JPWO2017006922A1 - COMPOSITION FOR PRODUCTION OF LIQUID CRYSTAL ALIGNMENT FILM, LIQUID CRYSTAL ALIGNMENT FILM USING THE COMPOSITION AND ITS MANUFACTURING METHOD, AND LIQUID CRYSTAL DISPLAY ELEMENT HAVING LIQUID CRYSTAL ALIGNMENT FILM - Google Patents

Abstract

The present invention provides a composition for producing a liquid crystal alignment film that can efficiently obtain a liquid crystal alignment film having a good quality by expanding the range of the light irradiation amount in which the alignment control ability is stably generated. The present invention is a composition for producing a liquid crystal alignment film comprising (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent, wherein the composition comprises A compound having a structure represented by the following formula (I) (wherein C1, C2, C3 and C4 each independently represents a phenyl group, a biphenyl group or a naphthyl group which may have a substituent). P1 and P2 each independently represent * -N = N- * (* represents a bonding position with C1, C2, C3, or C4); L represents the number of carbons that may have a substituent; N1 represents an integer of 0 to 5, m4 represents an integer of 1 to 5; n1 represents an integer of 0 to 5, and m4 represents an integer of 1 to 5. The composition for producing a liquid crystal alignment film is provided. [Chemical 1] [Selected figure] None

Description

The present invention relates to a composition for producing a liquid crystal alignment film, and more particularly to a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.
The present invention also relates to a liquid crystal alignment film produced using the composition, in particular, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, a substrate having the film, and a method for producing the same.
Furthermore, this invention relates to the liquid crystal display element which has this liquid crystal aligning film or board | substrate, and its manufacturing method.
In particular, the present invention relates to a composition for producing a liquid crystal alignment film, particularly a lateral electric field drive type, in which the light irradiation amount range is expanded and the production efficiency of the liquid crystal alignment film is increased in the photo-alignment method used for the alignment treatment of the liquid crystal alignment film. Composition for manufacturing liquid crystal alignment film for liquid crystal display element, liquid crystal alignment film manufactured using the composition or substrate having liquid crystal alignment film, liquid crystal display element having them, liquid crystal alignment film, and substrate having liquid crystal alignment film Alternatively, the present invention relates to a method for manufacturing a liquid crystal display element.

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

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

In addition to the conventional rubbing method, a photo-alignment method is known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. Compared with the conventional rubbing method, the photo-alignment method eliminates the need for rubbing, does not cause the generation of dust and static electricity, and can perform the alignment treatment even on the substrate of the liquid crystal display element having the uneven surface. There is an advantage that you can.
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.

As the photo-alignment method, a decomposition-type photo-alignment method, a photo-crosslinking type or a photo-isomerization type photo-alignment method, and the like are known.
The decomposition type photo-alignment method is, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. This is a method of aligning the liquid crystal by the method (for example, see Patent Document 1).

  The photo-crosslinking type or photoisomerization type photo-alignment method uses, for example, polyvinyl cinnamate, irradiates polarized ultraviolet rays, and performs a dimerization reaction (cross-linking reaction) at the double bond portion of two side chains parallel to the polarized light. This is a method of generating and aligning the liquid crystal in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, irradiation with polarized ultraviolet light causes an isomerization reaction at the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the polarization direction. Align (see Non-Patent Document 2, for example). Further, Patent Document 3 discloses a liquid crystal alignment film obtained by using a photo-alignment method by photocrosslinking, photoisomerization or photo-fleece rearrangement.

Japanese Patent No. 3893659 JP-A-2-37324 WO2014 / 054785

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

As described above, the photo-alignment method has a great advantage because it eliminates the rubbing process itself as compared with the rubbing method conventionally used industrially as an alignment treatment method for liquid crystal display elements. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
However, if the alignment controllability of the main component used in the photo-alignment method is too sensitive to the amount of polarized light, the alignment may be incomplete in part or all of the liquid crystal alignment film, and stable liquid crystal alignment cannot be realized. Occurs.

Accordingly, an object of the present invention is to increase the range of the light irradiation amount in which the alignment control ability is stably generated, and to efficiently obtain a high-quality liquid crystal alignment film, in particular, a composition for manufacturing a liquid crystal alignment film, particularly a lateral electric field drive. An object of the present invention is to provide a composition for producing a liquid crystal alignment film for a liquid crystal display device.
In addition to the above object or in addition to the above object, the object of the present invention is to provide a liquid crystal alignment film or a substrate having a liquid crystal alignment film produced using the composition, a liquid crystal display device having them, particularly a lateral electric field. An object of the present invention is to provide a drive type liquid crystal display element.
Furthermore, the objective of this invention provides the manufacturing method of a liquid crystal aligning film, the board | substrate which has a liquid crystal aligning film, or a liquid crystal display element, especially a horizontal electric field drive type liquid crystal display element in addition to the said objective in addition to the said objective. There is.

The inventors have found the following invention.
<1> (A) A photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range, and (B) a composition for producing a liquid crystal alignment film, which contains an organic solvent, particularly a lateral electric field drive type liquid crystal display element A composition for producing a liquid crystal alignment film,
The said composition in which this composition contains the compound which has a structure represented by following formula (I).
In the formula, each of C ₁ , C ₂ , C ₃ , and C ₄ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, or Branched alkoxy group, hydroxyl group, cyano group, dialkylamino group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear chain having 1 to 10 carbon atoms Or a phenyl group that may be substituted with a substituent selected from the first group consisting of a branched ester group, a linear or branched acyl group having 1 to 10 carbon atoms, a carboxyl group, an aldehyde group, and a nitro group Represents a biphenyl group or a naphthyl group;
P ₁ and P ₂ each independently represent * —N═N— * (* represents a bonding position with C ₁ , C ₂ , C ₃ or C ₄ );
L represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with a substituent selected from the first group. —CH ₂ — in L consists of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. It may be substituted with a group selected from the second group. However, groups selected from the second group are not adjacent to each other.
n1 represents an integer of 0 to 5, and m4 represents an integer of 1 to 5.

According to the present invention, a composition for producing a liquid crystal alignment film, particularly a lateral electric field drive type liquid crystal display element, which can efficiently obtain a liquid crystal alignment film with good quality by expanding the range of light irradiation amount in which alignment control ability is stably generated. A composition for producing a liquid crystal alignment film can be provided.
Further, according to the present invention, in addition to or in addition to the above effects, a liquid crystal alignment film or a substrate having a liquid crystal alignment film manufactured using the composition, a liquid crystal display device having them, particularly a lateral electric field drive type A liquid crystal display element can be provided.
Furthermore, according to the present invention, in addition to or in addition to the above effects, a method for producing a liquid crystal alignment film, a substrate having a liquid crystal alignment film, or a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element is provided. it can.

  The composition of the present invention comprises (A) a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range (WO 2014/054785 (the contents of which are incorporated herein in its entirety by reference)). (Hereinafter also referred to simply as a side chain polymer); and (B) an organic solvent, and a coating obtained by using this composition is similar to WO 2014/054785 by using a photo-alignment method using polarized light irradiation. In addition, a liquid crystal alignment film can be obtained.

The composition of this invention uses the compound which has a structure represented by the said Formula (I) for (A) component and (B) component.
The compound can be contained in the composition as the component (A), that is, as a part of the side chain polymer and / or as an additive other than the side chain polymer.

Hereinafter, embodiments of the present invention will be described in detail.
<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) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) a polymer composition containing an organic solvent, specifically a composition for producing a liquid crystal alignment film In particular, a step of applying a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element on a substrate having a conductive film for driving a horizontal electric field 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
In addition, the polymer composition, specifically, the composition for producing a liquid crystal alignment film, in particular, the composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element is a compound having a structure represented by the above formula (I) Containing.
Through the above steps, a liquid crystal alignment film to which alignment control ability is imparted, particularly a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In addition to the obtained substrate (first substrate), a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element can be obtained by preparing a second substrate.
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.

A method for manufacturing a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element,
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have Thereby, a liquid crystal display element, especially 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) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent are contained on a substrate having a conductive film for driving a lateral electric field. A polymer composition containing a compound having a structure represented by the above formula (I) is applied to form a coating film.

<Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
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, but are not limited to, a material that reflects light such as aluminum.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<Polymer composition>
A polymer composition, specifically, a composition for producing a liquid crystal alignment film, particularly a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, on a substrate having a conductive film for driving a horizontal electric field, particularly on the conductive film. Apply the object.
As described above, the polymer composition used in the production method of the present invention includes (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range; and (B) an organic solvent; And a compound having a structure represented by the above formula (I).

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

  (A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can react with light to cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement. The structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.

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

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

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, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents 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 side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m2 and R have the same definition as above.

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

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

The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, 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 is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definition as above.

The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
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 (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28 ), 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 —.

<< When the compound having the structure represented by the formula (I) constitutes a part of the side chain polymer >>
The compound having the structure represented by the above formula (I) can be contained in the composition so as to constitute a part of the side chain polymer.
In this case, using a polymerizable monomer represented by the following formula (II) so that a part of the side chain polymer has a structure represented by the above formula (I), It is good to form.
In formula (II), C ₁ , C ₂ , C ₃ , C ₄ , P ₁ , P ₂ and L have the same definition as above,
PL is a polymerizable group selected from the group consisting of the following formulas CL-13 to CL-17, and R ¹¹ is substituted with a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or halogen. Represents a linear or branched alkyl group having 1 to 10 carbon atoms,
* Represents a bonding position with L.

<< Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.
Further, as described above, when a part of the side chain polymer has a structure represented by the above formula (I), it is preferable to use a polymerizable monomer represented by the above formula (II).
In addition, when using the polymerizable monomer represented by the said Formula (II), the quantity is as follows. That is, when the total of the photoreactive side chain monomer having a photosensitive side chain and the liquid crystalline side chain monomer not containing the polymerizable monomer represented by the above formula (II) is 100 mol%, the above formula (II) The amount of the polymerizable monomer represented by 1) should be 1 to 50 mol%, preferably 1 to 30 mol%, more preferably 1 to 20 mol%.

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

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

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

  More specific examples of the liquid crystalline side chain monomer include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups. A structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.

Although this application can mention the compound represented by the following formula | equation (A01)-(A20) as a photoreactive and / or liquid crystalline side chain monomer, it is not limited to these.
In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents Represents 0 or 1; and Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. V represents 1 or 2.

(A) The side chain polymer can be obtained by the polymerization reaction of the above-described photoreactive side chain monomer exhibiting liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can.
When a part of the side chain polymer has a structure represented by the above formula (I), the polymerizable monomer represented by the above formula (II) is converted into a photoreactive side chain that does not exhibit liquid crystallinity. A side chain polymer can be obtained by copolymerizing with a monomer and a liquid crystalline side chain monomer, or by copolymerizing with a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer.
It can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

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

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylate compound include those described in [0152] of WO2014 / 054785.

  As a methacrylic acid ester compound, what is described in [0153] of WO2014 / 054785 gazette can be mentioned, for example.

  Examples of the vinyl compound, styrene compound, or maleimide compound include those described in [0154] of WO2014 / 054785.

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

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

  The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include those described in [0157] of WO2014 / 054785. 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 those described in [0158] of WO2014 / 054785. These compounds may be used alone or in combination of two or more.

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

  The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples thereof include those described in [0161] of WO2014 / 054785.

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

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

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

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

  The molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the resulting coating film, workability during coating film formation, and coating film uniformity. The weight average molecular weight is preferably 2000 to 1000000, more preferably 5000 to 200000.

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

In the polymer composition of the present embodiment, the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers may be mixed within the range. In that case, content of the other polymer in a resin component is 0.5 mass%-80 mass%, Preferably it is 1 mass%-50 mass%.
Examples of such other polymers include poly (meth) acrylate, polyamic acid, polyimide, polyamic acid ester, polyurea, diisocyanate compound and tetracarboxylic acid derivative, and polyamic acid-polyurea obtained by polymerizing diamine compound. Further, a polymer that is made of polyimide-polyurea or the like obtained by further imidization and is not a photosensitive side chain polymer capable of exhibiting liquid crystallinity can be used.

<< When the compound having the structure represented by the formula (I) is contained as an additive >>
The polymer composition used in the present invention can contain a compound having a structure represented by the above formula (I) as an additive other than the side chain polymer.

The compound having the structure represented by the formula (I) preferably has, independently at each end thereof, a terminal group selected from the group consisting of the following formulas CL-1 to CL-23.
In the formulas CL-1 to CL-23, * represents a position bonded to the structure represented by the above formula (I), particularly a position bonded to C ₁ or C _{4 of the} structure represented by the above formula (I). Show.
In the formulas CL-1 to CL-23, R ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms substituted with halogen. Represents an alkyl group;
R ¹² is substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a linear or branched chain having 1 to 12 carbon atoms or halogen. Represents a phenyl group, and a hydrogen atom is bonded to at least one of the ortho-position and para-position of the carbon atom to which the oxygen atom of the aromatic ring is bonded;
Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently R ¹³ , OR ¹³ or OCOR ¹³ (R ¹³ is a linear or branched hydrocarbon group having 1 to 4 carbon atoms). Provided that Z ₁₁ , Z ₁₂ and Z ₁₃ are all R ¹³ ;
BL represents a blocking group for protecting any isocyanate group of the following formulas BL-1 to BL-6; (in the formula, ** represents a bonding position with the isocyanate group).

  The compound having the structure represented by the formula (I) is independently represented at each end thereof by the above formulas CL-1 to CL-3, CL-5, CL-10, CL-12 to CL-14, and It is preferable to have a terminal group selected from the group consisting of CL-16 to CL-21.

The compound having the structure represented by the formula (I) preferably has a spacer group between C ₁ and the end group or between C ₄ and the end group.
The spacer groups are each independently —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH—, —CO—, —N. = And a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group (wherein —CH ₂ — in the alkylene group is independently —O Substituted with a group selected from the second group consisting of-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NHCOO-, -OCONH- and -CO-. Provided that the groups selected from the second group are not adjacent to each other).
When “—N =” is used as the spacer group, both of “=” may have a terminal group. That is, when “—N =” is used as the spacer group, the compound having the structure represented by the above formula (I) may have two end groups at one end or two end groups at both ends.

When the compound having the structure represented by the formula (I) is used as an additive, or when the (A) side chain polymer has the structure represented by the formula (I), the structure is Formulas (I1) to (I10) (wherein R ¹⁴ represents a hydrogen atom or a substituent selected from the first group), specifically, the following formulas (Ia) to (It) may be mentioned. Although it can, it is not limited to these.

  When using the compound which has a structure represented by the said Formula (I) as an additive, the content is 1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts More preferably, it is 1 to 15 parts by mass.

  In the photo-alignment method in which the composition of the present invention, that is, the liquid crystal aligning agent contains a compound having a structure represented by the above formula (I) to obtain a liquid crystal aligning film by irradiating polarized light, The range of light irradiation amount (so-called “irradiation amount margin”) in which the orientation control ability is stably generated can be expanded. In addition, by expanding the so-called “irradiation amount margin”, it is possible to obtain a liquid crystal alignment film in which the quality does not change even when the polarized light irradiation time slightly deviates from the control value in the manufacturing process of the liquid crystal alignment film. In addition, the manufacturing efficiency of the liquid crystal alignment film can be increased.

<< (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.

  The polymer composition used in the present invention contains other components in addition to the components (A) and (B) and the compound having the structure represented by the above formula (I), which is contained as an additive. May be. 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.

  Specific examples of the solvent (poor solvent) for improving the film thickness uniformity and the surface smoothness include those described in [0171] of WO2014 / 054785.

  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 for improving the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds described in [0174] of WO2014 / 054785.

  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 examples of the epoxy group-containing compound include those described in [0177] of WO2014 / 054785.

  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.
Examples of the photosensitizer include those described in [0179] of WO2014 / 054785.
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.

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

  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.

  For the photo-alignment method using a side chain polymer having a structure having a photocrosslinkable group, a photofleece rearrangement group or a group causing isomerization as a photoreactive group, WO2014 / 054785 (the content of this document is the whole Are included in the present application with reference to the same, and the same applies to the present application.

As described above, the lateral electric field drive type liquid crystal display element substrate produced by the composition of the present invention or the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate is excellent in reliability. Become.
In addition, since the composition of the present invention or the method of the present invention can expand the range of light irradiation amount (so-called “irradiation amount margin”) in which the alignment control ability of the liquid crystal alignment film is stably generated, the liquid crystal alignment film In this manufacturing process, even when the polarized light irradiation time slightly deviates from the control value, a liquid crystal alignment film having the same quality can be obtained, and the manufacturing efficiency of the liquid crystal alignment film can be increased. Therefore, the lateral electric field drive type liquid crystal display element substrate produced by the composition of the present invention or the method of the present invention or the horizontal electric field drive type liquid crystal display element having the substrate is suitable for a large-screen high-definition liquid crystal television or the like. Available to:
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

Abbreviations and structures of (meth) acrylate compounds and additives used in the examples are shown below.
<(Meth) acrylate compound>
MA-1 was synthesized by a synthesis method described in a patent document (WO2011-084546).
MA-2 was synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
MA-3 is a known substance (Acta Polymerica (1992), 43 (5), 283-87, etc.) and was synthesized using a known synthesis method.
MA-4 is an unpublished new compound such as literature, and its synthesis method will be described in detail in Synthesis Example 1 below.
MA-5 is a known substance (Chemical Communications (2012), 48 (80), 10010-10012, etc.) and was synthesized using a known synthesis method.
<Additives>
T-1 is a known substance (JP-A-1-56720 and the like) and was synthesized by a known synthesis method.

The abbreviations of organic solvents used in Examples and the like are as follows.
NMP: N-methyl-2-pyrrolidone.
BC: Butyl cellosolve.
THF: Tetrahydrofuran.
DMF: N, N-dimethylformamide.

<Measurement of molecular weight of polymer>
The molecular weight of the acrylic polymer in the examples is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex. It was measured.
Column temperature: 50 ° C
Eluent: DMF (as additives, lithium bromide monohydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, THF 10 mL / L)
Flow rate: 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

(Synthesis Example 1)
Synthesis of [MA-4]:

  To a 500 mL beaker, 2-aminoazotoluene (25.0 g, 111 mmol), pure water (50 ml), 12N hydrochloric acid aqueous solution (50 ml) were added, and while maintaining the reaction system at 0 ° C., a 20 wt% sodium nitrate aqueous solution (8.42 g) was added. 122 mmol) was added dropwise. After dripping, it stirred at 0 degreeC for 1 hour, phenol (10.4g) and 20 wt% sodium hydroxide aqueous solution (20.9g, 522mmol) were dripped, and it stirred at room temperature. After completion of the reaction, the reaction system was neutralized with 1N aqueous hydrochloric acid, and the precipitate was filtered. The residue was dissolved in ethyl acetate (1.5 L), washed with distilled water (600 mL), anhydrous magnesium sulfate was added to the organic layer for drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator, and the residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 2 volume ratio). [MA-4-1] (reddish brown solid) was obtained as 34. 0.1 g was obtained (yield 92%).

  In a 300 mL four-necked flask, [MA-4-1] (34.1 g, 103 mmol), 6-chloro-1-hexanol (15.4 g, 114 mmol), potassium carbonate (21.4 g, 155 mmol), potassium iodide ( 1.71 g, 10 mmol) and DMF (150 g) were added and stirred while heating to 100 ° C. After completion of the reaction, the reaction system was poured into distilled water (600 mL), the precipitate was filtered, washed with acetonitrile (200 mL), and dried to obtain 34.5 g of [MA-4-2] (reddish brown solid). Obtained (yield 78%).

[MA-4-2] (24.5 g, 57 mmol), triethylamine (7.48 g, 74 mmol), and THF (120 g) were added to a 300 mL four-necked flask. The system was cooled to 0 ° C., methacryloyl chloride (7.73 g, 74 mmol) was added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction system was poured into distilled water (600 mL), the precipitate was filtered, and the crude product was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 9 volume ratio) [MA-4]. 14.0 g of (orange solid) was obtained (49% yield). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [MA-4].
1H NMR (400 MHz, [D ₆ ] -DMSO): δ7.92-7.95 (d, 3H), 7.82-7.84 (d, 1H), 7.73-7.75 (d, 1H), 7.59-7.61 (d, 1H ), 7.47-7.48 (d, 2H), 7.35-7.37 (d, 1H), 7.13-7.15 (d, 2H), 6.03 (s, 1H), 5.67 (s, 1H), 4.08-4.13 (m, 4H ), 2.77 (s, 3H), 2.72 (s, 3H), 1.88 (s, 3H), 1.76-1.79 (t, 2H), 1.63-1.68 (t, 2H), 1.42-1.48 (t, 4H).

(Polymerization example 1)
MA-1 (13.3 g, 40.0 mmol) and MA-2 (18.4 g, 60.0 mmol) were dissolved in THF (182.3 g) and degassed with a diaphragm pump. '-Azobisisobutyronitrile (0.82 g, 5.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 50 ° C. to obtain a methacrylate polymer powder. This polymer had a number average molecular weight of 35,000 and a weight average molecular weight of 126,000. NMP (54.0 g) was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution (PMA-1) was obtained.

(Polymerization example 2)
MA-1 (13.3 g, 40.0 mmol), MA-2 (18.4 g, 60.0 mmol), MA-3 (2.35 g, 5.0 mmol) were dissolved in THF (138.1 g), After deaeration with a diaphragm pump, 2,2′-azobisisobutyronitrile (0.49 g, 3.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain a methacrylate polymer powder. The number average molecular weight of this polymer was 40000, and the weight average molecular weight was 90000. NMP (54.0 g) was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution (PMA-2) was obtained.

(Polymerization example 3)
MA-1 (13.3 g, 40.0 mmol), MA-2 (18.4 g, 60.0 mmol), MA-3 (4.70 g, 10.0 mmol) were dissolved in THF (147.5 g), After deaeration with a diaphragm pump, 2,2′-azobisisobutyronitrile (0.49 g, 3.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain a methacrylate polymer powder. This polymer had a number average molecular weight of 40,000 and a weight average molecular weight of 87,000. NMP (54.0 g) was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution (PMA-3) was obtained.

(Polymerization example 4)
MA-1 (13.3 g, 40.0 mmol), MA-2 (18.4 g, 60.0 mmol), MA-4 (2.49 g, 5.0 mmol) were dissolved in THF (138.6 g), After deaeration with a diaphragm pump, 2,2′-azobisisobutyronitrile (0.49 g, 3.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain a methacrylate polymer powder. This polymer had a number average molecular weight of 42,000 and a weight average molecular weight of 86,000. NMP (54.0 g) was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution (PMA-4) was obtained.

(Polymerization Example 5)
MA-1 (13.3 g, 40.0 mmol), MA-2 (18.4 g, 60.0 mmol), MA-5 (1.83 g, 5.0 mmol) were dissolved in THF (136.0 g), After deaeration with a diaphragm pump, 2,2′-azobisisobutyronitrile (0.49 g, 3.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 60 ° C. for 20 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain a methacrylate polymer powder. This polymer had a number average molecular weight of 41,000 and a weight average molecular weight of 85,000. NMP (54.0 g) was added to 6.0 g of the obtained powder, and dissolved by stirring at room temperature for 3 hours. By adding BC (40.0 g) to this solution and stirring, a methacrylate polymer solution (PMA-5) was obtained.

Example 1
Additive T-1 (0.03 g) was added to the obtained methacrylate polymer solution (PMA-1) (10.0 g), and the mixture was stirred at room temperature for 1 hour to obtain liquid crystal aligning agent A-1.
(Examples 2-4, Comparative Examples 1-2)
With the composition shown in Table 1, liquid crystal aligning agents A-2, A-3 and A-4 of Examples 2 to 4 were obtained using the same method as in Example 1. Moreover, the liquid crystal aligning agent B-1 and B-2 was prepared by the same method also in Comparative Examples 1-2.

<Creation of order parameter measurement board>
Using the liquid crystal aligning agent A-1 obtained above, a substrate for order parameter measurement was prepared in the following procedure. As the substrate, a quartz substrate having a size of 40 mm × 40 mm and a thickness of 1.0 mm was used.
The liquid crystal aligning agent A-1 obtained in Example 1 was filtered through a 1.0 μm filter, spin-coated on a quartz substrate, dried on a hot plate at 70 ° C. for 90 seconds, and then liquid crystal alignment with a film thickness of 100 nm. A film was formed. Next, the coating surface was irradiated with 5 to 60 mJ / cm ² of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 140 ° C. to 180 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.

  The liquid crystal aligning agents A-2, A-3, A-4, B-1 and B-2 obtained in Examples 2 to 4 and Comparative Examples 1 and 2 are the same as the liquid crystal aligning agent A-1. Using the method, an order parameter measurement substrate was prepared.

<Measurement of order parameters>
In order to measure the optical anisotropy of the liquid crystal alignment film using the substrate with the liquid crystal alignment film prepared above, S, which is an order parameter, was calculated from the absorbance of polarized light by the following equation.
In addition, the ultraviolet-ray visible near-infrared analysis photometer U-3100PC made from Shimadzu Corporation was used for the measurement of a light absorbency.

Here, A _para represents the absorbance in the direction parallel to the irradiated polarized UV direction, and A _per represents the absorbance in the direction perpendicular to the irradiated polarized UV direction. A _large represents the absorbance having a larger value by comparing the absorbance in the parallel direction and the vertical direction, and A _small represents the absorbance having a smaller value by comparing the absorbance in the parallel direction and the vertical direction. As the absolute value of the order parameter is closer to 1, it indicates that the orientation is more uniform.
The absolute value of the calculated order parameter S is shown in Table 2 using the following criteria.
○: S absolute value is 0.5 or more ○ Δ: S absolute value is 0.4 or more to less than 0.5 Δ: S absolute value is 0.3 or more to less than 0.4 ×: S absolute value Is less than 0.3

As shown in Table 2, the liquid crystal aligning agent A-1 of Example 1 to which the additive T-1 of the present invention was added was compared with the liquid crystal aligning agent B-1 of Comparative Example 1 in which the additive was not used. It was confirmed that the range of favorable order parameters was expanded to the high temperature side and / or the high irradiation amount side.
Moreover, also about the liquid crystal aligning agent A-2 to A-4 of Examples 2-4 using (meth) acrylate compound MA-3 and MA-4 which have a structure like the additive T-1 of this invention, Similar to the liquid crystal aligning agent A-1 of Example 1 to which the additive T-1 of the present invention was added, it was confirmed that the range of favorable order parameters was expanded to the high temperature side and / or the high irradiation amount side. It was.
Furthermore, the liquid crystal aligning agent B-2 of Comparative Example 2 using the (meth) acrylate compound MA-5 having one azobenzene skeleton has a better order parameter than the liquid crystal aligning agent B-1 of Comparative Example 1. The range has hardly expanded. Therefore, it was confirmed that two or more azobenzene skeletons are necessary for expanding the range of favorable order parameters.
From the results of the order parameters for the liquid crystal aligning agents A-1 to A-4 of Example 1 and Examples 2 to 4, the compound having the structure represented by the formula (I) of the present invention was converted into a side chain type compound. It can be seen that the irradiation margin can be expanded by using it so as to constitute a part of the molecule (Examples 2 to 4) or as an additive (Example 1).

Claims (23)

(A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) a composition for producing a liquid crystal alignment film, which comprises an organic solvent,
A compound in which the composition has a structure represented by the following formula (I) (wherein C ₁ , C ₂ , C ₃ , and C ₄ are each independently a halogen group, a linear chain having 1 to 10 carbon atoms) Or a branched alkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, or a dialkylamino group (the alkyl groups are each independently a linear or branched group having 1 to 10 carbon atoms) A chain alkyl group), a linear or branched ester group having 1 to 10 carbon atoms, a linear or branched acyl group having 1 to 10 carbon atoms, a carboxyl group, an aldehyde group, and a nitro group. Represents a phenyl group, a biphenyl group or a naphthyl group which may be substituted with a substituent selected from the group of 1;
P ₁ and P ₂ each independently represent * —N═N— * (* represents a bonding position with C ₁ , C ₂ , C ₃ or C ₄ );
L represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with a substituent selected from the first group. —CH ₂ — in L consists of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. It may be substituted with a group selected from the second group. However, groups selected from the second group are not adjacent to each other.
n1 represents an integer of 0 to 5, m4 represents an integer of 1 to 5)
The said composition containing.

  The composition according to claim 1, wherein the compound having a structure represented by the formula (I) constitutes a part of the side chain polymer. The compound having a structure represented by the formula (I) constituting a part of the side chain polymer is represented by the following formula (II):
(Wherein C ₁ , C ₂ , C ₃ , C ₄ , P ₁ , P ₂ and L have the same definition as above,
PL is a polymerizable group selected from the group consisting of the following formulas CL-13 to CL-17, and R ¹¹ is substituted with a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or halogen. Represents a linear or branched alkyl group having 1 to 10 carbon atoms,
* Represents the bonding position with L)
The composition of Claim 2 which is derived from the polymerizable monomer represented by these.

  The composition according to any one of claims 1 to 3, wherein the compound having the structure represented by the formula (I) is an additive other than the side chain polymer. The additive is independently bonded to both ends at each end group selected from the group consisting of the following formulas CL-1 to CL-23 (wherein * is bonded to the structure represented by the above formula (I)). A position, particularly a position where it is bonded to C ₁ or C _{4 of the} structure represented by the above formula (I) is shown.
In the formulas CL-1 to CL-23, R ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms substituted with halogen. Represents an alkyl group;
R ¹² is substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or a linear or branched chain having 1 to 12 carbon atoms or halogen. Represents a phenyl group, and a hydrogen atom is bonded to at least one of the ortho-position and para-position of the carbon atom to which the oxygen atom of the aromatic ring is bonded;
Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently R ¹³ , OR ¹³ or OCOR ¹³ (R ¹³ is a linear or branched hydrocarbon group having 1 to 4 carbon atoms). Provided that Z ₁₁ , Z ₁₂ and Z ₁₃ are all R ¹³ ;
BL represents a blocking group for protecting any isocyanate group of the following formulas BL-1 to BL-6; (in the formula, ** represents a bonding position with the isocyanate group).
A composition according to claim 4 having

  The additive is independently composed of the above-mentioned formulas CL-1 to CL-3, CL-5, CL-10, CL-12 to CL-14, and CL-16 to CL-21 at both ends thereof. The composition of Claim 4 or 5 which has the terminal group chosen from these. When the compound having the structure represented by the formula (I) is an additive other than the side chain polymer, a spacer group is provided between C ₁ and the end group or between C ₄ and the end group. Each of the spacer groups independently represents —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH—, —CO -, - N =, and the first linear or branched chain alkylene group having from which may have been a good C1-10 substituted with a substituent selected group (-CH 2 in the alkylene group _- are each independently And a group selected from the second group consisting of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. Provided that the groups selected from the second group are substituted with each other. The composition according to any one of claims 1 to 6, which is selected from the group consisting of: The structure represented by the formula (I) is any one of (I1) to (I10) (wherein R ¹⁴ represents a hydrogen atom or a substituent selected from the first group). The composition of any one of 1-7.

  The composition according to any one of claims 1 to 8, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece rearrangement. The component (A) 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, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents 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 composition of any one of Claims 1-9 which has any 1 type of photosensitive side chain chosen from the group which consists of.

The component (A) is represented by the following formulas (7) to (10)
(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—;
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;
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;
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 (provided that when n = 0, B is a single bond);
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ).
The composition according to any one of claims 1 to 9, which has any one kind of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formulas (11) to (13)
(In the formula, each A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
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;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m2 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those substituents. A group in which different 2 to 6 rings are 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 of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms (It may be substituted with an oxy group or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The composition according to any one of claims 1 to 9, which has any one kind of photosensitive side chain selected from the group consisting of:

(A) component is the following formula (14) or (15)
(In the formula, each A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
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;
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;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The composition of any one of Claims 1-9 which have the photosensitive side chain represented by these.

The component (A) is represented by the following formula (16) or (17) (wherein A is a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—). , -CH = CH-CO-O-, or -O-CO-CH = CH-;
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;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition of any one of Claims 1-9 which have the photosensitive side chain represented by these.

(A) component is a following formula (18) or (19)
(In the formula, A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O; -Represents-or -O-CO-CH = CH-;
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;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
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. The composition according to any one of claims 1 to 9, which has any one kind of photosensitive side chain selected from the group consisting of (which represents an oxy group).

The component (A) is represented by the following formula (20) (wherein A represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH). = CH-CO-O- or -O-CO-CH = CH-;
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;
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;
The composition according to any one of claims 1 to 9, which has a photosensitive side chain represented by the following formula: l represents an integer of 1 to 12, and m represents an integer of 0 to 2.

(A) component is following formula (21)-(31) (In formula, A and B have the same definition as the 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 (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28 ), 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 have a liquid crystalline side chain selected from the group consisting of a single bond, —CO—, —CH ₂ O—, —CH═N—, and —CF ₂ —. Item 17. The composition according to any one of Items 1 to 16.

The following formula (II) (wherein C ₁ , C ₂ , C ₃ , and C ₄ are each independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms) A linear or branched alkoxy group, a hydroxyl group, a cyano group, a dialkylamino group (wherein each alkyl group is independently a linear or branched alkyl group having 1 to 10 carbon atoms), 1 to carbon atoms Substituted with a substituent selected from the first group consisting of 10 linear or branched ester groups, linear or branched acyl groups having 1 to 10 carbon atoms, carboxyl groups, aldehyde groups, and nitro groups Represents a good phenyl group, biphenyl group, or naphthyl group;
P ₁ and P ₂ each independently represent * —N═N— * (* represents a bonding position with C ₁ , C ₂ , C ₃ or C ₄ );
L represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted with a substituent selected from the first group. —CH ₂ — in L consists of —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —NHCOO—, —OCONH— and —CO—. It may be substituted with a group selected from the second group. However, groups selected from the second group are not adjacent to each other.
n1 represents an integer of 0 to 5, and m4 represents an integer of 1 to 5;
PL is a polymerizable group selected from the group consisting of the following formulas CL-13 to CL-17, and R ¹¹ is substituted with a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or halogen. Represents a linear or branched alkyl group having 1 to 10 carbon atoms,
* Represents the bonding position with L)
A polymerizable monomer represented by:
The polymerizable monomer used in the production of a liquid crystal alignment film by forming a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range.

[I] The process of apply | coating the composition of any one of Claims 1-17 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 lateral electric field drive type liquid crystal display device manufactured by the method according to claim 19.   A lateral electric field drive type liquid crystal display device comprising the substrate according to claim 20. A step of preparing a substrate (first substrate) according to claim 20;
[I ′] A step of coating the composition according to any one of claims 1 to 17 on a 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 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 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 22.