KR102244413B1 - Method for producing substrate having liquid crystal alignment film for in-plane switching liquid crystal display elements - Google Patents

Abstract

The present invention provides a highly reliable transverse electric field drive type liquid crystal display device, which is highly efficient and provides an orientation control ability and is excellent in exposure characteristics. [I] (A) A photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) a polymer composition containing an organic solvent, on a substrate having a conductive film for driving a transverse electric field. A step of applying to the coated film obtained in [II] [I], a step of irradiating a polarized ultraviolet ray having an extinction ratio of 10:1 or higher; and a step of heating the coated film obtained in [III][II]; By having, the said subject is solved by the manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which the orientation control ability was given.

Description

Manufacturing method of a substrate having a liquid crystal alignment layer for a transverse electric field drive type liquid crystal display device {METHOD FOR PRODUCING SUBSTRATE HAVING LIQUID CRYSTAL ALIGNMENT FILM FOR IN-PLANE SWITCHING LIQUID CRYSTAL DISPLAY ELEMENTS}

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

A liquid crystal display element is known as a light-weight, thin, and low-power display device, and has made remarkable development in recent years, such as being used for large-sized television applications. The liquid crystal display element is configured by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes, for example. And in a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired alignment state between 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 predetermined direction between the substrates. In addition, in addition to the role of aligning the liquid crystal in a predetermined direction, such as a direction parallel to the substrate, the liquid crystal alignment film may require a role of controlling the pretilt angle of the liquid crystal. In such a liquid crystal alignment film, the ability to control the alignment of the liquid crystal (hereinafter, referred to as alignment control ability) is imparted by performing alignment treatment on the organic film constituting the liquid crystal alignment film.

As an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability, a rubbing method has been known conventionally. The rubbing method refers to the direction of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing), and rubbing (rubbing direction). It is a method of aligning the liquid crystal. This rubbing method has been used in a conventional liquid crystal display device manufacturing process because it can easily achieve a relatively stable alignment state of a liquid crystal. And, as the organic film used for the liquid crystal aligning film, a polyimide-based organic film having excellent reliability and electrical properties such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of a liquid crystal aligning film made of polyimide or the like, oscillation and generation of static electricity may be a problem. In addition, due to the recent high-definition of liquid crystal display devices and irregularities caused by electrodes on a corresponding substrate or switching active elements for liquid crystal drive, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment can be achieved. There were cases where there was no.

Therefore, as another alignment treatment method of a liquid crystal alignment film not subjected to rubbing, a photoalignment method is actively studied.

Although there are various methods for the photo-alignment method, linearly polarized light or collimated light forms anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal is aligned according to the anisotropy.

As the main photoalignment method, a decomposition type photoalignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition occurs using the polarization direction dependence of ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned with the polyimide left without decomposition (for example, refer to Patent Document 1).

Moreover, photo-crosslinking type and photo-isomerization type photo-alignment method are also known. For example, using polyvinyl cinnamate, polarized ultraviolet rays are irradiated, and a dimerization reaction (crosslinking reaction) is caused at the double bond portion of two side chains parallel to polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side-chain polymer having azobenzene in the side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarization, thereby aligning the liquid crystal in a direction orthogonal to the polarization direction (Example For example, see Non-Patent Document 2.).

As in the above example, in the alignment treatment method of the liquid crystal alignment film by the photo-alignment method, rubbing is unnecessary, and there is no fear of oscillation or generation of static electricity. In addition, alignment treatment can be performed also on a substrate of a liquid crystal display element having irregularities on the surface, and it is a method of alignment treatment of a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent Publication 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 eliminates the need for the rubbing process itself as compared to the rubbing method that has been industrially used as an alignment treatment method for a liquid crystal display element, and therefore has a great advantage. And, compared with the rubbing method in which the orientation control ability becomes almost constant by rubbing, in the optical orientation method, the irradiation amount of polarized light can be changed to control the orientation control ability. However, in the photo-alignment method, in the case of attempting to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of irradiation of polarized light is required, or stable alignment of liquid crystals may not be achieved in some cases.

For example, in the decomposition type photoalignment method described in Patent Literature 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp having an output of 500 W for 60 minutes, etc. It becomes necessary. Moreover, even in the case of a dimerization type or a photo-isomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Further, in the case of the photo-crosslinking type or photo-isomerizing type photo-alignment method, since the thermal stability and photo-stability of liquid crystal alignment are inferior, there is a problem that alignment failure and display exposure occur in the case of a liquid crystal display element. In particular, in a transverse electric field drive type liquid crystal display device, since liquid crystal molecules are switched in-plane, misalignment of the liquid crystal after liquid crystal drive is liable to occur, and display exposure resulting from AC drive is a major problem.

Therefore, in the photoalignment method, high efficiency of the alignment treatment and realization of stable liquid crystal alignment are required, and a liquid crystal alignment film or a liquid crystal aligning agent capable of imparting high alignment control ability to the liquid crystal alignment film with high efficiency is required.

In addition, according to the knowledge of the present inventors, in the liquid crystal display device of the transverse electric field drive method as described above, the obtained liquid crystal display device has a problem with the black level in color display, thereby causing a sense of incongruity in the color tone of the screen. I figured it out. This is considered to be a phenomenon caused by disturbance of the initial orientation, and is a problem to be solved.

It is an object of the present invention to provide a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, and a transverse electric field drive type liquid crystal display element having the substrate, which is highly efficient and imparts alignment control ability and has excellent exposure characteristics.

Further, an object of the present invention is to provide a transverse electric field drive type liquid crystal element capable of solving the problem of black level, and a liquid crystal alignment film for the element, in addition to the above object.

Another object of the present invention is to provide a method for manufacturing a substrate having a liquid crystal alignment film capable of expanding the margin area of the irradiation amount of polarized ultraviolet rays capable of realizing good alignment of liquid crystal in the liquid crystal alignment film.

The inventors of the present invention found out the following invention as a result of intensive examination in order to achieve the above-described subject.

<1> [I] (A) A photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A step of forming a coating film by applying the polymer composition containing the transverse electric field onto a substrate having a conductive film for driving a transverse electric field;

[II] A step of irradiating the coated film obtained in [I] with polarized ultraviolet rays having an extinction ratio of 10:1 or more; and

[III] 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 transverse electric field drive type liquid crystal display element to which an alignment control ability is imparted is obtained.

In <2> said <1>, it is good for (A) component to have a photosensitive side chain which causes photocrosslinking, photoisomerization, or photofleece transition.

In <3> said <1> or <2>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

[Formula 1]

In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH- is shown;

S is a C1-C12 alkylene group, and the hydrogen atom bonded to them may be substituted 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 substituted 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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;

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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be _{substituted with -NO 2} , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents 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=CH -Represents, and when the number of X becomes 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen It may be substituted with a group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;

For q1 and q2, one side is 1 and the other side is 0;

q3 is 0 or 1;

P and Q are each independently 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 combinations thereof; provided, however, that X When is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and when the number of P is 2 or more, Ps may be the same or different, and when the number of Qs is 2 or more, Qs may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0-2;

When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;

When l1 is 1, when T is a single bond, B also represents a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

In <4> said <1> or <2>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;

l represents the integer of 1-12;

m represents the integer of 0-2, m1 and m2 represent the integer of 1-3;

n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

[Formula 2]

In <5> said <1> or <2>, it is good for (A) component to have any 1 type of photosensitive side chain chosen from the group which consists of following formulas (11)-(13).

In the formula, A, X, l, m, m1 and R have the same definitions as above.

[Formula 3]

In <6> said <1> or <2>, it is good for (A) component to have a photosensitive side chain represented by following formula (14) or (15).

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

[Formula 4]

In <7> said <1> or <2>, it is good for (A) component to have a photosensitive side chain represented by following formula (16) or (17).

In the formula, A, X, l, and m have the same definitions as above.

[Formula 5]

In <8> said <1> or <2>, it is good for (A) component to have a photosensitive side chain represented by 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 represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms.

[Formula 6]

In <9> said <1> or <2>, it is good for (A) component to have a photosensitive side chain represented by following formula (20).

In the formula, A, Y ₁ , X, 1 and m have the same definitions as above.

[Formula 7]

In any one of <10> said <1>-<9>, it is good for (A) component to have any 1 type of liquid crystalline side chain selected from the group consisting of following formulas (21)-(31) .

In the formula, 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, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them. Each hydrogen atom may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing hetero A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;

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) WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent the integer of 1-3;

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 an alkyl group, Or it represents an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

[Formula 8]

The board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by any one of <11> said <1>-<10>.

<12> The transverse electric field drive type liquid crystal display element which has the board|substrate of said <11>.

<13> The process of preparing the substrate (1st substrate) of said <11>;

[I'] On the second substrate

(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A step of applying a polymer composition containing a to form a coating film;

[II'] A step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; And

[III'] Step of heating the coating film obtained in [II'];

The process of obtaining the liquid crystal aligning film to which the alignment control ability was given by having, and obtaining the 2nd board|substrate which has the liquid crystal aligning film; And

[IV] Step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;

By having a transverse electric field drive type liquid crystal display element, the manufacturing method of the liquid crystal display element.

<14> The transverse electric field drive type liquid crystal display element manufactured by said <13>.

<15> (A) a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A composition for producing a liquid crystal aligning film for a transverse electric field drive type liquid crystal display element containing.

Further, as another aspect, the following invention was found.

<P1> [I] (A) A photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A step of forming a coating film by applying the polymer composition containing the transverse electric field onto a substrate having a conductive film for driving a transverse electric field;

[II] A step of irradiating polarized ultraviolet rays having an extinction ratio of 10:1 or more to the coating film obtained in [I]; And

[III] 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 transverse electric field drive type liquid crystal display element to which an alignment control ability is imparted is obtained.

<P2> In said <P1>, it is good for (A) component to have a photosensitive side chain which causes photocrosslinking, photoisomerization, or photofleece transition.

In <P3> said <P1> or <P2>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

[Formula 9]

In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- It represents O- or -O-CO-CH=CH-;

S is a C1-C12 alkylene group, and the hydrogen atom bonded to them may be substituted 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 substituted 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 2 to 6 identical or different selected from their substituents. A ring is a group formed by bonding through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;

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 combinations thereof, and a hydrogen atom bonded to them May each independently be _{substituted with -NO 2} , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents 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= Shows CH-;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, It may be substituted with a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;

As for q1 and q2, one side is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of 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 combinations thereof to be. However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded 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 combinations thereof.

In <P4> said <P1> or <P2>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group consisting of following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;

l represents the integer of 1-12;

m represents the integer of 0-2, and m1 and m2 represent the integer of 1-3;

n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

[Formula 10]

In <P5> said <P1> or <P2>, it is good for (A) component to have any 1 type of photosensitive side chain chosen from the group which consists of following formulas (11)-(13).

In the formula, A, X, l, m, and R have the same definitions as above.

[Formula 11]

In <P6> said <P1> or <P2>, it is good for (A) component to have a photosensitive side chain represented by following formula (14) or (15).

In the formula, A, Y ₁ , X, 1, m1 and m2 have the same definitions as above.

[Formula 12]

In <P7> said <P1> or <P2>, it is good for (A) component to have a photosensitive side chain represented by following formula (16) or (17).

In the formula, A, X, l, and m have the same definition as above.

[Formula 13]

In <P8> said <P1> or <P2>, it is good for (A) component to have a photosensitive side chain represented by 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 represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. .

[Formula 14]

In <P9> said <P1> or <P2>, it is good for (A) component to have a photosensitive side chain represented by following formula (20).

In the formula, A, Y ₁ , X, 1 and m have the same definitions as above.

[Formula 15]

In any one of <P10> said <P1>-<P9>, what has (A) component has any 1 type of liquid crystalline side chain selected from the group consisting of following formulas (21)-(31) good.

In the formula, 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, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them Each hydrogen atom may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;

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) WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent the integer of 1-3;

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 an alkyl group. , Or an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

[Formula 16]

<P11> The board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by any one of said <P1>-<P10>.

<P12> The transverse electric field drive type liquid crystal display element which has the board|substrate of said <P11>.

<P13> The process of preparing the substrate (first substrate) of the <P11>;

[I'] On the second substrate

(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A step of applying a polymer composition containing a to form a coating film;

[II'] A step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; And

[III'] Step of heating the coating film obtained in [II'];

The process of obtaining the liquid crystal aligning film to which the alignment control ability was given by having, and obtaining the 2nd board|substrate which has the liquid crystal aligning film; And

[IV] Step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;

By having a transverse electric field drive type liquid crystal display element, the manufacturing method of the liquid crystal display element.

<P14> The transverse electric field drive type liquid crystal display element manufactured by said <P13>.

<P15> (A) a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A composition for producing a liquid crystal aligning film for a transverse electric field drive type liquid crystal display element containing.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, and a transverse electric field drive type liquid crystal display element having the substrate, which is highly efficient and provides an alignment control ability and has excellent exposure characteristics.

Since the transverse electric field drive type liquid crystal display device manufactured by the method of the present invention is highly efficient and has an orientation control ability, display characteristics are not impaired even if it is continuously driven for a long time.

Further, according to the present invention, in addition to the above effects, even under extreme conditions such as high temperature and high humidity, characteristics such as voltage retention are not deteriorated, and a transverse electric field-driven liquid crystal element having high reliability and the element thereof is provided. It is possible to provide a liquid crystal alignment film for.

1 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, a crosslinkable organic group is used in the photosensitive side chain, and the introduced anisotropy is small. It is a drawing of the case.
2 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, a crosslinkable organic group is used in the photosensitive side chain, and the introduced anisotropy is large. It is a drawing of the case.
3 is a diagram of one example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, using an organic group causing a fleece transition or isomerization in a photosensitive side chain, and introduction It is a drawing in the case of small anisotropy.
4 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, using an organic group causing a fleece transition or isomerization in a photosensitive side chain, and introduction It is a drawing in the case of a large anisotropy.

As a result of intensive research, the present inventors have obtained the following knowledge and have come to complete the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side-chain polymer (hereinafter, also referred to simply as a side-chain polymer) capable of expressing liquid crystallinity, and the coating film obtained by using the polymer composition is liquid crystal It is a film having a photosensitive side-chain type polymer capable of expressing properties. The orientation treatment is performed by polarized light irradiation without performing a rubbing treatment on this coating film. And after polarized light irradiation, it becomes the coating film (hereinafter also referred to as a liquid crystal aligning film) to which the orientation control ability was given through the process of heating the side chain polymer film. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently rearranged by self-organization. As a result, high-efficiency alignment treatment is realized as a liquid crystal alignment film, and a liquid crystal alignment film to which high alignment control ability is imparted can be obtained.

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

<Method of manufacturing a substrate having a liquid crystal alignment film> and <Method of manufacturing a liquid crystal display element>

The method for producing a substrate having a liquid crystal alignment film of the present invention,

[I] (A) A photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and

(B) organic solvent

A step of forming a coating film by applying the polymer composition containing the transverse electric field onto a substrate having a conductive film for driving a transverse electric field;

[II] A step of irradiating polarized ultraviolet rays having an extinction ratio of 10:1 or more to the coating film obtained in [I]; And

[III] Step of heating the coating film obtained in [II];

Has.

By the said process, the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which the alignment control ability was provided can be obtained, and the board|substrate which has the liquid crystal aligning film can be obtained.

Further, by preparing a second substrate other than the obtained substrate (first substrate), a transverse electric field drive type liquid crystal display device can be obtained.

For the second substrate, in place of a substrate having a conductive film for driving a transverse electric field, a substrate not having a conductive film for driving a transverse electric field is used, and steps [I] to [III] (conductive film for driving a transverse electric field) are used. Since a substrate that does not have a substrate is used, for convenience, in the present application, it may be abbreviated as steps [I'] to [III']) to obtain a second substrate having a liquid crystal alignment film to which the alignment control ability is imparted. I can.

The manufacturing method of the transverse electric field driving type liquid crystal display element,

[IV] Step of obtaining a liquid crystal display element by disposing the first and second substrates obtained above to face each other so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;

Has. Thereby, a transverse electric field drive type liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] of the production method of the present invention will be described.

<Step [I]>

In step [I], on a substrate having a conductive film for driving a transverse electric field, a polymer composition containing a photosensitive side-chain type polymer and an organic solvent that exhibits liquid crystal properties in a predetermined temperature range is applied to form a coating film.

<Substrate>

Although it does not specifically limit about a board|substrate, When the liquid crystal display element to be manufactured is a transmission type, it is preferable to use a board|substrate with high transparency. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

Further, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for transverse electric field drive>

The substrate has a conductive film for driving a transverse electric field.

Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. in the case where the liquid crystal display device is a transmissive type.

Further, in the case of a reflective liquid crystal display element, a material that reflects light such as aluminum may be mentioned as the conductive film, but is not limited thereto.

As a method of forming a conductive film on a substrate, a conventionally known method can be used.

<Polymer composition>

A polymer composition is applied on a substrate having a conductive film for driving a transverse electric field, particularly on a 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 polymer that exhibits liquid crystallinity in a predetermined temperature range.

(A) The side-chain type polymer reacts with light in a wavelength range of 250 nm to 400 nm, and preferably exhibits liquid crystallinity in a temperature range of 100°C to 250°C.

(A) It is preferable that the side chain type polymer has a photosensitive side chain which reacts to light in a wavelength range of 250 nm to 400 nm.

(A) It is preferable that the side chain type polymer has a mesogenic group in order to show liquid crystallinity in the temperature range of 100 degreeC-250 degreeC.

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

The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and the side chain is a mesogenic component such as a biphenyl group, terphenyl group, phenylcyclohexyl group, phenylbenzoate group, and azobenzene group, It has a structure having a photosensitive group bonded to the tip and reacting to crosslinking reaction or isomerization reaction in response to light, and has a main chain and a side chain bonded thereto, and the side chain may be a mesogen component, and a photo-freeze potential reaction is carried out. It can be made into a structure having a phenyl benzoate group.

As a more specific example of the structure of a photosensitive side chain type polymer membrane capable of expressing liquid crystallinity, a main chain consisting of at least one selected from the group consisting of hydrocarbons, acrylates, methacrylates, maleimide, norbornene and siloxane And, it is preferable that it is a structure which has a side chain which consists of at least 1 type of following formulas (1) to (6).

[Formula 17]

In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH- is shown;

S is a C1-C12 alkylene group, and the hydrogen atom bonded to them may be substituted 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 substituted 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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;

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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be _{substituted with -NO 2} , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents 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=CH -Represents, and when the number of X becomes 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen It may be substituted with a group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;

For q1 and q2, one side is 1 and the other side is 0;

q3 is 0 or 1;

P and Q are each independently 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 combinations thereof; provided, however, that X When is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and when the number of P is 2 or more, Ps may be the same or different, and when the number of Qs is 2 or more, Qs may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0-2;

When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;

When l1 is 1, when T is a single bond, B also represents a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

The side chain is preferably any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;

l represents the integer of 1-12;

m represents the integer of 0-2, m1 and m2 represent the integer of 1-3;

n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

[Formula 18]

The side chain is preferably any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).

In the formula, A, X, l, m, m1 and R have the same definitions as above.

[Formula 19]

It is good that the side chain is 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.

[Formula 20]

It is good that the side chain is a photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l, and m have the same definitions as above.

[Formula 21]

Moreover, it is good that a side chain is a photosensitive side chain represented by 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 represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms.

[Formula 22]

It is good that the side chain is a photosensitive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, 1 and m have the same definitions as above.

[Formula 23]

Moreover, it is good for the (A) side chain type polymer to have any 1 type of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

In the formula, 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, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them. Each hydrogen atom may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing hetero A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;

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) WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent the integer of 1-3;

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 an alkyl group, Or it represents an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

[Formula 24]

In this application, as a photoreactive and/or liquid crystalline side chain monomer, novel compounds (1) to (11) represented by the following formulas (1) to (11); and represented by the following formulas (12) to (17) Compounds (12) to (17) are provided.

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having a carbon number of 2 ~ ^10; R 10 represents a Br or CN; S represents an alkylene group having a carbon number of 2 ~ 10; u is 0 or 1 And Py represent a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group. Moreover, v represents 1 or 2.

[Formula 25]

[Formula 26]

[Formula 27]

<<The manufacturing method of photosensitive side chain type polymer>>

The photosensitive side chain type polymer capable of expressing the above liquid crystal properties can be obtained by polymerizing a photoreactive side chain monomer having the above photosensitive side chain and a liquid crystal side chain monomer.

[Liquid Crystalline Side Chain Monomer]

The liquid crystal 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 portion.

As the mesogenic group possessed by the side chain, it may be a group that forms a mesogen structure alone, such as biphenyl or phenylbenzoate, or may contribute to a mesogenic structure by hydrogen bonding between side chains such as benzoic acid. The following structures are preferable as the mesogenic group possessed by the side chain.

[Formula 28]

As a more specific example of a liquid crystalline side chain monomer, a main chain composed of at least one selected from the group consisting of hydrocarbons, (meth)acrylates, maleimide, norbornene and siloxanes, and the formulas (21) to (31) It is preferable that it is a structure having a side chain consisting of at least one of them.

(A) The side chain type polymer can be obtained by polymerization reaction of the photoreactive side chain monomer expressing the above-described liquid crystallinity. Moreover, it can obtain by copolymerization of a photoreactive side chain monomer which does not express liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer which expresses liquid crystallinity. 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 a radical polymerization reaction.

Specific examples of other monomers include unsaturated carboxylic acid, acrylic acid ester compound, methacrylic acid ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, and vinyl compound.

As a specific example of an unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc. are mentioned.

As an acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2, 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , And, 8-ethyl-8-tricyclodecyl acrylate, etc. are mentioned.

As a methacrylic acid ester compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate Toxictriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned. Cyclic ethers such as glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (3-ethyl-3-oxetanyl)methyl (meth)acrylate A (meth)acrylate compound having a group can also be used.

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

As a styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

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 that has been dealt with industrially can be used. Specifically, it can be produced by cation polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferred from the viewpoint of easiness of reaction control and the like.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating above the decomposition temperature. 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 ( Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxy ketals (dibutyl peroxide, etc.) Oxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate Substances (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) I can. 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 irradiation with light. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioxanthone , 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, iso Propylbenzoin 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 -Isoamyl dimethylaminobenzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl) Reel)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) -s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)- 5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylamino tea) Ryl) 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'-bis(2-chlorophenyl)-4,4',5,5'-tetra Kis (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-hydroxycyclohexylphenylketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1- Il)-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) And -1-(2-benzoyl)ethanone. These compounds may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side-chain type polymer capable of expressing liquid crystallinity is not particularly limited as long as the resulting polymer is dissolved. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, 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 mono Butyl 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, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxy butyl propionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide , 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropana Mid, etc. are mentioned.

These organic solvents may be used alone or may be used in combination. Moreover, even if it is a solvent which does not dissolve the produced|generated polymer, you may mix and use with the above-mentioned organic solvent within the range in which the produced|generated polymer does not precipitate.

Further, in radical polymerization, since oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, it is preferable to use the organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from 30°C to 150°C, but is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at an arbitrary 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 becomes difficult. Preferably it is 1 mass%-50 mass %, More preferably, it is 5 mass%-30 mass %. The initial reaction is carried out at a high concentration, and then, an organic solvent can be added.

In the above-described radical polymerization reaction, if the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the resulting polymer decreases, and if the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer increases. It is preferably-10 mol%. In addition, at the time of polymerization, various monomer components, solvents, initiators, and the like can also be added.

[Recovery of polymer]

In the case of recovering the produced polymer from the reaction solution of the photosensitive side-chain type polymer capable of expressing liquid crystallinity obtained by the above-described reaction, the reaction solution may be added to a poor solvent, and these polymers may be precipitated. . Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. I can. The polymer injected into the poor solvent and precipitated can be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, if the polymer recovered by precipitation is re-dissolved in an organic solvent and the operation of reprecipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and when three or more types of poor solvents selected from these are used, the efficiency of purification is further increased, so it is preferable.

The molecular weight of the side chain type polymer of the present invention (A) is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the resulting coating film, workability during formation of the coating film, and uniformity of the coating film. 2000-1000000 are preferable, More preferably, they are 5000-100000.

[Preparation of polymer composition]

It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, it is preferable that the polymer composition used in the present invention is prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side-chain type polymer capable of expressing the liquid crystal properties described above. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the above-described resin components may all be photosensitive side chain polymers capable of expressing the above-described liquid crystal properties, but other than those in the range not impairing the liquid crystal expression ability and photosensitive performance. Other polymers of may be mixed. In that case, 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, poly(meth)acrylate, polyamic acid, polyimide, and the like, and polymers other than photosensitive side-chain polymers capable of expressing liquid crystallinity.

<Organic solvent>

The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrroli Don, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclo Hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used individually or may be mixed and used.

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 film thickness uniformity and surface smoothness when a polymer composition is applied, compounds that improve adhesion between a liquid crystal aligning film and a substrate, and the like, but are not limited thereto.

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of the film thickness and surface smoothness.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol 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, 1-hexanol, n-hexane, n-pentane, n -Octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl, 3-methoxy ethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxy butyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2 -Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, etc. Solvents with low surface tension, etc. Can be lifted.

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

As a compound which improves the uniformity of the film thickness and surface smoothness, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Florade FC430, FC431 (manufactured by Sumitomo 3M), Asahigard (registered trademark) AG710 (manufactured by Asahi Glass), Suflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) ) And the like. The ratio of these surfactants to be used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, based on 100 parts by mass of the resin component contained in the polymer composition.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the functional silane-containing compound etc. shown below are mentioned.

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-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 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, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, etc. are mentioned.

In addition, in addition to improving the adhesion between the substrate and the liquid crystal alignment layer, the following additives of phenoplast-based or epoxy group-containing compounds are added to the polymer composition for the purpose of preventing deterioration of electrical properties due to backlight when configuring a liquid crystal display device. You may contain it in. Although specific phenoplast additives are shown below, it is not limited to this structure.

[Formula 29]

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are illustrated.

When a compound that improves adhesion to a substrate is used, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the resin component contained in the polymer composition. It's wealth. If the amount is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if the amount is more than 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 photosensitizers, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-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-biphenoyl Methylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naph Tooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3- Methylbenzooxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- Nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoinalkylether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone) ), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalenecarboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin, and the like.

Preferably, they are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In addition to those described above, in the polymer composition, as long as the effect of the present invention is not impaired, for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film, when it is set as a dielectric material or a conductive material, and furthermore, a liquid crystal aligning film. A crosslinkable compound may be added for the purpose of increasing the hardness and density of the film.

The method of applying the above-described polymer composition onto a substrate having a conductive film for driving a transverse electric field is not particularly limited.

As for the coating method, industrially, a method performed by screen printing, offset printing, flexo printing, inkjet method, or the like is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotation coating method), or a spray method, and may be used depending on the purpose.

After coating the polymer composition on a substrate having a conductive film for transverse electric field driving, 50 to 200°C, preferably 50 to 150°C, by heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. A coating film can be obtained by evaporating the solvent at °C. It is preferable that the drying temperature at this time is lower than the liquid crystal phase expression temperature of the side chain type polymer.

If the thickness of the coating film is too thick, it becomes disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be deteriorated. Therefore, preferably 5 nm to 300 nm, more preferably 10 nm It is -150 nm.

In addition, after the [I] process, it is also possible to set a process of cooling the substrate on which the coating film is formed to room temperature before the subsequent [II] process.

<Step [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays having an extinction ratio of 10:1 or more, preferably an extinction ratio of 15:1 or more, and more preferably an extinction ratio of 20:1 or more. The extinction ratio refers to the transmittance ratio of the P wave and the S wave of the polarizing plate at a specific wavelength used to cause a light reaction. When irradiating polarized ultraviolet rays on the film surface of the coating film, the polarized ultraviolet rays are irradiated from a certain direction to the substrate 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 according to the type of coating film to be used. And, for example, in order to selectively cause a photo-crosslinking reaction, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

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

<Step [III]>

In step [III], the coating film irradiated with ultraviolet rays polarized in step [II] is heated. By heating, orientation control ability can be imparted to the coating film.

Heating may be performed using a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared ray) type oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystal properties of the coating film to be used are expressed.

It is preferable that the heating temperature is within the temperature range of the temperature at which the side-chain polymer exhibits liquid crystallinity (hereinafter, referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the surface of the coating film is expected to be lower than the liquid crystal expression temperature when a photosensitive side-chain type polymer capable of expressing liquid crystal is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, as for the temperature range of the heating temperature after irradiation with polarized ultraviolet rays, a temperature 10°C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer to be used is the lower limit, and a temperature 10°C lower than the upper limit of the liquid crystal temperature range is the upper limit. It is preferable that it is a temperature in the range made into. When the heating temperature is lower than the above temperature range, the amplification effect of anisotropy due to heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the coating film state is in an isotropic liquid state (isotropic phase ), and in this case, it may become difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is equal to or higher than the glass transition temperature (Tg) at which a phase transition occurs from a solid phase to a liquid crystal phase on the surface of the side chain polymer or coating film, and isotropic phase transition causing a phase transition from the liquid crystal phase to the isotropic phase (isotropic phase). It refers to the temperature below the temperature (Tiso).

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

By having the above steps, in the production method of the present invention, it is possible to realize anisotropic introduction into a highly efficient coating film. In addition, a substrate on which a liquid crystal alignment layer is formed can be manufactured with high efficiency.

<Step [IV]>

Step [IV] does not have a conductive film obtained in [I'] to [III'] similarly to the substrate (first substrate) having a liquid crystal alignment film on the conductive film for transverse electric field driving obtained in [III]. Step of arranging the substrate (second substrate) on which the non-removable liquid crystal alignment film is formed to face each other through a liquid crystal, to produce a liquid crystal cell by a known method, and to produce a transverse electric field drive type liquid crystal display element to be. In the process [I'] to [III'], in the process [I], instead of the substrate having the conductive film for driving the transverse electric field, a substrate having no conductive film for driving the transverse electric field was used, and the process [ It can be carried out in the same manner as in 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 above-described conductive film, the explanation of the steps [I'] to [III'] is omitted.

If an example of the production of a liquid crystal cell or a liquid crystal display element is given, the first and second substrates described above are prepared, spacers are sprayed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other A method of bonding the substrates on one side and sealing by injecting liquid crystal under reduced pressure, or a method of bonding and sealing the substrates after dropping the liquid crystal on the surface of the liquid crystal alignment film sprayed with spacers can be illustrated. have. In this case, it is preferable to use a substrate having an electrode having a structure like a comb for driving a transverse electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, more preferably 2 µm to 10 µm. The 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 of manufacturing a substrate on which a coating film of the present invention is formed, after forming a coating film by applying a polymer composition on a substrate, polarized ultraviolet rays are irradiated. Subsequently, by heating, high-efficiency anisotropy introduction into the side-chain type polymer film is realized, and a substrate on which a liquid crystal alignment film having a liquid crystal alignment control ability is formed is produced.

In the coating film used in the present invention, the introduction of highly efficient anisotropic properties to the coating film is realized by using the principle of molecular rearrangement caused by self-organization based on photoreaction of the side chain and liquid crystallinity. In the production method of the present invention, in the case of a structure having a photo-crosslinkable group as a photoreactive group in the side chain polymer, a coating film is formed on the substrate using the side chain polymer, and then polarized ultraviolet rays are irradiated, and then, After heating, a liquid crystal display element is manufactured.

Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is referred to as the first embodiment, and an embodiment using a side chain type polymer having a structure having a photo-freese potential group or a group causing isomerization as the photoreactive group is used. Is referred to as a second form and described.

1 schematically illustrates an anisotropic introduction 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 aspect of the present invention. It is a drawing of one example. Fig. 1(a) is a diagram schematically showing a state of a side chain type polymer film before polarized light irradiation, Fig. 1(b) is a diagram schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 1(c) ) Is a diagram schematically showing the state of the side-chain polymer membrane after heating, in particular, when the introduced anisotropy is small, that is, in the first aspect of the present invention, the amount of ultraviolet irradiation in the [II] step maximizes ΔA. It is a schematic diagram in the case of being in the range of 1%-15% of the ultraviolet irradiation amount.

FIG. 2 schematically illustrates an anisotropic introduction treatment in a method for producing a liquid crystal alignment film using a side-chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first aspect of the present invention. It is a drawing of one example. Fig. 2(a) is a diagram schematically showing a state of a side chain type polymer film before polarized light irradiation, Fig. 2(b) is a diagram schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 2(c) ) Is a diagram schematically showing the state of the side-chain polymer membrane after heating, in particular, when the introduced anisotropy is large, that is, in the first aspect of the present invention, the amount of ultraviolet irradiation in the step [II] maximizes ΔA. It is a schematic diagram in the case of being in the range of 15%-70% of the ultraviolet irradiation amount.

Fig. 3 is a liquid crystal alignment film using a photo-isomerizing group as a photoreactive group or a side-chain type polymer having a photo-freeze potential group represented by the above-described formula (18) in the second aspect of the present invention. It is a drawing of one example schematically explaining the anisotropic introduction|transduction process in the manufacturing method of. Fig. 3(a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, Fig. 3(b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, and Fig. 3(c) ) Is a diagram schematically showing the state of the side-chain polymer membrane after heating, in particular, when the introduced anisotropy is small, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in the [II] step maximizes ΔA. It is a schematic diagram in the case of being in the range of 1%-70% of the ultraviolet irradiation amount.

4 is a method for producing a liquid crystal alignment film using a side-chain polymer having a structure having a photo-friction potential group represented by the above-described formula (19) as a photoreactive group in a second aspect of the present invention. It is a drawing of one example schematically explaining the introduction process of the anisotropy of. Fig. 4(a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, Fig. 4(b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation, and Fig. 4(c) ) Is a diagram schematically showing the state of the side chain type polymer membrane after heating, in particular, when the introduced anisotropy is large, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in the step [II] maximizes ΔA. It is a schematic diagram in the case of being in the range of 15%-70% of the ultraviolet irradiation amount.

In the first aspect of the present invention, in the anisotropic introduction treatment to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, first, first, A coating film 1 is formed on the substrate. As shown in Fig. 1(a), in the coating film 1 formed on the substrate, the side chains 2 have a structure in which the side chains 2 are randomly arranged. In accordance with the random arrangement of the side chains 2 of the coating film 1, the mesogen components and the photosensitive members of the side chains 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first aspect of the present invention, in the anisotropic introduction treatment to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, first, first, A coating film 3 is formed on the substrate. As shown in Fig. 2(a), in the coating film 3 formed on the substrate, the side chains 4 have a structure in which the side chains 4 are randomly arranged. In accordance with the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive members of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction treatment to the coating film, a photo-isomerizing group or a side-chain type polymer having a photo-freeze potential group represented by the above-described formula (18) is used. In the case of using a liquid crystal aligning film, when the ultraviolet irradiation amount of the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, the coating film 5 is formed on the substrate. As shown in Fig. 3(a), in the coating film 5 formed on the substrate, the side chains 6 have a structure in which the side chains 6 are randomly arranged. In accordance with the random arrangement of the side chains 6 of the coating film 5, the mesogenic components and the photosensitive members of the side chains 6 are also randomly oriented, and the side chain polymer film 5 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction treatment to the coating film, a liquid crystal alignment film using a side chain polymer having a structure having a photo-freeze potential group represented by the above-described formula (19) is used. WHEREIN: In the case where the ultraviolet irradiation amount of the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount maximizing ΔA, first, the coating film 7 is formed on the substrate. As shown in Fig. 4(a), in the coating film 7 formed on the substrate, the side chains 8 have a structure in which the side chains 8 are randomly arranged. In accordance with the random arrangement of the side chains 8 of the coating film 7, the mesogen components and the photosensitive members of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, the ultraviolet ray polarized with respect to the isotropic coating film 1 Investigate. Then, as shown in Fig. 1(b), among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group preferentially undergoes photoreaction such as dimerization reaction. Raises. As a result, the density of the side chain 2a subjected to the photoreaction is slightly increased in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 1.

In the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, the ultraviolet ray polarized with respect to the isotropic coating film 3 Investigate. Then, as shown in Fig. 2(b), among the side chains 4 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 4a having a photosensitive group preferentially undergoes photoreaction such as dimerization reaction. Raises. As a result, the density of the side chain 4a subjected to the photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 3.

In the second aspect of the present embodiment, the amount of ultraviolet irradiation in step [II] using a liquid crystal aligning film using a photo-isomerizing group or a side-chain polymer having a structure having a photo-freese potential group represented by the above-described formula (18) is used. In the case of being in the range of 1% to 70% of the ultraviolet irradiation dose in which ΔA is maximized, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Then, as shown in Fig. 3(b), among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6a having a photosensitive group preferentially undergoes a photoreaction such as an optical fleece potential. Raises. As a result, the density of the side chain 6a subjected to the photoreaction is slightly increased in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.

In the second aspect of the present embodiment, a coating film using a side-chain polymer having a structure having an optical fleece potential group represented by the above-described formula (19) is used, and the amount of ultraviolet irradiation in the step [II] maximizes ΔA. In the case of being in the range of 1% to 70% of the ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Then, as shown in Fig. 4(b), among the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 8a having a photosensitive group preferentially undergoes photoreaction such as a light fleece potential. Raises. As a result, the density of the side chain 8a subjected to the photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 7.

Next, in the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, the coating film 1 after polarization irradiation is heated, Make it a liquid crystal state. Then, as shown in FIG. 1(c), in the coating film 1, the amount of the crosslinking reaction which occurred between the direction parallel to the polarization direction of irradiated ultraviolet rays, and the direction perpendicular|vertical is different. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the polarization direction and the vertical direction of the irradiated ultraviolet rays is higher than that in the parallel direction, and the side chain (2) containing the mesogen component is rearranged by self-organization in a direction parallel to the polarization direction of the irradiated ultraviolet rays. do. As a result, the very small anisotropy of the coating film 1 caused by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 1.

Similarly, in the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, the coating film 3 after polarization irradiation is heated, Make it a liquid crystal state. Then, as shown in Fig. 2(c), in the side chain polymer film 3, the amount of the crosslinking reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to it. Therefore, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chain 4 containing the mesogenic component is rearranged. As a result, the small anisotropy of the coating film 3 caused by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 3.

Similarly, in the second aspect of the present embodiment, a coating film using a photo-isomerizing group or a side-chain type polymer having a structure having a photo-freeze potential group represented by the above-described formula (18) is used, and the ultraviolet ray in the step [II]. In the case where the irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 5 after polarization irradiation is heated to make it a liquid crystal state. Then, as shown in FIG. 3(c), in the coating film 5, the amount of the photo-fleece potential reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the direction perpendicular to it. In this case, since the liquid crystal alignment force of the light fleece potential body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than the liquid crystal alignment force of the side chain before the reaction, the mesogenic component is self-organized in a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The side chain 6 containing the is reorientated. As a result, the very small anisotropy of the coating film 5 caused by the photo fleece potential reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 5.

Similarly, in the second embodiment of the present embodiment, using a coating film using a side-chain polymer having a structure having an optical fleece potential group represented by the above-described formula (19), the amount of ultraviolet irradiation in the step [II] is maximized. In the case of being in the range of 1% to 70% of the ultraviolet irradiation amount, the coating film 7 after polarization irradiation is heated to make it a liquid crystal state. Then, as shown in FIG. 4(c), in the side-chain polymer film 7, the amount of the photo fleece potential reaction generated is different between the direction parallel to and perpendicular to the polarization direction of the irradiated ultraviolet rays. Since the anchoring force of the optical fleece potential body 8(a) is stronger than that of the side chain 8 before dislocation, when a certain amount or more of the optical fleece potential body is generated, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet rays to form a mesogenic component. The side chain (8) containing the is reorientated. As a result, the small anisotropy of the coating film 7 caused by the photo fleece potential reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 7.

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

And, in the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, it is possible to realize highly efficient introduction of anisotropy into the coating film.

Polarized ultraviolet rays that optimize the amount of polarized ultraviolet rays that are optimal for the introduction of highly efficient anisotropy into the coating film used in the present invention are the amount by which the photosensitive group in the coating film undergoes a photocrosslinking reaction, photoisomerization reaction, or photofriction potential reaction. Corresponds to the dose of irradiation. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, if there are few photosensitive groups in the side chains for photocrosslinking reaction, photoisomerization reaction, or photofriction potential reaction, the amount of photoreaction is not sufficient. In that case, even if heated after that, sufficient self-organization does not proceed. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays on a structure having a photocrosslinkable group, when the photosensitive group of the side chain for crosslinking reaction becomes excessive, the crosslinking reaction between the side chains proceeds too much. In that case, the resulting film becomes rigid and may hinder the progress of self-organization due to subsequent heating. In addition, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to the structure having a photo-freeze potential group, when the photosensitive group of the side chain reacting with the photo-freeze potential becomes excessive, the liquid crystal property of the coating film is too low. . In that case, the liquid crystalline property of the film obtained is also lowered, and there may be a case where the progress of self-organization by subsequent heating is hindered. In addition, in the case of irradiating polarized ultraviolet rays to a structure having an optical fleece potential group, if the irradiation amount of ultraviolet rays is too large, the side chain polymer is photodecomposed, and subsequent heating may hinder the progress of self-organization. have.

Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group of the side chain by irradiation with polarized ultraviolet rays is a photocrosslinking reaction, a photoisomerization reaction, or a photofriction potential reaction of the photosensitive group of the side chain type polymer film. It is preferable to set it as 0.1 mol%-40 mol%, and it is more preferable to set it as 0.1 mol%-20 mol%. By setting the amount of the photosensitive group in the side chain to photoreact in such a range, self-organization in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy formation in the film becomes possible.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the amount of photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the side chain of the side chain type polymer film, or the photofriction potential reaction Optimize. In addition to the subsequent heat treatment, high-efficiency, anisotropic introduction into the coating film used in the present invention is realized. In that case, it is possible to implement the preferable amount of polarized ultraviolet rays based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet rays and ultraviolet absorption in a vertical direction after irradiation with polarized ultraviolet rays are measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film, and the ultraviolet absorbance in the direction perpendicular to the polarization direction, is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays to realize the same are obtained. In the manufacturing method of the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of a liquid crystal aligning film can be determined based on the amount of polarized ultraviolet rays that realizes this ?Amax.

In the production method of the present invention, it is preferable to make the irradiation amount of polarized ultraviolet rays to the coating film used in the present invention in the range of 1% to 70% of the amount of polarized ultraviolet rays that realize ΔAmax, and 1% to 50%. It is more preferable to fall within the range of. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays that realize ΔAmax is 0.1 to 20 moles of the total photosensitive group of the side chain polymer film. % Corresponds to the amount of polarized ultraviolet rays for photocrosslinking reaction.

From the above, in the production method of the present invention, in order to realize the introduction of highly efficient anisotropy into the coating film, it is preferable to determine the preferable heating temperature as described above based on the liquid crystal temperature range of the side chain type polymer. . Therefore, for example, in the case where the liquid crystal temperature range of the side chain polymer used in the present invention is from 100°C to 200°C, the heating temperature after irradiation with polarized ultraviolet rays is preferably set to 90°C to 190°C. By doing so, in the coating film used in the present invention, greater anisotropy is imparted.

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

As described above, the substrate for a transverse electric field drive type liquid crystal display element manufactured by the method of the present invention or a transverse electric field drive type liquid crystal display element having the substrate is excellent in reliability, and is suitable for a high-definition liquid crystal TV with a large screen. Can be used.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

Example

The abbreviations used in the examples are as follows.

<Methacryl monomer>

[Formula 30]

MA1 was synthesized by the synthesis method described in Patent Document (WO2011-084546).

MA2 was synthesized by the synthesis method described in Patent Literature (Japanese Unexamined Patent Application Publication No. Hei 9-118717).

<Organic solvent>

THF ： Tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC ： Butyl Cellosolve

<Polymerization initiator>

AIBN: 2,2'-azobisisobutyronitrile

<Polymethacrylic acid synthesis example 1>

After MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g) and degassed with a diaphragm pump, 0.246 g (1.5 mmol) of AIBN was added and degassed again. After this, it reacted at 50 degreeC for 30 hours, and obtained the polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the obtained precipitate was filtered. This deposit was washed with diethyl ether, and dried under reduced pressure in a 40°C oven to obtain a methacrylate polymer powder.

NMP 54.0 g was added to 6.0 g of the obtained powder, and it stirred at room temperature for 3 hours. Further, 40.0 g of BCS was added to this solution, followed by stirring at room temperature for 1 hour to obtain a polymer solution (A1) having a solid content concentration of 6.0 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

<Polymethacrylic acid synthesis example 2>

Using the same method as in Synthesis Example 1, MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were polymerized in THF (85.45 g) in the presence of AIBN (0.14 g). A polymer solution (M2) of methacrylate was obtained.

<Example 1>

[Production of liquid crystal cell]

Example 1 Using the obtained liquid crystal aligning agent (M1), it produced the liquid crystal cell in the procedure as shown below. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film was used. The pixel electrode has a comb-shaped shape constituted by arranging a plurality of U-shaped electrode elements whose center portion is bent. The width of each electrode element in the short direction is 10 µm, and the spacing between the electrode elements is 20 µm. Since the pixel electrode forming each pixel is configured by arranging a plurality of U-shaped electrode elements with a central portion bent, the shape of each pixel is not a rectangular shape, and is bent at the center portion in the same manner as the electrode element. It has a shape that resembles a bold く character. Then, each pixel is divided up and down with the central bent portion as a boundary, and has a first area on the upper side of the bent portion and a second area on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the orientation treatment direction of the liquid crystal alignment layer described later is used as a reference, the electrode element of the pixel electrode is formed to have an angle of +15° (clockwise direction) in the first region of the pixel, and the pixel electrode is formed in the second region of the pixel. The electrode elements are formed to achieve an angle of -15° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational operation (inplane switching) of the liquid crystal in the substrate surface caused by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other. Consists of. The liquid crystal aligning agent (A1) obtained in Synthesis Example 1 was spin-coated on the prepared substrate on which the electrode was formed. Subsequently, it dried for 90 seconds with a 70 degreeC hot plate, and the liquid crystal aligning film with a film thickness of 100 nm was formed. Next, after irradiating 1 mJ/cm<2> of ultraviolet rays of 313 nm through a polarizing plate whose extinction ratio is a predetermined|prescribed value on the coating film surface, it heated for 10 minutes with a 150 degreeC hot plate, and the board|substrate with a liquid crystal aligning film was obtained. In the same way, the irradiation amount of ultraviolet rays is 1 mJ/cm 2 at 1 mJ/cm 2 to 10 mJ/cm 2, at 10 mJ/cm 2 at 10 mJ/cm 2 to 100 mJ/cm 2, and 50 mJ for 100 mJ/cm 2 or more. At /cm2 intervals, different substrates were prepared respectively. Further, a coating film was formed similarly to a glass substrate having a columnar spacer having a height of 4 µm on which no electrode was formed as a counter substrate, and the alignment treatment was performed. A sealing agent (made by Kyoritsu Chemical XN-1500T) was printed on the liquid crystal aligning film of one board|substrate. Subsequently, the other substrate was bonded with the liquid crystal alignment film surface facing each other so that the alignment direction was 0°, and then the sealing agent was thermally cured to produce an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Corporation) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell provided with the configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

(Orientation observation)

A liquid crystal cell was produced by the above method. Thereafter, a re-direction treatment was performed in an oven at 120° C. for 60 minutes. After that, the polarizing plate was observed through a polarizing microscope in a cross-Nicol state. When the liquid crystal cell was rotated to be in a black display state, the state in which there were no bright spots or poor alignment was said to be good. As a result of observing the orientation of each different substrate as described above with respect to the irradiation amount of ultraviolet rays, the irradiation margin with good orientation was as shown in Table 1.

<Examples 2 to 4>

A liquid crystal cell was manufactured using the same method as in Example 1. The extinction ratio of the used liquid crystal aligning material and a polarizing plate is put together in Table 1, and is shown.

<Black level evaluation>

Examples 1 to 4 The prepared liquid crystal cells were installed between two polarizing plates arranged so that the polarization axes were orthogonal, and the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cells was adjusted so that the luminance of the transmitted light became the smallest. Adjusted. The liquid crystal cell was observed using a digital CCD camera "C8800-21C" manufactured by Hamamatsu Photonics, and the luminance was quantified using the company's analysis software "ExDcam Image capture Software". did. If the luminance value of this liquid crystal cell is 500 to 550, "◎", if it is 550 to 600, "o", and more are set to "x".

<Comparative Examples 1 to 2>

A liquid crystal cell was produced in the same manner as in Examples 1-4 using the polarizing plate of extinction ratio 6:1. The black level was evaluated in the same manner as in Examples 1 to 4 using the obtained liquid crystal cell. The evaluation results are put together in Table 1 and shown.

In Table 1, in Examples 1 and 2, by using a filter having a high extinction ratio, a black level better than that of Comparative Example 1 using a filter having an extinction ratio of 6:1 was shown. Moreover, in Examples 1 and 2, the irradiation dose margin was expanded from 1-3 to 1-10 compared with Comparative Example 1. In the comparison between Examples 3 and 4 and Comparative Example 2, similarly, an improvement in the black level and an enlargement of the dose margin were observed.

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

Claims (14)

[I] (A) A photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and
(B) organic solvent
A step of forming a coating film by applying the polymer composition containing the transverse electric field onto a substrate having a conductive film for driving a transverse electric field;
[II] A step of irradiating the coated film obtained in [I] with polarized ultraviolet rays having an extinction ratio of 10:1 or more; and
[III] Step of heating the coating film obtained in [II];
As a method for producing a substrate having the liquid crystal alignment film to obtain a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which alignment control ability was provided by having
[II] The ultraviolet irradiation amount in the step is in the range of 1% to 70% of the amount of polarized ultraviolet rays realizing the maximum value of ΔA, which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in a perpendicular direction. , Way. The method of claim 1,
A method in which the component (A) has a photosensitive side chain causing photocrosslinking, photoisomerization, or photofleece transition. The method according to claim 1 or 2,
(A) component is the following formula (1)-(6)
(In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- It represents O- or -O-CO-CH=CH-;
S is a C1-C12 alkylene group, and the hydrogen atom bonded to them may be substituted 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 substituted 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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;
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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be _{substituted with -NO 2} , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents 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=CH -Represents, and when the number of X becomes 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen It may be substituted with a group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;
For q1 and q2, one side is 1 and the other side is 0;
q3 is 0 or 1;
P and Q are each independently 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 combinations thereof; provided, however, that X When is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and when the number of P is 2 or more, Ps may be the same or different, and when the number of Qs is 2 or more, Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0-2;
When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.)
A method having any one type of photosensitive side chain selected from the group consisting of.
[Formula 1]

The method according to claim 1 or 2,
(A) component is the following formula (7)-(10)
(In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- It 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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Represents, and when the number of X becomes 2, X may be the same or different;
l represents the integer of 1-12;
m represents the integer of 0-2, m1 and m2 represent the integer of 1-3;
n represents the integer of 0-12 (however, 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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be _{substituted with -NO 2} , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as _{Y 1)}
A method having any one type of photosensitive side chain selected from the group consisting of.
[Formula 2]

The method according to claim 1 or 2,
(A) component is the following formula (11)-(13)
(In the formula, A is each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH- is shown;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Represents, and when the number of X becomes 2, X may be the same or different;
l represents the integer of 1-12, m represents the integer of 0-2, and m1 represents the integer of 1-3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents It is a group formed by bonding through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN , -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group, or a hydroxy group or a C1-C6 alkyloxy group Represents an alkoxy group)
A method having any one type of photosensitive side chain selected from the group consisting of.
[Formula 3]

The method according to claim 1 or 2,
(A) component is the following formula (14) or (15)
(In the formula, A is each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH- is shown;
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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;
l represents the integer of 1-12, m1 and m2 represent the integer of 1-3) the method which has the photosensitive side chain represented by).
[Formula 4]

The method according to claim 1 or 2,
(A) component is the following formula (16) or (17)
(Wherein, A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O- CO-CH=CH- is shown;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Represents, and when the number of X becomes 2, X may be the same or different;
l represents the integer of 1-12, m represents the integer of 0-2)
A method having a photosensitive side chain represented by.
[Formula 5]

The method according to claim 1 or 2,
(A) component is the following formula (18) or (19)
(In the formula, A and B are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH- is shown;
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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;
For q1 and q2, one side is 1 and the other side is 0;
l represents the integer of 1 to 12, m1 and m2 represent the integer of 1 to 3;
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms) A method having any one type of photosensitive side chain selected from the group consisting of.
[Formula 6]

The method according to claim 1 or 2,
(A) component is the following formula (20) (in the formula, A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH -CO-O- or -O-CO-CH=CH- is shown;
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 the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Represents, and when the number of X becomes 2, X may be the same or different;
l represents the integer of 1-12, m represents the integer of 0-2) The method which has a photosensitive side chain represented by).
[Formula 7]

The method according to claim 1 or 2,
(A) component is the following formulas (21) to (31) (in the formula, A and B are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-,- NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH- is shown;
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, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them. Each hydrogen atom may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing hetero A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;
For q1 and q2, one side is 1 and the other side 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) WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent the integer of 1-3;
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 an alkyl group, Or it represents an alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -).
[Formula 8]

A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method according to claim 1 or 2. A transverse electric field drive type liquid crystal display device comprising the substrate according to claim 11. A step of preparing the substrate (first substrate) according to claim 11;
[I'] On the second substrate
(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and
(B) organic solvent
A step of applying a polymer composition containing a to form a coating film;
[II'] A step of irradiating a polarized ultraviolet ray having an extinction ratio of 10:1 or more to the coating film obtained in [I']; and
[III'] Step of heating the coating film obtained in [II'];
The process of obtaining the 2nd substrate which has the said liquid crystal aligning film, and obtaining the liquid crystal aligning film to which the alignment control ability was given by having
[IV] Step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;
By having a transverse electric field drive type liquid crystal display element, the manufacturing method of the liquid crystal display element. A transverse electric field drive type liquid crystal display device manufactured by the method according to claim 13.

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