis Example 6 in dichloromethane and spin-coating it on an optically isotropic substrate with a thickness of about 190 nm to form a side chain type polymer film on the substrate, the irradiation amount of polarized ultraviolet rays was Except 4500 mJ (the irradiation dose which becomes the maximum value of ΔA), it carried out similarly to the comparative example 1, and performed polarized ultraviolet irradiation and subsequent heat processing, and obtained the liquid crystal aligning film which introduced anisotropy into a film. At this time, ΔA before and after the heat treatment remained unchanged at 0.07, and the degree of orientation was also 0.12 at 314 nm, and amplification of ΔA and degree of orientation was not confirmed.

<Comparative example 3>

Except that the polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran, spin-coated on an optically isotropic substrate with a thickness of about 150 nm to form a side chain type polymer film on the substrate, and the irradiation amount of polarized ultraviolet rays was 900 mJ ( ΔA reached the maximum irradiation dose) and the subsequent heat treatment were 165° C., polarized ultraviolet irradiation and subsequent heat treatment were performed in the same manner as in Comparative Example 1 to obtain a liquid crystal aligning film in which anisotropy was introduced into the film. At this time, ΔA before and after the heat treatment remained unchanged at 0.07, and the degree of orientation was also 0.12 at 314 nm, and amplification of ΔA and degree of orientation was not confirmed.

<Comparative example 4>

Except that the polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran, spin-coated on an optically isotropic substrate with a thickness of about 150 nm to form a side chain type polymer film on the substrate, and the irradiation amount of polarized ultraviolet rays was 5 mJ ( ΔA reaches 10% of the maximum value of ΔA), the subsequent heat treatment is 200°C, and the liquid crystal temperature range of polymer 2 is not higher than that, and the polarized ultraviolet irradiation and subsequent heat treatment are performed in the same manner as in Comparative Example 1 to obtain a liquid crystal aligning film. . At this time, ΔA before and after heat treatment decreased from 0.07 to 0, and the orientation was also 0 at 314 nm, and the anisotropy in the polymer film disappeared.

<Preparation and Evaluation of Liquid Crystal Cell>

<Example 7>

Liquid crystal ZLI-4792 manufactured by Merck Japan was sandwiched between two substrates having a liquid crystal aligning film prepared in Example 1 to obtain an antiparallel liquid crystal cell. When the obtained liquid crystal cell was observed under crossed Nicols, uniform liquid crystal orientation without orientation defect was observed. In addition, two ITO substrates with the anisotropic liquid crystal alignment film were made, the liquid crystal ZLI-4792 was sandwiched between them, and the obtained liquid crystal unit cell was sandwiched by a pair of linear polarizers, thus making A TN (Twisted Nematic: twisted nematic) type liquid crystal display element in which the thickness of the liquid crystal is 6 μm. In this TN type liquid crystal display element, the drive of the liquid crystal was confirmed by applying a voltage to the ITO electrode. It was confirmed that there was no alignment defect on the entire surface of the liquid crystal display element, and uniform orientation changes of liquid crystals were confirmed by voltage application. The liquid crystal display element of this embodiment can be produced using the liquid crystal aligning film of this embodiment. The evaluation results are summarized in Table 1.

<Embodiment 8>

A liquid crystal cell was produced by the same method as in Example 7 using two substrates having a liquid crystal alignment film produced in Example 2. The results are shown in Table 1.

<Example 9>

A liquid crystal cell was produced by the same method as in Example 7 using two substrates having a liquid crystal alignment film produced in Example 3. The results are shown in Table 1.

<Example 10>

A liquid crystal cell was produced by the same method as in Example 7 using two substrates having a liquid crystal alignment film produced in Example 4. The results are shown in Table 1.

<Example 11>

A liquid crystal cell was produced by the same method as in Example 7 using two substrates having a liquid crystal alignment film produced in Example 5. The results are shown in Table 1.

<Example 12>

A liquid crystal cell was produced by the same method as in Example 7 using two substrates having a liquid crystal alignment film produced in Example 6. The results are shown in Table 1.

<Comparative example 5>

A liquid crystal cell was produced by the method similar to Example 7 using the board|substrate with the liquid crystal aligning film produced in the comparative example 1 of two pieces. The results are shown in Table 1.

<Comparative example 6>

A liquid crystal cell was produced by the method similar to Example 7 using the board|substrate with the liquid crystal aligning film produced in the comparative example 2 of two pieces. The results are shown in Table 1.

<Comparative example 7>

A liquid crystal cell was produced by the method similar to Example 7 using the board|substrate with the liquid crystal aligning film produced in the comparative example 3 of two pieces. The results are shown in Table 1.

<Comparative example 8>

A liquid crystal cell was produced by the method similar to Example 7 using the board|substrate with the liquid crystal aligning film produced in the comparative example 4 of two pieces. The results are shown in Table 1.

From the above evaluation results, it can be seen that the liquid crystal aligning film of the present invention produced by the manufacturing method of the liquid crystal aligning film of the present invention with a small amount of ultraviolet irradiation can provide a liquid crystal display element.

[Table 1]

Examples and Comparative Examples Orientation of liquid crystal Example 7 good Example 8 good Example 9 good Example 10 good Example 11 good Example 12 good Comparative Example 5 large number of orientation defects Comparative Example 6 no orientation Comparative Example 7 no orientation Comparative Example 8 no orientation

Possibility of industrial use

The manufacturing method of this invention can be used for manufacture of the liquid crystal aligning film which can realize efficient orientation process.

In addition, all the contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2011-260180 filed on November 29, 2011 are incorporated herein as disclosure of the specification of the present invention.

Explanation of symbols

1 Side chain type polymer membrane

2. 2a side chain

3 side chain type polymer membrane

4. 4a side chain

5 side chain type polymer membrane

6. 6a side chain

7 side chain type polymer membrane

8. 8a side chain

Claims (12)

1. a manufacture method for liquid crystal orientation film, comprising:

[I] embodies the work of the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate Sequence；

Described side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And

The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；

It is characterized in that, the ultraviolet irradiation amount of [II] operation reaches 1%～the 70% of the ultraviolet irradiation amount of maximum at Δ A In the range of, Δ A is the ultraviolet in parallel direction, the polarization direction with described polarized UV rays of described side chain type polymeric membrane The UV absorbance in the direction that absorbance is vertical with the polarization direction with described polarized UV rays of described side chain type polymeric membrane The difference of degree.

2. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the ultraviolet irradiation amount of [II] operation Reach in the range of the 1%～50% of maximum ultraviolet irradiation amount at described Δ A.

3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that the heating-up temperature of [III] operation It it is the temperature of the lower limit for height 10 DEG C of the temperature range embodying liquid crystal liquid crystal property than described side chain type polymeric membrane～than this temperature range Low 10 DEG C of the upper limit temperature in the range of temperature.

4. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that described in embody liquid crystal liquid crystal property Photonasty group contained in photosensitive side chain type macromolecule be diphenyl diimide, cinnamic acid, cinnamate, chalcone derivative, perfume (or spice) Legumin, tolan, phenol benzoate or derivatives thereof.

5. a manufacture method for liquid crystal orientation film, comprising:

[I] embodies the side chain type polymeric membrane of the photocrosslinking reaction of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate Operation；

Described photocrosslinking reaction side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And

The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；

[IV] is to illuminated described ultraviolet, the work of the side chain type polymeric membrane unpolarized ultraviolet of irradiation being then passed through heating Sequence；

It is characterized in that, the ultraviolet irradiation amount of [II] operation reaches 1%～the 70% of the ultraviolet irradiation amount of maximum at Δ A In the range of, Δ A is the ultraviolet in parallel direction, the polarization direction with described polarized UV rays of described side chain type polymeric membrane The UV absorbance in the direction that absorbance is vertical with the polarization direction with described polarized UV rays of described side chain type polymeric membrane The difference of degree.

6. the manufacture method of liquid crystal orientation film as claimed in claim 5, it is characterised in that the ultraviolet irradiation amount of [II] operation Reach in the range of the 1%～50% of maximum ultraviolet irradiation amount at described Δ A.

7. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that the heating-up temperature of [III] operation It it is the temperature of the lower limit for height 10 DEG C of the temperature range embodying liquid crystal liquid crystal property than described side chain type polymeric membrane～than this temperature range Low 10 DEG C of the upper limit temperature in the range of temperature.

8. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that by the ultraviolet of [IV] operation Line irradiates, and 20 moles of more than % of the photocrosslinking reaction group that described side chain type polymeric membrane is had react.

9. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that described in embody liquid crystal liquid crystal property Photonasty group contained in the side chain type macromolecule of photocrosslinking reaction be cinnamic acid, cinnamate, chalcone derivative, coumarin, two Phenylacetylene or derivatives thereof.

10. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that described side chain type polymeric membrane Being the structure including main chain and side chain, described main chain is constituted by selected from least one of hydrocarbon, acrylate and methacrylate, Described side chain represents with at least one in following formula (1)～(7)；

[changing 1]

In formula (1), A₁、B₁Separately represent singly-bound ,-O-,-CH₂-,-COO-,-OCO-,-CONH-or NH-CO-, Y₁It it is choosing From at least one group of the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, key on these groups The hydrogen atom closed can be separately by-NO₂,-CN ,-C=C (CN)₂,-C=CH-CN, halogen group, alkyl or alkoxyl Replace；X₁Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C₆H₄-, l1 represents the integer of 1～12, m1 table Showing the integer of 1～3, n1 represents the integer of 1～12；In formula (2), A₂、B₂、D₁Separately represent singly-bound ,-O-,-CH₂-、- COO-,-OCO-,-CONH-or NH-CO-, Y₂Selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8 At least one group of cyclic hydrocarbon, on these groups, the hydrogen atom of bonding can be separately by-NO₂,-CN ,-C=C (CN)₂,-C=CH-CN, halogen group, alkyl or alkoxyl replace；X₂Represent singly-bound ,-COO-,-OCO-,-N=N-,-C= C-,-C ≡ C-or C₆H₄-, R₁Represent hydrogen atom or the alkyl of carbon number 1～6；L2 represents the integer of 1～12, m2 represent 1～3 whole Number, n2 represents the integer of 1～12；In formula (3), A₃Represent singly-bound ,-O-,-CH₂-,-COO-,-OCO-,-CONH-or NH-CO-, X₃Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C₆H₄-, R₂Represent hydrogen atom or the alkane of carbon number 1～6 Base；L3 represents the integer of 1～12, and m3 represents the integer of 1～3；In formula (4), l4 represents the integer of 1～12；In formula (5), A₄Table Show singly-bound ,-O-,-CH₂-,-COO-,-OCO-,-CONH-or NH-CO-, X₄Expression-COO-, Y₃It is selected from phenyl ring, naphthalene nucleus and connection At least one group of phenyl ring, on these groups, the hydrogen atom of bonding can be separately by-NO₂,-CN ,-C=C (CN)₂、- C=CH-CN, halogen group, alkyl or alkoxyl replace；L5 represents the integer of 1～12, and m4 represents the integer of 1～3；Formula (6) In, A₅Represent singly-bound ,-O-,-CH₂-,-COO-,-OCO-,-CONH-or NH-CO-, R₃Represent selected from hydrogen atom ,-NO₂、-CN、- C=C (CN)₂,-C=CH-CN, halogen group, at least one group of alkoxyl of the alkyl of carbon number 1～6 and carbon number 1～6； L6 represents the integer of 1～12；On phenyl ring in formula (6), the hydrogen atom of bonding can be separately by-NO₂,-CN ,-C=C (CN)₂,-C=CH-CN, halogen group, alkyl or alkoxyl replace；In formula (7), A₆Represent singly-bound ,-O-,-CH₂-、-COO-、- OCO-,-CONH-or NH-CO-, B₃Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C₆H₄-；W₁It it is choosing From at least one group of the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, key on these groups The hydrogen atom closed can be separately by-NO₂,-CN ,-C=C (CN)₂,-C=CH-CN, halogen group, alkyl or alkoxyl Replace；L7 represents the integer of 1～12, and m5, m6 represent the integer of 1～3 respectively.

11. 1 kinds of liquid crystal orientation films, it is characterised in that by the liquid crystal orientation film according to any one of claim 1～10 Manufacture method and make.

12. 1 kinds of liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 11.