JPWO2017135130A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention relates to a polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogenic compound, and (C) an organic solvent. ADVANTAGE OF THE INVENTION According to this invention, the alignment control ability is provided with high efficiency, the liquid crystal aligning film excellent in the image sticking characteristic, the polymer composition which gives it, and a horizontal electric field drive type liquid crystal display element are provided.

Description

  The present invention relates to a novel polymer composition, a liquid crystal alignment film using the same, and a method for producing a substrate having the alignment film. Further, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent tilt angle characteristics.

  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 polyimide remaining without being decomposed (see Patent Document 1).

  In addition, a photo-alignment method using a photocrosslinking type is 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. Furthermore, a pretilt angle appears by irradiating polarized ultraviolet rays in an oblique direction (see Non-Patent Document 1). In addition, when a side chain polymer having coumarin in the side chain is used, polarized UV light is irradiated to cause a photocrosslinking reaction in the coumarin part of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction parallel to the polarization direction. (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. In addition, since the alignment direction can be controlled by ultraviolet rays in the photo-alignment method, it is possible to form a plurality of regions having different alignment directions (alignment division) in a pixel to compensate for viewing angle dependency.

  On the other hand, the liquid crystal alignment film also plays a role of providing a certain tilt angle (pretilt angle) to the liquid crystal, and the provision of the pretilt angle has become an important issue in the development of liquid crystal alignment films (patents). Reference 3-6).

Japanese Patent No. 3893659 Japanese Unexamined Patent Publication No. 02-223916 Japanese Unexamined Patent Publication No. 04-281427 Japanese Patent Laid-Open No. 05-043687 Japanese Unexamined Patent Publication No. 10-333153

S. Kobayashi et al., Journal of Photopolymer Science and Technology, Vol.8, No.2, pp25-262 (1995). M. Shadt et al., Nature.Vol381, 212 (1996).

  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 stable liquid crystal alignment may not be realized, for example, a large amount of polarized light irradiation is required. .

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 / cm ² to several tens J / cm ² 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 liquid crystal alignment films and liquid crystals that can impart high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for aligning agents.

The present invention provides a substrate having a liquid crystal alignment film for a liquid crystal display element having high efficiency and orientation control ability and excellent tilt angle characteristics, and a vertical electrolytic driving type liquid crystal display element having the substrate (for example, twisted nematic (TN : Twisted Nematic (LCD) element, Vertical Alignment (VA) liquid crystal display element, STN (Super-Twisted Nematic) liquid crystal display element, ECB (Electrically Controlled Birefringence) liquid crystal display element, and OCB (Optically Compensated Bend) ) Type liquid crystal display element).
In addition to the above object, the object of the present invention is to provide a vertical electrolytic drive type (for example, twisted nematic type liquid crystal display element, VA type liquid crystal display element, STN type liquid crystal display element, ECB type liquid crystal having improved tilt angle characteristics. It is to provide a display element and an OCB type liquid crystal display element) and a liquid crystal alignment film for the element. Note that the vertical electrolysis-driven liquid crystal display element is a method of driving liquid crystal molecules by applying an electric field in a direction perpendicular to the substrate surface.

As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogenic compound, and an organic solvent.

<2> In the above item <1>, the reactive mesogenic compound of the component (B) may be a compound represented by the following formula (I).
P-Sp-X-MG-X-Sp-P (I)
[In the formula (I),
P is a polymerizable group,
Sp is a spacer group having 1 to 20 carbon atoms,
X is a group or a single bond selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCO—O—,
MG is a mesogenic group or mesogenic supporting group, which group is preferably selected according to the following formula II:
_{^{- (A 1 -Z 1) m}} -A 2 -Z 2 -A 3 - (II)
(In the formula (II), A ¹ , A ² and A ³ are each independently 1,4-phenylene group, and one or two or more CH groups present in this group are also represented by N May be substituted or is a 1,4-cyclohexylene group, in which one CH ₂ group or _two non-adjacent CH ₂ groups are also represented by O and / or S May be substituted, or is a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, all of which are unsubstituted or one or more halogens, Optionally substituted by a cyano or nitro group, or by an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, in which one or more H atoms are F or Cl May be replaced by
Z ¹ and Z ² are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —CC═, —CH = CH-COO-, -OCO-CH = CH- or a single bond, and m is 0, 1 or 2.)].

  <3> In the above item <1> or <2>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.

  <4> In the above <1> or <2>, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

[Wherein, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded through a bonding group B, and the hydrogen atoms bonded thereto are each independently -COOR ₀ (wherein R ₀ is an alkyl having 1 to 5 carbon atoms). represents a _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms May be substituted with;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents an alkoxy group having 1 to 6 carbon atoms or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

<5> In any one of the above items <1> to <4>, the component (A) further has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (30). Is good.
Wherein A, B, R, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (26), the sum of all m is 2 or more, and m1, m2 and m3 are Each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁₁ and Z _{12 each} represent a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —.

<6> [I] The process of apply | coating the polymer composition as described in any of said <1>-<5> on the board | substrate which has an electrode for a liquid crystal drive, and forming a coating film;
[II] A step of irradiating the coating film obtained in [I] with ultraviolet rays polarized from an oblique direction; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for vertical electrolysis drive type liquid crystal display elements by which orientation control ability was provided by having.
<7> A substrate having a liquid crystal alignment film for a vertical electrolysis-driven liquid crystal display device manufactured by the manufacturing method according to the above <6>.
<8> A vertical electrolysis driving type liquid crystal display device having the substrate of <7> above.
<9> A twisted nematic liquid crystal display element or OCB type liquid crystal display element having the substrate of <7> above.

<10> a step of preparing the substrate (first substrate) of <7>above;
Steps [I] to [III] of <6> above are used to obtain a second substrate; and [IV] The liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal. A step of arranging the first and second substrates to face each other to obtain a liquid crystal display element;
A method for producing a liquid crystal display element, wherein a vertical electrolysis drive type liquid crystal display element is obtained.
<11> [IV] In the step, the first and second substrates are arranged to face each other so that the alignment directions are orthogonal to each other so that the liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal. A method for producing a twisted nematic liquid crystal display element, which is a process for obtaining a liquid crystal display element.
<12> A vertical electrolytic driving type liquid crystal display device manufactured according to the above <10>.
<13> A twisted nematic liquid crystal display device manufactured according to the above item <11>.

According to the present invention, a substrate having a liquid crystal alignment film with high efficiency and orientation control ability and excellent tilt angle characteristics, and a vertical electrolysis-driven liquid crystal display device having the substrate (for example, a twisted nematic liquid crystal display device, VA type) Liquid crystal display elements, STN liquid crystal display elements, ECB liquid crystal display elements, and OCB liquid crystal display elements) can be provided.
The vertical electrolysis driving type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, so that the display characteristics are not impaired even when continuously driven for a long time.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition The coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail.

<< (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
(A) The side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C to 300 ° C.
The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.

  (A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can react with light to cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement. The structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more 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.

  More specific examples of the structure of the photosensitive side chain polymer that can exhibit liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as maleimide and norbornene and siloxane, and a photosensitive side chain composed of at least one of the following formulas (1) to (6) It is preferable that it has a structure.

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded through a bonding group B, and the hydrogen atoms bonded thereto are each independently -COOR ₀ (wherein R ₀ is an alkyl having 1 to 5 carbon atoms). represents a _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms May be substituted with;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents an alkoxy group having 1 to 6 carbon atoms or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m and R have the same definition as above.

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , X, 1, m1, and m2 have the same definition as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.

The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definition as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

The side chain is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definition as above.

The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (30).
Wherein A, B, R, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (26), the sum of all m is 2 or more, and m1, m2 and m3 are Each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁₁ and Z _{12 each} represent a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —.

<< Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferred.

  More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene. And a polymerizable side group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain consisting of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitivity represented by the above formula (14) or (15). A photosensitive side chain, a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20). Has sex side chain It is preferable that the structure be

  As such a photoreactive side chain monomer, a monomer that exhibits a dimerization reaction or an isomerization reaction when irradiated with polarized ultraviolet rays is preferable. Examples of such a monomer include monomers selected from the following formulas M1-1 to M1-22.

(In the formula, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number of 2 to 9.)

(In the formula, R is an alkoxy group having 1 to 6 carbon atoms, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number of 2 to 9.)

[Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.

  More specific examples of the liquid crystalline side chain monomer include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups. A structure having a polymerizable group composed of at least one selected from the group consisting of siloxane and a side chain composed of at least one of the above formulas (21) to (30) is preferable.

  As a specific example of such a liquid crystalline monomer, for example, a monomer represented by a formula selected from the group consisting of the following formulas M2-1 to M2-10 can also be used.

(Wherein M1 is a hydrogen atom or a methyl group, R is an alkoxy group having 1 to 6 carbon atoms, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, It is a natural number.)

  (A) The side chain type polymer can be obtained by a copolymerization reaction of the above-described photoreactive side chain monomer exhibiting liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

  Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.

  Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  The content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 95 mol%, more preferably 30 mol% from the viewpoint of liquid crystal alignment. -90 mol% is still more preferable.

  The content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, more preferably 10 mol% to 70 mol%, from the viewpoint of liquid crystal alignment. Is more preferable.

  The side chain type polymer of the present invention may contain other side chains other than the photoreactive side chain and the liquid crystalline side chain. The content is the remaining portion when the total content of the photoreactive side chain and the liquid crystalline side chain is less than 100%.

  The method for producing the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

  As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent can be used.

  The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Sanic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

  The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- N-di-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2,4-cyclopentadi) N-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2, -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.

  The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

  The polymerization temperature during radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.

[Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

  The molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the resulting coating film, workability during coating film formation, and coating film uniformity. The weight average molecular weight is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.

<< (B) RM (reactive mesogenic compound) >>
In a preferred embodiment of the present invention, the reactive mesogenic compound used in the liquid crystal aligning agent is a compound represented by the following formula I:
P-Sp-X-MG-X-Sp-P (I)
[In the formula (I),
P is a polymerizable group,
Sp is a spacer group having 1 to 20 carbon atoms,
X is a group or a single bond selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCO—O—,
MG is a mesogenic group or mesogenic supporting group, which group is preferably selected according to the following formula (II):
_{^{- (A 1 -Z 1) m}} -A 2 -Z 2 -A 3 - (II)
(Where
A ¹ , A ² and A ³ are, independently of one another, a 1,4-phenylene group, one or more CH groups present in this group may also be replaced by N; Or a 1,4-cyclohexylene group, in which one CH ₂ group or _two non-adjacent CH ₂ groups may also be replaced by O and / or S, Or a 1,4-cyclohexenylene group or naphthalene-2,6-diyl group, all of which are unsubstituted or by one or more halogen, cyano or nitro groups, or Optionally substituted by alkyl groups, alkoxy groups or alkanoyl groups having 1 to 7 carbon atoms, in which one or more H atoms are substituted by F or Cl You may,
Z ¹ and Z ² are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —CC═, —CH = CH-COO-, -OCO-CH = CH- or a single bond, and m is 0, 1 or 2)].

Particularly suitable are polymerizable mixtures which contain at least two reactive mesogenic compounds, at least one of which is a compound of the formula I.
Bicyclic and tricyclic mesogenic compounds are preferred.
Halogen is preferably F or Cl.

Among the compounds represented by Formula I, MG is in Formula II, is Z ¹ and ^{Z 2, -COO -, - OCO} -, - CH 2 -CH 2 -, - CH = CH-COO -, - OCO- Particularly preferred are compounds in which CH═CH— or a single bond.

  A small group of preferred mesogenic groups represented by Formula II is shown below. For simplicity, in these groups, Phe is 1,4-phenylene and PheL is 1,4-phenylene substituted with at least one group L, where L is F, Cl or It is CN or an alkyl, alkoxy or alkanoyl group which has 1 to 4 carbon atoms and may be fluorinated, and Cyc is trans-1,4-cyclohexylene.

In these preferred groups, Z ¹ and Z ² have the meanings indicated for formula I above. Preferably, Z ¹ and Z ² are —COO—, —OCO—, —CH ₂ CH ₂ — or —CH═CH—COO—.
L is preferably F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OCF ₅ , In particular, F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ and OCF ₃ , most preferably F, CH ₃ , OCH ₃ and COCH ₃ .

  Particularly preferred are compounds wherein MG is selected from the following formula:

In these formulas, L has the above meaning and r is 0, 1 or 2.
In these preferred formulas, the group:

Is very preferably

And, again,

In these groups, each L independently has one of the above meanings.
R present in these preferred compounds has one of the meanings indicated for P- (Sp) _n- .

P is preferably CH ₂ ═CW—COO—, WCH═CH—O—,

Or selected from CH ₂ = CH-phenyl- (O) _K , where W is H, CH ₃ or Cl and k is 0 or 1.

  P is particularly preferably a vinyl group, acrylate group, methacrylate group, propenyl group or epoxy group, very particularly preferably an acrylate group.

As the spacer group Sp, all groups known to those skilled in the art for this purpose can be used. The spacer group Sp is preferably bonded to the polymerizable group P by an ester or ether group or by a single bond. The spacer group Sp preferably has from 1 to 20 carbon atoms, in particular from 1 to 12 carbon atoms, and also presents one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups. Are —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, A linear or branched alkylene group optionally substituted by —CO—O—, —CH (halogen) —, —CH (CN) —, —CH═CH— or —C≡C—. .

Representative spacer groups are, for example, — (CH ₂ ) ₀ —, — (CH ₂ CH ₂ O) _r —CH ₂ CH ₂ —, —CH ₂ CH ₂ —S—CH ₂ CH ₂ — or —CH ₂ CH _2. -NH-CH ₂ CH ₂ - and are, in these radicals, o is an integer from 2 to 12, and r is an integer of 1 to 3.

  Suitable spacer groups are, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyliminoethylene and 1-methylalkylene.

  In formula I, two P, Sp and X may be the same or different.

  Representative examples of polymerizable mesogenic compounds represented by Formula I are shown in the following compound list. However, this list is merely illustrative and does not limit the scope of the invention.

In these compounds, x and y are each independently 1 to 12, M ¹ is a hydrogen atom or a methyl group, and L ¹ and L ² are each independently H, halogen or CN. Or an alkyl group, alkoxy group or alkanoyl group having 1 to 7 carbon atoms.
These compounds are known in the literature or are commercially available.

<< (C) Organic solvent >>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. These may be used alone or in combination.

<Polymer composition>
A polymer composition is applied to the side of the substrate on which the electrode is formed.
The polymer composition used in the production method of the present invention comprises (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogenic compound, and (C) an organic compound. Contains a solvent.

[Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain polymer capable of exhibiting the liquid crystallinity already described. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers may be mixed within the range. In that case, content of the other polymer in a resin component is 0.5 mass%-80 mass%, Preferably it is 1 mass%-50 mass%.
Examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.

  The polymer composition used for this invention may contain components other than the said (A) component, (B) component, and (C) organic solvent. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate. However, the present invention is not limited to this.

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.

  These poor solvents may be used alone or in combination. When using the solvent as described above, it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

  Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, the addition of the following phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.

  Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4 4'-diaminodiphenylmethane and the like.

  When using the compound which improves adhesiveness with a board | substrate, it is preferable that the usage-amount is 0.1 mass part-30 mass parts with respect to 100 mass parts of the resin component contained in a polymer composition. More preferably, it is 1 mass part-20 mass parts. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

  A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.

As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino substituted Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

The method for producing a substrate having the liquid crystal alignment film of the present invention is as follows.
[I] (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a polymer composition containing a reactive mesogenic compound and an organic solvent, and an electrode for driving a liquid crystal Applying on a substrate having a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above-described steps, a vertical electrolysis-driven liquid crystal display element (for example, a twisted nematic liquid crystal display element, a vertical alignment type liquid crystal display element, an STN type liquid crystal display element, an ECB type liquid crystal display element, and an OCB type liquid crystal provided with alignment control ability) A liquid crystal alignment film for display element) can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In addition to the obtained substrate (first substrate), a second substrate is prepared, whereby a vertical electrolytic drive type liquid crystal display element (for example, a twisted nematic type liquid crystal display element, a vertical alignment type liquid crystal display element). STN liquid crystal display elements, ECB liquid crystal display elements, and OCB liquid crystal display elements) can be obtained.
As the second substrate, by using the above steps [I] to [III], a second substrate having a liquid crystal alignment film to which alignment control ability is imparted can be obtained.

The manufacturing method of the vertical electrolytic drive type liquid crystal display element
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have At that time, in the substrates with the first and second alignment films obtained above and having a tilt angle of 10 to 50 degrees, the rubbing direction (liquid crystal alignment) is parallel and the same direction (parallel alignment). If arranged in this manner, an OCB type liquid crystal display element can be obtained. When the same method is performed using two substrates with alignment films having a tilt angle of 80 to 90 degrees, a vertical alignment type liquid crystal display element can be obtained. A twisted nematic liquid crystal display element can be obtained if the rubbing directions are orthogonal to each other, that is, twisted about 90 degrees, and an STN type liquid crystal display element can be obtained if the rubbing directions are twisted about 260 degrees. . Further, when the substrates with the first and second alignment films obtained above are arranged so that the alignment treatment directions are parallel to each other and opposite to each other (anti-parallel), an ECB type liquid crystal display element can be obtained.

Hereinafter, each process of [I]-[III] and [IV] which the manufacturing method of this invention has is demonstrated.
<Process [I]>
In step [I], (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogenic compound, and an organic solvent are formed on a substrate having electrodes for driving liquid crystal. The polymer composition contained is applied to form a coating film.

<Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
As an electrode for driving the liquid crystal, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or the like is preferable. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
A conventionally known method can be used as a method of forming an electrode on the substrate.

The method for applying the polymer composition described above onto a substrate having an electrode for driving a liquid crystal is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. 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 polymer composition is applied on the substrate having the electrodes for driving the liquid crystal, it is 50 to 230 ° C., preferably 50 to 200 ° C., by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The solvent can be evaporated for 0.4 to 60 minutes, preferably 0.5 to 10 minutes to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.

<Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with ultraviolet rays polarized from an oblique direction. When irradiating the surface of the coating 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 coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

  The irradiation amount of polarized ultraviolet rays depends on the coating film used. The amount of irradiation is polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light. The amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.

  The irradiation direction of the polarized ultraviolet rays is usually 1 ° to 89 ° with respect to the substrate, preferably 10 ° to 80 °, particularly preferably 20 ° to 70 °. When this angle is too small, there is a problem that the pretilt angle becomes small, and when it is too large, there is a problem that the pretilt angle becomes high.

  As a method of adjusting the irradiation direction to the above angle, there are a method of tilting the substrate itself and a method of tilting the light source. It is more preferable to tilt the light source itself from the viewpoint of throughput.

<Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.

The heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk. The Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range which makes an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board | substrate with a liquid crystal aligning film can be manufactured highly efficiently.

<Process [IV]>
[IV] The process includes two substrates obtained in [III] arranged so that the side on which the liquid crystal alignment film is formed faces each other, a liquid crystal layer provided between the substrates, a substrate and a liquid crystal layer And a liquid crystal cell having the liquid crystal alignment film formed with the liquid crystal aligning agent of the present invention. As such a vertical electrolysis drive type liquid crystal display element of the present invention, a twisted nematic (TN) type, a vertical alignment (VA) type, a STN (Super-Twisted Nematic) type liquid crystal display element, an ECB (ECB) There are various types such as an electrically controlled birefringence (OCB) type liquid crystal display element and OCB alignment (OCB: Optically Compensated Bend).

  To give an example of the production of a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Thus, to obtain a twisted nematic type element, the ultraviolet light exposure directions are orthogonal to each other. To obtain other elements, the other substrate is bonded as described above, and the liquid crystal is injected under reduced pressure. Examples include a method of sealing, a method of performing sealing by bonding a substrate after dropping liquid crystal on a liquid crystal alignment film surface on which spacers are dispersed, and the like. The spacer diameter at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

  The obtained liquid crystal display element is preferably annealed for further alignment stability. The heating temperature is the phase transition temperature of the liquid crystal, preferably 10 to 160 ° C, more preferably 50 to 140 ° C.

The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.

  Therefore, the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.

  And in the coating film used for the method of this invention, the irradiation amount of the polarized ultraviolet-ray to a coating film, and the heating temperature in heat processing are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.

  The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film. Corresponds to the irradiation amount of polarized ultraviolet rays to optimize the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, if the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating. On the other hand, as a result of irradiating polarized ultraviolet rays to the structure having a photocrosslinkable group in the coating film used in the present invention, the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating. In addition, when the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.

  Therefore, in the coating film used in the present invention, the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferable to make it 0.1 mol%-40 mol% of the photosensitive group which has, and it is more preferable to set it as 0.1 mol%-20 mol%. By making the amount of the photo-reactive side chain photosensitive group within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and the formation of highly efficient anisotropy in the film is possible. Become.

  In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

  That is, the ultraviolet absorption in the direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet absorption in the vertical direction after irradiation with polarized ultraviolet light are measured for the coating film used in the present invention. 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 of ΔA (ΔAmax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained. In the production method of 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 amount of polarized ultraviolet rays to realize this ΔAmax.

  In the production method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays realizing ΔAmax. More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays realizing ΔAmax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

  From the above, in the production method of the present invention, in order to achieve highly efficient anisotropy introduction into the coating film, a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

  By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.

  As described above, the vertical electrolytic driving type liquid crystal display element substrate manufactured by the method of the present invention or the vertical electrolytic driving type liquid crystal display element having the substrate has excellent reliability and has a large screen. It can be suitably used for high-definition liquid crystal televisions.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

Abbreviations used in the examples are as follows.
<Methacrylic monomer>

<Liquid crystal compound>

MA1 was synthesized with reference to Macromolecules 2007, 40, 6355-6360.
PLC1 was purchased and used.
As PLC2, LC242 (BASF), which is commercially available, was used.
PLC4 was synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
PLC5 is a novel compound that has not been published yet. PLC5 was synthesized using PLC4 and PLC5-1, and details thereof will be described in “<Synthesis of Compound PLC5>” below. In addition, PLC5-1 was synthesize | combined by the synthesis method as described in literature (Liquid Crystals (2005), 32 (8), 1031-1044.).
As the PLC6, commercially available M6BC (manufactured by Midori Chemical Co., Ltd.) was used.

<Synthesis of Compound PLC5>
In a 500 mL four-necked flask, compound PLC4 (20.00 g, 65.3 mmol), compound PLC5-1 (14.09 g, 71.8 mmol), EDC (15.02 g, 78.4 mmol), DMAP (0.80 g, 6.53 mmol) and THF (200 g) were added, and the reaction was performed at 23 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (2 L) was added, and the aqueous layer was removed by a liquid separation operation. The organic layer was washed 3 times with distilled water (500 mL), and then the organic layer was dried over magnesium sulfate. Then, filtration and evaporation of the solvent with an evaporator gave Compound PLC5-2 as an oily compound. Subsequently, pyridinium p-toluenesulfonic acid (indicated as PPTS) (1.59 g, 6.3 mmol) and ethanol (100 g) were added to the obtained compound PLC5-2, and the mixture was heated and stirred at 60 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 19.2 g (yield 69%) of compound PLC5.
¹ H-NMR (400 MHz, CDCl3, δ ppm): 8.22-8.18 (2H, m), 8.17-8.14 (2H, m), 7.36-7.32 (2H, m), 7.00-6.96 (2H, m), 6.12- 6.11 (1H, m), 5.57-5.55 (1H, m), 4.20-4.16 (2H, m), 4.06 (2H, t), 1.96-1.95 (3H, m), 1.90-1.46 (8H, m).

The conditions for measuring the molecular weight of the resin are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Shodex column (KD-803, KD-805),
Column temperature: 50 ° C.
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) at 10 ml / L),
Flow rate: 1.0 ml / min,
Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4) manufactured by Polymer Laboratories , 1,000, 1,000).

<Organic solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

<Polymerization initiator>
AIBN: 2,2′-azobisisobutyronitrile

<Methacrylate polymer synthesis example 1>
MA1 (28.6 g, 50.0 mmol) is dissolved in NMP (163.7 g), degassed with a diaphragm pump and purged with nitrogen, then AIBN (0.25 g, 1.5 mmol) is added and degassed again. Ventilated and purged with nitrogen. Thereafter, the mixture was reacted at 60 ° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (5000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder P1. The number average molecular weight of the obtained methacrylate polymer was 46,000, and the weight average molecular weight was 119,600.
NMP (114.0 g) was added to the resulting methacrylic polymer powder (A) (6.0 g), and dissolved by stirring at room temperature for 5 hours. BCS (30.0g) was added to this solution, and liquid crystal aligning agent B1 was obtained by stirring at room temperature for 5 hours.

<Example 1>
0.04 g (10% by mass with respect to the solid content) of the liquid crystalline compound PLC1 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B2.
When the obtained liquid crystal aligning agent B2 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Example 2>
0.10 g (25% by mass with respect to the solid content) of the liquid crystalline compound PLC1 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B3.
When the obtained liquid crystal aligning agent B3 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Example 3>
0.10 g (25% by mass with respect to the solid content) of the liquid crystalline compound PLC2 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B4.
When the obtained liquid crystal aligning agent B4 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Comparative Example 1>
0.10 g (25% by mass with respect to the solid content) of the liquid crystalline compound PLC3 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent D1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B5.
When the obtained liquid crystal aligning agent B5 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Comparative Example 2>
0.10 g (25% by mass with respect to solid content) of the liquid crystalline compound PLC4 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B6.
When the obtained liquid crystal aligning agent B6 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Comparative Example 3>
0.10 g (25% by mass with respect to the solid content) of the liquid crystalline compound PLC5 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent B7.
When the obtained liquid crystal aligning agent B7 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Comparative example 4>
0.10 g (25% by mass based on solid content) of the liquid crystalline compound PLC6 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 1, and the mixture is stirred at room temperature for 3 hours. Then, a liquid crystal aligning agent B8 was prepared.
When the obtained liquid crystal aligning agent B8 was preserve | saved for one day with the freezer and thawed | decompressed, the deposit was not confirmed.

<Example 4>
[Production of liquid crystal cell]
Using the liquid crystal aligning agent B3 obtained in Example 1, a twisted nematic liquid crystal cell was produced according to the procedure shown below.
The liquid crystal aligning agent B3 obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern was formed, dried on a hot plate at 70 ° C. for 90 seconds, and then horizontally with respect to the substrate. A polarized ultraviolet ray of 313 nm tilted by 40 ° was irradiated by 50 mJ / cm ² and heated for 10 minutes on a 200 ° C. hot plate to form a liquid crystal alignment film having a thickness of 100 nm. After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Subsequently, after bonding with two board | substrates so that the orientation direction might be orthogonal, the sealing agent was hardened and the empty cell was produced. A liquid crystal MLC-2003 (C080) (trade name, manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method to produce a twisted nematic liquid crystal cell. The produced liquid crystal cell was then placed in a 120 ° C. hot-air circulating oven for 1 hour to realign the liquid crystal.

<Example 5>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the angle of the polarized ultraviolet light was changed to 30 °.

<Example 6>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the polarized ultraviolet irradiation angle was 45 °.

<Example 7>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the liquid crystal aligning agent B4 was used instead of the liquid crystal aligning agent B3.

<Example 8>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent B4 was used instead of the liquid crystal aligning agent B3.

<Example 9>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal aligning agent B4 was used instead of the liquid crystal aligning agent B3.

<Example 10>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal aligning agent B2 was used instead of the liquid crystal aligning agent B3.

<Comparative Example 5>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the liquid crystal aligning agent B1 was used instead of the liquid crystal aligning agent B3 in Example 4.

<Comparative Example 6>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal aligning agent B1 was used instead of the liquid crystal aligning agent B3.

<Comparative Examples 7 to 10>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal aligning agents B5 to B8 were used instead of the liquid crystal aligning agent B3.

(Pretilt angle measurement)
The pretilt angle (°) of the twisted nematic liquid crystal cell was measured by “Axo Scan” manufactured by Axo Metrix and using the Mueller matrix method.

The results were as shown in Table 1 below.

  As shown in Table 1, in Examples 4 to 10 in which the reactive mesogen compound as the component (B) was added, the obtained liquid crystal alignment film exhibited a pretilt angle suitable for the twisted nematic mode. On the other hand, in Comparative Examples 5 and 6 using the liquid crystal aligning agent to which the reactive mesogenic compound as the component (B) is not added, the pretilt angle is 50 ° to 58 °, which is not suitable for the twisted nematic mode. There wasn't. In Comparative Examples 7 to 10, which are examples in which a compound that is not a mesogenic compound was added, the pretilt angle was 0 °.

  As described above, an arbitrary pretilt can be exhibited by irradiating ultraviolet rays obliquely onto the alignment film including the liquid crystal compound in the examples according to the present invention. It is possible to provide a liquid crystal alignment film suitable for the twisted nematic mode.

<Example 11>
A liquid crystal cell was produced in the same manner as in Example 6, and then irradiated with 5 J / cm ^{2 of} UV through a 365 nm bandpass filter from the outside of the liquid crystal cell.
(Voltage holding ratio (VHR) evaluation)
For evaluation of VHR, a voltage of 5 V was applied to the obtained liquid crystal cell at a temperature of 60 ° C. for 60 μs, and a holding voltage of the liquid crystal cell was measured after 16.67 ms.

The results were as shown in Table 2 below.

As shown in Table 2, since the voltage holding ratio is improved by polymerizing the liquid crystalline compound in the liquid crystal cell by irradiating with 365 nm ultraviolet light in Example 11 according to the present invention, the long-term reliability is excellent. A liquid crystal display element can be provided.

Claims (13)

(A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range (B) A polymer composition containing a reactive mesogenic compound and (C) an organic solvent. The polymer composition according to claim 1, wherein the reactive mesogenic compound of component (B) is a compound represented by the following formula (I).
P-Sp-X-MG-X-Sp-P (I)
[In the formula (I),
P is a polymerizable group,
Sp is a spacer group having 1 to 20 carbon atoms,
X is a group or a single bond selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCO—O—,
MG is a mesogenic group or mesogenic supporting group, which group is preferably selected according to the following formula II:
_{^{- (A 1 -Z 1) m}} -A 2 -Z 2 -A 3 - (II)
(In the formula (II), A ¹ , A ² and A ³ are each independently 1,4-phenylene group, and one or two or more CH groups present in this group are also represented by N May be substituted or is a 1,4-cyclohexylene group, in which one CH ₂ group or _two non-adjacent CH ₂ groups are also represented by O and / or S May be substituted, or is a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, all of which are unsubstituted or one or more halogens, Optionally substituted by a cyano or nitro group, or by an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, in which one or more H atoms are F or Cl May be replaced by
Z ¹ and Z ² are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —CC═, —CH = CH-COO-, -OCO-CH = CH- or a single bond, and m is 0, 1 or 2.)].   The polymer composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition. The polymer composition according to claim 1 or 2, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

[Wherein, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded through a bonding group B, and the hydrogen atoms bonded thereto are each independently -COOR ₀ (wherein R ₀ is an alkyl having 1 to 5 carbon atoms). represents a _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms May be substituted with;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents an alkoxy group having 1 to 6 carbon atoms or the same definition as Y ₁ ;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof].
(A) component is following formula (21)-(31) [In formula, A and B have the same definition as the above;
Wherein A, B, R, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (26), the sum of all m is 2 or more, and m1, m2 and m3 are Each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁₁ and Z _{12 each} represent a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —. ] The polymer composition as described in any one of Claims 1-4 which has any 1 type of liquid crystalline side chain chosen from the group which consists of].

[I] The process of apply | coating the composition as described in any one of Claims 1-5 on the board | substrate which has an electrode for liquid-crystal drive, and forming a coating film;
[II] A step of irradiating the coating film obtained in [I] with ultraviolet rays polarized from an oblique direction; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which alignment control ability was provided by having.   A substrate having a liquid crystal alignment film produced by the method according to claim 6.   A vertical electrolytic driving type liquid crystal display device comprising the substrate according to claim 7.   A twisted nematic liquid crystal display element or OCB type liquid crystal display element comprising the substrate according to claim 7. Preparing a substrate (first substrate) according to claim 7;
A step of obtaining a second substrate by using the steps [I] to [III] according to claim 6; and [IV] The liquid crystal alignment films of the first and second substrates face each other through the liquid crystal. And obtaining a liquid crystal display element by arranging the first and second substrates to face each other;
A method for producing a liquid crystal display element, wherein a vertical electrolysis drive type liquid crystal display element is obtained.   [IV] A liquid crystal display element in which the first and second substrates are arranged to face each other so that the alignment directions are orthogonal to each other so that the liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal A method for producing a twisted nematic liquid crystal display element, which is a step of obtaining   A vertical electrolytic driving type liquid crystal display device manufactured by the method according to claim 10. A twisted nematic liquid crystal display device manufactured by the method according to claim 11.