JPWO2013081066A1 - Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a method for producing a liquid crystal alignment film that enables highly efficient anisotropy to be introduced into the film without rubbing, and provides a liquid crystal alignment film and a liquid crystal display element. [I] forming a photosensitive side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range on a substrate; [II] irradiating the side chain polymer film with polarized ultraviolet rays; And [III] a method for producing a liquid crystal alignment film comprising a step of heating the side chain polymer film irradiated with ultraviolet rays, wherein the amount of ultraviolet irradiation in the step [II] is that of the side chain polymer film In addition, the present invention is characterized in that it is within the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, which is the difference between the ultraviolet light absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet light absorbance in the direction perpendicular thereto. To do. .

Description

  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, and in particular, 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 It is related with the used liquid crystal display element.

  The liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

  That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.

  A rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction). This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. As an organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of dust or static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized.
Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed.
There are various photo alignment methods. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

A decomposition type photo-alignment method is known as a main photo-alignment method. For example, the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the remaining polyimide without being decomposed (see Patent Document 1).
In addition, photocrosslinking type and photoisomerization type photo-alignment methods are also known. For example, polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see Non-Patent Document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, irradiation with polarized ultraviolet light causes an isomerization reaction at the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the polarization direction. Oriented (see Non-Patent Document 2).

  As in the above example, the liquid crystal alignment film alignment treatment method by the photo alignment method eliminates the need for rubbing, and there is no fear of generation of dust or static electricity. An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent No. 3893659

M.M. Shadt et al. , Jpn. J. et al. Appl. Phys. 31, 2155 (1992) K. Ichimura et al. Chem. Rev. 100, 1847 (2000)

  As described above, the photo-alignment method does not require a rubbing process as compared with a rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .

For example, in the decomposition type photo-alignment method described in 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. Become. Even in the case of a dimerization type or photoisomerization type photo-alignment method, a large amount of ultraviolet irradiation of about several J (joule) to several tens of J may be required. Furthermore, in the case of the photo-crosslinking type or photoisomerization type photo-alignment method, since the thermal stability and light stability of the liquid crystal alignment are inferior, there is a problem that alignment failure or display burn-in occurs when a liquid crystal display element is used. was there.
Therefore, in the photo-alignment method, there is a demand for higher efficiency of alignment treatment and realization of stable liquid crystal alignment, and production of a liquid crystal alignment film that can impart high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for method development.

Therefore, an object of the present invention is to provide a method for producing a liquid crystal alignment film that enables high-efficiency and good liquid crystal alignment control using light.
Another object of the present invention is to provide a liquid crystal alignment film manufactured by realizing a highly efficient alignment process using light using the method for manufacturing a liquid crystal alignment film.
Furthermore, an object of the present invention is to provide a liquid crystal display element including a liquid crystal alignment film manufactured by realizing a highly efficient alignment process using light.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The method for producing a liquid crystal alignment film of the present invention uses a method in which an alignment treatment is performed by irradiation with polarized light without using a rubbing treatment, using a photosensitive side chain polymer film capable of exhibiting liquid crystallinity. And after polarized light irradiation, the process which heats the 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 process after the irradiation of polarized light, a highly efficient alignment process is realized in the liquid crystal alignment film, and high alignment efficiency and good alignment control ability are imparted. Can be realized.
The gist of the present invention is as follows.
(1) [I] A step of forming a photosensitive side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range on a substrate;
[II] A method for producing a liquid crystal alignment film, comprising: irradiating the side chain polymer film with polarized ultraviolet light; and [III] heating the side chain polymer film irradiated with ultraviolet light. ,
[II] The amount of UV irradiation in the step maximizes ΔA, which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV. The manufacturing method of the liquid crystal aligning film characterized by being in the range of 1%-70% of ultraviolet irradiation amount.

(2) The method for producing a liquid crystal alignment film according to (1), wherein the ultraviolet irradiation amount in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount that maximizes the ΔA.
(3) The heating temperature in the step [III] is a temperature ranging from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film exhibits liquid crystallinity to a temperature 10 ° C. lower than the upper limit of the temperature range. The manufacturing method of the liquid crystal aligning film as described in said (1) or (2) which is.
(4) The photosensitive group contained in the photosensitive side chain polymer exhibiting liquid crystallinity is azobenzene, stilbene, cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan, phenylbenzoate, or a derivative thereof. The method for producing a liquid crystal alignment film according to any one of (1) to (3) above.

(5) [I] A step of forming a photocrosslinkable side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range on a substrate;
[II] A step of irradiating the photocrosslinkable side chain polymer film with polarized ultraviolet light, and [III] a step of heating the side chain polymer film irradiated with ultraviolet light. [IV] The irradiation of the ultraviolet light. Then, a method for producing a liquid crystal alignment film comprising a step of irradiating non-polarized ultraviolet rays to the heated side chain polymer film,
[II] The amount of UV irradiation in the step maximizes ΔA, which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV. The manufacturing method of the liquid crystal aligning film characterized by being in the range of 1%-70% of ultraviolet irradiation amount.
(6) The method for producing a liquid crystal alignment film according to (5), wherein the ultraviolet irradiation amount in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount that maximizes the ΔA.
(7) The temperature in the range from [10] higher than the lower limit of the temperature range in which the side chain polymer film exhibits liquid crystallinity to the temperature lower by 10 ° C. than the upper limit of the temperature range. The manufacturing method of the liquid crystal aligning film as described in said (5) or (6) which is.
(8) The liquid crystal according to any one of the above (5) to (7), wherein 20 mol% or more of the photocrosslinkable group of the side chain polymer film reacts by ultraviolet irradiation in the step [IV]. A method for producing an alignment film.
(9) The above (5) to (5), wherein the photosensitive group contained in the photocrosslinkable side chain polymer exhibiting liquid crystallinity is cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan, or a derivative thereof. The method for producing a liquid crystal alignment film according to any one of (8).

(10) The side chain type polymer film includes at least one main chain composed of at least one selected from the group consisting of hydrocarbons, acrylates and methacrylates, and at least one of the following formulas (1) to (7): The manufacturing method of the liquid crystal aligning film of any one of said (1)-(9) which is a structure which has a side chain represented by these.

(In Formula (1), A ₁ and B ₁ each independently represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and Y ₁ is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are independent of each other. May be substituted with —NO ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyl group, or an alkyloxy group, wherein X ₁ is a single bond, —COO—. , -OCO -, - N = N -, - C = C -, - C≡C-, or C ₆ H ₄ - represents, (also referred to as _{l 1)} l1 represents an integer of 1 to 12, m1 is 1 represents an integer of 1 to 3, and n1 represents an integer of 1 to 12. In formula (2), A ₂ , B ₂ , D ₁ independently represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and Y ₂ represents a benzene ring, naphthalene ring, biphenyl ring. , Furan ring, pyrrole ring, and at least one group selected from the group consisting of cyclic hydrocarbons having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are independently —NO ₂ , —CN, —C ═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyl group, or an alkyloxy group, where X ₂ is a single bond, —COO—, —OCO—, —N═N—. , -C = C -, - C≡C- , or C ₆ H ₄ - represents, _{R 1} represents a hydrogen atom, or (also referred to as _{l 2) .l2} represents an alkyl group having 1 to 6 carbon atoms is 1 12 represents an integer, m2 represents an integer of 1 to 3, and n2 represents an integer of 1 to 12. . To formula (3) in, _{A 3} is a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH-, or an NH-CO-, _{X 3} is a single bond, - COO—, —OCO—, —N═N—, —C═C—, —C≡C—, or C ₆ H ₄ —, wherein R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. represents .L3 (also referred to as _{l 3)} represents an integer of 1 to 12, in m3 is an integer of 1-3. equation (4), (also referred to as _{l 4)} l4 represents an integer of 1 to 12. In Formula (5), A ₄ represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, X ₄ represents —COO—, Y ₃ is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring, and each hydrogen atom bonded thereto is independently —N O ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyl group, or an alkyloxy group may be substituted. l5 (also referred to as _{l 5)} represents an integer of 1 to 12, m4 represents an integer of 1-3. In Formula (6), A ₅ represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and R ₃ represents a hydrogen atom, —NO ₂ , -CN, -C = C (CN) ₂ , -C = CH-CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, and an alkyloxy group having 1 to 6 carbon atoms. Represents a group of species. l6 (also referred to as _{l 6)} represents an integer of 1 to 12. _-NO 2 each independently hydrogen atom bonded to the benzene ring in formula _{(6), -CN, -C =} C (CN) 2, -C = CH-CN, a halogen group, an alkyl group, or an alkyl group May be substituted. In Formula (7), A ₆ represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and B ₃ represents a single bond, —COO—. , —OCO—, —N═N—, —C═C—, —C≡C—, or C ₆ H ₄ —. W ₁ is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are each Independently, it may be substituted with —NO ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyl group, or an alkyloxy group. l7 represents an integer of 1 to 12, and m5 and m6 each represents an integer of 1 to 3. )

(11) A liquid crystal alignment film manufactured by the method for manufacturing a liquid crystal alignment film according to any one of (1) to (10) above.
(12) A liquid crystal display device having the liquid crystal alignment film according to (11).

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the liquid crystal aligning film which enables highly efficient orientation processing is provided.
Moreover, the liquid crystal aligning film which enables highly efficient alignment processing can be provided using the manufacturing method of the liquid crystal aligning film. Furthermore, it is possible to provide a liquid crystal display device including a liquid crystal alignment film manufactured by realizing a highly efficient alignment process using the liquid crystal alignment film.

It is a figure of one example which illustrates typically the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film of the 1st form of this invention. (A) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, especially when the introduced anisotropy is small, that is, the above [I] to [IV] of the present invention. In the manufacturing method of the liquid crystal aligning film which has a process of (II), it is a schematic diagram when the ultraviolet irradiation amount of a [II] process exists in the range of 1%-15% of the ultraviolet irradiation amount which makes (DELTA) A the maximum. (B) is a figure which shows typically the state of the side chain type polymer film after polarized light irradiation, (c) is a figure which shows typically the state of the side chain type polymer film after a heating. (D) is a figure which shows typically the state of the side chain type polymer film irradiated with non-polarized light after a heating. The first form will be described later.

It is a figure of one example which illustrates typically the anisotropy introduction process in the manufacturing method of the liquid crystal aligning film of the 1st form of the present invention, especially when the introduced anisotropy is large, ie, the present invention In the method for producing a liquid crystal alignment film having the steps [I] to [IV], the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA. It is a schematic diagram in the case. (A) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, (b) is a figure which shows the state of the side chain type polymer film after polarized light irradiation typically. (C) is a diagram schematically showing the state of the side chain polymer film after heating, and (d) schematically shows the state of the side chain polymer film irradiated with non-polarized light after heating. FIG.

It is a figure of one example which illustrates typically the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film of the 2nd form of this invention, and especially a side chain type polymer is above-mentioned Formula (6). In the case of the structure represented, that is, in the production method having the steps [I] to [III] of the present invention, in the case where the side chain type polymer film having the structure represented by the formula (6) is used, [II] It is a schematic diagram when the amount of ultraviolet irradiation in the step is within a range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA. (A) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, (b) is a figure which shows the state of the side chain type polymer film after polarized light irradiation typically. (C) is a figure which shows typically the state of the side chain type polymer film after a heating. The second form will be described later.

It is a figure of one example which illustrates typically the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film of the 2nd form of this invention, and especially a side chain type polymer is above-mentioned Formula (7). In the case of the structure represented, that is, in the production method having the steps [I] to [III] of the present invention, when the side chain type polymer having the structure represented by the formula (7) is used, [ II] It is a schematic diagram when the ultraviolet ray irradiation amount in the step is within a range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA. (A) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, (b) is a figure which shows the state of the side chain type polymer film after polarized light irradiation typically. (C) is a figure which shows typically the state of the side chain type polymer film after a heating.

  The photosensitive side chain polymer film that can exhibit liquid crystallinity used in the method for producing a liquid crystal alignment film of the present invention is a photosensitive side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range. . And the side chain couple | bonded with a principal chain has photosensitivity, can respond to light, and can raise | generate a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement. The photosensitive group that binds to the main chain is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable. In this case, even if exposed to external stress 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 polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure.

  In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film. The polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip. A structure having a photosensitive group bonded to a moiety, which undergoes a crosslinking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogenic component, and A structure having a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction can be obtained.

  As a more specific example of the structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity, it is composed of at least one selected from the group consisting of hydrocarbon, acrylate, methacrylate, maleimide and siloxane. A structure having a main chain and a side chain composed of at least one of the following formulas (1) to (7) is preferable.

(A ₁ , B ₁ , X _1, Y ₁ , 11, m 1, n 1 in formula (1) are as defined above, and A ₂ , B ₂ , D _{1 in} formula (2) _, X ₂ , Y ₂ , R ₁ , l2, m2, and n2 are as defined above, and A ₃ , X ₃ , R ₂ , l3, and m3 in formula (3) are as defined above. 14 in formula (4) is as defined above, and A ₄ , X ₄ , Y ₃ , 15 and m4 in formula (5) are as defined above, and formula (6) _{a 5,} R _3, l6 in are as defined above _a 6 in. formula _{(7), B 3, W} 1, l7, m5, m6 are as defined above.)

  The side chain represented by the above formulas (1) to (7) has a structure having groups such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, and azobenzene as mesogenic components. And at the tip, it has a photosensitive group that undergoes a dimerization reaction in response to light and undergoes a crosslinking reaction, or has a main chain and a side chain bonded thereto, and the side chain also becomes a mesogenic component. And having at least one of phenylbenzoate groups that undergo a photo-Fries rearrangement reaction.

上記式（８）中、Ｅ_１は、単結合、−Ｏ−、−ＣＨ_２−、−ＣＯＯ、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−を表し、Ｚは単結合、−ＣＯＯ、−ＯＣＯ−、−Ｎ＝Ｎ−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、又はＣ₆Ｈ₄−を表し、ｋ１は１〜１２の整数を表し、ｐ１、ｑ１はそれぞれ独立して０〜３の整数を表し、Ｒ_４は水素原子、−ＮＯ_２、−ＣＮ、−Ｃ＝Ｃ（ＣＮ）_２、−Ｃ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜６のアルキルオキシ基、カルボキシル基、又はその組み合わせからなる基を表す。In the present invention, the side chain polymer film may be used in combination with a side chain structure having no photoreactivity within a range not losing liquid crystallinity and photoreactivity. For example, a structure like the following formula (8) can be mentioned.

In the above formula (8), E ₁ represents a single bond, —O—, —CH ₂ —, —COO, —OCO—, —CONH—, —NH—CO—, and 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, and p1 and q1 each independently represents 0. Represents an integer of ˜3, and R ₄ represents a hydrogen atom, —NO ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyloxy group having 1 to 6 carbon atoms, carboxyl The group which consists of group or its combination is represented.

Hereinafter, the photosensitive side chain polymer film capable of exhibiting liquid crystallinity used in the method for producing a liquid crystal alignment film of the present invention is simply referred to as a side chain polymer film of the present invention.
In the method for producing a liquid crystal alignment film of the present invention, after forming a coating film on a substrate using the side chain polymer of the present invention, polarized ultraviolet rays are irradiated. Next, a highly efficient anisotropy is introduced into the side chain polymer film by heating, and a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured. In the method for producing a liquid crystal alignment film of the present invention, a side chain polymer is obtained by utilizing the principle of molecular reorientation induced by the photoreaction and liquid crystallinity of the side chain polymer film of the present invention. Realizes highly efficient anisotropy introduction into the film. Furthermore, in the method for producing a liquid crystal alignment 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 a substrate using the side chain polymer of the present invention, The anisotropy introduced into the polymer film can be fixed by irradiating the ultraviolet ray, and then heating and then irradiating the non-polarized ultraviolet ray.

  FIG. 1 shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the method for producing a liquid crystal alignment film of the present invention. It is a figure of one example typically demonstrated. FIG. 1 (a) is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 1 (b) is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. FIG. 1 (c) is a diagram schematically showing a state of the side chain polymer film after heating, and FIG. 1 (d) is a side chain polymer film after non-polarized light irradiation. In the method for producing a liquid crystal alignment film having the steps [I] to [IV] of the present invention, particularly when the introduced anisotropy is small, [II] It is a schematic diagram in case the ultraviolet irradiation amount of a process exists in the range of 1%-15% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 2 shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a photocrosslinkable group as a photoreactive group in the method for producing a liquid crystal alignment film of the present invention. It is a figure of one example typically demonstrated. FIG. 2A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 2B is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. 2 (c) is a diagram schematically showing a state of the side chain polymer film after heating, and FIG. 2 (d) is a side chain polymer film after non-polarized light irradiation. In the method for producing a liquid crystal alignment film having the steps [I] to [IV] of the present invention, particularly when the introduced anisotropy is large, [II] It is a schematic diagram in case the ultraviolet irradiation amount of a process exists in the range of 15%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 3 shows a method for producing a liquid crystal alignment film according to the present invention, which is a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (6) as a photoreactive group. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a manufacturing method. FIG. 3A is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, and FIG. 3B is a schematic diagram of the state of the side chain polymer film after polarized light irradiation. FIG. 3 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the above-described aspect of the present invention. In a manufacturing method which has the process of [I]-[III], it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum. .

  FIG. 4 shows a method for producing a liquid crystal alignment film according to the present invention, wherein a liquid crystal alignment film using a side chain type polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (7) as a photoreactive group. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a manufacturing method. FIG. 4A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 4B is a schematic diagram of the state of the side chain polymer film after irradiation with polarized light. FIG. 4 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is large, that is, the above-mentioned of the present invention. In a manufacturing method which has the process of [I]-[III], it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum. .

Hereinafter, an embodiment using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, and a side chain polymer having a structure having a photofleece rearrangement group as a photoreactive group An embodiment using this will be described as a second embodiment.
In the method for producing a liquid crystal alignment film according to the first aspect of the present invention, in the process of introducing anisotropy into the side-chain polymer film, the ultraviolet irradiation amount at which the ultraviolet irradiation amount in the step [II] maximizes ΔA When the content is in the range of 1% to 15%, first, the side chain polymer film 1 of the present invention is formed on the substrate. As shown in FIG. 1A, the side chain polymer film 1 of the present invention formed on a substrate has a structure in which the side chains 2 are randomly arranged. According to the random arrangement of the side chain 2 of the side chain polymer film 1, the mesogenic component and the photosensitive group of the side chain 2 are also randomly oriented, and the side chain polymer film 1 is isotropic.

  In the method for producing a liquid crystal alignment film according to the first aspect of the present invention, in the process of introducing anisotropy into the side-chain polymer film, the ultraviolet irradiation amount at which the ultraviolet irradiation amount in the step [II] maximizes ΔA Is within the range of 15% to 70%, first, the side chain type polymer film 3 of the present embodiment is formed on the substrate. As shown in FIG. 2A, the side chain type polymer film 3 of the present invention formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chain 4 of the side chain polymer film 3, the mesogenic component and the photosensitive group of the side chain 4 are also randomly oriented, and the side chain polymer film 2 is isotropic.

  In the method for producing a liquid crystal alignment film according to the second aspect of the present invention, a structure having an optical fleece rearrangement group represented by the above formula (6) in the anisotropy introduction treatment to the side chain polymer film In the case of using the liquid crystal alignment film using the side chain type polymer of [II], when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, First, the side chain polymer film 5 of the present invention is formed on a substrate. As shown in FIG. 3A, the side chain polymer film 5 of the present invention formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the side chain polymer film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain polymer film 5 is isotropic.

  In the method for producing a liquid crystal alignment film according to the second aspect of the present invention, a structure having an optical fleece rearrangement group represented by the above formula (7) in the anisotropy introduction treatment to the side chain polymer film In the case of using the liquid crystal alignment film using the side chain type polymer of [II], when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, First, the side chain polymer film 7 of the present invention is formed on a substrate. As shown in FIG. 4A, the side chain polymer film 7 of the present invention formed on the substrate has a structure in which the side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the side chain polymer film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the side chain polymer film 7 is isotropic.

  In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, this isotropic side of the present invention. The chain polymer film 1 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 1B, the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 2a subjected to photoreaction becomes slightly higher 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 embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, this isotropic side of the present invention. The chain polymer film 3 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 2B, the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 4a subjected to photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, a small anisotropy is imparted to the side chain type polymer film 3 of the present invention.

  In the second embodiment of the present invention, ultraviolet irradiation in the step [II] is performed using a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group, represented by the above formula (6). When the amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic side chain 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 the photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 6a subjected to photoreaction becomes slightly higher 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 embodiment of the present invention, using the liquid crystal alignment film using the side chain type polymer having the structure having the optical fleece rearrangement group represented by the above formula (7), ultraviolet irradiation in the step [II] When the amount is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the isotropic side chain 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 the photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 8a subjected to photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, a small anisotropy is imparted to the side chain polymer film 7 of the present invention.

  Next, in the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, The side chain polymer film 1 is heated to a liquid crystal state. Then, as shown in FIG.1 (c), in the side chain type polymer film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light. As a result, the very small anisotropy of the side chain polymer film 1 of the present invention induced by the photocrosslinking reaction is amplified by heat, and the larger anisotropy is present in the side chain polymer film 1 of the present invention. Will be granted.

  Similarly, in the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the present invention after irradiation with polarized light. The side chain polymer film 3 is heated to a liquid crystal state. Then, as shown in FIG. 2C, in the side chain type polymer film 3, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light. As a result, the small anisotropy of the side chain polymer film 3 of the present invention induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted in the side chain polymer film 3 of the present invention. Will be.

  Similarly, in the second embodiment of the present invention, using the liquid crystal alignment film using the side chain type polymer having the structure having the optical fleece rearrangement group represented by the above formula (6), [II] step In the case where the UV irradiation amount is in the range of 1% to 70% of the UV irradiation amount that maximizes ΔA, the side chain polymer film 5 of the present invention after polarized light irradiation is heated to a liquid crystal state. . Then, as shown in FIG. 3 (c), in the side chain type polymer film 5, the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. . In this case, since the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light. The side chain 6 containing the mesogenic component is reoriented. As a result, the very small anisotropy of the side chain polymer film 5 of the present invention induced by the photofleece rearrangement reaction is amplified by heat, and is more anisotropic in the side chain polymer film 5 of the present invention. Sex will be given.

  Similarly, in the second embodiment of the present invention, using the liquid crystal alignment film using the side chain type polymer having the structure having the optical Fleece rearrangement group represented by the above formula (7), [II] step In the case where the UV irradiation amount is in the range of 1% to 70% of the UV irradiation amount that maximizes ΔA, the side-chain polymer film 7 of the present invention after polarized light irradiation is heated to a liquid crystal state. . Then, as shown in FIG. 4 (c), in the side chain polymer film 7, the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. . Since the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light. The side chain 8 containing the mesogenic component is reoriented. As a result, the small anisotropy of the side chain polymer film 7 of the present invention induced by the photofleece rearrangement reaction is amplified by heat, and the larger anisotropy is present in the side chain polymer film 7 of the present invention. Will be granted.

Furthermore, in the first embodiment of the present invention, when the photoreactive group of the side chain polymer of the present invention is a photocrosslinkable group, as shown in FIG. 1 (d) and FIG. 2 (d), As shown in Fig. 1 (c) and Fig. 2 (c), anisotropy is induced in the side chain polymer film by self-organization of mesogens, and then the large anisotropy induced by non-polarized light irradiation. Sex is fixed.
Therefore, in the method for producing a liquid crystal alignment film of the present invention, the side-chain polymer film of the present invention is irradiated with polarized ultraviolet rays and subjected to heat treatment. Further, in the case of the first embodiment of the present invention, after the heat treatment By sequentially performing non-polarized light irradiation, a liquid crystal alignment film having anisotropy introduced with high efficiency can be obtained.
And in the manufacturing method of the liquid crystal aligning film of this invention, the irradiation amount of the polarized ultraviolet-ray to the side chain type polymer film of this invention, and the heating temperature in heat processing are optimized. Thereby, introduction of anisotropy into the side chain type polymer film can be realized with high efficiency.

  As a result of intensive studies, the present inventor has obtained the following knowledge. That is, the optimum irradiation amount of polarized ultraviolet light for introducing highly efficient anisotropy into the side chain polymer film of the present invention is that the photo-sensitive group in the side chain polymer film is subjected to photocrosslinking reaction or photoisomerization. It corresponds to the irradiation amount of polarized ultraviolet rays that optimizes the amount of reaction or photofleece rearrangement reaction. As a result of irradiating the side-chain polymer film of the present invention with polarized ultraviolet rays, a sufficient amount of photoreaction can be obtained when there are few photogroups in the side chain that undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction. Not. In that case, sufficient self-organization does not proceed even after heating.

  On the other hand, when the side chain polymer film of the present invention is irradiated with polarized ultraviolet rays to the structure having a photocrosslinkable group, the crosslink reaction in the side chain occurs when the photopolymer of the side chain undergoing the crosslink reaction becomes excessive. Will progress too much. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating. In addition, when the side chain type polymer film of the present invention is irradiated with polarized ultraviolet rays to the structure having the light fleece rearrangement group, the side chain type becomes excessive when the side chain photosensitive group that undergoes the light fleece rearrangement reaction becomes excessive. The liquid crystallinity of the polymer film will be too low. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly due to subsequent overheating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photofleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side chain polymer of the present invention is photodegraded and then self-organized by overheating. May interfere with progress.

  Therefore, in the side chain type polymer film of the present invention, the optimum amount of the side chain photosensitive group that undergoes photocrosslinking reaction, photoisomerization reaction, or photofleece rearrangement reaction by irradiation with polarized ultraviolet rays is the side chain type high molecular weight film. It is preferable to make it 0.1 mol%-40 mol% of the photosensitive group which a molecular film has, and it is more preferable to set it as 0.1 mol%-20 mol%. In the present invention, by setting the amount of the photoreactive side chain photosensitive group within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and the highly efficient anisotropy in the film is achieved. Formation is possible.

  In the method for producing a liquid crystal alignment film of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement in the side chain of the side chain polymer film Optimize the amount of reaction. In combination with the subsequent heat treatment, high-efficiency introduction of anisotropy into the side chain polymer film is realized. In this case, a suitable amount of polarized ultraviolet light can be determined based on the evaluation of ultraviolet absorption of the side chain polymer film of the present invention.

  That is, with respect to the side chain polymer film of the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption in the vertical direction after irradiation with polarized ultraviolet light are measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, is evaluated. Then, 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 light that realizes it are obtained. In the method for producing a liquid crystal alignment film according to the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the irradiation amount of polarized ultraviolet rays that realizes this ΔAmax.

  In the method for producing a liquid crystal alignment film of the present invention, the irradiation amount of polarized ultraviolet rays on the side chain polymer film of the present invention is in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ΔAmax. Is preferable, and it is more preferable to set it within the range of 1% to 50%. In the side chain type polymer film of the present invention, the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ΔAmax is the total amount of photosensitive groups of the side chain type polymer film. 0.1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

  Next, in the method for producing a liquid crystal alignment film of the present invention, the side chain polymer film of the present invention is irradiated with polarized ultraviolet light, and then the side chain polymer film is heated. The side chain polymer film of the present invention is a polymer film that can exhibit liquid crystallinity in a predetermined temperature range. The heat treatment after irradiation with polarized ultraviolet rays can be determined based on the temperature at which the liquid crystallinity of the side chain polymer film is developed. That is, the heating temperature after irradiation with polarized ultraviolet rays ranges from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film of the present invention exhibits liquid crystallinity (hereinafter referred to as a liquid crystal temperature range). The temperature is preferably in the range up to 10 ° C. lower than the upper limit.

  The side chain polymer film of the present invention is heated after irradiation with polarized ultraviolet rays to be in a liquid crystal state, and self-organizes in a direction parallel to the polarization direction to be reoriented. As a result, the small anisotropy of the side chain polymer film of the present invention induced by the photocrosslinking reaction, photoisomerization reaction, and photofleece rearrangement reaction is amplified by heat. However, even when the side chain polymer film of the present invention exhibits a liquid crystal state by heating, if the heating temperature is low, the viscosity of the side chain polymer film in the liquid crystal state is high and realignment due to self-organization is not possible. It becomes difficult to occur. For example, when the heating temperature is in the range from the lower limit of the liquid crystal temperature range of the side chain polymer film of the present invention to a temperature higher by 10 ° C., the anisotropy amplification effect due to heat in the side chain polymer film of the present invention Cannot be sufficient.

  Further, even if the side chain polymer film of the present invention exhibits a liquid crystal state by heating, if the heating temperature is high, the state of the side chain polymer film becomes close to an isotropic liquid state, and self-organization This makes it difficult to reorient in one direction. For example, when the heating temperature is higher than the temperature lower by 10 ° C. from the upper limit of the liquid crystal temperature range of the side chain polymer film of the present invention, the anisotropy amplification effect due to heat in the side chain polymer film of the present invention Cannot be sufficient.

  As described above, the method for producing a liquid crystal alignment film of the present invention is suitable on the basis of the liquid crystal temperature range of the side chain polymer film in order to achieve highly efficient anisotropy introduction into the side chain polymer film. Determine the appropriate heating temperature. As described above, the heating temperature after irradiation with polarized ultraviolet light is 10 ° C. lower than the lower limit of the liquid crystal temperature range of the side chain polymer film, and the upper limit is 10 ° C. lower than the upper limit of the liquid crystal temperature range. The temperature is within the range. Therefore, for example, when the liquid crystal temperature range of the side chain polymer film of the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is preferably 110 ° C. to 190 ° C. By so doing, greater anisotropy is imparted to the side chain polymer film of the present invention.

The alignment treatment in the method for manufacturing a liquid crystal alignment film of the present invention has been described above. Next, the method for manufacturing a liquid crystal alignment film of the present invention will be described.
The method for producing a liquid crystal alignment film of the present invention includes the following steps [1] to [III] or the following steps [1] to [IV] in the following order. Then, a liquid crystal alignment film into which anisotropy is introduced is manufactured with high efficiency.
[I] forming a photosensitive side chain polymer film capable of exhibiting liquid crystallinity on a substrate;
[II] A step of irradiating the side chain type polymer film obtained in the step [I] with polarized ultraviolet rays [III] A step of heating the side chain type polymer film irradiated with the polarized ultraviolet rays in the step [II] [IV] A step of irradiating the non-polarized ultraviolet rays onto the side chain polymer film that has been irradiated with the ultraviolet rays and then heated The steps [I] to [III] of the method for producing a liquid crystal alignment film of the present invention Or each process of the following [1]-[IV] processes is explained.

  In step [I], the side chain polymer film of the present invention on the substrate is formed. The substrate is not particularly limited. For example, in addition to a glass substrate, a transparent substrate such as a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. In consideration of application of the obtained liquid crystal alignment film, a substrate on which an ITO (Indium Tin Oxide) electrode for driving a liquid crystal or the like is formed is used from the viewpoint of simplifying the manufacturing process of the liquid crystal display element. Is also possible. In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used. In this case, an electrode using a material that reflects light such as aluminum can also be used.

  When the side chain 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 applying the solution-like side chain polymer film. The method of coating is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an ink jet method, or the like is common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.

After the solution-like side chain polymer film of the present invention is applied on the substrate, it is 20 ° C. to 180 ° C., preferably 40 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The side chain polymer membrane of the present invention can be obtained by evaporating the solvent at ˜150 ° C. If the thickness of the side chain polymer film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element to which the liquid crystal alignment film is applied, and if it is too thin, the reliability of the liquid crystal display element may be lowered. It is 5 nm to 300 nm, more preferably 10 nm to 100 nm.
In addition, it is also possible to provide the process of cooling the board | substrate with which the side chain type polymer film was formed to room temperature after the [I] process and before the following [II] process.

In step [II], the side chain polymer film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the side chain polymer film with polarized ultraviolet rays, 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 having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the side chain polymer film to be used. For example, ultraviolet rays having a wavelength in the range of 250 nm to 400 nm can be selected and used so that a photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
As described above, the irradiation amount of the polarized ultraviolet light is preferably in the range of 1% to 70% of the amount of the polarized ultraviolet light that realizes ΔAmax of the side chain polymer film of the present invention to be used. More preferably, it is within the range of 50% to 50%.

In step [III], the side chain polymer film irradiated with the ultraviolet light polarized in step [II] is heated. For the heating, a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven is used. As described above, the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the side chain polymer film of the present invention to be used is developed. That is, the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the upper limit of the liquid crystal temperature range, with the temperature being 10 ° C. higher than the lower limit of the liquid crystal temperature range in which the side chain polymer film of the present invention used exhibits liquid crystallinity. It is preferable that the temperature is within a range where the lower temperature is the upper limit.
By having the above steps, the method for producing a liquid crystal alignment film of the present invention realizes highly efficient introduction of anisotropy into the side chain polymer film. And the liquid crystal aligning film of this invention can be manufactured highly efficiently.
In step [IV], the ultraviolet light is irradiated, and then the heated side chain polymer film is irradiated with unpolarized ultraviolet light. By this step, the side chain polymer film of the present invention that remains unreacted in the step [II] and is reoriented in the step [III] undergoes a crosslinking reaction, and the orientation is stabilized.
It is preferable to react 20 mol% or more of the photocrosslinkable group of the side chain polymer film by ultraviolet irradiation in the step [IV]. In other words, if 20 mol% or more of the photocrosslinkable group does not remain in the step [II], it is not easy to sufficiently stabilize the alignment in this step. This is because the re-orientated photoreactive group is difficult to be fixed in the aligned state. In the case of the above formulas (6) and (7), when this step is performed, it is not easy to exert the effect of the present invention.

The embodiment of the present invention will be described in more detail with reference to examples. In addition, this invention is limited to these and is not interpreted.
<Synthesis Example 1>
By heating 4,4′-biphenyldiol and 1,6-dibromohexane under alkaline conditions, 4 ′-(6-bromohexyloxy) biphenyl-4-ol was synthesized. This product was reacted with lithium methacrylate to give 2- (4′-hydroxybiphenyl-4-yloxy) hexyloxy methacrylate. Subsequently, 4-basic cinnamoyl 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 was reacted with methacrylic acid 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 alkaline conditions. This product was reacted with methacrylic acid chloride under basic conditions to obtain a compound represented by the following formula (11).
<Synthesis Example 4>
4- (6-hydroxyhexyloxy) iodophenol was synthesized by heating 4-iodophenol and 6-chloro-1-hexanol under alkaline conditions. This product was reacted with 2-methyl-3-butyn-2-ol and then heated under alkaline conditions to obtain 4- (6-hydroxyhexyloxy) ethynylbenzene (Compound A). In another route, 4-methoxycinnamic acid chloride and 4-iodophenol were reacted to synthesize 4-iodophenyl-3- (4-methoxyphenyl) acrylate (Compound B). Subsequently, a compound represented by the following formula (12) was obtained by reacting compound A and compound B under basic conditions.

<Synthesis Example 5>
After synthesizing 4- (6-hydroxyhexyloxy) benzoic acid by heating 1-hydroxybenzoic acid and 1-hydroxy-6-hexanol under alkaline conditions, 4- (6-hydroxyhexyloxy) benzoic acid is added by adding thionyl chloride. Hydroxyhexyloxy) benzoic acid chloride was obtained. This product was reacted with p-methoxyphenol under basic conditions to obtain a compound represented by the following formula (13).
<Synthesis Example 6>
The methacrylic acid ester represented by the above formula (9) was dissolved in tetrahydrofuran and polymerized by adding azobisisobutyronitrile (AIBN) as a reaction initiator to obtain a polymer 1. The polymer 1 exhibited liquid crystallinity in the temperature range of 116 ° C to 315 ° C.
<Synthesis Example 7>
The methacrylic acid ester represented by the above formula (10) was dissolved in tetrahydrofuran and polymerized by adding azobisisobutyronitrile (AIBN) as a reaction initiator to obtain a polymer 2. This polymer 2 exhibited liquid crystallinity in the temperature range of 135 ° C to 187 ° C.

<Synthesis Example 8>
The methacrylic acid ester represented by the above formula (10) and the methacrylic acid ester represented by the above formula (11) are dissolved in tetrahydrofuran at a ratio of 25 to 75, and azobisisobutyronitrile (AIBN) is used as a reaction initiator. Was added for polymerization to obtain a polymer 3. The polymer 3 exhibited liquid crystallinity in the temperature range of 146 ° C to 183 ° C.
<Synthesis Example 9>
The methacrylic acid ester represented by the above formula (12) was dissolved in tetrahydrofuran and polymerized by adding azobisisobutyronitrile (AIBN) as a reaction initiator to obtain a polymer 4. The polymer 4 exhibited liquid crystallinity in the temperature range of 66 ° C to 320 ° C.
<Synthesis Example 10>
Polymer 5 was obtained by dissolving the methacrylic acid ester represented by the above formula (13) in tetrahydrofuran, adding azobisisobutyronitrile (AIBN) as a reaction initiator and polymerizing. The polymer 5 exhibited liquid crystallinity in the temperature range of 143 ° C to 283 ° C.

<Creation of liquid crystal alignment film with anisotropy introduced>
<Example 1>
The polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride and spin-coated on an optically isotropic substrate with a thickness of about 190 nm to form a side chain polymer film on the substrate. Formed. When the ultraviolet absorption spectrum was measured using this substrate, the maximum absorbance was 0.89 at 314 nm. The side chain polymer film on the obtained substrate was irradiated with ultraviolet rays converted to linearly polarized light using a Grand Taylor prism.

  The side-chain polymer film on the substrate thus obtained was used to measure the ultraviolet absorption spectrum, and the side-chain polymer film was measured in a direction perpendicular to the UV absorbance in the direction parallel to the polarization direction of the irradiated polarized UV light. ΔA, which is the difference from the ultraviolet absorbance, was evaluated. ΔA reaches a maximum of 0.2 at 314 nm when irradiated with polarized ultraviolet light at a wavelength of 365 nm, but 650 mJ is irradiated so that ΔA is 0.065 (a difference of 32% with respect to the maximum value). Subsequently, the substrate was heated to 155 ° C., and the side chain polymer film was kept as a liquid crystal phase for 5 minutes. Then, it cooled to room temperature and obtained the board | substrate which has the side chain type polymer film into which the anisotropy was introduce | transduced in the film | membrane. At that time, ΔA was amplified to 1.8, and the degree of orientation was 0.73. Next, a substrate having a liquid crystal alignment film was obtained by irradiating the substrate having an anisotropically introduced side chain polymer film with non-polarized ultraviolet rays having a wavelength of 365 nm in terms of 1500 mJ.

<Example 2>
The polymer 1 obtained in Synthesis Example 6 was used, and the irradiation with polarized ultraviolet rays was performed in the same manner as in Example 1 except that the irradiation amount with polarized ultraviolet rays was 500 mJ (the irradiation amount with which ΔA was 25% of the maximum value of ΔA). The heat treatment was performed. As a result, ΔA before and after the heat treatment was amplified from 0.05 to 1.85, and the degree of orientation at that time was 0.74 at 314 nm. Thereafter, unpolarized ultraviolet rays were irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.
<Example 3>
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 (maximum value of ΔA). The amount of irradiation was 10% ΔA), and irradiation with polarized ultraviolet rays and subsequent heat treatment were performed in the same manner as in Example 1 except that the subsequent heat treatment was performed at 165 ° C. for 5 minutes. As a result, ΔA before and after the heat treatment was amplified from 0.03 to 1.6, and the degree of orientation at that time was 0.72 at 314 nm. Thereafter, 1000 mJ of non-polarized ultraviolet rays was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.
<Example 4>
Using the polymer 3 obtained in Synthesis Example 8, the polarized ultraviolet light irradiation and the subsequent treatment were performed in the same manner as in Example 3 except that the irradiation amount of the polarized ultraviolet light was 20 mJ (the irradiation amount at which ΔA was 40% of the maximum value of ΔA). The heat treatment was performed. As a result, ΔA before and after the heat treatment was amplified from 0.12 to 1.6, and the degree of orientation at that time was 0.62 at 314 nm. Thereafter, 1000 mJ of non-polarized ultraviolet rays was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.

<Example 5>
The polymer 4 obtained in Synthesis Example 9 was dissolved in methylene chloride, and a side chain polymer film was formed on the substrate by spin-coating to an optically isotropic substrate with a thickness of about 220 nm. Irradiation with polarized ultraviolet rays was performed in the same manner as in Example 1 except that the irradiation amount of polarized ultraviolet rays was 300 mJ (irradiation amount at which ΔA was 29% of the maximum value of ΔA), and the subsequent heat treatment was performed at 200 ° C. for 5 minutes. The heat treatment was performed. As a result, ΔA before and after the heat treatment was amplified from 0.04 to 1.4, and the degree of orientation at that time was 0.62 at 294 nm. Thereafter, in the same manner as in Example 1, 5000 mJ of non-polarized ultraviolet rays was irradiated to obtain a substrate having a liquid crystal alignment film.
<Example 6>
The polymer 5 obtained in Synthesis Example 10 was dissolved in methylene chloride and spin-coated on an optically isotropic substrate with a thickness of about 220 nm to form a side chain polymer film on the substrate. Irradiation with polarized ultraviolet rays was carried out in the same manner as in Example 1 except that the irradiation amount of polarized ultraviolet rays was 1000 mJ (irradiation amount at which ΔA was 49% of the maximum value of ΔA), and the subsequent heat treatment was carried out at 180 ° C. for 5 minutes. The heat treatment was performed. As a result, ΔA before and after the heat treatment was amplified from 0.07 to 1.7, and a substrate having a liquid crystal alignment film having an alignment degree of 0.72 at 262 nm was obtained.

<Comparative Example 1>
The polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride and spin-coated on an optically isotropic substrate with a thickness of about 190 nm to form a side chain polymer film on the substrate. Formed. When the ultraviolet absorption spectrum was measured using this substrate, the maximum absorbance was 0.89 at 314 nm. The side chain polymer film on the obtained substrate was irradiated with ultraviolet rays converted to linearly polarized light using a Grand Taylor prism.
The side-chain polymer film on the substrate thus obtained was used to measure the ultraviolet absorption spectrum, and the side-chain polymer film was measured in a direction perpendicular to the UV absorbance in the direction parallel to the polarization direction of the irradiated polarized UV light. ΔA, which is the difference from the ultraviolet absorbance, was evaluated. ΔA reaches a maximum of 0.2 at 314 nm when irradiated with polarized ultraviolet light at a wavelength of 365 nm, but 650 mJ is irradiated so that ΔA is 0.065 (a difference of 32% with respect to the maximum value). Subsequently, the substrate was heated to 155 ° C., and the side chain polymer film was kept as a liquid crystal phase for 5 minutes. Then, it cooled to room temperature and obtained the board | substrate which has the liquid crystal aligning film into which the anisotropy was introduce | transduced in the film | membrane. At that time, ΔA was amplified to 1.8, and the degree of orientation was 0.73.

<Comparative Example 2>
The polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride and spin-coated on an optically isotropic substrate with a thickness of about 190 nm to form a side chain polymer film on the substrate. A liquid crystal in which anisotropy was introduced into the film was carried out in the same manner as in Comparative Example 1 except that the irradiation amount of polarized ultraviolet light was 4500 mJ (the irradiation amount at which ΔA was the maximum value). An alignment film was obtained. At this time, ΔA before and after the heat treatment did not change from 0.07 to 0.07, the degree of orientation was 0.12 at 314 nm, and amplification of ΔA and the degree of orientation was not confirmed.
<Comparative Example 3>
The polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran and spin-coated on an optically isotropic substrate with a thickness of about 150 nm to form a side chain polymer film on the substrate. The irradiation with polarized ultraviolet light and the subsequent heat treatment were performed in the same manner as in Comparative Example 1 except that the irradiation amount of polarized ultraviolet light was 900 mJ (the irradiation amount at which ΔA was the maximum value) and the subsequent heat treatment was 165 ° C. A liquid crystal alignment film having an introduced directionality was obtained. At this time, ΔA before and after the heat treatment did not change from 0.07 to 0.07, the degree of orientation was 0.12 at 314 nm, and amplification of ΔA and the degree of orientation was not confirmed.

<Comparative Example 4>
The polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran and spin-coated on an optically isotropic substrate with a thickness of about 150 nm to form a side chain polymer film on the substrate. The same as Comparative Example 1 except that the irradiation amount of polarized ultraviolet rays was set to 5 mJ (the irradiation amount at which ΔA was 10% of the maximum value ΔA), and the subsequent heat treatment was set to 200 ° C. above the liquid crystal temperature range of polymer 2. Were subjected to polarized ultraviolet irradiation and subsequent heat treatment to obtain a liquid crystal alignment film. At this time, ΔA before and after the heat treatment decreased from 0.07 to 0, and the orientation became 0 at 314 nm, and the anisotropy in the polymer thin film disappeared.

<Creation and evaluation of liquid crystal cell>
<Example 7>
Using two substrates having the liquid crystal alignment film prepared in Example 1, an anti-parallel liquid crystal cell sandwiching liquid crystal ZLI-4792 manufactured by Merck Japan Ltd. was obtained. When the obtained liquid crystal cell was observed under crossed Nicols, uniform liquid crystal alignment without alignment failure was observed. In addition, two ITO substrates with a liquid crystal alignment film introduced with such anisotropy are produced, and a liquid crystal ZLI-4792 is sandwiched between them, and the obtained liquid crystal cell is further paired with a pair of linear polarizing plates. By sandwiching, a TN (Twisted Nematic) type liquid crystal display element having a liquid crystal thickness of 6 μm was produced. In this TN type liquid crystal display element, it was confirmed that the liquid crystal was driven by applying a voltage to the ITO electrode. The liquid crystal display element was confirmed to have no alignment defect over the entire surface, and a uniform change in the alignment of the liquid crystal due to voltage application was confirmed. The liquid crystal display element of this embodiment was able to be manufactured using the liquid crystal alignment film of this embodiment. The evaluation results are summarized in Table 1.
<Example 8>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Example 2. The results are shown in Table 1.
<Example 9>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Example 3. The results are shown in Table 1.
<Example 10>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Example 4. The results are shown in Table 1.

<Example 11>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Example 5. The results are shown in Table 1.
<Example 12>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Example 6. The results are shown in Table 1.
<Comparative Example 5>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Comparative Example 1. The results are shown in Table 1.
<Comparative Example 6>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Comparative Example 2. The results are shown in Table 1.
<Comparative Example 7>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Comparative Example 3. The results are shown in Table 1.
<Comparative Example 8>
A liquid crystal cell was prepared in the same manner as in Example 7 using the two substrates having the liquid crystal alignment film prepared in Comparative Example 4. The results are shown in Table 1.
From the above evaluation results, it was found that the liquid crystal alignment film of the present invention produced by using the method for producing a liquid crystal alignment film of the present invention with a small amount of ultraviolet irradiation can provide a liquid crystal display element.

The production method of the present invention is useful for producing a liquid crystal alignment film that enables highly efficient alignment treatment.
It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-260180 filed on November 29, 2011 are cited herein as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 Side chain type polymer film 2, 2a Side chain 3 Side chain type polymer film 4, 4a Side chain 5 Side chain type polymer film 6, 6a Side chain 7 Side chain type polymer film 8, 8a Side chain

Claims (12)

[I] A step of forming a photosensitive side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range on a substrate;
[II] A method for producing a liquid crystal alignment film, comprising: irradiating the side chain polymer film with polarized ultraviolet light; and [III] heating the side chain polymer film irradiated with ultraviolet light. ,
[II] The amount of UV irradiation in the step maximizes ΔA, which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV. The manufacturing method of the liquid crystal aligning film characterized by being in the range of 1%-70% of ultraviolet irradiation amount.   The method for producing a liquid crystal alignment film according to claim 1, wherein the ultraviolet irradiation amount in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount that maximizes the ΔA.   The heating temperature in the step [III] is a temperature in a range from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film exhibits liquid crystallinity to a temperature 10 ° C. lower than the upper limit of the temperature range. Item 3. A method for producing a liquid crystal alignment film according to Item 1 or 2.   The photosensitive group contained in the photosensitive side chain polymer exhibiting liquid crystallinity is azobenzene, stilbene, cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan, phenylbenzoate, or a derivative thereof. The manufacturing method of the liquid crystal aligning film of 1-3. [I] a step of forming a photocrosslinkable side chain polymer film that exhibits liquid crystallinity in a predetermined temperature range on a substrate;
[II] A step of irradiating the photocrosslinkable side chain polymer film with polarized ultraviolet light, and [III] a step of heating the side chain polymer film irradiated with ultraviolet light. [IV] The irradiation of the ultraviolet light. Then, a method for producing a liquid crystal alignment film comprising a step of irradiating non-polarized ultraviolet rays to the heated side chain polymer film,
[II] The amount of UV irradiation in the step maximizes ΔA, which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV. The manufacturing method of the liquid crystal aligning film characterized by being in the range of 1%-70% of ultraviolet irradiation amount.   6. The method for producing a liquid crystal alignment film according to claim 5, wherein the ultraviolet irradiation amount in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount that maximizes the ΔA.   The heating temperature in the step [III] is a temperature in a range from a temperature 10 ° C. higher than the lower limit of the temperature range in which the side chain polymer film exhibits liquid crystallinity to a temperature 10 ° C. lower than the upper limit of the temperature range. Item 7. A method for producing a liquid crystal alignment film according to Item 5 or 6.   The method for producing a liquid crystal alignment film according to claim 5, wherein 20 mol% or more of the photocrosslinkable group of the side chain polymer film reacts by ultraviolet irradiation in the step [IV].   9. The photosensitive group contained in the photocrosslinkable side chain polymer that exhibits liquid crystallinity is cinnamic acid, cinnamic acid ester, chalcone, coumarin, tolan, or a derivative thereof. A method for producing a liquid crystal alignment film. The side chain polymer film is represented by a main chain composed of at least one selected from the group consisting of hydrocarbon, acrylate, and methacrylate, and at least one of the following formulas (1) to (7). The method for producing a liquid crystal alignment film according to claim 1, wherein the structure has a side chain.

(In Formula (1), A ₁ and B ₁ each independently represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and Y ₁ is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are each independently _{-NO 2, -CN, -C = C} (CN) 2, -C = CH-CN, a halogen group, an alkyl group, or may be substituted with an alkyl group .X ₁ is a single bond, -COO-, —OCO—, —N═N—, —C═C—, —C≡C—, or C ₆ H ₄ —, wherein l1 represents an integer of 1 to 12, and m1 represents an integer of 1 to 3. , N1 represents an integer of 1 to 12. In formula (2), A ₂ , B ₂ and D ₁ are each independently Represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and Y ₂ represents a benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring. , And at least one group selected from the group consisting of cyclic hydrocarbons having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are independently —NO ₂ , —CN, —C═C (CN) _2. , -C = CH-CN, a halogen group, an alkyl group, or an alkyloxy group, 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 having 1 to 6 carbon atoms, l2 represents an integer of 1 to 12, and m2 represents 1 to 3. Represents an integer, and 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—, wherein X ₃ is a single bond, —COO—, —OCO—, —N═N—, —C═C -, - C≡C-, or C ₆ H ₄ - represents, _{R 2} is .l3 represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms is an integer of 1 to 12, m3 is from 1 to 3 In the formula (4), 14 represents an integer of 1 to 12. In the formula (5), A ₄ represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, -CONH-, or an NH-CO-, _{X 4} represents -COO-, _{Y 3} is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, and biphenyl ring, attached thereto Each independently represents —NO ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, It may be substituted with a kill group or an alkyloxy group. l5 represents an integer of 1 to 12, and 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—, and R ₃ represents a hydrogen atom, —NO ₂ , -CN, -C = C (CN) ₂ , -C = CH-CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, and an alkyloxy group having 1 to 6 carbon atoms. Represents a group of species. l6 represents an integer of 1 to 12. _-NO 2 each independently hydrogen atom bonded to the benzene ring in formula _{(6), -CN, -C =} C (CN) 2, -C = CH-CN, a halogen group, an alkyl group, or an alkyl group May be substituted. In Formula (7), A ₆ represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, or NH—CO—, and B ₃ represents a single bond, —COO—. , —OCO—, —N═N—, —C═C—, —C≡C—, or C ₆ H ₄ —. W ₁ is at least one group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded thereto are each Independently, it may be substituted with —NO ₂ , —CN, —C═C (CN) ₂ , —C═CH—CN, a halogen group, an alkyl group, or an alkyloxy group. l7 represents an integer of 1 to 12, and m5 and m6 each represents an integer of 1 to 3. )   The liquid crystal aligning film manufactured by the manufacturing method of the liquid crystal aligning film of any one of Claims 1-10.   The liquid crystal display element which has a liquid crystal aligning film of Claim 11.

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