JP6744717B2 - Method for manufacturing substrate having liquid crystal alignment film for in-plane switching type liquid crystal display device - Google Patents

Description

The present invention relates to a method of manufacturing a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent image sticking characteristics.

The liquid crystal display element is known as a light-weight, thin, and low-power-consumption display device, and in recent years, it has been used in a large-sized television and has made remarkable progress. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates having electrodes. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal has a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a constituent member of a liquid crystal display element, is formed on a surface of a substrate holding 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 have 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. The ability to control the orientation of the liquid crystal in the liquid crystal alignment film (hereinafter referred to as the orientation control ability) is given by performing an alignment treatment on the organic film forming the liquid crystal alignment film.

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

However, the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like sometimes causes problems such as dust generation and static electricity generation. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness due to the electrodes on the corresponding substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be evenly rubbed with the cloth, and the uniform In some cases, the alignment of the liquid crystal could not be realized.

Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film without rubbing.

There are various photo-alignment methods, but anisotropy is formed in the organic film forming the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

As a main optical alignment method, a decomposition type optical alignment method is known. For example, the polyimide film is irradiated with polarized ultraviolet rays to cause anisotropic decomposition by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (for example, see Patent Document 1).

Further, photocrosslinking type and photoisomerizing type photoalignment methods are also known. For example, polyvinyl cinnamate is used to irradiate polarized ultraviolet light to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in the direction orthogonal to the polarization direction (for example, see Non-Patent Document 1). Also, when a side chain type polymer having azobenzene as a side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction in the azobenzene part of the side chain parallel to the polarized light, and the liquid crystal is directed in the direction orthogonal to the polarization direction. Orient (see, for example, Non-Patent Document 2).

As in the above examples, the alignment treatment method for the liquid crystal alignment film by the photo-alignment method does not require rubbing, and there is no concern about dust generation or static electricity generation. Further, the alignment treatment can be performed even on the substrate of the liquid crystal display element having the uneven surface, which is a method of aligning the liquid crystal alignment film suitable for the industrial production process.

Japanese Patent No. 3893659

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

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

For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, which requires a long time and a large amount of ultraviolet irradiation. Become. Further, also in the case of the dimerization type or photoisomerization type photo-alignment method, a large amount of UV irradiation of about several J (joule) to several tens of J may be required. Further, in the case of the photocrosslinking type or photoisomerization type photoalignment method, the thermal stability and the photostability of the alignment of the liquid crystal are inferior. was there. In particular, in a horizontal electric field drive type liquid crystal display element, liquid crystal molecules are switched in-plane, so that alignment deviation of the liquid crystal after the liquid crystal drive is likely to occur, and display burn-in caused by AC drive is a major problem.

Therefore, in the photo-alignment method, there is a demand for higher efficiency of alignment treatment and realization of stable liquid crystal alignment, and a liquid crystal alignment film or liquid crystal capable of highly imparting high alignment control ability to the liquid crystal alignment film There is a need for an aligning agent.

The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, which is provided with a highly efficient alignment control ability and is excellent in image sticking characteristics, and a horizontal electric field drive type liquid crystal display device having the substrate. With the goal.
Further, in addition to the above objects, an object of the present invention is to provide a high-reliability lateral electric field drive type liquid crystal element which does not deteriorate characteristics such as voltage holding ratio even under severe conditions such as high temperature and high humidity. And to provide a liquid crystal alignment film for the device.

The inventors of the present invention have found the following inventions as a result of earnestly studying to achieve the above object.
<1> A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent, particularly, liquid crystal alignment for a horizontal electric field drive type liquid crystal display device. A composition for producing a film,
The (A) side chain type polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure,
In the cyclic amine structure, two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S) (in the formula, R ¹¹ is a single bond or an optionally substituted hydrocarbon group,
X is a single bond, an oxygen atom, a sulfur atom, -CO-, -CO-O- or -O-CO-,
R ¹² is an optionally substituted hydrocarbon group. However, when X is not a single bond, R ¹¹ and R ¹² may be bonded to each other to form a ring structure. ), the phenol structure has at least one carbon atom in the ortho position with respect to the hydroxyl group has a substituent represented by the following formula (S): A combined composition, particularly a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device.

<2> In the above item <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries transition.
<3> In the above item <1> or <2>, the first repeating unit has the following formula (1-1) (in the formula (1-1), R is a hydrogen atom or a methyl group, and R ¹¹ is Each may be the same or different and has the same definition as above, each X may be the same or different and has the same definition as above and R ¹² is each the same. Or B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and m is an integer of 0 to 4). Was
The second repeating unit is the following formula (1-2) (in the formula (1-2), R is a hydrogen atom or a methyl group, and R ¹¹ may be the same or different, and X has the same definition as above, each X may be the same or different and has the same definition as above, and each R ¹² may be the same or different and has the same definition as above. However, n is an integer of 0 to 3).

<4> In any one of the above items <1> to <3>, the first repeating unit is represented by the following formula (1-1-1) (in the formula (1-1-1), R represents a hydrogen atom or methyl. A group, A ¹ is a single bond or a divalent linking group, R ¹³ may be the same or different and each is an alkyl group having 1 to 5 carbon atoms, B ¹ is a hydrogen atom, An oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group),
The second repeating unit is the following formula (1-2-1) (in the formula (1-2-1), R is a hydrogen atom or a methyl group, and A ¹ is a single bond or a divalent linking group. And R ¹³ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

<5> In any one of the above items <1> to <4>, the component (A) has any one kind of photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.

Wherein, A, B, 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 to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R ⁵¹ represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has 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 represented and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- It 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is an aromatic ring, When the number of P is 2 or more, P may be the same or different, and when the number of Q is 2 or more, Q may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

<6> In any one of the above items <1> to <4>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10). Good.
Wherein A, B, D, Y ₁ , X, Y ₂ , and R ⁵¹ have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, m1 and m2 represent integers of 1 to 3;
n represents an integer of 0 to 12 (however, when n=0, B is a single bond).

<7> In any one of the above items <1> to <4>, the component (A) has any one kind of photosensitive side chains selected from the group consisting of the following formulas (11) to (13). Good.
Where A, X, l, m, m1 and R ⁵¹ have the same definition as above.

<8> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

<9> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
Where A, X, l and m have the same definitions as above.

<10> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C(CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

<11> In any one of the above items <1> to <4>, the component (A) preferably has a photosensitive side chain represented by the following formula (20).
Where A, Y ₁ , X, l and m have the same definition as above.

<12> In any one of the above items <1> to <11>, the component (A) has any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31). Good.
Wherein A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen _{atom, -NO 2, -CN, -CH =} C (CN) 2, -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26). ), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a.

<13> [I] A step of applying a composition according to any one of the above items <1> to <12> onto a substrate having a conductive film for driving an in-plane electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II];
A method for producing a substrate having the liquid crystal alignment film, wherein a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device having an alignment control ability is obtained by having the above.
<14> A substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, which is manufactured by the method according to <13> above.
<15> A horizontal electric field drive type liquid crystal display device including the substrate according to <14>.

<16> A step of preparing the substrate (first substrate) according to <14>above;
[I′] A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent is applied onto a second substrate. A step of forming a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet light;
[III'] A step of heating the coating film obtained in [II'];
And (IV) liquid crystal alignment of the first and second substrates via liquid crystal, wherein a liquid crystal alignment film having alignment controllability is obtained by A step of arranging the first and second substrates so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which comprises: providing a liquid crystal display element of the lateral electric field drive type.

As another aspect, they have found the following invention.
<P1> [I] (A) A photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, in which two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S). At least one carbon atom of ortho-positions with respect to the cyclic amine structure having two substituents or a hydroxyl group has the following formula (S) (wherein R ¹¹ is a single bond or substituted). Is a hydrocarbon group which may be present, X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—, and R ¹² is an optionally substituted carbon group. A hydrogen group, provided that when X is not a single bond, R ¹¹ and R ¹² may combine with each other to form a ring structure). A side chain type polymer having one or more selected repeating units and (B) a polymer composition containing an organic solvent are applied onto a substrate having a conductive film for driving an in-plane electric field to form a coating film. Process;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II];
A method for producing a substrate having the liquid crystal alignment film, wherein a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device having an alignment control ability is obtained by having the above.

<P2> In the above <P1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries transition.
<P3> In the above <P1>, the repeating unit is represented by the following formula (1-1) or (1-2) (in formula (1-1) and formula (1-2), R represents a hydrogen atom or a methyl group. And A ¹ is a single bond or a divalent linking group, R ¹¹ is a single bond or an optionally substituted hydrocarbon group, and X is a single bond, an oxygen atom, or sulfur, respectively. Atom, -CO-, -CO-O- or -O-CO-, and R< ¹² > is an optionally substituted hydrocarbon group, provided that when X is not a single bond, R<^11>. And R ¹² may combine with each other to form a ring structure, In the formula (1-1), B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and m Is an integer of 0 to 4. In the formula (1-2), n is an integer of 0 to 3.).

<P4> In the above <P1>, the repeating unit is represented by the following formula (1-1-1) or (1-2-1) (formula (1-1-1) and formula (1-2-1)). , R is a hydrogen atom or a methyl group, A ¹ is a single bond or a divalent linking group, R ¹³ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or a carbon atom. An alkyl group of the formulas 1 to 5. In the formula (1-1-1), B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group. Characteristic manufacturing method.

<P5> In the above <P1> or <P2>, it is preferable that the component (A) has any one kind of photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

Wherein, A, B, 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 to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R ⁵¹ represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has 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=. Represents CH-;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- It 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 a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. Is a group selected from. However, when X is -CH=CH-CO-O- or -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is an aromatic ring;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

<P6> In the above <P1> or <P2>, the component (A) may have any one kind of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
Wherein A, B, D, Y ₁ , X, Y ₂ , and R ⁵¹ have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, m1 and m2 represent integers of 1 to 3;
n represents an integer of 0 to 12 (however, when n=0, B is a single bond).

<P7> In the above <P1> or <P2>, it is preferable that the component (A) has a photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
Wherein A, X, l, m and R ⁵¹ have the same definition as above.

<P8> In the above <P1> or <P2>, the component (A) preferably has a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , X, 1, m1 and m2 have the same definitions as above.

<P9> In the above <P1> or <P2>, the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
Where A, X, l and m have the same definitions as above.

<P10> In the above <P1> or <P2>, the component (A) preferably has a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definitions as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C(CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

<P11> In <P1> or <P2> above, the component (A) preferably has a photosensitive side chain represented by the following formula (20).
Where A, Y ₁ , X, l and m have the same definition as above.

<P12> In any one of the above items <P1> to <P11>, the component (A) has any one kind of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31). Good.
Wherein A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen _{atom, -NO 2, -CN, -CH =} C (CN) 2, -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) ), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a.

<P13> A substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, which is manufactured by any of the above <P1> to <P12>.
<P14> A horizontal electric field drive type liquid crystal display device including the substrate of <P13>.

<P15> A step of preparing the substrate (first substrate) of <P13>above;
[I′] A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent is applied onto a second substrate. A step of forming a coating film;
[II'] a step of irradiating the coating film obtained in [I'] with polarized ultraviolet light; and a step of heating the coating film obtained in [III'] [II'];
And (IV) a liquid crystal alignment film of the first and second substrates via a liquid crystal. So as to face each other so that the first and second substrates are arranged to face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which comprises: providing a liquid crystal display element of the lateral electric field drive type.

<P16> A horizontal electric field drive type liquid crystal display element manufactured by the above <P15>.
<P17> (A) A photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, in which two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S) (in the formula, R ¹¹ Is a single bond or an optionally substituted hydrocarbon group, X is a single bond, an oxygen atom, a sulfur atom, -CO-, -CO-O- or -O-CO-, and R ¹² is Is a hydrocarbon group which may be substituted, provided that when X is not a single bond, R ¹¹ and R ¹² may be bonded to each other to form a ring structure). A cyclic amine structure having two or a phenol structure having at least one carbon atom in the ortho position with respect to a hydroxyl group having a substituent represented by the following formula (S) A composition for producing a liquid crystal alignment film for a lateral electric field driving type liquid crystal display device, which comprises a side chain polymer having the above repeating unit and (B) an organic solvent.

<P18> In the above <P17>, the repeating unit is represented by the following formula (1-1) or (1-2).

In formulas (1-1) and (1-2), R represents a hydrogen atom or a methyl group, A ¹ represents a single bond or a divalent linking group, and R ¹¹ represents a single bond or a substituent. Optionally a hydrocarbon group, X is a single bond, an oxygen atom, a sulfur atom, —CO—, —CO—O— or —O—CO—, and R ¹² is each substituted. Optionally a hydrocarbon group. However, when X is not a single bond, R ¹¹ and R ¹² may be bonded to each other to form a ring structure. In formula (1-1), B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and m is an integer of 0 to 4. In formula (1-2), n is an integer of 0-3.
<P19> In the above <P17>, the repeating unit is represented by the following formula (1-1-1) or (1-2-1).

In formulas (1-1-1) and (1-2-1), R represents a hydrogen atom or a methyl group, A ¹ represents a single bond or a divalent linking group, and R ¹³ represents carbon. It is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In formula (1-1-1), B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, which is provided with a highly efficient alignment control ability and is excellent in image sticking characteristics, and a horizontal electric field drive type liquid crystal display device having the substrate. You can
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not deteriorated even when continuously driven for a long time.
Further, according to the present invention, in addition to the above-mentioned effects, even under severe conditions such as high temperature and high humidity, characteristics such as voltage holding ratio are not deteriorated, and a lateral electric field drive type liquid crystal element having high reliability, and A liquid crystal alignment film for a device can be provided.

It is a diagram of one example schematically illustrating an anisotropic introduction process in the method for producing a liquid crystal alignment film used in the present invention, using a crosslinkable organic group in the photosensitive side chain, introduced anisotropic It is a figure when the sex is small. It is a diagram of one example schematically illustrating an anisotropic introduction process in the method for producing a liquid crystal alignment film used in the present invention, using a crosslinkable organic group in the photosensitive side chain, introduced anisotropic It is a figure when the nature is large. It is a diagram of one example schematically illustrating the anisotropic introduction treatment in the method for producing a liquid crystal alignment film used in the present invention, using an organic group that causes Fries transition or isomerization in the photosensitive side chain, It is a figure when the anisotropy is small. It is a diagram of one example schematically illustrating the anisotropic introduction treatment in the method for producing a liquid crystal alignment film used in the present invention, using an organic group that causes Fries transition or isomerization in the photosensitive side chain, It is a figure when the anisotropy is large.

As a result of earnest studies, the present inventor has completed the present invention by obtaining the following knowledge.
The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter, also simply referred to as side chain type polymer). The coating film obtained by using the material is a film having a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. This coating film is not subjected to rubbing treatment, but is subjected to orientation treatment by polarized light irradiation. Then, after irradiation of polarized light, a coating film (hereinafter, also referred to as a liquid crystal alignment film) having an alignment control ability is obtained through a step of heating the side chain type polymer film. At this time, the slight anisotropy generated by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is effectively re-aligned by self-assembly. As a result, highly efficient alignment treatment can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
<Method for producing substrate having liquid crystal alignment film> and <Method for producing liquid crystal display element>
The method for producing a substrate having a liquid crystal alignment film of the present invention,
[I] A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent, particularly liquid crystal alignment for a horizontal electric field drive type liquid crystal display device. A composition for producing a film,
The (A) side chain type polymer has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure,
In the cyclic amine structure, two carbon atoms adjacent to a nitrogen atom are each represented by the following formula (S) (in the formula, R ¹¹ is a single bond or an optionally substituted hydrocarbon group,
X is a single bond, an oxygen atom, a sulfur atom, -CO-, -CO-O- or -O-CO-,
R ¹² is an optionally substituted hydrocarbon group. However, when X is not a single bond, R ¹¹ and R ¹² may be bonded to each other to form a ring structure. ), the phenol structure has at least one carbon atom in the ortho position with respect to the hydroxyl group has a substituent represented by the following formula (S): A step of forming a coating film by applying a combined composition, particularly a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, onto a substrate having a conductive film for a horizontal electric field drive;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II];
Have.

Through the above steps, it is possible to obtain a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device having an alignment control ability, and it is possible to obtain a substrate having the liquid crystal alignment film.

Further, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a lateral electric field drive type liquid crystal display element can be obtained.
As the second substrate, the above steps [I] to [III] (for lateral electric field driving) are used except that a substrate having no lateral electric field driving conductive film is used in place of the substrate having the lateral electric field driving conductive film. Since a substrate having no conductive film is used, for convenience, in the present application, steps [I′] to [III′] may be abbreviated) to provide a liquid crystal alignment film having alignment control ability. Two substrates can be obtained.

The manufacturing method of a lateral electric field drive type liquid crystal display element is
[IV] A step of arranging the first and second substrates obtained above so as to face each other with the liquid crystal alignment films of the first and second substrates facing each other through the liquid crystal, to obtain a liquid crystal display element;
Have. Thereby, a lateral electric field drive type liquid crystal display device can be obtained.

Hereinafter, each of the steps [I] to [III] and [IV] of the production method of the present invention will be described.
<Process [I]>
In the step [I], a polymer composition containing a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving an in-plane electric field. To form a coating film.

<Substrate>
The substrate is not particularly limited, but when the manufactured liquid crystal display element is a transmissive type, it is preferable to use a highly transparent substrate. In that case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used.

<Conductive film for driving lateral electric field>
The substrate has a conductive film for driving an in-plane electric field.
When the liquid crystal display element is a transmissive type, the conductive film may be, for example, ITO (Indium Tin Oxide: indium tin oxide), IZO (Indium Zinc Oxide: indium zinc oxide), but is not limited thereto.
In the case of a reflective liquid crystal display element, the conductive film may be a material that reflects light, such as aluminum, but is not limited thereto.
As a method for forming the conductive film on the substrate, a conventionally known method can be used.

<Polymer composition>
The polymer composition is applied onto a substrate having a conductive film for driving an in-plane electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent.

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

[Repeat unit]
The side chain polymer (A) has at least one repeating unit selected from the group consisting of a first repeating unit having a cyclic amine structure and a second repeating unit having a phenol structure.
In the cyclic amine structure, two carbon atoms adjacent to the nitrogen atom each have two substituents represented by the above formula (S).
In the phenol structure, at least one carbon atom among the carbon atoms in the ortho position to the hydroxyl group has a substituent represented by the above formula (S).

As the cyclic amine structure, the number of carbon atoms forming the ring structure is preferably 2 or more and 7 or less, and more preferably 5.
Further, in the above-mentioned phenol structure, the position where the hydroxyl group is bonded in the benzene ring is arbitrary, but the position is preferably a position para to the carbon atom bonded to the main chain side in the benzene ring.

More specifically, the preferable structure of the repeating unit (a1) has a hindered amine structure when it has a cyclic amine structure, and is a structure represented by the following formula (1-1).
On the other hand, when it has a phenol structure, it has a hindered phenol structure and is a structure represented by the following formula (1-2).

In formulas (1-1) and (1-2), R is a hydrogen atom or a methyl group, A ¹ is a single bond or a divalent linking group, and in formula (1-1), B ¹ is , A hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and m is an integer of 0 to 4. In formula (1-2), n is an integer of 0-3. The definitions of R ¹¹ , X and R ¹² are the same as those in the above formula (S).

In the formula (S), the formula (1-1), and the formula (1-2), the hydrocarbon group represented by R ¹¹ is specifically a divalent chain hydrocarbon group having 1 to 10 carbon atoms, Examples thereof include a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Of these, a methylene group or an alkylene group having 2 to 5 carbon atoms is preferable. Specific examples of the alkylene group having 2 to 5 carbon atoms include an ethylene group, a propylene group, a butylene group, a pentylene group and the like, and these may be linear or branched. Moreover, examples of the substituent that the hydrocarbon group may have include a halogen atom such as a fluorine atom and a chlorine atom, and a hydroxyl group.

In formula (S), formula (1-1) and formula (1-2), when -R ¹¹ -X- is not a single bond, preferably -CO-O-, -CH ₂ -CO. -, or _-CH 2 -CH (OH) - it is.

In the above formula (S), the above formula (1-1) and the above formula (1-2), R ¹² is specifically an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or carbon. The aralkyl group of several 7-13 can be mentioned. In this case, the hydrogen atom of the benzene ring of the aryl group and aralkyl group may be substituted with a formyl group or an alkoxy group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-butyl group, an i-butyl group and a t-butyl group. And so on;
Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 4-formylphenyl group, 3,4,5-trimethoxyphenyl group and the like;
Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group and the like.
Examples of the ring structure formed by combining R ¹¹ and R ¹² with each other include a group in which one hydrogen atom is removed from furan, thiophene, 2H-pyran, 4H-pyran and the like.

In the above formula (S), the above formula (1-1) and the above formula (1-2), as —R ¹¹ —X—R ¹² , preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl. Group, n-butyl group, 2-butyl group, i-butyl group, t-butyl group, phenyl group, benzyl group, benzoyl group, 4-formylbenzoyl group, 2-hydroxy-2-phenylethyl group, 2-oxo 2-(3,4,5-trimethoxyphenyl)ethyl group and the like can be mentioned. Further, —R ¹¹ —X—R ¹² is more preferably an alkyl group having 1 to 5 carbon atoms, and in the above formula (1-1), a methyl group or an ethyl group is particularly preferable, and the above formula (1- In case of 2), a methyl group or a t-butyl group is particularly preferable.

In the above formula (1-1), m is preferably 0, and in the above formula (1-2), n is preferably 0 or 1. In the relationship with m and n, and the relationship with -R ¹¹ -X-R ¹² , the formula (1-1) and the formula (1-2) are preferably the following formula (1-1-1). ) And the following formula (1-2-1).

In formulas (1-1-1) and (1-2-1), R ¹³ is an alkyl group having 1 to 5 carbon atoms, and in formula (1-2-1), R ¹⁴ is It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The definitions of R, A ¹ and B ¹ are the same as those in the above formula (1-1) and the above formula (1-2). )

In the formula (1-1), the formula (1-2), the formula (1-1-1) and the formula (1-2-1), a divalent linking group is preferable as A ¹ . Examples of the divalent linking group represented by A ¹ include those represented by the following formula (A1).

In the formula, A ¹¹ is a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, or a phenylene group, and A ¹² is a single bond, —O—, —CO—, —CO—O—, or -O-CO-, A ¹³ is a single bond, or an optionally substituted methylene group or an alkylene group having 2 to 5 carbon atoms, A ¹⁴ is a single bond, -O-, It is -CO-, -CO-O-, -O-CO-, -NR'-, or -NR'-CO-O-, and R'is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, all of A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are a single bond. *1 represents a bond that bonds to a carbon atom of a cyclic amine structure or a carbon atom of a phenol structure.

In the above formula (A1), examples of the alkylene group having 2 to 5 carbon atoms of A ¹¹ and A ¹³ include those exemplified for R ¹¹ . Moreover, as the substituent which the methylene group of A ¹³ or the alkylene group having 2 to 5 carbon atoms may have, those exemplified for the above R ¹¹ can be mentioned. Further, examples of the alkyl group having 1 to 6 carbon atoms of R′ include those exemplified for R ¹² .

Examples of the divalent linking group represented by the above formula (A1) include groups represented by formulas (A1-1) to (A1-17), but are not limited thereto.
In formulas (A1-1) to (A1-17), *1 represents a bond bonded to a carbon atom of the cyclic amine structure or a carbon atom of the phenol structure.

In the above formulas (A1-1) to (A1-17), in order to suitably improve the durability of the obtained liquid crystal alignment film, the divalent linking group for A ¹ is preferably the formula (A1-2). ), the formula (A1-5), the formula (A1-8), the formula (A1-10), the formula (A1-11), the formula (A1-16) and the formula (A1-17). And more preferably one represented by any one of formula (A1-2), formula (A1-5) and formula (A1-10).

In the above formulas (1-1) and (1-1-1), examples of the halogen atom for B ¹ include a fluorine atom and a chlorine atom.
In the above formulas (1-1) and (1-1-1), examples of the monovalent organic group represented by B ¹ include those represented by the following formula (B1).

In the formula, B ¹¹ is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —O—CO—NR″—, or —CO—NR″—. , R″ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. B ¹² is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a monovalent heterocyclic group having 3 to 10 carbon atoms, or 3 to 15 carbon atoms. Which is an alicyclic hydrocarbon group, and the hydrogen atom of these groups may be substituted.
In the above formula (B1), examples of the alkyl group having 1 to 6 carbon atoms for R″ include those exemplified for R ¹² .

In the above formula (B1), the alkyl group having 1 to 15 carbon atoms of B ¹² may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.;
Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, 4-ethylphenyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group and anthryl group;
Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl group, phenethyl group, α-methylbenzyl group, naphthylmethyl group and the like;
Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms include nitrogen-containing heterocyclic compounds such as piperidine, morpholine, pyridine and pyrazine;
Examples of the alicyclic hydrocarbon group having 3 to 15 carbon atoms include cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, and the like.

Moreover, examples of the substituent that each of the above groups of B ¹² may have include a halogen atom such as a fluorine atom and a chlorine atom, a hydroxyl group, a nitro group, and a cyano group.

The monovalent organic group represented by the above formula ^{(B1) (-B 11 -B 12} ), for example, a methyl group, n- butyl group, n- pentyl group, t-pentyl group, n- octyl group, Benzyl group, 4-ethylphenyl group, 4-methylcyclohexyl group, methoxy group, octyloxy group, cyclohexyloxy group, acetyl group, acetyloxy group, tetradecanoyl group, α-methylbenzyloxy group, piperidinocarbonyl group, Moro morpholinopropane carbonyl group, 2-hydroxy-2-methyl-propoxy group, and _-O-CONH-C 6 _{H 5} and the like.

In formula (1-1) and formula (1-1-1) above, B ¹ is preferably a hydrogen atom, an oxygen atom, or a chlorine atom in order to suitably improve the durability of the obtained liquid crystal alignment film. , Methyl group, n-butyl group, n-pentyl group, t-pentyl group, benzyl group, methoxy group, octyloxy group, acetyl group, acetyloxy group, cyclohexyloxy group, and more preferably hydrogen. It is an atom, an oxygen atom, a methyl group, a benzyl group, or an octyloxy group.

The repeating unit (a1) having a hindered amine structure is specifically represented by the following formulas (a1-1-1) to (a1-1-20) (wherein R is a hydrogen atom or a methyl group). I can list things.

The monomer giving the repeating unit (a1) having the hindered amine structure can be easily synthesized by combining conventional methods of organic chemistry. For example, in the case of a monomer that gives the repeating unit of the above formula (a1-1-1) to formula (a1-1-16), a halogenated (meth)acryloyl and the following formula (C-1) (in the formula: , A ¹³ , A ¹⁴ , B ¹ and R ^{13 have} the same definitions as those described above.) in accordance with a known esterification reaction. .. Further, as long as it is a monomer which gives the repeating unit of the above formula (a1-1-17) or formula (a1-1-18), 2-propenyl halide or 9-decyl halide and the following formula (C- It can be obtained by reacting the compound represented by 1) with a known etherification reaction. Further, as long as it is a monomer which gives the repeating unit of the above formula (a1-1-19) or the formula (a1-1-20), it is a halogenated (meth)acryloyl and OH-in the following formula (C-1). the NH 2 _{^- -} a ^{13 -A} 14 and compound was replaced with, it can be obtained by reacting according to known amidation reaction.

Moreover, as each of the above-mentioned monomers, a commercially available product may be used, and for example, 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 1,2,2,6,6-methacrylic acid are used. Pentamethyl-4-piperidyl is commercially available from Hitachi Chemical Co., Ltd. as FA-712HM and FA-711MM, respectively.

As the repeating unit (a1) having a hindered phenol structure, specifically, the following formulas (a1-2-1) to (a1-2-10) (wherein R is a hydrogen atom or a methyl group). Can be mentioned.

The monomer that gives the repeating unit (a1) having the hindered phenol structure can be easily synthesized by combining conventional methods of organic chemistry.
As the repeating unit (a1), those having a hindered amine structure are preferable to those having a hindered phenol structure in order to suitably improve the durability of the obtained liquid crystal alignment film.

The polymer [A] may have the repeating unit (a1) alone or in combination of two or more. Although the mechanism is not clear, since the polymer [A] has the repeating unit (a1), the ultraviolet light radiated from a backlight or the like is favorably absorbed by the polymer [A], and the ultraviolet light It is presumed that the effect of (1) becomes difficult to extend to at least one polymer selected from the group consisting of polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine and its imidized polymer. This makes it possible to maintain the alignment performance of the liquid crystal even after long-term use, and it is possible to obtain a liquid crystal display element having long-term durability. In addition, the content ratio of the repeating unit (a1) in the polymer [A] (or the copolymerization ratio of the monomer giving the repeating unit (a1)) in enhancing the effect is the total weight of the polymer [A]. (Or, the total weight of the monomers used in synthesizing the polymer [A]) is preferably 1% by weight or more, more preferably 1% by weight or more and 50% by weight or less, and further preferably Is 1% by weight or more and 30% by weight or less, and particularly preferably 1% by weight or more and 20% by weight or less.

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

The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and the side chain has a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip. And a structure having a photosensitive group that is cross-linked or isomerized in response to light, which has a main chain and a side chain bonded thereto, and the side chain also serves as a mesogenic component, and The structure can have a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction.

A more specific example of the structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity is composed of at least one selected from the group consisting of hydrocarbon, acrylate, methacrylate, maleimide, norbornene and siloxane. It is preferable that the structure has a main chain and a side chain composed of at least one of the following formulas (1) to (6).

Wherein, A, B, 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 to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R ⁵¹ represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has 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 represented and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- It 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is an aromatic ring, When the number of P is 2 or more, Ps may be the same or different, and when the number of Q is 2 or more, Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer of 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 also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

The side chain is preferably a photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
Wherein A, B, D, Y ₁ , X, Y ₂ , and R ⁵¹ have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, m1 and m2 represent integers of 1 to 3;
n represents an integer of 0 to 12 (however, when n=0, B is a single bond).

The side chain is preferably a photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
Where A, X, l, m, m1 and R ⁵¹ have the same definition as above.

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

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).
Where A, X, l and m have the same definitions as above.

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

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

Further, the (A) side chain type polymer preferably has any one kind of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
Wherein A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen _{atom, -NO 2, -CN, -CH =} C (CN) 2, -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26). ), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a.

The present application provides compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and/or liquid crystal side chain monomers; and the following formulas (12) to (17). Compounds (12) to (17) represented by are provided.
In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents Represents 0 or 1; and Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. Further, v represents 1 or 2.

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

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

More specific examples of the liquid crystal side chain monomer include a main chain composed of at least one selected from the group consisting of hydrocarbon, (meth)acrylate, maleimide, norbornene and siloxane, and the above formula (21). It is preferable that the structure has a side chain consisting of at least one of

The side chain type polymer (A) can be obtained by a polymerization reaction of the above-mentioned photoreactive side chain monomer that exhibits liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystal side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystal side chain monomer. it can. Further, it can be copolymerized with other monomers within a range that does not impair the ability to exhibit liquid crystallinity.

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

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.
Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl 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- Examples include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 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, anthrylmethyl 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- Examples include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. A (meth)acrylate compound having a cyclic ether group such as glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (3-ethyl-3-oxetanyl)methyl (meth)acrylate is also used. be able to.

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

The method for producing the side chain type polymer of the present embodiment is not particularly limited, and a general-purpose method industrially handled can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anion polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoint of easy reaction control.

As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-cleavage type chain transfer (RAFT) polymerization reagents can be used.

The 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 (peroxides). Hydrogen, tert-butyl hydroxide peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxy cyclohexane) Etc.), alkyl peresters (peroxy neodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, Sodium persulfate, ammonium persulfate, etc.) and azo compounds (azobisisobutyronitrile, 2,2′-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used alone 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 a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4′-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, and 2-hydroxy. 2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate isoamyl, 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- [P-N,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-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2 , 2'-bi Sus(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-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadiene-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-benzothiazole-2(3H)-ylidene)-1-(2- Examples thereof include benzoyl)ethanone. These compounds may be used alone or in a mixture of two or more.

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

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

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide , 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, 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, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether. , Diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropione 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 and 3-butoxy-N,N-dimethylpropanamide.

These organic solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the produced polymer may be used as a mixture with the above-mentioned organic solvent as long as the produced polymer does not precipitate.
Further, in the radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore it is preferable to use the organic solvent that is degassed to the extent possible.

The polymerization temperature during 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. Further, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes 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 reaction can be performed at a high concentration in the initial stage, and then an organic solvent can be added.

In the above radical polymerization reaction, when the ratio of the radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and when it is small, the molecular weight of the obtained polymer becomes large. It is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Also, various monomer components, solvents, initiators, etc. can be added during the polymerization.

[Recovery of polymer]
When the generated polymer is recovered from the reaction solution of the photosensitive side chain type polymer capable of expressing liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent to remove the heavy solvent. The coalescence should be allowed to settle. 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, water and the like. The polymer precipitated by pouring it into a poor solvent can be collected by filtration and then dried at room temperature or under normal pressure or reduced pressure by heating. Further, by repeating the operation of re-dissolving the precipitated and recovered polymer in an organic solvent and re-precipitating and recovering it 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 the purification efficiency is further improved.

The molecular weight of the (A) side chain type polymer of the present invention is measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film. The weight average molecular weight is preferably 2000 to 1,000,000, and more preferably 5,000 to 100,000.

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

In the polymer composition of the present embodiment, all the resin components described above may be photosensitive side chain polymers capable of expressing the above-mentioned liquid crystallinity, but do not impair the liquid crystal expressing ability and the photosensitivity. Other polymers than those may be mixed in the range. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
Such other polymers include, for example, polymers made of poly(meth)acrylate, polyamic acid, polyimide and the like, which are not photosensitive side chain type polymers capable of exhibiting liquid crystallinity.

<Organic solvent>
The organic solvent used in 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, Dimethyl sulfone, hexamethyl sulfoxide, 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 mono Acetate, 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, Examples include dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether and the like. These may be used alone or in combination.

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

Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.
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 mono Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono n-butyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl- 3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, Dihexyl ether, 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 acetate, methyl pyruvate , Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropione Butyl acid, 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 A Ter-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n- Solvents having a low surface tension such as butyl ester and isoamyl lactate can be used.

These poor solvents may be used alone or in combination of two or more. When the above-mentioned solvent is used, it is preferably 5% by mass to 80% by mass of the entire solvent, and more preferably, so that the solubility of the entire solvent contained in the polymer composition is not significantly lowered. Is 20% by mass to 60% by mass.

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

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the functional silane-containing compounds shown below.
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-triethoxysilyl- 1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane Examples thereof include silane 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 phenoplast-based or epoxy group-containing compound for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display device is configured. The 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, 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-4,4'-diaminodiphenylmethane Are exemplified.

When a compound that improves the adhesion to the substrate is used, its amount is preferably 0.1 parts by mass to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. , And more preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesiveness 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 sensitizers and triplet sensitizers are preferred.
As the photosensitizer, an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino-substituted , Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3). -Methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenoylmethylene)- 3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluoro) Benzoylmethylene)-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-biphenoylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, Acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin, etc. is there.
Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In the polymer composition, in addition to the above-mentioned ones, a dielectric or a conductive substance, 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 effect of the present invention is not impaired, Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and the density of the liquid crystal alignment film.

The method of applying the above-mentioned polymer composition onto a substrate having a conductive film for driving an in-plane electric field is not particularly limited.
As a coating method, industrially, a method generally used is screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (spin coating method), and a spray method, and these may be used depending on the purpose.

After coating the polymer composition on a substrate having a conductive film for driving an in-plane electric field, it is heated to 50 to 200° C., preferably 50 to 200° C. by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. The solvent can be evaporated at 150° C. to obtain a coating film. The drying temperature at this time is preferably lower than the temperature at which the liquid crystal phase of the side chain type polymer appears.
If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, the thickness is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. Is.
It is also possible to provide a step of cooling the substrate on which the coating film is formed to room temperature after the step [I] and before the subsequent step [II].

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

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

<Process [III]>
In step [III], the coating film irradiated with the ultraviolet light polarized in step [II] is heated. The heating can impart orientation controllability to the coating film.
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 coating film used exhibits the liquid crystallinity.

The heating temperature is preferably within a temperature range where the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal manifestation temperature). In the case of a thin film surface such as a coating film, the liquid crystal development temperature of the coating film surface is expected to be lower than the liquid crystal development temperature when a photosensitive side chain type polymer capable of developing liquid crystallinity is observed in bulk. It Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal manifestation temperature of the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10° C. lower than the lower limit of the temperature range of the liquid crystal manifestation temperature of the side chain type polymer used, and 10° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that the temperature is within the range of up to. If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy 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), in which case it may be difficult to reorient in one direction due to self-assembly.
The liquid crystal expression temperature is equal to or higher than the glass transition temperature (Tg) at which the side chain type polymer or the coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and the liquid crystal phase changes from the isotropic phase (isotropic phase). The temperature is equal to or lower than the isotropic phase transition temperature (Tiso) at which a phase transition occurs.
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 as described in step [I].

By having the above process, the manufacturing method of this invention can implement|achieve highly efficient introduction of anisotropy into a coating film. Then, the substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<Process [IV]>
The step [IV] is the same as the step (I′) to [III′] described above in which the substrate (first substrate) having the liquid crystal alignment film on the conductive film for lateral electric field driving obtained in [III] is used. The obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is arranged so as to face both liquid crystal alignment films via a liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of producing and manufacturing a horizontal electric field drive type liquid crystal display element. The steps [I′] to [III′] are the same as those in the step [I] except that a substrate having no lateral electric field driving conductive film is used instead of the substrate having the lateral electric field driving conductive film. It can be performed in the same manner as steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I'] to [III'] is only the presence or absence of the conductive film described above, 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 device, the above-mentioned first and second substrates are prepared, spacers are scattered 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 it, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which spacers are scattered, and then the substrates are bonded and sealed. , Etc. can be illustrated. At this time, it is preferable to use a substrate having an electrode having a comb-like structure for driving an in-plane electric field as the substrate on one side. At this time, 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 a pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a coated substrate of the present invention, a polymer composition is applied onto a substrate to form a coating film, and then polarized ultraviolet rays are irradiated. Then, by heating, a highly efficient anisotropy is introduced into the side chain type polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
In the coating film used in the present invention, a highly efficient anisotropy is introduced into the coating film by utilizing the principle of molecular reorientation induced by photoreaction of side chains and self-assembly based on liquid crystallinity. .. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain type polymer, after forming a coating film on the substrate using the side chain type polymer, polarized ultraviolet light After irradiating and then heating, a liquid crystal display element is prepared.

Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, and a structure having a photo-Fries rearrangement group or a group that causes isomerization as the photoreactive group An embodiment using the side chain type polymer will be described as a second embodiment.

FIG. 1 schematically illustrates an anisotropy-introducing treatment in a method for producing a liquid crystal alignment film using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated in FIG. FIG. 1A is a diagram schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 1B is a diagram schematically showing the state of the side chain type polymer film after irradiation with polarized light. FIG. 1( c) is a diagram schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is small, that is, FIG. 3 is a schematic diagram in a case where the amount of ultraviolet ray irradiation in the step [II] is in the range of 1% to 15% of the amount of ultraviolet ray irradiation that maximizes ΔA in Embodiment 1.

FIG. 2 schematically illustrates an anisotropy-introducing treatment in the method for producing a liquid crystal alignment film using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated in FIG. FIG. 2A is a diagram schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 2B is a schematic diagram of the state of the side chain type polymer film after irradiation with polarized light. 2(c) is a diagram schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is large, that is, FIG. 3 is a schematic diagram in the case where the amount of ultraviolet ray irradiation in the step [II] is in the range of 15% to 70% of the amount of ultraviolet ray irradiation that maximizes ΔA in the first embodiment.

FIG. 3 shows a side chain type polymer having a structure having an optical Fries rearrangement group represented by the above formula (18) or a photoisomerizable group as the photoreactive group in the second embodiment of the present invention. FIG. 5 is a diagram of an example schematically illustrating an anisotropy introducing process in the used method for producing a liquid crystal alignment film. FIG. 3A is a diagram schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 3B is a diagram schematically showing the state of the side chain type polymer film after irradiation with polarized light. FIG. 3( c) is a diagram schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is small, that is, 2 is a schematic diagram in a case where the amount of ultraviolet ray irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet ray irradiation that maximizes ΔA in the second aspect. FIG.

FIG. 4 is a view showing a method of manufacturing a liquid crystal alignment film using a side chain type polymer having a structure having a photo-Fries rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically an anisotropic introduction process in a method. FIG. 4A is a diagram schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 4B is a schematic diagram of the state of the side chain type polymer film after irradiation with polarized light. FIG. 4( c) is a diagram schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is large, that is, 2 is a schematic diagram in a case where the amount of ultraviolet ray irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet ray irradiation that maximizes ΔA in the second aspect. FIG.

In the first embodiment of the present invention, in the process of introducing anisotropy to the coating film, the ultraviolet irradiation dose in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation dose that maximizes ΔA. In this case, first, the coating film 1 is formed on the substrate. As shown in FIG. 1A, a coating film 1 formed on a substrate has a structure in which side chains 2 are randomly arranged. According to the random arrangement of the side chains 2 of the coating film 1, the mesogenic components and the photosensitive groups of the side chains 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first embodiment of the present invention, in the process of introducing anisotropy to the coating film, the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA. In this case, first, the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second embodiment of the present invention, a side chain type structure having a photoisomerizable group or a photo-Fries rearrangement group represented by the above formula (18) in the process of introducing anisotropy into the coating film. When a liquid crystal alignment film using a polymer is used and the amount of UV irradiation in the step [II] is within the range of 1% to 70% of the amount of UV irradiation that maximizes ΔA, first, on the substrate. A coating film 5 is formed on. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. According to the random arrangement of the side chains 6 of the coating film 5, the mesogenic components of the side chains 6 and the photosensitive groups are also randomly oriented, and the side chain type polymer film 5 is isotropic.

In the second embodiment of the present invention, liquid crystal alignment using a side chain type polymer having a structure having an optical Fries rearrangement group represented by the above formula (19) in the treatment for introducing anisotropy into the coating film. When the film is used and the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, first, the coating film 7 is formed on the substrate. .. As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first embodiment of the present invention, in the case where the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, this isotropic coating film 1 is obtained. On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 1(b), the photosensitive group of the side chain 2a having the photosensitive group of the side chains 2 arranged in the direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a dimerization reaction or the like. It causes a light reaction. As a result, the density of the photoreacted side chains 2a is slightly increased in the polarization direction of the irradiation ultraviolet rays, and as a result, the coating film 1 is imparted with a very small anisotropy.

In the first embodiment of the present invention, when the ultraviolet ray irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, this isotropic coating film 3 is formed. On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 2B, the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet rays preferentially undergoes a dimerization reaction or the like. It causes a light reaction. As a result, the density of the photoreacted side chains 4a becomes higher in the polarization direction of the irradiation ultraviolet rays, and as a result, the coating film 3 is imparted with a small anisotropy.

In the second embodiment, a liquid crystal alignment film using a photoisomerizable group or a side chain type polymer having a structure having a photo-Fries rearrangement group represented by the above formula (18) is used, When the ultraviolet ray irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 3B, the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in the direction parallel to the polarization direction of ultraviolet rays preferentially undergoes the optical Fries rearrangement or the like. It causes a light reaction. As a result, the density of the photoreacted side chains 6a is slightly increased in the polarization direction of the irradiation ultraviolet rays, and as a result, the coating film 5 is imparted with a very small anisotropy.

In the second embodiment, a coating film using a side chain type polymer having a structure having a photo-Fries rearrangement group represented by the above formula (19) is used, and the ultraviolet irradiation dose in the step [II] is used. Is within the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 4B, the photosensitive group of the side chain 8a having the photosensitive group of the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet rays preferentially undergoes the optical Fries rearrangement or the like. It causes a light reaction. As a result, the density of the photoreacted side chains 8a increases in the polarization direction of the irradiation ultraviolet rays, and as a result, the coating film 7 is imparted with a small anisotropy.

Then, in the first embodiment of the present invention, when the ultraviolet ray irradiation amount in the step [II] is within a range of 1% to 15% of the ultraviolet ray irradiation amount that maximizes ΔA, the coating film 1 after polarized light irradiation is obtained. Is heated to a liquid crystal state. Then, as shown in FIG. 1C, in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the cross-linking reaction occurring in the direction parallel to the polarization direction of the irradiation ultraviolet light is very small, this cross-linking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light becomes higher than the liquid crystallinity in the parallel direction, and self-organizes in the direction parallel to the polarization direction of the irradiated ultraviolet light to re-align the side chain 2 containing the mesogenic component. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and the coating film 1 is given a larger anisotropy.

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

Similarly, in the second embodiment, a coating film using a photoisomerizable group or a side chain type polymer having a structure having an optical Fries rearrangement group represented by the above formula (18) is used. Then, when the ultraviolet ray irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the coating film 5 after polarized light irradiation is heated to be in a liquid crystal state. Then, as shown in FIG. 3C, in the coating film 5, the amount of the generated photo-Fries rearrangement reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet rays and the direction perpendicular thereto. In this case, the liquid crystal alignment force of the optical Fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, so that self-organization occurs in the direction perpendicular to the polarization direction of the irradiated ultraviolet light. The side chain 6 containing the mesogenic component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photo-Fries rearrangement reaction is amplified by heat, and a larger anisotropy is given to the coating film 5.

Similarly, in the second embodiment, a coating film using a side chain type polymer having a structure having an optical Fries rearrangement group represented by the above formula (19) is used, and When the irradiation amount of ultraviolet rays is in the range of 1% to 70% of the irradiation amount of ultraviolet rays that maximizes ΔA, the coating film 7 after irradiation with polarized light is heated to be in a liquid crystal state. Then, as shown in FIG. 4C, in the side chain type polymer film 7, the amount of the photo-Fries rearrangement reaction generated differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. .. Since the anchoring force of the optical Fleece dislocation body 8(a) is stronger than that of the side chain 8 before the dislocation, when a certain amount or more of the optical Fleece dislocation body is generated, it self-assembles in the direction parallel to the polarization direction of the irradiation ultraviolet light. The side chain 8 containing the mesogenic component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photo-Fries rearrangement reaction is amplified by heat, and the coating film 7 is given a larger anisotropy.

Therefore, the coating film used in the method of the present invention is a liquid crystal alignment film excellent in anisotropy introduced by highly anisotropically introduced by performing irradiation of polarized ultraviolet light to the coating film and heat treatment sequentially. can do.

Then, in the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film and the heating temperature in the heat treatment are optimized. Thereby, highly efficient introduction of anisotropy into the coating film can be realized.

The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group in the coating film undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photo-Fries rearrangement reaction. Corresponds to the irradiation dose of polarized UV that optimizes the dose. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, a sufficient amount of photoreaction cannot be obtained when there are few photosensitive groups in the side chains that undergo photocrosslinking reaction, photoisomerization reaction, or photo-Fries rearrangement reaction. .. In that case, even if it heats after that, sufficient self-organization does not advance. On the other hand, in the coating film used in the present invention, as a result of irradiating the structure having a photocrosslinkable group with polarized ultraviolet light, if the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive, the crosslinking reaction between the side chains may occur. It will progress too much. In that case, the obtained film may become rigid and hinder the progress of self-assembly due to subsequent heating. Further, in the coating film used in the present invention, when the structure having a photo-Fries rearrangement group is irradiated with polarized ultraviolet rays, and the photosensitive group of the side chain for photo-Fries rearrangement reaction becomes excessive, the liquid crystallinity of the coating film becomes high. Will be too low. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly due to subsequent heating. Furthermore, when polarized UV light is irradiated to the structure having a photo-Fries rearrangement group, if the amount of UV light is too high, the side chain type polymer is photolyzed and the subsequent heating hinders the progress of self-assembly. May be.

Therefore, in the coating film used in the present invention, the optimum amount of the photocrosslinking reaction, the photoisomerization reaction, or the photo-Fries rearrangement reaction of the photosensitive group of the side chain upon irradiation with polarized ultraviolet light is the side chain type polymer film. It is preferably 0.1 to 40 mol %, and more preferably 0.1 to 20 mol% of the photosensitive group of. By setting the amount of the photoreactive side chain photosensitive group in such a range, self-assembly in the subsequent heat treatment is efficiently advanced, and highly efficient anisotropy formation in the film is possible. Become.

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

That is, with respect to the coating film used in the present invention, after the polarized UV irradiation, the UV absorption in the direction parallel to the polarization direction of the polarized UV and the UV absorption in the vertical direction are measured, respectively. From the measurement result of the ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption in the vertical direction in the coating film, is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays that realizes the maximum value are obtained. In the manufacturing method of the present invention, a preferable amount of polarized ultraviolet light to be irradiated in manufacturing the liquid crystal alignment film can be determined on the basis of the polarized ultraviolet light irradiation amount that realizes ΔAmax.

In the production method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film used in the present invention is preferably within the range of 1% to 70% of the amount of polarized ultraviolet rays that achieves ΔAmax. More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that achieves ΔAmax is 0. This corresponds to the amount of polarized ultraviolet light that causes 1 mol% to 20 mol% to undergo a photocrosslinking reaction.

From the above, in the production method of the present invention, in order to realize the introduction of highly efficient anisotropy to the coating film, with the liquid crystal temperature range of the side chain type polymer as a reference, a suitable heating temperature as described above is set. Good to set. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100° C. to 200° C., it is desirable that the heating temperature after irradiation with polarized ultraviolet rays be 90° C. to 190° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the substrate for a lateral electric field drive type liquid crystal display device manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display device having the substrate becomes excellent in reliability and has a large screen and high definition. It is suitable for use in LCD televisions and the like.
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

Methacrylic monomers MA1 to MA5 used in the examples are shown below.
MA1 and M2 were each synthesized as follows. That is, MA1 was synthesized by the synthesis method described in Patent Document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (JP-A-9-118717).
MA3 used was commercially available.
As MA4, commercially available M6BC (manufactured by Midori Kagaku Co., Ltd.) was used.
MA5 is a novel compound that has not been published in the literature. MA5 was synthesized using MA2 and MA5-1, and details thereof will be described below in “<Synthesis of Compound MA5>”. MA5-1 was synthesized by the synthesis method described in the literature (Liquid Crystals (2005), 32(8), 1031-1044.).

In addition, the abbreviations of the reagents used in this example are shown below.
(Organic solvent)
THF: tetrahydrofuran.
NMP: N-methyl-2-pyrrolidone.
BC: Butyl cellosolve.
(Organic synthesis reagent)
EDC: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.
DMAP: 4-dimethylaminopyridine.
(Polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile.

<Synthesis of Compound MA5>
In a 500 mL four-necked flask, compound MA2 (20.00 g, 65.3 mmol), compound MA5-1 (14.09 g, 71.8 mmol), EDC (15.02 g, 78.4 mmol), DMAP (0.80 g, 6.53 mmol) and THF (200 g) were added and the reaction was carried out at 23°C. After the reaction was traced by HPLC and the completion of the reaction was confirmed, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (2 L) was added, and the aqueous layer was removed by liquid separation operation. The organic layer was washed with distilled water (500 mL) three times, and then the organic layer was dried over magnesium sulfate. Then, the compound MA5-2 was obtained as an oily compound by filtering and distilling off the solvent with an evaporator. Subsequently, pyridinium p-toluenesulfonic acid (denoted as PPTS) (1.59 g, 6.3 mmol) and ethanol (100 g) were added to the obtained compound MA5-2, and the mixture was heated and stirred at 60°C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 19.2 g (yield 69%) of compound MA5.
¹ H-NMR(400MHz, CDCl3, δppm): 8.22-8.18(2H, m), 8.17-8.14(2H, m), 7.36-7.32(2H, m), 7.00-6.96(2H, m), 6.12- 6.11(1H, m), 5.57-5.55(1H, m), 4.20-4.16(2H, m), 4.06(2H, t), 1.96-1.95(3H, m), 1.90-1.46(8H, m).

<Synthesis example 1>
MA1 (1.99 g, 6.0 mmol), MA2 (7.35 g, 24.0 mmol), MA3 (0.33 g, 1.5 mmol) were dissolved in THF (85.45 g) and degassed with a diaphragm pump. After that, AIBN (0.246 g, 1.5 mmol) was added and degassing was performed again. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (2000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. Liquid crystal aligning agent solution A1 was obtained by adding BC (40.0 g) to this solution and stirring.

<Synthesis example 2>
MA1 (9.97 g, 30.0 mmol), MA3 (0.41 g, 1.8 mmol), MA4 (11.47 g, 30.0 mmol) were dissolved in THF (126.7 g) and degassed with a diaphragm pump. After that, AIBN (0.49 g, 3.0 mmol) was added and the mixture was degassed again to replace nitrogen. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at 40° C. for 3 hours. Liquid crystal aligning agent solution A2 was obtained by adding BC (40.0 g) to this solution and stirring.

<Synthesis example 3>
MA1 (9.97 g, 30.0 mmol), MA3 (0.41 g, 1.8 mmol), MA5 (12.79 g, 30 mmol) were dissolved in THF (134.1 g) and degassed with a diaphragm pump. After that, AIBN (0.49 g, 3.0 mmol) was added and the mixture was degassed again to replace nitrogen. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. Liquid crystal aligning agent solution A3 was obtained by adding BC (40.0 g) to this solution and stirring.

<Example 1>
Using the liquid crystal aligning agent A1 obtained in Synthesis Example 1, a liquid crystal cell was prepared by the procedure shown below. The substrate was a glass substrate having a size of 30 mm×40 mm and a thickness of 0.7 mm, and the one on which the comb-teeth-shaped pixel electrode formed by patterning the ITO film was arranged was used.

The pixel electrode had a comb-tooth shape formed by arranging a plurality of V-shaped electrode elements each having a bent central portion. The width of each electrode element in the lateral direction was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode that forms each pixel is configured by arranging a plurality of bent V-shaped electrode elements in the central portion, the shape of each pixel is not rectangular but the central portion is similar to the electrode element. It had a shape resembling a bold, doglegged shape.
Each pixel was divided into upper and lower parts with a central bent portion as a boundary, and had a first region on the upper side and a second region on the lower side of the bent portion. Comparing the first region and the second region of each pixel, the forming directions of the electrode elements of the pixel electrodes forming them are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is used as a reference, the electrode elements of the pixel electrode are formed so as to form an angle (clockwise) of +15° in the first region of the pixel and in the second region of the pixel. The electrode element of the pixel electrode was formed so as to form an angle (clockwise) of −15°. That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the plane of the substrate are mutually different. It was configured to be in the opposite direction.

<<Preparation of Liquid Crystal Cell>>
The liquid crystal aligning agent A1 obtained in Synthesis Example 1 was spin-coated on the prepared substrate with electrodes. Then, it was dried on a hot plate at 70° C. for 90 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm at 10 mJ/cm ² through a polarizing plate and then heated on a hot plate at 140° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm, on which an electrode was not formed, as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Kagaku) was printed on the liquid crystal alignment film on one of the substrates. Next, the other substrate was bonded so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 0°, and then the sealant was thermally cured to prepare an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Ltd.) was injected into this empty cell by a reduced pressure injection method, the injection port was sealed, and a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element was obtained. Obtained.

<Example 2 and Example 3>
In Example 2, the same method as in Example 1 was used except that the liquid crystal aligning agent A2 was used to heat the hot plate at 200° C., and the liquid crystal aligning agent A3 was used to heat the hot plate in 180° C. in Example 3. A liquid crystal cell was prepared.

<Evaluation of liquid crystal cell>
[Evaluation of liquid crystal alignment]
When the liquid crystal display device manufactured as described above was observed with an optical microscope, those in which light leakage was not observed were evaluated as "good" in liquid crystal alignment, and those in which light leakage was observed were evaluated as "defective" in liquid crystal.

<<Voltage Holding Rate (VHR) Evaluation>>
Using the liquid crystal cell produced above, a voltage of 5 V was applied for 60 μs at 70° C., and the voltage after 16.67 ms was measured to measure the voltage holding ratio. This initial voltage holding ratio was set to VHR1 (%). Then, under a constant temperature environment of 70° C., an AC voltage of 16 Vpp was applied for 168 hours at a frequency of 30 Hz. Then, after short-circuiting the pixel electrode and the counter electrode of the liquid crystal cell, the voltage holding ratio was measured by the same method as described above. This voltage holding ratio was set to VHR2 (%).
The reduction amount ΔVHR (%) of the voltage holding ratio was calculated from the following formula and is shown in Table 1.
ΔVHR (%)=VHR1-VHR2
A voltage holding ratio measuring device VHR-1 manufactured by Toyo Corp. was used for measuring the voltage holding ratio.
The results of the liquid crystal alignment and VHR of Example 1 are shown in Table 1.

<Comparative Example 1>
MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were dissolved in THF (85.45 g) and deaerated with a diaphragm pump, then AIBN (0.246 g, 1). 0.5 mmol) was added and the mixture was degassed again. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (2000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. Liquid crystal aligning agent solution B1 was obtained by adding BC (40.0 g) to this solution and stirring. A liquid crystal cell was prepared in the same manner as in Example 1 except that the polymer solution obtained by the above method was used as the liquid crystal aligning agent B1, and the voltage holding ratio was measured and the liquid crystal aligning property was evaluated. The results are shown in Table 1.

<Comparative example 2>
MA1 (9.97 g, 30.0 mmol) and MA4 (11.47 g, 30 mmol) were dissolved in THF (124.3 g) and deaerated with a diaphragm pump, and then AIBN (0.49 g, 3.0 mmol). ) Was added and the mixture was degassed again and replaced with nitrogen. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at 40° C. for 3 hours. Liquid crystal aligning agent solution B2 was obtained by adding BC (40.0 g) to this solution and stirring. The polymer solution obtained by the above method was used as the liquid crystal aligning agent B2. A liquid crystal cell was prepared in the same manner as in Example 1 except that the heating temperature on the hot plate was 200° C., and the voltage holding ratio was measured and the liquid crystal orientation was evaluated. The results are shown in Table 1.

<Comparative example 3>
MA1 (9.97 g, 30.0 mmol) and MA5 (12.79 g, 30 mmol) were dissolved in THF (131.8 g) and deaerated with a diaphragm pump, and then AIBN (0.49 g, 3.0 mmol). ) Was added and the mixture was degassed again and replaced with nitrogen. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (4000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.
54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. Liquid crystal aligning agent solution B3 was obtained by adding BC (40.0 g) to this solution and stirring. The polymer solution obtained by the above method was used as the liquid crystal aligning agent B3. A liquid crystal cell was prepared in the same manner as in Example 1 except that the heating temperature on the hot plate was 180° C., the voltage holding ratio was measured, and the liquid crystal orientation was evaluated. The results are shown in Table 1.

<Comparative example 4>
MA3 (0.33 g, 10.0 mmol) was dissolved in THF (30.9 g), deaeration was performed by a diaphragm pump, AIBN (0.08 g, 0.5 mmol) was added, and deaeration was performed again. .. Then, the reaction was carried out at 50° C. for 24 hours to obtain a polymer solution T1 of methacrylate. To 50 g of the liquid crystal aligning agent solution B1, 0.8 g of T1 was added to obtain a liquid crystal aligning agent B4. A liquid crystal cell was prepared in the same manner as in Example 1 except that the polymer solution obtained by the above method was used as the liquid crystal aligning agent B4, and the voltage holding ratio was measured. The results are shown in Table 1.

From Table 1, it was revealed that it is possible to form liquid crystal alignment films in Examples 1 to 3 which exhibit good liquid crystal alignment properties while maintaining good electrical characteristics. Further, it can be seen that the voltage holding ratio decreases in Comparative Example 1, Comparative Example 2, and Comparative Example 3 which do not have MA3. Further, it can be seen that Comparative Example 4 having MA3 but not copolymerized with the side chain type polymer does not exhibit good liquid crystal alignment.

Figure 1
1 side chain type polymer membrane 2, 2a side chain Fig. 2
3 Side chain type polymer film 4, 4a Side chain Fig. 3
5 Side chain type polymer membrane 6, 6a Side chain Fig. 4
7 Side chain type polymer membrane 8, 8a Side chain

Claims (15)

A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) an organic solvent,
The (A) side chain polymer has at least one repeating unit selected from the group consisting of first repeating units having a cyclic amine structure,
The first repeating unit has the following formula (1-1) (in the formula (1-1), R is a hydrogen atom or a methyl group, A ¹ is a single bond or a divalent linking group, and R ¹¹ Each is the same or different and is a single bond or an optionally substituted hydrocarbon group, X ¹ may be the same or different, and each is a single bond, an oxygen atom or sulfur. Atom, —CO—, —CO—O— or —O—CO—, and R ¹² is the same or different, and is an optionally substituted hydrocarbon group, provided that X is X. ^{When 1} is not a single bond, R ¹¹ and R ¹² may be bonded to each other to form a ring structure, and B ¹ is a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or a monovalent organic group. , M is an integer of 0 to 4),
The component (A) is represented by the following formulas (1) to (6)
(Wherein, A, B, 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 to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R ⁵¹ represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has 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 represented and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- It 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is an aromatic ring, When the number of P is 2 or more, P may be the same or different, and when the number of Q is 2 or more, Q may be the same or different;
l1 is 0 or 1;
l2 is an integer of 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 also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
The above-mentioned polymer composition having any one kind of photosensitive side chain selected from the group consisting of:

The composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photo-Fries transition. The first repeating unit has the following formula (1-1-1) (in formula (1-1-1), R, A ¹ and B ¹ have the same definitions as above, and R ¹³ has the same meaning. May be different or different and is an alkyl group having 1 to 5 carbon atoms), and the composition according to claim 1 or 2.

The composition according to any one of claims 1 to 3, wherein the first repeating unit is derived from the following formula MA3.

The component (A) is represented by the following formulas (7) to (10).
(Wherein, A, B, 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally 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 represented 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, m1 and m2 represent integers of 1 to 3;
n represents an integer of 0 to 12 (when n=0, B is a single bond);
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R ⁵¹ represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1. )
The composition according to any one of claims 1 to 4, which has any one kind of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formulas (11) to (13).
(In the formula, 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 represented 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 ⁵¹ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a selected from those substituents. phase different 2-6 rings, a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, Or a group formed by bonding via a bonding group B representing —O—CO—CH═CH—, and the hydrogen atoms bonded to them are each independently —COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon atom). represents the number 1-5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 carbon atoms To 5 may be substituted with an alkyloxy 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 4, which has any one kind of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formula (14) or (15)
(In the formula, A 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. phase different 2-6 rings, a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, Or a group formed by bonding via a bonding group B representing —O—CO—CH═CH—, and the hydrogen atoms bonded to them are each independently —COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon atom). represents the number 1-5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 carbon atoms ~ 5 may be substituted with an alkyloxy group;
l represents an integer of 1 to 12, and m1 and m2 represent integers of 1 to 3)
The composition according to any one of claims 1 to 4, which has a photosensitive side chain represented by:

The component (A) is represented by the following formula (16) or (17)
(In the formula, A is a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, or -O- Represents 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 represented 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 4, which has a photosensitive side chain represented by:

The component (A) is represented by the following formula (18) or (19)
(Wherein, A, B are each independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-COO Represents -, or -O-CO-CH=CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. 2 to 6 different rings are groups bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon number 1 to 1). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms Optionally 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, m1 and m2 represent integers of 1 to 3;
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C(CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group)
The composition according to any one of claims 1 to 4, which has any one kind of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formula (20) (wherein A is a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH). Represents =CH-CO-O-, or -O-CO-CH=CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or selected from those substituents. phase different 2-6 rings, a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, Or a group formed by bonding via a bonding group B representing —O—CO—CH═CH—, and the hydrogen atoms bonded to them are each independently —COOR ₀ (in the formula, R ₀ is a hydrogen atom or a carbon atom). represents the number 1-5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 carbon atoms ~ 5 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 represented and the number of X is 2, X may be the same or different;
(1 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 4, which has a photosensitive side chain.

The component (A) has the following formulas (21) to (31) (wherein A and B have the same definitions as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen _{atom, -NO 2, -CN, -CH =} C (CN) 2, -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing Represents a heterocycle, 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 represent 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - wherein with any one liquid crystalline side chain selected from the group consisting of a representative) Item 11. The composition according to any one of items 1 to 10.

[I] A step of applying the composition according to any one of claims 1 to 11 onto a substrate having a conductive film for driving an in-plane electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II];
A method for producing a substrate having the liquid crystal alignment film, wherein a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device having an alignment control ability is obtained by having the above. A substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display device, which is produced by the method according to claim 12. A horizontal electric field drive type liquid crystal display device comprising the substrate according to claim 13. A step of preparing a substrate (first substrate) according to claim 13;
[I′] A polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent is applied onto a second substrate. A step of forming a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet light;
[III'] A step of heating the coating film obtained in [II'];
And (IV) liquid crystal alignment of the first and second substrates via liquid crystal, wherein a liquid crystal alignment film having alignment controllability is obtained by A step of arranging the first and second substrates so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which comprises: providing a liquid crystal display element of the lateral electric field drive type.

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