JPWO2017199986A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

【選択図】なし
ADVANTAGE OF THE INVENTION According to this invention, the novel polymer composition which provides the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements which was provided with the highly efficient alignment control ability and was excellent in the image sticking characteristic, and a horizontal electric field drive type using the same A liquid crystal alignment film for a liquid crystal display element is provided. The present invention has (A) a side chain (a1) having a photoreactive site represented by the following formula (a), and a photoreactive site different from the photoreactive site represented by the following formula (a). The present invention relates to a polymer composition containing a side chain (a2) and a side chain polymer having a side chain (a3) that exhibits liquid crystallinity; and (B) an organic solvent.
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element using the same, and a polymer film suitable for the production of an optical element with controlled molecular alignment such as a retardation film and a polarization diffraction element. .

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

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

A rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction). This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. As an organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of dust or static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized.
Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed.

  There are various photo alignment methods. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy. The main alignment methods are “photolytic type” that causes anisotropic decomposition of the molecular structure by irradiation with polarized UV light, and polyvinyl cinnamate is used to irradiate polarized UV light, and two sides parallel to the polarized light. "Dimerization type" that causes a dimerization reaction (crosslinking reaction) at the double bond portion of the chain (see, for example, Patent Document 1), when a side chain polymer having azobenzene in the side chain is used Irradiation with polarized ultraviolet rays causes an isomerization reaction at the azobenzene moiety in the side chain parallel to the polarized light, and aligns the liquid crystal in a direction perpendicular to the polarization direction (for example, see Non-Patent Document 2). It is known.

  On the other hand, in recent years, a new photo-alignment method (hereinafter also referred to as an alignment amplification method) using a photosensitive side chain polymer capable of exhibiting liquid crystallinity has been studied. This is because a film having a photosensitive side chain polymer capable of exhibiting liquid crystallinity is subjected to an alignment treatment by polarized light irradiation, and then the side chain polymer film is heated, and then the alignment control ability is improved. The applied coating film is obtained. 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 imparted with a high alignment control ability can be obtained (see, for example, Patent Document 2).

  Furthermore, since the polymer film obtained by this alignment amplification method exhibits birefringence due to molecular orientation, it can be used as various optical elements such as a retardation film in addition to the use of a liquid crystal alignment film. it can.

Japanese Patent No. 3893659 WO2014 / 054785

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

  The optimal irradiation dose of polarized ultraviolet rays for introducing highly efficient anisotropy into liquid crystal alignment films used in alignment amplification methods is the irradiation dose of polarized ultraviolet rays that optimizes the amount of photoreactive reaction of photosensitive groups in the coating film. Corresponding to As a result of irradiating polarized ultraviolet rays to the liquid crystal alignment film used in the alignment amplification method, if there are few photoreactive side groups, the amount of photoreaction will not be sufficient. In that case, sufficient self-organization does not proceed even after heating. On the other hand, if the photoreactive side-chain photosensitive group becomes excessive, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.

  Currently, some of the liquid crystal alignment films used in the alignment amplification method have a narrow range of the optimal amount of polarized ultraviolet light irradiation because of the high sensitivity of the photoreactive group in the polymer used. is there. As a result, a decrease in manufacturing efficiency of the liquid crystal display element is a problem.

  Furthermore, when the firing temperature of the liquid crystal alignment film is low, the reliability of the liquid crystal display element may be lowered due to the influence of the residual solvent, etc., but the liquid crystal aligning agent obtained by the alignment amplification method is not suitable for polymer liquid crystals. Since baking cannot be performed at a temperature equal to or higher than the liquid crystal expression temperature, the baking temperature is generally low, and the residual solvent contributes to a decrease in reliability.

  In view of the above, an object of the present invention is to provide a liquid crystal alignment film having a wide process margin that can be adjusted to an optimal polarized ultraviolet ray irradiation amount and an optimal baking temperature, with high efficiency and alignment control ability.

  As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.

<1> (A) Side chain (a1) having a photoreactive site represented by the following formula (a), side having a photoreactive site different from the photoreactive site represented by the following formula (a) A side chain polymer having a chain (a2) and a side chain (a3) exhibiting liquid crystallinity; and (B) a polymer composition containing an organic solvent.

  <2> In the above item <1>, the side chain (a2) may be a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.

  <3> In the above item <1> or <2>, the side chain (a2) is any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6), It is preferable that the side chain has a photoreactive site different from the photoreactive site represented by the formula (a).

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 groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and binds to them. Each hydrogen atom is independently —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy having 1 to 5 carbon atoms. May be substituted with groups;
R represents a hydroxy group, 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; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
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.

<4> In any one of the above items <1> to <3>, the side chain (a3) is any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). It is good.
In which A and B 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;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 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 ₁ and Z _{2 each} represents a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —.

<5> [I] The process of apply | coating the composition in any one of said <1>-<4> on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
<6> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of <5>.
<7> A lateral electric field drive type liquid crystal display device having the substrate of <6> above.
<8> Step of preparing the substrate (first substrate) of <6>above;
[I ′] A step of applying the polymer composition of any one of the above <1> to <17> on the second substrate to form 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 ′];
Obtaining a liquid crystal alignment film imparted with alignment control ability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment films of the first and second substrates via liquid crystal The liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
<9> A lateral electric field drive type liquid crystal display device manufactured according to the above <8>.

  According to the present invention, a polymer having a specific structural unit can be obtained, and when the obtained polymer is used as a liquid crystal alignment film, it exhibits better alignment in a wider range of UV irradiation than a conventional polymer. Thereby, in order to implement | achieve the various characteristics calculated | required by a liquid crystal display element, when performing a photo-alignment process, it can carry out by various polarized UV irradiation doses conventionally, and productivity improves. As a result, a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which has high efficiency and high alignment control ability and excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate are obtained with high yield. Can be provided.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as a side chain polymer) that can exhibit liquid crystallinity, and is obtained using the polymer composition. The obtained coating film 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 the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

  Moreover, in the polymer composition in this invention, the side chain type polymer which is (A) component contains the side chain represented by the said Formula (a). Thereby, the liquid crystal aligning film obtained from the polymer composition of this invention shows favorable orientation in a wider UV irradiation amount as a UV irradiation amount at the time of manufacture. In this phenomenon, the photoreactive site represented by the above formula (a) has fluorescence characteristics due to a long conjugated system, and thereby absorbs ultraviolet rays. Therefore, the use of a polymer obtained by copolymerizing a monomer having a photoreactive site represented by the above formula (a) was considered to increase the irradiation margin. These include the inventor's view on the mechanism of the present invention, and do not restrict the present invention.

  Moreover, in the polymer composition in the present invention, in addition to the side chain polymer as the component (A) and the organic solvent as the component (B), a tetracarboxylic acid derivative and a diamine compound are used as the component (C). Polyamic acid produced by polymerization reaction, or polyimide produced by imidizing polyamic acid, polyurea produced by polymerizing diisocyanate compound and diamine compound, diisocyanate compound and tetracarboxylic acid derivative, Polyurea polyamic acid produced by polymerizing a diamine compound and polyurea polyimide produced by imidizing polyurea polyamic acid can also be contained.

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

<Polymer composition>
A polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention is:
(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
A side chain (a1) having a photoreactive site represented by the following formula (a),
A side chain (a2) having a photoreactive site different from the photoreactive site represented by the following formula (a), and a side chain (a3) exhibiting liquid crystallinity
And (B) an organic solvent.

<< (A) Side chain polymer >>
The side chain polymer of the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
A side chain (a1) having a photoreactive site represented by the above formula (a);
A side chain (a2) having a photoreactive site different from the photoreactive site represented by the formula (a),
And a side chain (a3) that exhibits liquid crystallinity.

The (A) component 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 side chain type polymer of the component (A) preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The side chain polymer of the component (A) preferably has a side chain (a3) that exhibits liquid crystallinity in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.

<<< Side Chain (a2): Side Chain Having Photoreactive Site Different from Photoreactive Site Represented by Formula (a) >>>
The side chain polymer of the component (A) has a side chain (a2) having a photoreactive site different from the photoreactive site represented by the formula (a). Here, “having a photoreactive site different from the photoreactive site represented by formula (a)” has a photoreactive site, but the photoreactive site represented by formula (a) is It means that it does not have. That is, the side chain (a2) is a side chain that has a site that undergoes a crosslinking reaction, an isomerization reaction, or a photofleece rearrangement in response to light, and that does not have a photoreactive site represented by the formula (a). That is.

  The side chain type polymer of component (A) has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light. 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 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 (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, It has a structure having a main chain composed of at least one selected from the group consisting of radical polymerizable groups such as norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6). Is preferred.

In the above formulas (1) to (6), A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—. , -CH = CH-CO-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 groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and binds to them. Each hydrogen atom is independently —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy having 1 to 5 carbon atoms. May be substituted with groups;
R represents a hydroxy group, 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; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
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.

  According to a preferred embodiment of the present invention, the side chain (a2) is any one photosensitive side chain selected from the group consisting of the above formulas (1) to (6), It is a side chain having a photoreactive site different from the photoreactive site represented.

The side chain (a2) 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 (a2) may be any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definition as above.

The side chain (a2) is preferably a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , l, m1 and m2 have the same definition as above.

The side chain (a2) 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.

Further, the side chain (a2) is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, 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 (a2) 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.

<<< Side Chain (a1): Side Chain Having Photoreactive Site Represented by Formula (a) >>>
Moreover, the side chain type polymer of the component (A) contains a side chain (a1) having a photoreactive site represented by the following formula (a).

  As the side chain (a1), for example, a side chain represented by the following formula (a1-1) is preferable.

In the formula (a1-1), L is a linear or branched alkylene having 1 to 16 carbon atoms.
In formula (a1-1), X represents a single bond, —O—, —C (═O) —O—, or —O—C (═O) —.

<<< Side Chain (a3): Side Chain Expressing Liquid Crystalline >>>
Further, the side chain polymer of the component (A) contains a side chain (a3) that exhibits liquid crystallinity. Here, the side chain (a3) is a side chain that exhibits liquid crystallinity, and is itself a side chain that can exhibit mesogenicity, or by dimerizing by hydrogen bonding or the like, mesogenicity is achieved. A side chain that can be expressed.

That is, as the side chain (a3) that exhibits liquid crystallinity in the side chain polymer of the component (A), for example, any one liquid crystal selected from the group consisting of the following formulas (21) to (31) A side chain is preferred.
In which A, B, 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 (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 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 ₁ and Z _{2 each} represents 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 liquid crystal properties is a monomer having a structural unit represented by the formula (a), a photoreaction different from the photoreactive site represented by the formula (a). It can be obtained by polymerizing a photoreactive side chain monomer (M1) having a reactive site and a liquid crystalline side chain monomer (M2).

[Monomer having a structural unit represented by the formula (a)]
Examples of the monomer having the structural unit represented by the formula (a) include a compound represented by the following formula (am1-1).

In the formula (am1-1), L is a linear or branched alkylene having 1 to 16 carbon atoms.
In formula (am1-1), X represents a single bond, —O—, —C (═O) —O—, or —O—C (═O) —.
In the formula (am1-1), PL is a polymerizable group and represents a polymerizable group selected from the group consisting of the following formulas PL-1 to PL-5. In the formulas PL-1 to PL-5, R ¹ and R ² , R ³ are each a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a C 1-10 carbon atom substituted with halogen. A linear or branched alkyl group is represented (* represents a bonding position with L).

  Some of these monomers are commercially available, and some can be produced from known substances by known production methods.

[Photoreactive side chain monomer (M1)]
The photoreactive side chain monomer is a monomer capable of forming a polymer having the photosensitive side chain (a2) at the side chain site 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 photoreactive side chain monomers include (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and siloxanes. A polymerizable group composed of at least one selected from the group consisting of the above and a photosensitive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formulas (7) to ( 10) a photosensitive side chain comprising at least one of the above, a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitive side chain represented by the above formula (14) or (15). 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 photosensitive side chain represented by the above formula (20). With structure Preferably there is.

  More specific examples of the monomer (M1) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and siloxanes. A polymerizable group composed of at least one selected from the group consisting of: a structure that exhibits photoreactivity and liquid crystallinity composed of at least one of the above formulas (1) to (6), preferably, for example, A structure that exhibits photoreactivity and liquid crystallinity comprising at least one of the above formulas (7) to (10), and photoreactivity and liquid crystallinity that comprises at least one of the above formulas (11) to (13). Structure, structure expressing photoreactivity and liquid crystallinity expressed by the above formula (14) or (15), photoreactivity and liquid expressed by the above formula (16) or (17) Structure that exhibits crystallinity, structure that exhibits photoreactivity and liquid crystallinity represented by the above formula (18) or (19), structure that exhibits photoreactivity and liquid crystallinity represented by the above formula (20) It is preferable that the structure has

  The monomer (M1) is polymerized in the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38 to MA42, MA44 and MA46, and their compounds. The polymerizable group of the compound having methacrylate as a functional group is replaced with a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is good that it is at least one selected from compounds. In particular, the monomer (M1) may have (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

  MA1 to MA46 can be synthesized as follows.

MA1 can be synthesized by a synthesis method described in a patent document (WO2011-084546).
MA2 can be synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
MA3 can be synthesized by a synthesis method described in non-patent literature (Macromolecules 2002, 35, 706-713).
MA4 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA5 can be synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 2010-18807).
MA6 to MA9 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
As MA10, commercially available M6BC (manufactured by Midori Chemical Co., Ltd.) can be used.
MA11-13 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA14-18 are commercially available, and M4CA, M4BA, M2CA, M3CA, and M5CA (all manufactured by Midori Chemical Co., Ltd.) can be used.
MA19-23 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
MA24 can be synthesized by a synthesis method described in non-patent literature (Polymer Journal, Vol. 29, No. 4, pp 303-308 (1997)).
MA25 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA26 and MA27 are the synthesis methods described in non-patent literature (Macromolecules (2012), 45 (21), 8547-8554) and non-patent literature (Liquid Crystals (1995), 19 (4), 433-40), respectively. Can be synthesized.
MA28 to 33 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA34 to 39 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
MA40 and 41 can be synthesized by a synthesis method described in a patent document (Japanese translations of PCT publication No. 2009-511431).
MA42 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA43 can be synthesized by a synthesis method described in a patent document (WO2012-115129).
MA44 can be synthesized by the synthesis method described in the patent document (WO2013-1333078).
MA45 can be synthesized by a synthesis method described in a patent document (WO2008-072652).
MA46 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).

[Monomer (M2) having a structure exhibiting only liquid crystallinity and its production method]
The monomer (M2) having a structure that exhibits only liquid crystallinity is a monomer that allows a polymer derived from the monomer to exhibit liquid crystallinity and to 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. The following structure is preferable as the mesogenic group of the side chain.

  More specific examples of the monomer (M2) having a structure exhibiting only liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, A structure having a structure composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and at least one of the above formulas (21) to (31). Is preferred.

  The monomer (M2) is a polymer of the above formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45, and compounds having methacrylate as a polymerizable group in these compounds. At least one selected from the group consisting of compounds in which the group is replaced by a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane It is good to be. In particular, the monomer (M2) may have (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

[Monomer having crosslinkable group (M3)]
The polymer as component (A) is (M-3) a monomer having a crosslinkable group, specifically, the following formulas (G-1), (G-2), (G-3) and (G-4). And a monomer (M3) having at least one group selected from the group consisting of: a monomer having a structure represented by the following formula (0).

(In the formula (0), S, A, P, X, Q, B, T, 11 and 12 represent the same meaning as defined in the formula (1), and G represents the above (G-1), (G- 2) represents a group selected from (G-3) and (G-4), a broken line represents a bond, and R ⁵⁰ is selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group. And when there are a plurality of R ^{50 s} , they may be the same or different from each other, t is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ has 1 carbon atom. Represents a group selected from an alkyl group of ~ 3 and a phenyl group.)

[Monomer having structure represented by formula (0)]
More specific examples of the monomer having the structure represented by the above formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, It preferably has a polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and a structure represented by the above formula (0).

  Among such monomers, specific examples of the monomer having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether. Among them, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5 Examples include hexene and 1,7-octadiene monoepoxide.

Specific examples of the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.
Specific examples of the monomer having an aziridine include those in which the epoxy structure of the monomer having an epoxy group is replaced with aziridine or 1-methylaziridine.

  Examples of the monomer having an oxetane group include (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyl-oxetane, 3- (acryloyloxymethyl) -3- Methyl-oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- ( Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2 -(Ac Royloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane are preferred, and 3- (methacryloyloxymethyl) -3-ethyl- And oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, and the like.

  As the monomer having a thietane group, for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with a thietane group is preferable.

  As the monomer having an azetan group, for example, a monomer in which an oxetane group of a monomer having an oxetane group is replaced with an azetan group is preferable.

  Among the above, a monomer having an epoxy group and a monomer having an oxetane group are preferable from the viewpoint of availability and the like, and a monomer having an epoxy group is more preferable. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of availability.

[Monomer having nitrogen-containing aromatic heterocyclic group (M4)]
The polymer (A1) and / or the polymer (A2) is, as desired, a monomer (M4) having at least one group selected from the group consisting of (M-4) a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. ); May be formed.

The nitrogen-containing aromatic heterocycle is selected from the group consisting of the following formula [20a], formula [20b] and formula [20c] (wherein Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms). It may be an aromatic cyclic hydrocarbon containing at least one, preferably 1 to 4 structures selected.

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
Of these, for example, a pyridine ring is preferred.

  When the polymer as the component (A) has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, an ionic impurity when the polymer composition of the present invention is used as a liquid crystal alignment film. In order to reduce the elution of the liquid crystal and promote the cross-linking reaction of the cross-linkable group, more specifically the cross-linking reaction of the group represented by the formula (0), or to obtain a more durable liquid crystal alignment film be able to. In order to produce a polymer having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, the monomer (M4) has the structural unit represented by the monomer (M1) and the formula (a). The monomer and the monomer (M2) may be copolymerized with the monomer (M3) if desired.

  The monomer (M4) is selected from the group consisting of hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane. It preferably has a polymerizable group composed of at least one kind and a structure having a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. NH in the amide group and urethane group may or may not be substituted. Examples of the substituent in the case where it may be substituted include an alkyl group, an amino-protecting group, and a benzyl group.

  Among such monomers, as a monomer having a nitrogen-containing aromatic heterocyclic group, specifically, for example, 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate, 2- (3-pyridylcarbonyloxy) Examples include ethyl (meth) acrylate, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.

  Specific examples of the monomer having an amide group or a urethane group include 2- (4-methylpiperidin-1-ylcarbonylamino) ethyl (meth) acrylate and 4- (6-methacryloyloxyhexyloxy) benzoic acid. Examples include N- (tertiary butyloxycarbonyl) piperidin-4-yl ester, 4- (6-methacryloyloxyhexyloxy) benzoic acid 2- (tertiary butyloxycarbonylamino) ethyl ester, and the like.

  (M-4) A monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group is represented by the above formulas MA6 to MA8 and MA33, and Polymerizability in which the polymerizable group of the compound having a methacrylate as a polymerizable group in the compound is selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane It may be at least one selected from the group consisting of compounds in which the group is replaced.

  As described above, it can be copolymerized with other monomers as long as the photoreactivity and / or 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 method for producing at least two kinds of polymers of the present invention is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, a monomer having a structural unit represented by the above formula (a), a photoreactive side chain monomer having a photoreactive site different from the photoreactive site represented by the above formula (a) ( It can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of M1) and the liquid crystalline side chain monomer (M2). 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 peroxycyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Acid-tert-amyl ester), 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 monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) the monomer (M2) having a structure that exhibits only liquid crystallinity are copolymerized to form at least two kinds of polymers of the present invention. The organic solvent used in the reaction for obtaining each is not particularly limited as long as the produced 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 produced | generated polymer, you may mix and use the above-mentioned organic solvent in the range which the produced | generated polymer 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 the produced polymer is recovered from the reaction solution obtained by the above-described reaction, the reaction solution may be poured into a poor solvent to precipitate these polymers. 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 the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and coating film uniformity. The weight average molecular weight is preferably 2000 to 2000000, and more preferably 5000 to 150,000. Or the said weight average molecular weight becomes like this. Preferably it is 2000-1 million, More preferably, it is 5000-200000.

<< (B) 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.

<< Arbitrary ingredient >>
The polymer composition used for this invention may contain components other than the said (A), (B) and (C) component. 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.

  In the polymer composition, in addition to the above-described ones, a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired. Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.

[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 includes the above-described component (A) and the above-described solvent and compound that improve the film thickness uniformity and surface smoothness, and the compound that improves the adhesion between the liquid crystal alignment film and the substrate. Etc. are preferably prepared as a solution in an organic solvent. Here, the content of the component (A) 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 this embodiment, in addition to the component (A), other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired. 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.

<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for producing a substrate having the liquid crystal alignment film of the present invention is as follows.
[I] (A) Side chain (a1) having a photoreactive site represented by the above formula (a), side having a photoreactive site different from the photoreactive site represented by the above formula (a) A side chain polymer having a chain (a2) and a side chain (a3) that exhibits liquid crystallinity; and (B) a polymer composition containing an organic solvent, a conductive film for lateral electric field driving Applying on a substrate having a coating to form 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 steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In the second aspect of the present invention, a method for producing a substrate having the liquid crystal alignment film of the present invention comprises:
[I] (A) Side chain (a1) having a photoreactive site represented by the above formula (a), side having a photoreactive site different from the photoreactive site represented by the above formula (a) A side chain polymer having a chain (a2) and a side chain (a3) that exhibits liquid crystallinity; and (B) a polymer composition containing an organic solvent, a conductive film for lateral electric field driving Applying on a substrate having a coating to form 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 steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field drive type liquid crystal display element can be obtained.
The second substrate is replaced with a substrate having no lateral electric field driving conductive film instead of a substrate having no lateral electric field driving conductive film, except that the above steps [I] to [III] (lateral electric field driving For the sake of convenience, the substrate having no conductive film is sometimes referred to as processes [I ′] to [III ′] in some cases for the sake of convenience. Two substrates can be obtained.

The manufacturing method of the horizontal electric field drive type liquid crystal display element is:
[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 Thereby, a horizontal electric field drive 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 polymer composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving a lateral electric field. 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.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for driving lateral electric field>
The substrate has a conductive film for driving a lateral electric field.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
In the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

The method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field 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 onto the substrate having the conductive film for driving the transverse electric field, it is 50 to 200 ° 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 at 150 ° C. 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 polarized ultraviolet rays. 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%.

<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 a temperature range of a temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). In the case of a thin film surface such as a coating film, the liquid crystallinity expression temperature of the coating film surface may be lower than the liquid crystallinity expression temperature when a photosensitive side chain polymer capable of expressing liquid crystallinity is observed in bulk. is expected. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystallinity 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 upper limit of the liquid crystal temperature range, with the temperature being 10 ° C. lower than the lower limit of the temperature range of the liquid crystalline expression temperature of the side chain polymer used. It is preferable that the temperature is in a range where the temperature is the 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 crystallinity temperature is equal to or higher 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). Refers to a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

  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]>
The step [IV] is performed in the same manner as the above [I ′] to [III ′] in the same manner as the substrate (first substrate) obtained in [III] and having a liquid crystal alignment film on the conductive film for driving a horizontal electric field. The obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of manufacturing a lateral electric field drive type liquid crystal display element. The steps [I ′] to [III ′] are the same as the steps [I] except that a substrate having no lateral electric field driving conductive film is used instead of the substrate having the lateral electric field driving conductive film. It can carry out similarly to process [I]-[III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.

  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. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. , Etc. can be illustrated. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a horizontal electric field as the substrate on one side. 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 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 lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.

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

M1 and M2 as monomers having a photoreactive group used in the examples, M3 as a monomer having a liquid crystal group, HBAGE as a monomer having a crosslinking group, and A1 as a monomer having an amide group are shown below.
M1, M2, and M3 were each synthesized as follows. That is, M1 was synthesized by a synthesis method described in a patent document (WO2011-084546). M2 was synthesized by a synthesis method described in a patent document (WO2014 / 054785 pamphlet). M3 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). A polymer formed using M1 as a monomer has photoreactivity and liquid crystallinity, and a polymer formed using M3 as a monomer has only liquid crystallinity.
The monomer A1 to be copolymerized was synthesized by a synthesis method described in a patent document (WO2014 / 054785 pamphlet).
As HBAGE (hydroxybutyl acrylate glycidyl ether), a commercially available product was used.

In addition, the abbreviations of the reagents used in this example are shown below.
(Diisocyanate component)
ISPDA: Isophorone diisocyanate (diamine component)
DDM: 4,4′-diaminodiphenylmethane Me-4APhA: N-methyl-2- (4-aminophenyl) ethylamine Me-DADPA: 4,4′-diaminodiphenyl (N-methyl) amine (tetracarboxylic dianhydride) )
TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (organic solvent)
THF: Tetrahydrofuran NMP: N-ethyl-2-pyrrolidone BCS: Butyl cellosolve (polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile

<Photo-alignment polymer synthesis example P1>
M1 (2.99 g: 0.15 mol%), M2 (1.31 g: 0.05 mol%), M3 (14.71 g: 0.80 mol%) were dissolved in NMP (79.21 g), and the solution was removed with a diaphragm pump. After deaeration, AIBN (0.30 g) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (450 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P1.

<Photoalignment polymer synthesis examples P2 to P3>
The methacrylate polymer powders P2 to P3 were synthesized using the same method as in the photoalignment polymer synthesis example P1 except that the composition shown in Table 1 was used.

<Polymer synthesis example L1>
As tetracarboxylic dianhydride component, 4.85 g of TDA, 3.67 g of ISPDA as diisocyanate component, 5.89 g of DDM, 0.35 g of Me-DADPA, 0.25 of Me-4APhA as diamine component The resulting solution was reacted in 85.06 g of NMP at room temperature for 18 hours to obtain a polyamic acid (L1) solution having a concentration of 15 wt%.

<Example 1>
The methacrylate polymer powder P1 (1.2 g) obtained in the photoalignment polymer synthesis example P1 was added to NMP (12.8 g), and the mixture was dissolved by stirring at room temperature for 1 hour. Thereafter, BCS (6.0 g) was added and stirred to obtain a polymer solution T1. This polymer solution T1 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

<Example 2>
The methacrylate polymer powder P1 (0.36 g) obtained in the photoalignment polymer synthesis example P1 was added to NMP (8.04 g), and stirred at room temperature for 1 hour to dissolve. To this solution, the polymer solution T2 was obtained by adding and stirring the polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g). This polymer solution T2 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

<Control 1>
The methacrylate polymer powder P2 (1.2 g) obtained in the photoalignment polymer synthesis example P2 was added to NMP (12.8 g), and the mixture was dissolved by stirring at room temperature for 1 hour. Thereafter, BCS (6.0 g) was added and stirred to obtain a polymer solution CT1. This polymer solution CT1 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 2>
The methacrylate polymer powder P3 (1.2 g) obtained in the photoalignment polymer synthesis example P3 was added to NMP (12.8 g), and stirred at room temperature for 1 hour to dissolve. Thereafter, BCS (6.0 g) was added and stirred to obtain a polymer solution CT2. This polymer solution CT2 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 3>
The methacrylate polymer powder P2 (0.36 g) obtained in the photoalignment polymer synthesis example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polymer solution CT3 was obtained by adding and stirring the polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g). This polymer solution CT3 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 4>
The methacrylate polymer powder P3 (0.36 g) obtained in the photoalignment polymer synthesis example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added and stirred to obtain a polymer solution CT4. This polymer solution CT4 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

  About the liquid crystal aligning agent T1-2 of Examples 1-2, and liquid crystal aligning agent CT1-CT4 of control 1-4, the polymer seed | species used and its content, the content of other polymers, a solvent, and its content are as follows. Table 2 summarizes.

<Production of liquid crystal cell>
The liquid crystal aligning agent (T1) obtained in Example 1 was filtered through a 0.45 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C. for 90 seconds, and a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the coating film surface was irradiated with 5 to 30 mJ / cm ² of 313 nm ultraviolet rays via a polarizing plate, and then heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which liquid crystals were aligned in parallel.
Similarly, a liquid crystal cell was prepared using the liquid crystal aligning agent T2 obtained in Example 2 and the liquid crystal aligning agents CT1 to CT4 obtained in Controls 1 to 4.

<Orientation evaluation>
The liquid crystal cells prepared in Examples 1 and 2 and Controls 1 to 4 were placed between two polarizing plates arranged so that their polarization axes were orthogonal, and the backlight was turned on with no voltage applied, and transmitted. The arrangement angle of the liquid crystal cell was adjusted so that the luminance of light was minimized. Visually check the liquid crystal cell. When this liquid crystal cell was well aligned and no fluid alignment was confirmed, “◯” was indicated, when the aligned one was confirmed “Δ”, and when it was not aligned, “X” was indicated.

<Evaluation of voltage holding ratio (VHR)>
Using the liquid crystal cell produced above, a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C., a voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio (VHR). . The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
The VHR results of Examples 1-2 and Controls 1-4 are shown in Table 3 together with the results of <orientation evaluation> and the “total photoreactive group amount” in the photo-alignment polymer component.

From Table 2, in Examples 1 and 2, by copolymerizing monomers having two different types of photoreactive groups, better orientation in a wide range of UV irradiation dose than a polymer obtained by copolymerizing each of them alone. It is shown that VHR is improved by further blending polyamic acid.

Claims (9)

(A) Side chain (a1) having a photoreactive site represented by the following formula (a), side chain (a2) having a photoreactive site different from the photoreactive site represented by the following formula (a) And a side chain polymer having a side chain (a3) that exhibits liquid crystallinity; and (B) a polymer composition containing an organic solvent.

  The composition according to claim 1, wherein the side chain (a2) is a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition. The side chain (a2) is represented by the following formulas (1) to (6).
(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 groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and binds to them. Each hydrogen atom is independently —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy having 1 to 5 carbon atoms. May be substituted with groups;
R represents a hydroxy group, 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; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
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 photosensitive side chain selected from the group consisting of: a side chain having a photoreactive site different from the photoreactive site represented by the formula (a). 2. The composition according to 2.

The side chain (a3) is represented by the following formulas (21) to (31).
Wherein A and B 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;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 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 ₁ and Z ₂ represent a single bond, —CO—, —CH ₂ O—, —CH═N—, —CF ₂ —)
The composition according to any one of claims 1 to 3, which is any one liquid crystalline side chain selected from the group consisting of:

[I] The process of apply | coating the composition as described in any one of Claims 1-4 on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.   A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, produced by the method according to claim 5.   A lateral electric field drive type liquid crystal display element comprising the substrate according to claim 6. Preparing a substrate (first substrate) according to claim 6;
[I '] The process of apply | coating the polymer composition as described in any one of Claims 1-17 on a 2nd board | substrate, and forming 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 ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element. A lateral electric field drive type liquid crystal display device manufactured by the method according to claim 8.