WO2016186190A1

WO2016186190A1 - Polymer composition, liquid crystal alignment agent, liquid crystal alignment film, substrate comprising said liquid crystal alignment film, and liquid crystal display element comprising said liquid crystal alignment film

Info

Publication number: WO2016186190A1
Application number: PCT/JP2016/064963
Authority: WO
Inventors: 隆之根木; 達哉名木; 功一朗別府
Original assignee: 日産化学工業株式会社
Priority date: 2015-05-20
Filing date: 2016-05-20
Publication date: 2016-11-24
Also published as: CN107849330B; JP6858349B2; TW201708507A; KR102540422B1; JPWO2016186190A1; CN107849330A; KR20180008677A; TWI719984B

Abstract

The present invention provides a polymer composition for manufacturing a liquid crystal alignment film in which the alignment control functionality is stable, the range of the amount of irradiated light that is generated can be enlarged, and the voltage retention rate is improved. Specifically, the present invention provides a composition for manufacturing liquid crystal alignment film for an in-plane switching liquid crystal display element.　The polymer composition comprises (A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity, and (B) an organic solvent, and one of the at least two polymers comprises a crosslinking group.

Description

Polymer composition, liquid crystal alignment agent, liquid crystal alignment film, substrate having the liquid crystal alignment film, and liquid crystal display element having the liquid crystal alignment film

The present invention relates to a polymer composition for a liquid crystal aligning agent, in particular, a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element, consisting of the composition alone, consisting essentially of the composition or the composition. A liquid crystal aligning agent having liquid crystal, particularly a liquid crystal aligning agent for a horizontal electric field drive type liquid crystal display element, a liquid crystal alignment film formed from the liquid crystal aligning agent, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, and the liquid crystal alignment film The present invention relates to a substrate, particularly a substrate for a horizontal electric field drive type liquid crystal display element, and a liquid crystal display element having the substrate, in particular, a horizontal electric field drive type 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 component of the liquid crystal display element, and is formed on the 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, 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

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.

The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. With the goal.
Specifically, an object of the present invention is to increase the range of light irradiation amount in which the alignment control ability is stably generated, and to efficiently obtain a high-quality liquid crystal alignment film, a polymer composition for producing a liquid crystal alignment film The object is to provide a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.

In addition to the above object, an object of the present invention is to provide a lateral electric field drive type liquid crystal device having an improved voltage holding ratio and a polymer composition for producing a liquid crystal alignment film for the device, specifically, a lateral electric field. The object is to provide a composition for producing a liquid crystal alignment film for a drive type liquid crystal display element.
Furthermore, the object of the present invention is not limited to the above object, or in addition to the above object, the liquid crystal aligning agent comprising only the composition, consisting essentially of the composition, or having the composition, The object is to provide a liquid crystal alignment film produced using a liquid crystal alignment agent, a substrate having the liquid crystal alignment film, the liquid crystal alignment film and / or a liquid crystal display element having the substrate, particularly a lateral electric field drive type liquid crystal display element. .
In addition to or in addition to the above object, the object of the present invention is to provide a method for producing the liquid crystal alignment film, a method for producing a substrate having the liquid crystal alignment film, the liquid crystal liquid crystal alignment film and / or the substrate. Another object of the present invention is to provide a method for manufacturing a liquid crystal display element having a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element.

The inventors have found the following invention.
<1> (A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity; and (B) an organic solvent;
A polymer composition comprising:
The composition described above, wherein one of the at least two polymers has a crosslinkable group.
<2> In the above item <1>, one of the polymers (A1) and the other polymer (A2) out of at least two kinds of polymers may be different in the amount of a structure that exhibits photoreactivity.
<3> In the above item <2>, the amount of the structure expressing the photoreactivity of the polymer (A1) is preferably larger than the amount of the structure expressing the photoreactivity of the polymer (A2).

<4> In any one of the above items <1> to <3>, the crosslinkable group is represented by the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein A broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R ^{50 s} , they may be the same or different from each other; t is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. It may be at least one group.

<5> In any one of the above items <2> to <4>, the crosslinkable group may be included in the polymer (A1).
<6> In any one of the above items <2> to <5>, the polymer (A1) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. Is good.
<7> In any one of the above items <2> to <6>, the polymer (A2) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. Is good.
<8> In any one of the above items <1> to <7>, at least two kinds of polymers each preferably have a structure exhibiting photoreactivity and liquid crystallinity, and a structure exhibiting only liquid crystallinity.

<9> Structures that exhibit photoreactivity in the above <1> to <8>, particularly structures that exhibit photoreactivity and liquid crystallinity in <8>
The following formulas (1) to (6)
(Wherein A, B and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other 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 atom bonded to each independently represents —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 a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO ₂ , —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 structure may be any one selected from the group consisting of:

<10> The structures that exhibit photoreactivity in the above <1> to <8>, particularly the structures that exhibit photoreactivity and liquid crystallinity in <8> are represented by the following formulas (7) to (10).
(Wherein A, B and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other 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 atom bonded to each independently represents —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 structure may be any one selected from the group consisting of:

<11> The structures that exhibit photoreactivity in the above <1> to <8>, particularly the structures that exhibit photoreactivity and liquid crystallinity in <8> are represented by the following formulas (11) to (13).
(Wherein A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—) Or represents —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 m1 represents an integer of 1 to 3;
R 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 a phase selected from those substituents. Each of the hydrogen atoms bonded to them is independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5). -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 (It may be substituted with an oxy group or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The structure may be any one selected from the group consisting of:

<12> The structure exhibiting photoreactivity in the above <1> to <8>, particularly the structure exhibiting photoreactivity and liquid crystallinity in <8> is represented by the following formula (14) or (15):
(Wherein each A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or represents —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 bonded to each other 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;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
It is good that the structure is represented by

<13> The structure that exhibits photoreactivity in the above <1> to <8>, particularly the structure that exhibits photoreactivity and liquid crystallinity in <8> 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═. Represents 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)
It is good that the structure is represented by

<14> The structure exhibiting photoreactivity in the above <1> to <8>, particularly the structure exhibiting photoreactivity and liquid crystallinity in <8> is represented by the following formula (18) or (19):
(Wherein 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 bonded to each other 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 represents 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. It may be any one structure selected from the group consisting of (which represents an oxy group).

<15> A structure that exhibits photoreactivity in the above <1> to <8>, particularly a structure that exhibits photoreactivity and liquid crystallinity in <8> is represented by the following formula (20) (where A is A bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or —O—CO—CH═CH— To express;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other 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 m represents an integer of 0 to 2.

<16> In any one of the above items <8> to <15>, the structure that exhibits only liquid crystallinity has the following formulas (21) to (31):
Wherein A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ may be any one structure selected from the group consisting of a single bond, —CO—, —CH ₂ O—, —CH═N—, and —CF ₂ —.

<17> In any one of the above items <2> to <16>, the amount of the structure expressing the photoreactivity of the polymer (A1) may exhibit a liquid crystallinity and a structure expressing the photoreactivity of the polymer (A1). When the total with the structure is 100 mol%, α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80),
The amount of the structure expressing the photoreactivity of the polymer (A2) is 0.95α mol% or less when the structure expressing the photoreactivity of the polymer (A2) and the structure exhibiting liquid crystallinity are 100 mol%. Preferably, it is 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%.
<18> In any one of the above items <2> to <17>, the weight average molecular weight of the polymer (A1) is β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, More preferably, the weight average molecular weight of the polymer (A2) is 0.1β to 0.9β, preferably 0.2β to 0.8β, more preferably 0.3β to 0.7β. There should be.
<19> In any one of the above items <2> to <18>, when the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%. %, More preferably 60 to 80 wt%.

<20> In any one of the above items <1> to <19>, the monomer (M1) in which at least two kinds of polymers have a structure that exhibits (M-1) photoreactivity and liquid crystallinity; and (M-2) And a monomer (M2) having a structure exhibiting only liquid crystallinity.
<21> In the above item <20>, the monomer (M1) preferably has a structure represented by any one of the above formulas (1) to (20).
<22> In the above item <20> or <21>, the monomer (M2) may have a structure represented by the above formulas (21) to (31).

<23> In any one of the above items <20> to <22>, the monomer (M1) is represented by the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38. It is preferable that it is at least one selected from the group consisting of MA42, MA44 and MA46.
<24> In any one of the above items <20> to <23>, the monomer (M2) is selected from the group consisting of the following formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43, and MA45. It is good to be at least one selected.

<25> In any one of the above items <1> to <24>, the polymer (A1) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity;
(M-2) Monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-3) Formulas (G-1), (G-2), (G-3) and (G-4) ( In the formula, a broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms and a phenyl group, and when there are a plurality of R ^{50 s} , they may be the same or different. T is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. A monomer (M3) having at least one group selected from:
It is good to form.

<26> In the above item <25>, the (M-3) monomer (M3) is represented by the following formula (0):
(In the formula (0), A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH— Represents CO—O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the 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;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein the broken line represents a bond, R ⁵⁰ represents a hydrogen atom, a halogen atom or a carbon number) Represents a group selected from 1 to 3 alkyl groups and phenyl groups, and when there are a plurality of R ^{50 s} , they may be the same or different from each other; t is an integer of 1 to 7; J is O, S, NH or NR ⁵¹ , wherein R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
It is good to have the structure represented by these.

<27> In the above <25> or <26>, the polymer (A1) is
(M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group;
It is good to form further.
<28> In any one of the above items <1> to <27>, the polymer (A2) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity;
(M-2) a monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-4) at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. Having monomer (M4);
It is good to form.

<29> In the above <27> or <28>, (M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, It may be at least one selected from the group consisting of the following formulas MA6 to MA8 and MA33.

<30> In any one of the above items <25> to <29>, when the total of the monomer (M1) and the monomer (M2) is 100 mol%, the polymer (A1) has a monomer (M1) of α mol% ( α is 15 or more, preferably 15 to 100, more preferably 20 to 80) and the remainder is monomer (M2),
The polymer (A2) has a monomer (M1) of 0.95α mol% or less, preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%, and the remainder is monomer (M2 ) To be formed.
<31> A liquid crystal aligning agent having the polymer composition according to any one of the above items <1> to <30>.
<32> A liquid crystal alignment film formed from the liquid crystal aligning agent according to <31>.
<33> [I] A step of applying the polymer composition of <1> to <30> above onto a substrate having a conductive film for driving a lateral 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];
A method for producing a liquid crystal alignment film, which obtains a liquid crystal alignment film imparted with an alignment control ability.

<34> A substrate having the liquid crystal alignment film of <32>.
<35> [I] A step of applying the polymer composition according to any one of the above <1> to <30> onto a substrate having a conductive film for driving a lateral 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];
The manufacturing method of the board | substrate which has a liquid crystal aligning film which obtains the liquid crystal aligning film to which the alignment control ability was provided by having.
<36> A liquid crystal display device having the substrate of <34> above.
<37> a step of preparing the substrate (first substrate) of <34>above;
[I ′] A step of applying the polymer composition according to any one of claims 1 to 26 on a second substrate to form a coating film;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a liquid crystal display element.

According to the present invention, there are provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
Specifically, according to the present invention, a polymer 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, Specifically, a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element can be provided.
Further, according to the present invention, in addition to the above effects, a lateral electric field drive type liquid crystal element having an improved voltage holding ratio and a polymer composition for producing a liquid crystal alignment film for the element, specifically, a lateral electric field drive type A composition for producing a liquid crystal alignment film for a liquid crystal display element can be provided.
Furthermore, according to the present invention, in addition to or in addition to the above effects, the liquid crystal aligning agent comprising the composition alone, consisting essentially of the composition only, or having the composition, the liquid crystal alignment A liquid crystal alignment film manufactured using an agent, a substrate having the liquid crystal alignment film, a liquid crystal alignment element having the liquid crystal alignment film and / or the substrate, particularly a lateral electric field drive type liquid crystal display element can be provided.

According to the present invention, in addition to or in addition to the above effects, the method for manufacturing the liquid crystal alignment film, the method for manufacturing the substrate having the liquid crystal alignment film, the liquid crystal liquid crystal alignment film and / or the liquid crystal having the substrate A method for manufacturing a display element, particularly a lateral electric field drive type liquid crystal display element, can be provided.
Since the liquid crystal display element of the present invention, in particular the lateral electric field drive type liquid crystal display element, is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.
Further, according to the present invention, in addition to the above effect or in addition to the above effect, a liquid crystal display element having improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface, particularly a lateral electric field driven liquid crystal An element and a liquid crystal alignment film for the element can be provided.

The present application provides a polymer composition for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element.
Moreover, this application provides the liquid crystal aligning agent which consists only of this composition, consists essentially of this composition, or has this composition, especially the liquid crystal aligning agent for lateral electric field drive type liquid crystal display elements.
Furthermore, the present application relates to a liquid crystal alignment film formed from the liquid crystal alignment agent, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, a substrate having the liquid crystal alignment film, particularly a substrate for a horizontal electric field drive type liquid crystal display element, and A liquid crystal display device having the substrate, particularly a lateral electric field drive type liquid crystal display device is provided.
Hereinafter, it explains in detail in order.

<Polymer composition for liquid crystal aligning agent>
The present application provides a polymer composition for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element.
The polymer composition of the present application is
(A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity; and (B) an organic solvent;
Containing.
Moreover, 1 type of polymer has a crosslinkable group among at least 2 types of polymers.
Furthermore, among at least two kinds of polymers, one polymer (A1) and the other polymer (A2) have different amounts of structures that exhibit photoreactivity. In particular, the amount of the structure expressing the photoreactivity of one polymer (A1) is preferably larger than the amount of the structure expressing the photoreactivity of the other polymer (A2).

<< Crosslinkable group >>
In the present specification, the crosslinkable group refers to a substituent capable of crosslinking with a carboxyl group by heat.
When at least one of the two polymers has a crosslinkable group, when the polymer composition is formed on the liquid crystal alignment film, the liquid crystal alignment film has a voltage holding ratio (VHR) or the like. High reliability can be given. This is considered to be because when the liquid crystal alignment film is used, the crosslinkable group acts like a crosslinker, thereby improving the film density and reducing the elution of ionic impurities into the liquid crystal.

Examples of the crosslinkable group include, but are not limited to, an epoxy group, an oxetane group, a blocked isocyanate group, a thiirane group, and a thietane group.
Specifically, the crosslinkable group is, for example, at least one group selected from the group consisting of the following formulas (G-1), (G-2), (G-3) and (G-4). It is good.
Wherein the dashed line represents a bond, R ⁵⁰ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a group selected from phenyl group, the same as or different from each other if R ⁵⁰ is more T is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group.
The crosslinkable group may be present at the end of some side chains of the polymer.
Moreover, it is good to have a crosslinking | crosslinked group at least in the polymer with a relatively large quantity of the structure which expresses photoreactivity, ie, a polymer (A1). The crosslinkable group should be substantially not included in a polymer having a relatively small amount of structure that exhibits photoreactivity, that is, the polymer (A2).

<< Nitrogen-containing aromatic heterocyclic group, etc. >>
Of the at least two polymers of the present invention, at least one polymer may further have at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. Note that both of the at least two polymers may further have at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. In this case, each polymer can have the same or different nitrogen-containing aromatic heterocyclic group.

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

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

Of at least two types of polymers, one type of polymer has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, thereby further improving the reliability such as voltage holding ratio (VHR). Can do. This is thought to be because these groups trap ionic impurities.

Each of the at least two polymers preferably has a structure that exhibits photoreactivity and liquid crystallinity, and a structure that exhibits only liquid crystallinity. In this specification, “liquid crystallinity only” in “structure that expresses only liquid crystallinity” is a term used when considering “photoreactivity” and “liquid crystallinity”. The expression “only” means that “liquid crystallinity” is expressed but “liquidity” is not expressed.

<(A) Polymer having photoreactive structure and liquid crystal structure>
In the present specification, the “structure that exhibits photoreactivity” refers to a structure that reacts with light in a certain wavelength range, particularly light with a wavelength range of 250 nm to 400 nm. For example, the structure has a side chain of a polymer. Is good.
In the present specification, “photoreactivity” is not particularly limited, but means that it reacts with light to show a crosslinking reaction, an isomerization reaction, or a photo-Fries rearrangement, and preferably shows a crosslinking reaction. It is good. In the case of using a polymer having a “structure that exhibits photoreactivity”, the achieved orientation control ability can be stably maintained for a long period of time even when exposed to an external stress such as heat.
In the present specification, the “structure exhibiting liquid crystallinity” refers to a structure exhibiting liquid crystallinity in a certain temperature range, in particular, a temperature range of 100 to 300 ° C., for example, a mesogenic group or a mesogenic component in a polymer side chain. It is preferable that the structure has
When a polymer having a “structure that exhibits liquid crystallinity” is used, stable liquid crystal alignment can be obtained when the polymer is used as a liquid crystal alignment film.

The polymer structure preferably has, for example, a main chain and a side chain bonded to the main chain, and the side chain has a “structure that exhibits photoreactivity” and a “structure that exhibits liquid crystallinity”. The “structure that exhibits photoreactivity” and the “structure that exhibits liquid crystallinity” may be included in the same side chain or in different side chains. Preferably, the polymer is provided with a structure that exhibits photoreactivity and liquid crystallinity in a certain side chain, and a structure that exhibits only liquid crystallinity in another side chain.
When the “structure that exhibits photoreactivity” and the “structure that exhibits liquid crystallinity” have the same side chain, a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, or an azobenzene group; When the side chain has a “structure that expresses photoreactivity” that is bonded to the tip and exhibits a crosslinking reaction or isomerization reaction in response to light, the side chain is a “structure that exhibits liquid crystallinity” In some cases, the structure is a mesogenic component and has a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction, which is a “structure that exhibits photoreactivity”.

Specific examples of the main chain of at least two polymers of the present invention are not particularly limited, but each independently includes hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, It may be composed of at least one selected from the group consisting of radically polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane.

<< Photoreactive structure >>
The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by any one selected from the group consisting of formulas (1) to (6). In the formula, A, B, D, S, Y ₁ , Y ₂ , R, X, Cou, q1 and q2, q3, P and Q, l1, l2, H, and I have the same definitions as described above. Have.

The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by any one selected from the group consisting of formulas (7) to (10). In the formula, A, B, D, Y ₁ , X, 1, m, m1, m2, n, Y ₂ , and R have the same definition as described above.

The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by any one selected from the group consisting of formulas (11) to (13). In the formula, A, X, l, m, m1 and R have the same definition as described above.

The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by the formula (14) or (15). In the formula, A, Y ₁ , l, m1, and m2 have the same definition as described above.

The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by the formula (16) or (17). In the formula, A, X, l and m have the same definition as described above.

The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by the formula (18) or (19). In the formula, A, B, Y ₁ , q ₁ , q 2, l, m 1, m 2, and R ₁ have the same definition as described above.

The structure that exhibits photoreactivity, in particular, the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by the formula (20). In the formula, A, Y ₁ , X, 1 and m have the same definition as described above.

<< Structure that exhibits only liquid crystallinity >>
The structure exhibiting only liquid crystallinity is preferably a structure represented by any one selected from the group consisting of formulas (21) to (31). In the formula, A, B, Y ₃ , R ₃ , q 1, q 2, l, m, m 1, m ₂ , m 3, R ₂ , Z ₁ , Z ₂ have the same definition as described above.

<< Amount of structure expressing photoreactivity of each of at least two polymers >>
In each of at least two kinds of polymers, when the total of the structure expressing photoreactivity and the structure expressing only liquid crystallinity is 100 mol%,
The amount of the structure expressing the photoreactivity of the polymer (A1) is α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80),
The amount of the structure expressing the photoreactivity of the polymer (A2) should be less than the amount of the structure expressing the photoreactivity of the polymer (A1), specifically 0.95α mol% or less, preferably The content is 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%.
By using polymers having different amounts of structures that exhibit photoreactivity, it is considered to have the following effects. That is, the orientation by ultraviolet irradiation is determined by the polymer (polymer (A1)) having a relatively large structure that exhibits photoreactivity. On the other hand, a polymer (polymer (A2)) having a relatively small structure that exhibits photoreactivity but a relatively large structure that exhibits liquid crystallinity (polymer (A2)) is aligned according to the alignment defined by the polymer (A1). Of the at least two types of polymers, each polymer can share the function of each and exhibit the function effectively.

<< Weight average molecular weight of each of at least two polymers >>
Further, of at least two kinds of polymers, one of the weight average molecular weights is β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, more preferably 60,000 to 150,000). And
The other weight average molecular weight is 0.1β to 0.9β, preferably 0.2β to 0.8β, more preferably 0.3β to 0.7β.
In the present specification, unless otherwise specified, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) method.
In particular, the polymer (A1) having a relatively large amount of structure that exhibits photoreactivity has a weight average molecular weight of β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 20 10,000, more preferably 60,000 to 150,000)
The polymer (A2) having a relatively small amount of structure that exhibits photoreactivity has a weight average molecular weight of 0.1β to 0.9β, preferably 0.2β to 0.8β, more preferably 0.3β to It should be 0.7β.

By using at least two polymers having different weight average molecular weights, when the polymer is formed as a liquid crystal alignment film, the polymer having a large weight average molecular weight is relatively lower layer of the liquid crystal alignment film (relative to the substrate). On the other hand, a polymer having a small weight average molecular weight tends to be formed in a relatively upper layer (layer relatively far from the substrate) of the liquid crystal alignment film.
By having such a configuration, it is considered that the following effects are exhibited.
That is, the polymer (A1) having a relatively large structure that exhibits photoreactivity and a large weight average molecular weight is formed in a relatively lower layer (a layer relatively closer to the substrate) of the liquid crystal alignment film. On the other hand, the polymer (A2) having a relatively small structure that exhibits photoreactivity and a small weight average molecular weight is formed in a relatively upper layer (a layer far from the substrate) of the liquid crystal alignment film. In this situation, when irradiated with polarized ultraviolet rays, the polymer (A1) in the lower layer (layer relatively close to the substrate) is oriented according to the polarized ultraviolet rays. On the other hand, it is considered that the polymer (A2) of the upper layer (layer relatively far from the substrate) is oriented along the orientation of the polymer (A1).

<< Weight ratio of at least two polymers >>
When the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%, more preferably 60 to 80 wt%. ) Should be the remainder.
The polymer (A1) and the polymer (A2) have two or more of the above three characteristics, ie, “amount of structure that develops photoreactivity”, “weight average molecular weight”, and “weight ratio”. It is preferred to have properties, preferably all three properties.

<Methods for producing at least two types of polymers>
The production method of the at least two polymers of the present invention is not particularly limited as long as it has the above-described configuration.
For example, at least two polymers of the present invention include (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) a monomer having a structure that exhibits only liquid crystallinity. (M2);
Specifically, the polymer (A1) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity;
(M-2) a monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-3) a monomer having a crosslinkable group, specifically, the above formulas (G-1), (G-2), Monomer (M3) having at least one group selected from the group consisting of (G-3) and (G-4), more specifically the following formula (0) (in formula (0), A, B, S, T, X, P, Q, 11, 12, and G have the same definition as above, and a monomer having a structure represented by:
It is good to form.
When the polymer (A1) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, the polymer (A1)
(M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group;
It is good to form further.

The polymer (A2) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) a monomer (M2) having a structure that exhibits only liquid crystallinity;
It is good to form.
In addition, when the polymer (A2) has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, the polymer (A2) is:
(M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group;
It is good to form further.
Further, when the polymer (A2) has a crosslinkable group, the polymer (A2) may further be formed to further include the above-described (M-3) monomer (M3).
In addition, the polymer (A1) and the polymer (A2) may have other monomers in addition to the above-mentioned monomers and may be formed by copolymerization within a range not impairing the photoreactive property and / or liquid crystallinity. Good.
As described above, at least two kinds of polymers of the present invention are formed having the monomer (M1) and the monomer (M2), but the total of the monomer (M1) and the monomer (M2) is 100 mol%. In the polymer (A1) of at least two kinds of polymers, the monomer (M1) is α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80) and the balance is the monomer (M2). ) To be formed.
In the polymer (A2), the monomer (M1) is 0.95α mol% or less, preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%, and the remainder is monomer. It may be formed so as to be (M2).
In addition, it is preferable that the monomer (M1) and the monomer (M2) used in the polymer (A1) and the polymer (A2) are common to each other.

<< Monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity and its production method >>
At least two polymers of the present invention have the monomer (M1) having a structure that exhibits the above-described photoreactivity and liquid crystallinity; and (M-2) the monomer (M2) having a structure that exhibits only liquid crystallinity. It is good to obtain by forming and specifically copolymerizing.

[Monomer (M1) having a structure exhibiting photoreactivity and liquid crystallinity]
The monomer (M1) having a structure that develops photoreactivity and liquid crystallinity may form a polymer having a structure that develops photoreactivity and liquid crystallinity at the side chain site of the polymer when the polymer is formed. It is a monomer that can be used.
As the structure that exhibits photoreactivity at the side chain site, the following structures and derivatives thereof are preferable.

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

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

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

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

[Monomer (M2) having a structure exhibiting only liquid crystallinity and its production method]
The monomer (M2) having a structure that exhibits only liquid crystallinity is a monomer that allows a polymer derived from the monomer to exhibit liquid crystallinity and to form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.

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

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

<< Monomer having crosslinkable group (M3) >>
As described above, the polymer (A1) or, if desired, the polymer (A2) is an (M-3) monomer having a crosslinkable group, specifically, the following formulas (G-1), (G-2), ( A monomer (M3) having at least one group selected from the group consisting of G-3) and (G-4), more specifically a monomer having a structure represented by the following formula (0): It is good to be formed.

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

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

Specific examples of the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.

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

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

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

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

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

<< Monomer having nitrogen-containing aromatic heterocyclic group (M4) >>
As described above, the polymer (A1) or the polymer (A2) optionally has (M-4) at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. Monomer (M4);

When the polymer (A1) or the polymer (A2) has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group, the polymer composition of the present invention has an ionicity. In order to reduce the elution of impurities and promote the cross-linking reaction of the cross-linkable group, more specifically, the cross-linking reaction of the group represented by the above formula (0), or a more durable liquid crystal alignment film Obtainable. In order to produce a polymer having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, the monomer (M4) is replaced with the monomer (M1) and the monomer (M2), and optionally with the monomer (M3). What is necessary is just to copolymerize.
The monomer (M4) is selected from the group consisting of hydrocarbons, (meth) acrylates, itaconates, fumarate, maleates, α-methylene-γ-butyrolactone, radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane. It preferably has a polymerizable group composed of at least one kind and a structure having a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. NH in the amide group and urethane group may or may not be substituted. Examples of the substituent in the case where it may be substituted include an alkyl group, an amino-protecting group, and a benzyl group.

Among such monomers, specific examples of the monomer having a nitrogen-containing aromatic heterocyclic group include 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate and 2- (3-pyridylcarbonyloxy). And ethyl (meth) acrylate, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.

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

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

As described above, it can be copolymerized with other monomers as long as the photoreactivity and / or liquid crystallinity is not impaired.
Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

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

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing at least two kinds of polymers of the present invention is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, the monomer (M1) having a structure that exhibits the above-described photoreactivity and liquid crystallinity; the monomer (M2) having a structure that exhibits only liquid crystallinity; and a monomer having a crosslinkable group (M3) if desired. ), And optionally, cationic polymerization or radical polymerization using a vinyl group of a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, an anion It can be produced by polymerization. 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.

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

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

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

Monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and Monomer (M2) having a structure that exhibits only liquid crystallinity; optionally, a monomer (M3) having a crosslinkable group; and further if desired A monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group is copolymerized and used in the reaction to obtain each of at least two polymers of the present invention. The organic solvent is not particularly limited as long as the produced polymer is soluble. Specific examples are given below.

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

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

The polymerization temperature at the time of radical polymerization can be selected from any temperature of 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 The content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.

[Recovery of polymer]
When the produced polymer is recovered from the reaction solution obtained by the above-described reaction, the reaction solution may be poured into a poor solvent to precipitate these polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. 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.

[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 includes at least two kinds of polymers having the structure that expresses (A) the photoreactivity and the structure that exhibits the liquid crystallinity described above, and one of the polymers has a crosslinkable group. It is a resin component to be included. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

In the polymer composition of the present embodiment, the resin component described above may be at least two types of polymers having the above-described (A) structure that exhibits photoreactivity and the structure that exhibits liquid crystallinity. In addition, other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
Examples of such other polymers include poly (meth) acrylates, polyamic acids, polyimides, and the like, and examples include polymers that are not polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity. .

<(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 may contain components other than the above components (A) and (B). In particular, when the polymer composition of the present invention is used for a liquid crystal alignment film for a liquid crystal display element, particularly for a horizontal electric field drive type liquid crystal display element, it may contain components other than the components (A) and (B). Good. For example, when the polymer composition is applied to a substrate, particularly a substrate for a liquid crystal display element, more particularly a substrate for a lateral electric field drive type liquid crystal display element, the film thickness uniformity and the surface smoothness are improved. Although a solvent, a compound, a compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board | substrate can be mentioned, it is not limited to this.

<(C) Amine compound>
The polymer composition used in the present invention may have (C) a specific amine compound as a component other than the components (A) and (B).
The specific amine compound as the component (C) specifically has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is an aliphatic hydrocarbon group or It can be an amine compound bonded to a non-aromatic cyclic hydrocarbon group. By containing such an amine compound in the polymer composition of the present invention, when the polymer composition of the present invention is used as a liquid crystal alignment film, elution of ionic impurities is reduced, and the crosslinking of the crosslinkable group described above is achieved. For promoting the reaction, more specifically, the crosslinking reaction of the group represented by the above formula (0), a liquid crystal alignment film having higher durability can be obtained.
The specific amine compound is not particularly limited as long as it exhibits the following effects i) and / or ii) when the polymer composition used in the present invention forms a liquid crystal alignment film. i) Adsorbs ionic impurities in the liquid crystal at the liquid crystal alignment film interface and / or ii) exhibits improved voltage holding ratio.
The amount of the specific amine compound is not particularly limited as long as the above effect is obtained, but is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention. It is good that it is a mass part.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
Specific examples of the divalent non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. Preferably, it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and even more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound has the following formula [20a], formula [20b] and formula [20c] (wherein Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms) And an aromatic cyclic hydrocarbon containing at least 1, preferably 1 to 4 structures selected from the group consisting of:

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
More preferred amine compounds are those represented by the following formula A- [1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing group. The amine compound is preferably an aromatic heterocyclic ring. In Formula A- [1], Y ₁₂ is not particularly limited as long as Y ₁₂ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferred Y ₁₁ in formula A- [1] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. It is good to be. Examples of the non-aromatic cyclic hydrocarbon group include the above-described structures. Y ₁₁ is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y ₁₁ is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, —CH ₂ — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁₁ is —O—, —NH—, —CO—O—. , —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, — C (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring. In addition, a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.

Specific examples of the divalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like.

Specific examples of the divalent heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring. , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring And acridine ring.

Y ₁₂ in the formula A- [1] is a nitrogen-containing aromatic heterocyclic ring, and as described above, at least one selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c] An aromatic cyclic hydrocarbon containing the structure Specific examples thereof include the structure described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring and a phthalazine ring are preferable.

From the viewpoint of ease of electrostatic interaction such as salt formation and hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide, Y ₁₁ is a formula [20a], a formula included in Y ₁₂ It is preferable that it is combined with a substituent not adjacent to [20b] and formula [20c].
Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y ₁₂ in formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, sulfur You may contain hetero atoms, such as an atom and a nitrogen atom.

A preferred combination of Y ₁₁ and Y ₁₂ in the formula A- [1] is a group in which Y ₁₁ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Y ₁₂ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, A benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₂ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. May be contained.
Further preferred amine compounds of the formula A- [2] (in the following formula, Y ₁₃ is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y ₁₄ Is a single bond, or —O—, —NH—, —S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms, and the total of carbon atoms of Y ₁₃ and Y ₁₄ Is an amine compound represented by: Y ₁₅ is a nitrogen-containing aromatic heterocyclic ring.

Y ₁₃ in the formula A- [2] is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, trio A cycloeicosane ring, a tricyclodecosan ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. More preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring. Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

—CH ₂ — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁₃ is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —C ( CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O—, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring. In addition, a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group. The cyclic hydrocarbon group and the heterocyclic ring mentioned here have the same meaning as defined for Y ₁₁ in the formula A- [1].

Y ₁₄ in the formula A- [2] is a single bond, —O—, —NH—, —S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y ₁₄ are given below.

For example, a single bond, —O—, —NH—, —S—, —SO ₂ —, a hydrocarbon group having 1 to 19 carbon atoms, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —CF ₂ —, —C (CF ₃ ) ₂ —, —CH (OH) —, —C (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, — O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O—, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane Ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring , Anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine Ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, Phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring and the like. Y ₁₄ may contain two or more of these.

Specific examples including two or more of these include —NH—CH ₂ —, —NH—C ₂ H ₄ —, —NH—C ₃ H ₆ —, —NH—C ₄ H ₈ —, —S—CH ₂ —, —S—C ₂ H ₄ —, —S—C ₃ H ₆ —, —S—C ₄ H ₈ —, —O—CH ₂ —, —O—C ₂ H ₄ —, —O—C ₃ H ₆ —, —O—C ₄ H ₈ —, —NH—CO—CH ₂ —, —NH—CO—C ₂ H ₄ —, —NH—CO—C ₃ H ₆ —, —NH—CO—C ₄ H ₈ —, —CO—CH ₂ —, —CO—C ₂ H ₄ —, —CO—C ₃ H ₆ —, —CO—C ₄ H ₈ —, —CO—NH—CH ₂ —, —CO —NH—C ₂ H ₄ —, —CO—NH—C ₃ H ₆ —, —CO—NH—C ₄ H ₈ —, —NH—CH ₂ —CH (CH ₃ ) —, —NH—C ₂ H ₄ —CH (CH ₃ ) — , —NH—C ₃ H ₆ —CH (CH ₃ ) —, —NH—C ₄ H ₈ —CH (CH ₃ ) —, —S—CH ₂ —CH (CH ₃ ) —, —S—C ₂ H _4- CH (CH ₃ ) —, —S—C ₃ H ₆ —CH (CH ₃ ) —, —S—C ₄ H ₈ —CH (CH ₃ ) —, —O—CH ₃ —CH (CH ₃ ) —, —O—C ₂ H ₄ —CH (CH ₃ ) —, —O—C ₃ H ₆ —CH (CH ₃ ) —, —O—C ₄ H ₈ —CH (CH ₃ ) —, —NH— CO—CH ₂ —CH (CH ₃ ) —, —NH—CO—C ₂ H ₄ —CH (CH ₃ ) —, —NH—CO—C ₃ H ₆ —CH (CH ₃ ) —, —NH—CO —C ₄ H ₈ —CH (CH ₃ ) —, —CH (OH) —CH ₂ —, —CH (OH) —C ₂ H ₄ —, —CH (OH) —C ₃ H ₆ —, —CH ( OH) -C ₄ H ₈ —, —CH (CH ₂ OH) —CH ₂ —, —CH (CH ₂ OH) —C ₂ H ₄ —, —CH (CH ₂ OH) —C ₃ H ₆ —, —CH (CH ₂ OH) —C ₄ H ₈ —, —NH—CH (CH ₂ OH) —CH ₂ —, —CO—NH—CH (CH ₂ OH) —CH ₂ —, —NH—CO—CH (CH ₂ OH) —CH ₂ —, —CO—CH (CH ₂ OH) —CH ₂ —, —S—CH (CH ₂ OH) —CH ₂ —, —O—CH (CH ₂ OH) —CH ₂ —, —CH ( N (CH ₃ ) ₂ ) —, —C ₆ H ₄ —O—, —C ₆ H ₄ —NH—, —C ₆ H ₄ —CO—NH—, —C ₆ H ₄ —NH—CO—, — C ₆ H ₄ —CO—, —C ₆ H ₄ —CH ₂ —, —C ₆ H ₄ —S— and the like can be mentioned.

Y ₁₅ in the formula A- [2] is a nitrogen-containing aromatic heterocyclic ring and has the same definition as Y _{12 in} the formula A- [1]. Specific examples may include the same structure as Y ₁₂ described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.

From the viewpoint of ease of electrostatic interaction such as salt formation and hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide, Y ₁₄ is a formula [20a] or formula included in Y _15. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c].
Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y ₁₅ in the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom or a sulfur atom. And may contain a hetero atom such as a nitrogen atom.

In the preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2], Y ₁₃ is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y ₁₄ is a single bond, having 1 carbon atom To 10 linear or branched alkylene groups, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, _{_{_{_{-SO 2 -, - CF 2 -}}}} , - C (CF 3) 2 -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O _{_{, -O-Si (CH 3)}} 2 -O -, - CH (OH) -, - NH-CH 2 -, - NH-C 2 H 4 -, - NH-C 3 H 6 -, - NH-C ₄ H ₈ —, —S—CH ₂ —, —S—C ₂ H ₄ —, —S—C ₃ H ₆ —, —S—C ₄ H ₈ —, —O—CH ₂ —, —O—C ₂ H ₄ —, —O—C ₃ H ₆ —, —O—C ₄ H ₈ —, —NH—CO—CH ₂ —, —NH—CO—C ₂ H ₄ —, —NH—CO—C ₃ _{_{_{_{H 6 -, - NH-CO}}}} -C 4 H 8 -, - CO-CH 2 -, - CO-C 2 H 4 -, - CO-C 3 H 6 -, - CO-C 4 H 8 -, - CO—NH—CH ₂ —, —CO—NH—C ₂ H ₄ —, —CO—NH—C ₃ H ₆ —, —CO—NH—C ₄ H ₈ —, —NH—CH ₂ —CH (CH _{_{3) -, - NH-C}} 2 H 4 - CH (CH ₃ ) —, —NH—C ₃ H ₆ —CH (CH ₃ ) —, —NH—C ₄ H ₈ —CH (CH ₃ ) —, —S—CH ₂ —CH (CH ₃ ) —, —S—C ₂ H ₄ —CH (CH ₃ ) —, —S—C ₃ H ₆ —CH (CH ₃ ) —, —S—C ₄ H ₈ —CH (CH ₃ ) —, —O—CH ₃ —CH (CH ₃ ) —, —O—C ₂ H ₄ —CH (CH ₃ ) —, —O—C ₃ H ₆ —CH (CH ₃ ) —, —O—C ₄ H ₈ —CH (CH ₃ ) —, —NH—CO—CH ₂ —CH (CH ₃ ) —, —NH—CO—C ₂ H ₄ —CH (CH ₃ ) —, —NH—CO—C ₃ H ₆ —CH (CH ₃ ) —, —NH—CO—C ₄ H ₈ —CH (CH ₃ ) —, —CH (OH) —CH ₂ —, —CH (OH) —C ₂ H ₄ —, —CH (OH) —C ₃ H ₆ -, _{_{_{_{CH (OH) -C 4 H 8}}}} -, - CH (CH 2 OH) -CH 2 -, - CH (CH 2 OH) -C 2 H 4 -, - CH (CH 2 OH) -C 3 H 6 - , —CH (CH ₂ OH) —C ₄ H ₈ —, —NH—CH (CH ₂ OH) —CH ₂ —, —CO—NH—CH (CH ₂ OH) —CH ₂ —, —NH—CO— CH (CH ₂ OH) —CH ₂ —, —CO—CH (CH ₂ OH) —CH ₂ —, —S—CH (CH ₂ OH) —CH ₂ —, —O—CH (CH ₂ OH) —CH ₂ —, —CH (N (CH ₃ ) ₂ ) —, —C ₆ H ₄ —O—, —C ₆ H ₄ —NH—, —C ₆ H ₄ —CO—NH—, —C ₆ H ₄ — _{_{_{NH-CO -, - C 6}}} H 4 -CO -, - C 6 H 4 -CH 2 -, - C 6 H 4 -S-, cyclopropane ring, cyclobutane ring, Clopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, Fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, and Y ₁₅ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring An imidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

In a more preferable combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2], Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane A ring, a cycloheptane ring, a norbornene ring, or an adamantane ring, and Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) ₂ —, —CH (OH) —, —NH—CH ₂ —, —S— CH ₂ —, —O—CH ₂ —, —O—C ₂ H ₄ —, —NH—CO—CH ₂ —, —CO—CH ₂ —, —CO—NH—CH ₂ —, —NH—CH ₂ _{_{-CH (CH 3) -, -}} S-CH 2 -CH (CH 3) -, - O _{_{_{_{CH 3 -CH (CH 3) -}}}} , - NH-CO-CH 2 -CH (CH 3) -, - CH (OH) -CH 2 -, - CH (OH) -C 2 H 4 -, - CH ( CH ₂ OH) —CH ₂ —, —NH—CH (CH ₂ OH) —CH ₂ —, —CO—NH—CH (CH ₂ OH) —CH ₂ —, —NH—CO—CH (CH ₂ OH) —CH ₂ —, —CO—CH (CH ₂ OH) —CH ₂ —, —S—CH (CH ₂ OH) —CH ₂ —, —O—CH (CH ₂ OH) —CH ₂ —, —CH ( N (CH ₃ ) ₂ ) —, —C ₆ H ₄ —O—, —C ₆ H ₄ —NH—, —C ₆ H ₄ —CO—NH—, —C ₆ H ₄ —NH—CO—, — _{_{_{_{C 6 H 4 -CO -, -}}}} C 6 H 4 -CH 2 -, - C 6 H 4 -S-, cyclopropane ring, cyclobutane ring, cyclopentane , Cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, a benzene ring, a naphthalene ring, tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, phenanthrene ring, or phenalene ring, Y ₁₅ is a pyrrole Ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or It is a phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

In a more preferable combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2], Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, or A cyclohexane ring, and Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—. , -NH-CO -, - CO -, - CH (OH) -, - NH-CH 2 -, - S-CH 2 -, - O-CH 2 -, - NH-CO-CH 2 -, - CO —CH ₂ —, —CO—NH—CH ₂ —, —NH—CH ₂ —CH (CH ₃ ) —, —S—CH ₂ —CH (CH ₃ ) —, —O—CH ₃ —CH (CH ₃ _{_{) -, - NH-CO-}} CH 2 -CH (CH 3) -, - CH (OH) -CH _{_{_{_{-, - CH (OH) -C}}}} 2 H 4 -, - CH (CH 2 OH) -CH 2 -, - NH-CH (CH 2 OH) -CH 2 -, - CO-NH-CH (CH 2 OH ) —CH ₂ —, —NH—CO—CH (CH ₂ OH) —CH ₂ —, —CO—CH (CH ₂ OH) —CH ₂ —, —S—CH (CH ₂ OH) —CH ₂ —, —O—CH (CH ₂ OH) —CH ₂ —, —CH (N (CH ₃ ) ₂ ) —, —C ₆ H ₄ —O—, —C ₆ H ₄ —NH—, —C ₆ H ₄ — CO—NH—, —C ₆ H ₄ —NH—CO—, —C ₆ H ₄ —CO—, —C ₆ H ₄ —CH ₂ —, —C ₆ H ₄ —S—, cyclopropane ring, cyclobutane ring , Cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene A tetrahydronaphthalene ring, fluorene ring, or an anthracene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or It is a benzimidazole ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

A particularly preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y ₁₄ is , Single bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CH (OH) —, benzene ring, naphthalene ring, fluorene ring, or anthracene Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
Specific examples of the specific amine compound of the component (C) of the present invention include compounds M1 to M156.

More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156. More preferably, M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.

<(D) component>
The polymer composition used for this invention may have the following (D) components as components other than the said (A) and (B) component.
That is, the component (D) is a compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted (hereinafter also referred to as compound D).
The compound D is not particularly limited as long as the compound D has one or more alkoxysilyl groups and one or more urea structures substituted at both the 1-position and the 3-position. From the viewpoint of properties and the like, a compound represented by the following formula (d) is one of preferred examples.

(Wherein X ¹⁰² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, and R ¹⁰² is a hydrogen atom Or represents an alkyl group, and when n is 2 or more, R ¹⁰² becomes alkylene together with other R ¹⁰² , or when n is 1 to 6, it also binds to X ¹⁰² to form a ring together with X ¹⁰² And L may represent an alkylene having 2 to 20 carbon atoms, and R ¹⁰³ and R ¹⁰⁴ may each independently represent an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or (It is an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.)

R ¹⁰³ and R ¹⁰⁴ in the formula (d) are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, but availability of raw materials and reactivity From the viewpoint, methyl or ethyl is preferable.

Examples of L in the formula (d) include alkylene having 2 to 20 carbon atoms, but trimethylene is preferable from the viewpoint of obtaining the raw material.

As q in the formula (d), 2 or 3 is preferable, and 3 is particularly preferable.
As n in Formula (d), 1, 2 or 3 is preferable, and 1 or 2 is particularly preferable.

One embodiment of the compound of component (D) is a compound in which X ¹⁰² is a divalent organic group, R ¹⁰² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-1) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-1) is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (D) is a compound in which X ¹⁰² is a divalent organic group, R ¹⁰² together forms an alkylene, and L is trimethylene.

Such a compound represented by the formula (2-2) can be obtained by reacting 2.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing two NH.

X in the compound represented by the formula (2-2) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

In one embodiment of the compound of component (D), X ¹⁰² is a divalent organic group, one of R ¹⁰² is a hydrogen atom, and the other is also bonded to X ¹⁰² to form a ring, A compound in which L is trimethylene.

Such a compound represented by the formula (2-3) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-3) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

One embodiment of the compound of component (D) is a compound in which X ¹⁰² is a trivalent organic group, R ¹⁰² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-4) can be obtained by reacting a triamine compound with 3.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-4) is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (D) is a compound in which X ¹⁰² is a monovalent organic group, R ¹⁰² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-5) can be obtained by reacting a monoamine compound with 1.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-5) is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (D) is a compound in which X ¹⁰² is a monovalent organic group, R ¹⁰² is bonded to X ¹⁰² to form a ring, and L is trimethylene.

Such a compound represented by the formula (2-6) can be obtained by reacting 1.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing one NH.

X in the compound represented by the formula (2-6) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

In the reaction between the amine and the isocyanate, the amount of the isocyanate compound used may be 0.98 equivalent times to 1.2 equivalent times with respect to one NH or NH ₂ group. More preferably, it is 1.0 equivalent times to 1.05 equivalent times.

The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sulfoxide, sulfolane, etc. Sulfur aprotic polar solvent; pyridine, pyridines picoline and the like. These solvents may be used alone or as a mixture of two or more thereof. Preferred are toluene, acetonitrile, ethyl acetate and tetrahydrofuran, and more preferred are acetonitrile and tetrahydrofuran.

The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the solvent is used in an amount of 0.1 to 100 times the amount of the isocyanate compound. It may be used. The amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited but is, for example, −90 to 150 ° C., preferably −30 to 100 ° C., and more preferably 0 ° C. to 80 ° C.
The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

A catalyst may be added to shorten the reaction time. Examples thereof include dibutyltin dilaurate, dioctyltin bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dibutyltin diacetate, etc. Organoethyl compounds of: triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N, N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2.2.2 -Amines such as octane, 1,8-diazabicyclo [5.4.0] undecene, 1,5-diazabicyclo [4.3.0] nonene-5; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid, etc. of Inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; bismuth compounds such as bismuth tris (2-ethylhexanoate); quaternary An ammonium salt etc. are mentioned. These catalysts may be used alone or in combination of two or more. These catalysts are preferably liquid or soluble in the reaction solvent.

When a catalyst is added, the catalyst may be used in an amount of 0.005 wt% to 100 wt%, preferably 0.05 wt% to 10 wt%, based on the total amount (mass) of the compound having an isocyanate group. Preferably, it is 0.1 wt% to 5 wt%. If an organotin compound, a titanium compound, or a bismuth compound is used as the catalyst, the amount is preferably 0.005 wt% to 0.1 wt%.
This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
Specific examples of the preferred component (D) include compounds represented by any one of S1 to S4.

When the amount of the component (D) component is too large, the liquid crystal orientation and the pretilt angle are affected. When the amount is too small, the effect of the present invention cannot be obtained. Therefore, the amount of the component (D) compound added is preferably 0.1 to 20% by mass and more preferably 1 to 10% by mass with respect to the polymer of the (A) component.

Furthermore, although the polymer composition used for this invention can mention the following as components other than the said (A) and (B) component, it is not limited to these.
The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. Examples include solvents having surface tension.

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

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), 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 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

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

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

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

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

A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, methylcoumarin and the like.
Aromatic 2-hydroxy ketone (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.

<Liquid crystal aligning agent>
The present application has a polymer composition as described above, or consists essentially of the polymer composition as described above, or a liquid crystal aligning agent composed of only the polymer composition as described above, particularly for a liquid crystal display element, more particularly laterally. A liquid crystal aligning agent for an electric field driven liquid crystal display element is provided.

<Liquid crystal alignment film> or <Substrate having liquid crystal alignment film>
This application provides the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent, especially the liquid crystal aligning film for liquid crystal display elements, and more especially for a horizontal electric field drive type liquid crystal display element.
In addition, the present application relates to a liquid crystal alignment film formed from the liquid crystal alignment agent described above, particularly a substrate having a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, particularly a liquid crystal display element. A substrate for a horizontal electric field drive type liquid crystal display element is provided.

<Method for manufacturing liquid crystal alignment film> or <Method for manufacturing substrate having liquid crystal alignment film>
The liquid crystal alignment film described above is
[I] The process of apply | coating the above-mentioned polymer composition or the above-mentioned liquid crystal aligning agent on a board | substrate, for example 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];
Thus, a liquid crystal alignment film imparted with an alignment control ability, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, or a substrate having the liquid crystal alignment film can be obtained.

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

<< Step [I] >>
In step [I], a coating film is formed by applying the polymer composition of the present invention, which exhibits liquid crystallinity in a predetermined temperature range, onto a substrate having a conductive film for driving a lateral electric field.

The method for applying the polymer composition described above or the liquid crystal aligning agent 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 or the liquid crystal aligning agent is applied on the substrate having the conductive film for driving the transverse electric field, the heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven is used. Preferably, the solvent can be evaporated at 50 to 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 polymer of the component (A) of the present invention. Here, the liquid crystal phase expression temperature of the polymer of component (A) is a temperature at which at least two polymers of component (A) exhibit a liquid crystal phase as a whole.
If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.

<< Step [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 light 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 polymer of the component (A) of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). In the case of the surface of a thin film such as a coating film, the liquid crystallinity expression temperature on the coating film surface is expected to be lower than the liquid crystallinity expression temperature when the polymer of the component (A) of the present invention is observed in bulk. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystallinity expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystalline expression temperature of the polymer of the component (A) of the present invention used, It is preferable that the temperature is in a range where the upper limit is 10 ° C. lower than the upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystalline expression temperature is equal to or higher than the glass transition temperature (Tg) at which the polymer or coating film surface of the component (A) of the present invention undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase ( A temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition in the isotropic phase.

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].

By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board | substrate with a liquid crystal aligning film can be manufactured highly efficiently.

<Liquid crystal display element> and <Method for manufacturing liquid crystal display element>
The present application provides a liquid crystal display element having a substrate having a liquid crystal alignment film obtained as described above, particularly a lateral electric field drive type liquid crystal display element.

Specifically, in addition to the substrate having the liquid crystal alignment film (first substrate) obtained above, a second substrate is prepared, whereby a lateral electric field drive type liquid crystal display element can be obtained.
When the second substrate uses a substrate having no lateral electric field driving conductive film instead of the substrate having the lateral electric field driving conductive film, the second electric field driving conductive film as in the first substrate is used. In some cases, a substrate having In addition, the second substrate preferably has a liquid crystal alignment film as in the first substrate.

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.

<Process [IV]>
The step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving. The obtained liquid crystal alignment film-attached substrate (second substrate) is arranged to face each other with the liquid crystal alignment film facing each other through the liquid crystal, and a liquid crystal cell is manufactured by a known method. This is a step of manufacturing a drive type liquid crystal display element. The steps [I ′] to [III ′] can be performed in the same manner as the steps [I] to [III] except for the difference in the presence or absence of the conductive film for driving the lateral electric field in the step [I]. 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 to seal, 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, when a lateral electric field driving type liquid crystal display element is manufactured, it is preferable to use a substrate having electrodes having a structure like a comb for driving an electric field on one side.
The diameter of the spacer 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.

As described above, the polymer composition or the liquid crystal aligning agent of the present invention, the liquid crystal alignment film formed using the composition or the liquid crystal aligning agent, the substrate having the alignment film, and the liquid crystal alignment film or substrate are provided. The liquid crystal display element formed in this manner, in particular the lateral electric field drive type liquid crystal display element, has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

M1 as a monomer having a photoreactive group used in Examples, M2 as a monomer having a liquid crystal group, HBAGE as a monomer having a crosslinking group, and A1 as a monomer having an amide group are shown below.
M1 and M2 were synthesized as follows. That is, M1 was synthesized by the synthesis method described in the patent document (WO2011-084546). M2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717). A polymer formed using M1 as a monomer has photoreactivity and liquid crystallinity, and a polymer formed using M2 as a monomer has only liquid crystallinity.
The monomer A1 to be copolymerized was synthesized by the synthesis method described in Synthesis Example 1 below.
As HBAGE (hydroxybutyl acrylate glycidyl ether), a commercially available product was used.

In addition, the abbreviations of the reagents used in this example are shown below.
(Organic solvent)
THF: tetrahydrofuran.
NMP: N-ethyl-2-pyrrolidone.
EDC: N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide (condensing agent).
DMAP: 4-dimethylaminopyridine.
PB: propylene glycol monobutyl ether.
(Polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile.

<Synthesis Example 1>
Synthesis of compound A1

In a 1 L four-necked flask, compound [A] (63.42 g, 287 mmol), compound [B] (50.00 g, 406 mmol), EDC (93.43 g, 487 mmol), DMAP (4.96 g, 40.6 mmol) , THF (500 g) was added, and the reaction was performed at 23 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into distilled water (3 L), ethyl acetate (1 L) was added, and the aqueous layer was removed by a liquid separation operation. Thereafter, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried over magnesium sulfate. Thereafter, filtration and evaporation of the solvent with an evaporator gave 86.3 g of Compound [A1] as an oily compound (yield 92%).
¹ H-NMR (400 MHz, CDCl3, δ ppm): 8.81-8.79 (2H, dd), 7.86-7.85 (2H, dd), 6.16-6.14 (1H, m), 5.62-5.60 (1H, m), 4.63- 4.61 (2H, m), 5.62-5.60 (2H, m), 4.63-4.61 (2H, m), 4.52-4.60 (2H, m), 1.97-1.95 (3H, m).

<Polymer synthesis example P1>
M1 (1.66 g: 0.1 mol%) and M2 (13.79 g: 0.9 mol%) were dissolved in THF (146.42 g), and after deaeration with a diaphragm pump, AIBN (0.82 g ) And deaerated again. Thereafter, the mixture was reacted at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (300 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P1.

<Polymer synthesis examples P2 to P4>
The methacrylate polymer powders P2 to P4 were synthesized using the same method as in the polymer synthesis example P1, except that the composition shown in Table 1 was used.

<Example 1>
Add the methacrylate polymer powder P1 (0.105 g) obtained in Polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.245 g) obtained in Polymer Synthesis Example P2 to NMP (5.65 g) at room temperature. Stir for 1 hour to dissolve. To this solution, PB (4.0 g) was added and stirred to obtain a polymer solution T1. This polymer solution T1 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

<Control 1>
The methacrylate polymer powder P2 (0.35 g) obtained in Polymer Synthesis Example P2 was added to NMP (5.65 g), and dissolved by stirring for 1 hour at room temperature. By adding PB (4.0 g) to this solution and stirring, a control polymer solution CT1 was obtained. This polymer solution was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

<Control 2>
The methacrylate polymer powder P3 (0.35 g) obtained in Polymer Synthesis Example P3 was added to NMP (5.65 g), and dissolved by stirring for 1 hour at room temperature. To this solution, PB (4.0 g) was added and stirred to obtain a control polymer solution CT2. This polymer solution was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

<Control 3>
The methacrylate polymer powder P4 (0.35 g) obtained in Polymer Synthesis Example P4 was added to NMP (5.65 g), and stirred at room temperature for 1 hour to dissolve. By adding PB (4.0 g) to this solution and stirring, a control polymer solution CT3 was obtained. This polymer solution was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

For the liquid crystal aligning agent T1 of Example 1 and the liquid crystal aligning agents CT1 to CT3 of Controls 1 to 3, the polymer types used and their wt%, and for Example 1, two types of polymers were used. Amount of photoreactive group, monomer species from which “photoreactive group” and “liquid crystalline group” in each polymer are derived, “amount of photoreactive group” in the monomer, and liquid crystal aligning agent derived therefrom The “total photoreactive group amount” is summarized in Table 2 below.
The “photoreactive group amount in each polymer” and “total photoreactive group amount” in Table 2 can be determined, for example, as follows.

That is, in the liquid crystal aligning agent T1 of Example 1, polymer seed | species P1 and P2 are used, P1 is 30 wt% and P2 is used 70 wt% in the total weight. As described above, the monomer from which the “photoreactive group” in the polymer species P1 is derived is M1. M2 has only a “liquid crystalline group”. “The amount of photoreactive groups in each polymer” is a mol% value of “photoreactive groups” when the total of “liquid crystalline groups” and “photoreactive groups” is 100 mol%. The “photoreactive group amount” of the polymer species P1 is 100 × {0.1 / (0.1 + 0.9)}, which is 10 mol%. Similarly, the “photoreactive group amount” in the polymer species P2 is 20 mol%.
The “total photoreactive group amount” is determined from the weight ratio of the polymer species P1 and P2 and the “photoreactive group amount” in the polymer species P1 and P2, and is 0.1 mol% × 0.3 (P1 0.17 mol% is obtained from (the seed is derived from 30 wt%) + 0.2 mol% × 0.7 (the P2 seed is derived from 70 wt%).

<Production of liquid crystal cell>
The liquid crystal aligning agent (T1) obtained in Example 1 was filtered through a 0.45 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C. for 90 seconds, and a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the surface of the coating film was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 to 80 mJ / cm ² and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which liquid crystals were aligned in parallel.
Similarly, liquid crystal cells were prepared using the liquid crystal alignment agents CT1, CT2 and CT3 obtained in Controls 1 to 3.

<Orientation evaluation>
The liquid crystal cell produced in Example 1, Controls 1 to 3 was placed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, the backlight was turned on with no voltage applied, and the transmitted light was transmitted. The arrangement angle of the liquid crystal cell was adjusted so that the luminance was minimized. Visually check the liquid crystal cell. When this liquid crystal cell was well aligned and no fluid alignment was confirmed, “◯” was indicated, when the aligned one was confirmed “Δ”, and when it was not aligned, “X” was indicated.

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

From Table 3, in Example 1, two polymers having different photoreactive group amounts are used, and a polymer having a relatively large photoreactive group amount has an epoxy group (derived from HBAGE). Thus, it can be seen that the film shows a good orientation and a good VHR in a wide range of UV irradiation doses.
Specifically, when Example 1 and Control 1 are compared, they have almost the same amount of total photoreactive groups (Example 1: 0.17; Control 1: 0.20), and both are epoxy. A polymer having a group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group is used, whereby VHR shows almost the same value. However, in both, in Example 1, two types (P1 and P2) are used as the polymer type, while in Control 1, only one type (P2) is used as the polymer type. This difference, In Example 1, UV irradiation dose 50 mJ / cm ² and while excellent orientation in 80 mJ / cm ² is confirmed, UV irradiation amount in the control 1 50 mJ / cm ² and 80 mJ / cm ² in at unoriented It can be seen that Example 1 shows better orientation in a wide range of UV irradiation dose and VHR also has a desired value as compared with Control 1.
Comparing Example 1 with Control 2, both have approximately the same amount of total photoreactive groups (Example 1: 0.17; Control 2: 0.20), thereby allowing them to have a wide range of UV irradiation. It shows good orientation in the amount. However, in both, in Example 1, two types (P1 and P2) are used as polymer species, and a polymer having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group is used in the two types of polymers. On the other hand, in Control 2, only one type (P3) is used as the polymer type. Due to this difference, VHR shows a desired value in Example 1, whereas VHR is lower than the desired value in Control 2, and Example 1 has a wider range of UV irradiation than Control 2. It can be seen that the amount shows good orientation and VHR also takes the desired value.
When Example 1 and Control 3 are compared, both have the same total photoreactive group amount (Example 1: 0.17; Control 3: 0.17), but two polymer types (P1 and P2). ) And a polymer having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group in the two types of polymers, while in Control 3, only one type (P4) is used as the polymer type, The P4 is different in that it does not have an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group. Due to this difference, Example 1 shows good orientation in a wide range of UV irradiation doses and VHR also shows a desired value, whereas in Control 3, VHR is lower than the desired value and the UV irradiation amount is also related. It can be seen that the desired characteristics cannot be achieved at any dose.

Claims

(A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity; and (B) an organic solvent;
A polymer composition comprising:
The composition as described above, wherein one of the at least two polymers has a crosslinkable group.
The composition according to claim 1, wherein, of the at least two kinds of polymers, one polymer (A1) and the other polymer (A2) are different from each other in the amount of structures that exhibit photoreactivity.
The composition according to claim 2, wherein the amount of the structure expressing the photoreactivity of the polymer (A1) is larger than the amount of the structure expressing the photoreactivity of the polymer (A2).
The crosslinkable group has the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein the broken line represents a bond, R 50 represents a hydrogen atom, a halogen atom) Represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and when there are a plurality of R 50 s , they may be the same or different from each other, t is an integer of 1 to 7, J is O, S NH represents NR 51 , and R 51 represents at least one group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a group selected from a phenyl group. A composition according to claim 1.
The composition according to any one of claims 2 to 4, wherein the crosslinkable group has in the polymer (A1).
The composition according to any one of claims 2 to 5, wherein the polymer (A1) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group.
The composition according to any one of claims 2 to 6, wherein the polymer (A2) further has at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group.
The composition according to any one of claims 1 to 7, wherein each of the at least two polymers has a structure that exhibits photoreactivity and liquid crystallinity, and a structure that exhibits only liquid crystallinity.
The structure expressing the photoreactivity is
The following formulas (1) to (6)
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other 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 atom bonded to each independently represents —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 a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —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 according to any one of claims 1 to 8, which has a structure selected from the group consisting of:
The structure expressing the photoreactivity is
The following formulas (7) to (10)
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other 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 atom bonded to each independently represents —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 8, which has a structure selected from the group consisting of:
The structure expressing the photoreactivity is
The following formulas (11) to (13)
(Wherein A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—) Or represents —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 m1 represents an integer of 1 to 3;
R 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 a phase selected from those substituents. Each of the hydrogen atoms bonded to them is independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5). -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 (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 8, which has a structure selected from the group consisting of:
The structure expressing the photoreactivity is
Following formula (14) or (15)
(Wherein each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or represents —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 bonded to each other 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;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The composition according to any one of claims 1 to 8, which has a structure represented by:
The structure expressing the photoreactivity is
The following formula (16) or (17) (wherein A is a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—) Represents 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 according to any one of claims 1 to 8, which has a structure represented by:
The structure expressing the photoreactivity is
Following formula (18) or (19)
(Wherein 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 bonded to each other 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 represents 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 8, which has a structure selected from the group consisting of: an oxy group.
The structure expressing the photoreactivity is
The following formula (20) (wherein A is 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 bonded to each other 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 8, wherein l represents an integer of 1 to 12, and m represents an integer of 0 to 2.
The structure that exhibits only liquid crystallinity has the following formulas (21) to (31).
Wherein A and B have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 each represent a structure selected from the group consisting of a single bond, —CO—, —CH 2 O—, —CH═N—, and —CF 2 —. 16. The composition according to any one of 15.
The amount of the structure that exhibits photoreactivity of the polymer (A1) is α mol when the total of the structure that exhibits photoreactivity and the structure that exhibits liquid crystallinity of the polymer (A1) is 100 mol%. % (Α is 15 or more),
The amount of the structure expressing the photoreactivity of the polymer (A2) is 0.95α mol% when the structure expressing the photoreactivity of the polymer (A2) and the structure exhibiting liquid crystallinity are 100 mol%. The composition according to any one of claims 2 to 16, which is:
The weight average molecular weight of the polymer (A1) is β (β is 30,000 or more), and the weight average molecular weight of the polymer (A2) is 0.1β to 0.9β. A composition according to 1.
The composition according to any one of claims 2 to 18, wherein the polymer (A1) is 20 to 95 wt% when the total weight of the polymer (A1) and the polymer (A2) is 100 wt%.
The at least two polymers are formed of (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and a monomer (M2) having a structure that exhibits only liquid crystallinity. The composition according to any one of claims 1 to 19.
The monomer (M1) has a structure represented by any one of the formulas (1) to (20), and the monomer (M2) has a structure represented by the formulas (21) to (31). Item 21. The composition according to item 20.
The monomer (M1) is at least one selected from the group consisting of the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38 to MA42, MA44 and MA46. And
The monomer (M2) is at least one selected from the group consisting of the following formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45. Composition.
The polymer (A1) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity;
(M-2) Monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-3) Formulas (G-1), (G-2), (G-3) and (G-4) ( In the formula, a broken line represents a bond, R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms and a phenyl group, and when there are a plurality of R 50 s , they may be the same or different. T is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. A monomer (M3) having at least one group selected from:
The composition according to any one of claims 1 to 22, wherein the composition is formed.
The (M-3) monomer (M3) is represented by the following formula (0):
(In the formula (0), A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH— Represents CO—O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the 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;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein the broken line represents a bond, R 50 represents a hydrogen atom, a halogen atom or a carbon number) Represents a group selected from 1 to 3 alkyl groups and phenyl groups, and when there are a plurality of R 50 s , they may be the same or different from each other; t is an integer of 1 to 7; J is O, S, NH or NR 51 , wherein R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
The composition of Claim 22 which has a structure represented by these.
The polymer (A1) is
(M-4) a monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group;
The composition according to claim 23 or 24, further comprising:
The polymer (A2) is
(M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity;
(M-2) a monomer (M2) having a structure exhibiting only liquid crystallinity; and (M-4) at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. Having monomer (M4);
The composition according to any one of claims 1 to 25, wherein the composition is formed.
The monomer (M4) having at least one group selected from the group consisting of (M-4) nitrogen-containing aromatic heterocyclic group, amide group and urethane group is selected from the group consisting of the following formulas MA6 to MA8 and MA33. 27. The composition according to claim 25 or 26, wherein the composition is at least one selected.
When the total of the monomer (M1) and the monomer (M2) is 100 mol%,
The polymer (A1) is formed such that the monomer (M1) is α mol% (α is 15 or more) and the monomer (M2) is a residue,
The composition according to any one of claims 23 to 27, wherein the polymer (A2) is formed such that the monomer (M1) is 0.95α mol% or less and the monomer (M2) is a residue. .
A liquid crystal aligning agent comprising the polymer composition according to any one of claims 1 to 28.
A liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 29.
[I] A step of applying the polymer composition according to any one of claims 1 to 28 on a substrate having a conductive film for driving a transverse 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];
A method for producing a liquid crystal alignment film, which obtains a liquid crystal alignment film imparted with an alignment control ability.
A substrate having a liquid crystal alignment film according to claim 30.
[I] A step of applying the polymer composition according to any one of claims 1 to 28 on a substrate having a conductive film for driving a transverse 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];
The manufacturing method of the board | substrate which has a liquid crystal aligning film which obtains the liquid crystal aligning film to which the alignment control ability was provided by having.
A liquid crystal display device having the substrate according to claim 32.
Preparing a substrate (first substrate) according to claim 32;
[I ′] A step of coating the second substrate with the polymer composition according to any one of claims 1 to 28 to form a coating film;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a liquid crystal display element.