KR20160030959A - Polymer composition and liquid crystal alignment film for in-plane-switching-type liquid crystal display element - Google Patents

Abstract

Disclosed is a novel polymer composition imparting a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type, which is provided with a high controllability of orientation control with high efficiency and excellent in burning property, and a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type . The present invention solves the above problems by (A) a polymer composition containing (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a polyurea, and (C) an organic solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film for a liquid crystal display device, a polymer composition, and a liquid crystal alignment film for a transversal electric field driving type liquid crystal display device. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a novel polymer composition, a liquid crystal alignment film for a transverse electric field driven liquid crystal display device using the same, and a method for producing a substrate having the alignment film. More particularly, the present invention relates to a novel method for producing a liquid crystal display element having excellent burn-in characteristics.

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

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

Conventionally, a rubbing method is known as an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon or polyester in a predetermined direction, To orient the liquid crystal. This rubbing method has been used in a manufacturing process of a conventional liquid crystal display element since a relatively stable liquid crystal alignment state can be realized easily. As an organic film used for a liquid crystal alignment film, a polyimide-based organic film having excellent reliability and electrical characteristics such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of oscillation or static electricity is a problem in some cases. In addition, since the liquid crystal display element of recent years has a high precision and the surface of the liquid crystal alignment film can not be uniformly rubbed with the cloth due to the irregularity caused by the electrode or the switching active element for driving the liquid crystal on the corresponding substrate, There was no case.

Therefore, as another method of aligning the liquid crystal alignment film without rubbing, a photo alignment method is actively studied.

There are various methods for the photo alignment, but anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is oriented in accordance with the anisotropy.

As a main photoalignment method, a photoalignment method of a decomposition type is known. In this method, polarized ultraviolet rays are irradiated to a polyimide film, for example, and anisotropic decomposition is generated by utilizing polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide remaining ungraded (see, for example, Patent Document 1).

As another optical alignment method, a photo-crosslinking type or a photoisomerization type optical alignment method is also known. In the photo-crosslinking-type photo alignment method, for example, polyvinyl cinnamate is used and a dimerization reaction (cross-linking reaction) is generated in a double bond portion of two side chains parallel to polarized light by irradiation with polarized ultraviolet light . Then, the liquid crystal is oriented in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In the photo-isomerization photo-alignment method, when a side-chain polymer having azobenzene as a side chain is used, polarized ultraviolet light is irradiated to generate an isomerization reaction in the azobenzene moiety of a side chain parallel to the polarized light, (For example, refer to Non-Patent Document 2).

As in the example described above, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, rubbing is not required and there is no risk of generation of oscillation or static electricity. The substrate of the liquid crystal display element having irregularities on the surface can be subjected to an alignment treatment, and this 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 has a great advantage because it does not require the rubbing process itself as compared with the conventionally used rubbing method as an alignment processing method of a liquid crystal display element. Compared to the rubbing method in which the alignment control ability is almost constant by rubbing, in the photo alignment method, the alignment control ability can be controlled by changing the irradiation amount of the polarized light. However, in the photo alignment method, when it is desired to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of polarized light may be required to be irradiated, and stable alignment of the liquid crystal may not be realized.

For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output power of 500 W for 60 minutes, and a large amount of ultraviolet irradiation It becomes necessary. Further, even in the case of the dimerization or optical isomerization type photo-alignment method, a large amount of ultraviolet light irradiation in a number of J (line) to several tens J may be required. Further, in the case of the photo-crosslinking type or photo-isomerization type optical alignment method, the thermal stability and optical stability of alignment of the liquid crystal are deteriorated, so that there is a fear that alignment failure or display burn-in may occur when the liquid crystal display element is used. Particularly, in a liquid crystal display device of a transversely-field-driven type, liquid crystal molecules are switched in a plane, alignment deviation of liquid crystals after liquid crystal driving is likely to occur, and display burn-in resulting from AC driving becomes a big problem.

Therefore, in the photo alignment method, it is required to achieve high efficiency of alignment treatment and realization of stable liquid crystal alignment, and a liquid crystal alignment film and a liquid crystal alignment agent capable of highly imparting a high alignment control ability to the liquid crystal alignment film are required.

The present invention relates to a novel polymer composition which gives a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type, which has high controllability of orientation with high efficiency and is excellent in burning property, a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type, And to provide a substrate having the alignment film and a transverse electric field driven liquid crystal display element having the substrate. It is also an object of the present invention to provide a liquid crystal alignment film having an improved voltage holding ratio even by low-temperature firing and a method of manufacturing a substrate having the liquid crystal alignment film.

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found the following inventions.

≪ 1 > (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range,

(B) polyurea,

And

(C) an organic solvent

, Particularly a polymer composition for producing a liquid crystal alignment film for a transverse electric field driven liquid crystal display device.

≪ 2 > The photosensitive resin composition according to < 1 >, wherein the component (A) has a photosensitive side chain which causes photo crosslinking, photoisomerization, or light free transition.

<3> It is preferable that the polyurea of the component (B) is obtained by subjecting the diisocyanate component and the diamine component to a polymerization reaction in the above item <1> or <2>.

&Lt; 4 &gt; The polyurethane resin composition according to &lt; 4 &gt;, wherein the polyurea of component (B) comprises a diisocyanate component, a carboxylic acid derivative having two or more carboxylic acid moieties and / or an anhydride thereof, Which is obtained by polymerization reaction.

<5> In the above-mentioned <3> or <4>, it is preferable that the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (1) to (6)

[Chemical Formula 1]

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH- O-, or -O-CO-CH = CH-;

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;

X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;

Cou is 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 , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof; , When X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring and the number of P is 2 or more , The P groups may be the same or different and when Q is 2 or more, the Q groups may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

<7> The photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (7) to (10)

Wherein A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above;

l represents an integer of 1 to 12;

m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;

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

(2)

<8> The photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (11) to (13)

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

(3)

<9> In any one of <1> to <5>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m ₁ and m 2 have the same definitions as above.

[Chemical Formula 4]

<10> In any one of the above items <1> to <5>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (16) or (17).

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

[Chemical Formula 5]

<11> In any one of the above items <1> to <5>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q ₁ , q 2, m ₁ , and m 2 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 .

[Chemical Formula 6]

<12> The photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) has a photosensitive side chain represented by the following formula (20)

Wherein A, Y ₁ , X, l and m have the same definitions as above.

(7)

<13> The liquid crystal display panel according to any one of <1> to <12>, wherein the component (A) has at least one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31) .

Wherein A and B have the same definitions as above;

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, 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 represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

q1 and q2 are one in one and zero in the other;

m represents an integer of 0 to 2, provided that the sum of all m in the formulas (23) to (24) is 2 or more, and the formulas (25) to (26) , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, , Or an alkyloxy group;

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

[Chemical Formula 8]

[14] [I] A process for forming a coating film by applying any one of the above-mentioned compositions <1> to <13> onto a substrate having a conductive film for driving a transverse electric field;

[II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

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

To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted.

<15> A substrate having a liquid crystal alignment film for a liquid crystal display device of the lateral electric field type manufactured by the method of <14>.

<16> A transverse electric field driving type liquid crystal display element having the substrate of <15> above.

<17> preparing a substrate (first substrate) of <15>;

[I '] on the second substrate

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,

(B) polyurea, and

(C) an organic solvent

To form a coating film;

 Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; and

 Heating the coating film obtained in [III '] [II'];

To obtain a liquid crystal alignment film having the alignment control ability, and obtaining a second substrate having the liquid crystal alignment film; and

[IV] a step of arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates are opposed to each other through the liquid crystal to obtain a liquid crystal display element;

To obtain a transverse electric field driven liquid crystal display element.

<18> A transverse electric field driving type liquid crystal display device manufactured by the above-mentioned <17>.

On the other hand, the following inventions have been found out.

&Lt; P1 &gt; [I] (A) A photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range,

(B) polyurea,

And

(C) an organic solvent

On a substrate having a conductive film for driving a transverse electric field to form a coating film;

[II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

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

To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted.

<P2> In the above item <P1>, it is preferable that the component (A) has a photosensitive side chain which causes photo-crosslinking, optical isomerization or light-free transition.

<P3> In the above-mentioned <P1> or <P2>, it is preferable that the polyurea of the component (B) is obtained by polymerizing a diisocyanate component and a diamine component.

<P4> In <P3>, it is preferable that the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate.

<P5> It is preferable that the component (A) in any one of <P1> to <P4> has any one of the photosensitive side chains selected from the group consisting of the following formulas (1) to (6).

[Chemical Formula 9]

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH- O-, or -O-CO-CH = CH-;

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;

X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH-;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonding to them are each independently -NO ₂ -CN, -CH═C (CN) ₂ , -CH═CH- Group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

P and Q each independently represent 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, to be. Provided that when X is -CH = CH-CO-O- or -O-CO-CH = CH-, then P or Q on the side to which -CH = CH- is an aromatic ring;

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

<P6> In any one of <P1> to <P4>, it is preferable that the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

Wherein A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above;

l represents an integer of 1 to 12;

m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;

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

[Chemical formula 10]

<P7> It is preferable that the component (A) in any one of <P1> to <P4> has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).

In the formula, A, X, l, m, m2 and R have the same definitions as above.

(11)

<P8> In any one of <P1> to <P4>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , X, l, m 1 and m 2 have the same definitions as above.

[Chemical Formula 12]

<P9> In any one of <P1> to <P4>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (16) or (17).

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

[Chemical Formula 13]

<P10> In any one of <P1> to <P4>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q ₁ , q 2, m ₁ , and m 2 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 .

[Chemical Formula 14]

<P11> In any one of <P1> to <P4>, it is preferable that the component (A) has a photosensitive side chain represented by the following formula (20).

Wherein A, Y ₁ , X, l and m have the same definitions as above.

[Chemical Formula 15]

<P12> It is preferable that in any one of <P1> to <P11>, the component (A) has any one kind of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31) .

Wherein A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, 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 represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

(25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), m represents an integer of 1 to 12, and m represents an integer of 0 to 2, , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, , Or an alkyloxy group;

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

[Chemical Formula 16]

<P13> A substrate having a liquid crystal alignment film for a liquid crystal display device of a transverse electric field driving type manufactured by any one of <P1> to <P12>.

<P14> A transverse electric field driving type liquid crystal display element having the substrate of the above <P13>.

<P15> preparing a substrate (first substrate) of the above <P13>;

[I '] on the second substrate

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,

(B) polyurea, and

(C) an organic solvent

To form a coating film;

Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; and

Heating the coating film obtained in [III '] [II'];

To obtain a liquid crystal alignment film having the alignment control ability, and obtaining a second substrate having the liquid crystal alignment film; and

The first and second substrates are opposed to each other so that the liquid crystal alignment layers of the first and second substrates are opposed to each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;

To obtain a transverse electric field driven liquid crystal display element.

&Lt; P16 &gt; A transverse electric field driven liquid crystal display device manufactured by the above &lt; P15 &gt;.

(A) A photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,

(B) polyurea, and

(C) an organic solvent

A liquid crystal alignment layer for liquid crystal display element, and a liquid crystal alignment layer for liquid crystal alignment layer.

<P18> In the above <P17>, it is preferable that the polyurea of the component (B) is obtained by polymerizing a diisocyanate component and a diamine component.

<P19> In the above <P18>, it is preferable that the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type, which has high controllability of alignment with high efficiency and excellent in burning property, and a transverse electric field driven liquid crystal display element having the substrate.

Since the transverse electric field driven liquid crystal display device manufactured by the method of the present invention has the alignment control ability with high efficiency, the display characteristics are not hindered even when the liquid crystal display device is continuously driven for a long time.

Further, in the present invention, by including the polyurea as the component (B) in the polymer composition, it is possible to provide a transverse electric field drive type liquid crystal device having excellent voltage holding ratio even by low temperature firing and a liquid crystal alignment film for the device. That is, according to the present invention, even when residual solvent (N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone which is a high boiling point solvent) remains in low temperature firing, The retention ratio can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram illustrating one example of a process for schematically describing anisotropy introduction treatment in the process for producing a liquid crystal alignment film used in the present invention. In the case where a crosslinkable organic group is used as a photosensitive side chain, Fig.
Fig. 2 is an example of a schematic illustration of an introduction process of anisotropy in the process for producing a liquid crystal alignment film used in the present invention. In the case where a cross-linkable organic group is used as a photosensitive side chain and the introduced anisotropy is large Fig.
Fig. 3 is an example of a schematic illustration of the process of introducing anisotropy in the process for producing a liquid crystal alignment film used in the present invention. In Fig. 3, an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, And the anisotropy is small.
Fig. 4 is an example of a schematic illustration of an introduction process of anisotropy in the process for producing a liquid crystal alignment film used in the present invention, in which an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, And the anisotropy is large.

As a result of intensive studies, the present inventors have obtained the following findings and have completed the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter, simply referred to as a side chain type polymer), and a coating film obtained using the above polymer composition , And a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. This coating film is subjected to orientation treatment by polarized irradiation without rubbing treatment. After the polarized light irradiation, the side chain type polymer film is heated to form a coating film (hereinafter also referred to as a liquid crystal alignment film) imparted with orientation control ability. At this time, the small anisotropy expressed by the polarized light irradiation becomes a driving force, and the liquid crystal side-chain type polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment as a liquid crystal alignment film can be realized, and a liquid crystal alignment film having high alignment control capability can be obtained.

In the polymer composition of the present invention, polyurea is used as the component (B) in addition to the side-chain polymer as the component (A) and the organic solvent as the component (C). Thus, it was unexpected that the voltage retention ratio of the liquid crystal alignment film was significantly improved even at low temperature baking. Particularly, the use of a specific polyurea has increased the effect. The inventors of the present invention have considered that these phenomena are due to addition of the component (B), and that the components (A) and (B) exhibit mutual action and dramatically increase the desired effect , These include the inventor's view of the mechanism of the present invention and are not meant to be limiting of the present invention).

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

&Lt; Manufacturing Method of Substrate Having Liquid Crystal Alignment Film &gt; &lt; Production Method of Liquid Crystal Display Element &

A method of manufacturing a substrate having a liquid crystal alignment film of the present invention includes:

[I] A photosensitive resin composition comprising: (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range;

(B) polyurea, and

(C) an organic solvent

On a substrate having a conductive film for driving a transverse electric field to form a coating film;

[II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

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

Respectively.

By this process, it is possible to obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which alignment control ability is imparted, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a transverse electric field driving type liquid crystal display element can be obtained.

The second substrate may be a substrate which does not have a conductive film for driving a transversal electric field, instead of the substrate having a conductive film for driving a transversal electric field, but the steps [I] to [III] A second substrate having a liquid crystal alignment film imparted with orientation control ability can be obtained by using the process [I '] to [III'] in the present invention for convenience) have.

A method of manufacturing a transverse electric field driven liquid crystal display element,

[IV] a step of arranging the first and second substrates obtained above so as to oppose each other with the liquid crystal alignment layer facing the liquid crystal alignment layers of the first and second substrates to obtain a liquid crystal display element;

Respectively. As a result, a transverse electric field driven liquid crystal display element can be obtained.

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

&Lt; Process [I] &gt;

In the step [I], a polymeric composition containing a photosensitive side chain type polymer, liquid crystal, polyurea and an organic solvent which exhibits liquid crystallinity in a predetermined temperature range is applied on a substrate having a conductive film for transverse electric field driving, .

<Substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable that a substrate having high transparency is used. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.

Also, considering the application to a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used.

&Lt; Conductive film for driving a transverse electric field &

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

When the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) may be used as the conductive film, but the present invention is not limited thereto.

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

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

&Lt; Polymer composition &gt;

The polymer composition is applied onto a substrate having a conductive film for driving a transverse electric field, in particular, on a conductive film.

The polymer composition used in the production method of the present invention comprises (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a polyurea, and (C) an organic solvent .

<< (A) Side chain type polymer >>

The component (A) is a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range.

The side chain type polymer (A) preferably reacts with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

The side chain type polymer (A) preferably has a photosensitive side chain reacting with light in a wavelength range of 250 nm to 400 nm.

The side chain type polymer (A) preferably has a mesogen group in order to exhibit liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

The side chain type polymer (A) has a side chain having photosensitivity to the main chain, and can react with light to cause a crosslinking reaction, an isomerization reaction, or a light free potential. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction or a light-free potential in response to light is preferable, and it is more preferable to cause a crosslinking reaction. In this case, even when 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 capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the structure has a mesogen component which is rigid in the side chain structure. In this case, when the side chain type polymer is used as the liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

The structure of the polymer is, for example, a polymer having a main chain and a side chain bonded to the main chain, and the side chain thereof has a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, , A structure having a photosensitive group bonded to the tip and capable of reacting with light to perform a crosslinking reaction or an isomerization reaction, or a structure having a main chain and side chains bonded thereto, the side chains of which may be a mesogen component, And a phenylbenzoate group which carries out the reaction.

More specific examples of the structure of the photosensitive side chain type polymer capable of manifesting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene , A main chain composed of at least one kind selected from the group consisting of a radical polymerizing group such as vinyl, maleimide and norbornene, and a siloxane, and side chains comprising at least one of the following formulas (1) to (6) Structure.

[Chemical Formula 17]

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH- O-, or -O-CO-CH = CH-;

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;

X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;

Cou is 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 , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof; , When X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring and the number of P is 2 or more , The P groups may be the same or different and when Q is 2 or more, the Q groups may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

The side chain may be any one of the photosensitive side chains selected from the group consisting of the following formulas (7) to (10).

Wherein A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above;

l represents an integer of 1 to 12;

m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;

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

[Chemical Formula 18]

The side chain may be any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).

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

[Chemical Formula 19]

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m ₁ and m 2 have the same definitions as above.

[Chemical Formula 20]

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).

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

[Chemical Formula 21]

The side chain may be a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definitions as above.

R ₁ 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 .

[Chemical Formula 22]

The side chain may be a photosensitive side chain represented by the following formula (20).

Wherein A, Y ₁ , X, l and m have the same definitions as above.

(23)

The side chain type polymer (A) preferably has any one kind of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

Wherein A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, 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 represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

m represents an integer of 0 to 2, provided that the sum of all m in the formulas (23) to (24) is 2 or more, and the formulas (25) to (26) , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, , Or an alkyloxy group;

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

&Lt; EMI ID =

<< Preparation of Photosensitive Side Chain Polymer >>

The photosensitive side chain type polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having a photosensitive side chain and a liquid crystal side chain monomer.

 [Photoreactive side chain monomer]

The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.

As the photoreactive group of the side chain, the following structures and derivatives thereof are preferable.

(25)

More specific examples of the photoreactive side chain monomer include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide, norbornene , A polymerizable group composed of at least one kind selected from the group consisting of a radical polymerizable group and a siloxane of the formula (1), and a photosensitive side chain comprising at least one of the above-mentioned formulas (1) to (6) (14) or (15), a photosensitive side chain composed of at least one of the above-mentioned formulas (7) to (10), a photosensitive side chain comprising at least one of the formulas (11) The photosensitive side chain represented by the formula (16) or (17), the photosensitive side chain represented by the formula (18) or (19) and the photosensitive side chain represented by the formula (20).

The present invention provides novel compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and / or liquid crystalline side chain monomers.

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 represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.

(26)

(27)

The present invention also provides novel compounds (12) to (17) represented by the following formulas (12) to (17) as photoreactive and / or liquid crystalline side chain monomers.

R represents a hydrogen atom or a methyl group, S represents an alkylene group of 2 to 10 carbon atoms, v represents 1 or 2, and u represents 0 or 1, provided that in formula (12) (12), S represents an alkylene group having 2 to 9 carbon atoms, and in the formula (14), S represents an alkylene group having 1 to 10 carbon atoms.

(28)

[Liquid crystalline side chain monomer]

The liquid crystal side chain monomer is a monomer from which the polymer originating from the monomer can express liquid crystallinity and the polymer can form a mesogen group at a side chain site.

As a mesogen group in the side chain, biphenyl or phenylbenzoate alone may be a mesogen structure, and benzoic acid or the like may be a mesogen structure by hydrogen bonding between side chains. The mesogen group of the side chain is preferably the following structure.

[Chemical Formula 29]

More specific examples of the liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide, norbornene , A polymerizable group composed of at least one kind selected from the group consisting of a radical polymerizable group and a siloxane of the formula (21), and a side chain comprising at least one of the above-mentioned formulas (21) to (31).

The side chain type polymer (A) can be obtained by a polymerization reaction of a photoreactive side chain monomer that exhibits the liquid crystallinity described above. In addition, copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that do not exhibit liquid crystallinity and copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity can be obtained. Further, it can be copolymerized with other monomers within a range that does not inhibit the liquid crystalline property.

Other monomers include, for example, industrially available monomers capable of radical polymerization.

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

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2- ethoxy ethyl acrylate , 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- methoxyethyl methacrylate, 2-methoxybutyl methacrylate, 2- Methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. Cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and (3-ethyl-3-oxetanyl) methyl (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.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

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 method which is industrially handled can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoint of easy control of reaction and the like.

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

The radical thermal polymerization initiator is a compound which generates a radical by heating at a decomposition temperature or higher. Examples of such a radical thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as acetyl peroxide and benzoyl peroxide, and hydroperoxides, (Di-tert-butyl peroxide, dicumyl peroxide, and di-lauroyl peroxide), peroxyketal (dibutyl peroxide, etc.) (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester and the like), and alkyl peroxides (Such as potassium persulfate, sodium persulfate and ammonium persulfate), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.) . These radical thermal polymerization initiators may be used singly or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylzanthone, 2,4- Ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin Benzoanthrone, 2-methyl-1- [4- (methylthio) phenoxy] -2-methylpentanoic acid, 2,2-diethoxyacetophenone, 2,2- Phenyl] -2-morpholinopropane-1-one, ethyl 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (T-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis ( (Trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - 2,6-di (Trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p- dimethylaminostyryl) benzothiazole, 2- mercaptobenzothiazole, 2, 3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' bis (2,4-dibromophenyl) -4,4 ', 5,5'- 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- Methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone , Bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- , 4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'- Di (t-butylperoxycarbonyl) benzoate, 3,4'-di (methoxycarbonyl) -4,3'-di Phenol, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol- ) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl- Thiazol -2 (3H) - and the like ylidene) -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 manifesting liquid crystallinity is not particularly limited as long as the resulting polymer dissolves. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, 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, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene, diethylene glycol, propylene Carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyl acetate Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, Propyl propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy- Propane amide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Further, even a solvent which does not dissolve the produced polymer may be mixed with the above-described organic solvent within the range in which the produced polymer is not precipitated.

Further, in the radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited. Therefore, it is preferable to use an organic solvent which has been degassed to the extent possible.

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

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the resulting polymer is small, and if it is small, the molecular weight of the obtained polymer is large. Mol% to 10 mol%. In the polymerization, various monomer components, solvents, initiators, etc. may be added.

 [Recovery of Polymer]

In the case of recovering the resulting polymer from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above-described reaction, the reaction solution may be put into a poor solvent to precipitate the polymer . Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or under normal pressure. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the side chain type polymer (A) of the present invention is preferably such that the weight average molecular weight measured by GPC (Gel Permeation Chromatography) Preferably from 2,000 to 1,000,000, and more preferably from 5,000 to 100,000.

[Preparation of polymer composition]

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

In the polymer composition of the present embodiment, the above-mentioned resin component may be all of the photosensitive side chain type polymers capable of exhibiting the above-described liquid crystallinity, but in addition to the above, Of other polymer may be mixed. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such another polymer includes, for example, a polymer which is composed of poly (meth) acrylate, polyamic acid, polyimide or the like, and is not a photosensitive side chain type polymer capable of exhibiting liquid crystallinity.

<< Component (B) >>

The polymer composition used in the present invention has polyurea as component (B). Preferably, the component (B) is a polymer obtained by polymerizing a diisocyanate component and a diamine component.

<<< Diisocyanate Ingredients >>>

As the diisocyanate component which is a raw material of the component (B), for example, aromatic diisocyanate, aliphatic diisocyanate and the like can be given. Preferred diisocyanate components are aromatic diisocyanates, aliphatic diisocyanates.

Here, the aromatic diisocyanate means that the group R of the diisocyanate structure (O = C = N-R-N = C = O) includes a structure containing an aromatic ring. Further, the aliphatic diisocyanate means that the group R of the isocyanate structure has a cyclic or acyclic aliphatic structure.

Specific examples of the aromatic diisocyanate include o-phenylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, toluene diisocyanates (for example, 2,4-diisocyanate tolylene), 1,4 Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 2,2'-bis (phenyl 4-diisocyanate) propane, 4,4'-diisocyanate diphenylmethane, 4 , 4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, and 2,2'-diisocyanate benzophenone. . The aromatic diisocyanate is preferably tolylene 2,4-diisocyanate. Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, and the like. The aliphatic diisocyanate is preferably isophorone diisocyanate. Among them, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferable from the viewpoints of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferred from the viewpoints of availability, polymerization reactivity and voltage holding ratio Do.

<<< Diamine Ingredients >>>

Examples of the diamine component which is a raw material of the component (B) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines and urea bond-containing diamines.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'- Dimethyldicyclohexylamine, isophoronediamine, and the like.

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, Diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino- 2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene , 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'- Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis Bis (4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) benzene, Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- Bis (4-aminophenyl) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, 4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, (4-aminophenyl) ethane, 1,3-bis (4-amyl Bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis Bis (4-aminophenyl) decane, 1,1-bis (4-aminophenyl) decane, Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, , Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di -Dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane- Bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] Heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.

Examples of the aromatic-aliphatic diamine include diamines represented by the following formula [DAM].

(30)

(Wherein,

Ar represents a benzene ring or a naphthalene ring,

R ₁ is an alkylene group having 1 to 5 carbon atoms, and

R ₂ is a hydrogen atom or a methyl group.)

Specific examples of the aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, Amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (4-aminobutyl) aniline, 3- (4-aminobutyl) aniline, 4- Aniline, 4- (5-methylaminobutyl) aniline, 4- (5-aminopentyl) aniline, 4- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- Amine and the like.

Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, Diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole Sol and the like.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6- 2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino- Diamino-5-methylnonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

Examples of urea bond-containing diamines include N, N'-bis (4-aminophenethyl) urea and the like.

In the component (B), the diamine component to be polymerized with the diisocyanate component may contain a diamine having a side chain for vertical alignment within the range not hindering the effect of the present invention.

The diamine component in the component (B) may contain the following diamines.

(31)

(Wherein m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, h is an integer of 1 to 3, and j is an integer of 0 to 3.)

By introducing these diamines, it is advantageous to further improve the voltage holding ratio (also referred to as VHR) of a liquid crystal display element using a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention. These diamines are preferred from the viewpoint of excellent accumulation charge reduction effect of such liquid crystal display elements.

In addition, as the diamine component in the component (B), a diaminosiloxane and the like represented by the following formula may be mentioned.

(32)

(Wherein m is an integer of 1 to 10)

The diamine component in the component (B) may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when used as a liquid crystal alignment film. The mixing ratio at that time is not limited.

The molecular weight of the polyurea as the component (B) is preferably from 1 to 100, more preferably from 1 to 10, more preferably from 1 to 10, and more preferably from 1 to 10. The molecular weight of the polyurea as the component (B) Is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

A known synthetic method can be used to obtain the polymer of the component (B) by the polymerization reaction of the diisocyanate component and the diamine component of each raw material. Generally, the diisocyanate component and the diamine component are reacted in an organic solvent. The reaction between the diisocyanate component and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

The organic solvent used for the reaction of the diisocyanate component and the diamine component is not particularly limited as long as the resulting polyurea dissolves.

Specific examples thereof are given below.

Examples of the organic solvent usable herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, But are not limited to, methyl ethyl 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 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, di Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, Amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate , Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylacetamide, propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, Dimethyl propanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyurea, the polyurea may be mixed with the solvent in the range where the produced polyurea does not precipitate.

In addition, since moisture in the organic solvent causes the polymerization reaction to be inhibited, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

When the diisocyanate component and the diamine component are reacted in an organic solvent, the diamine component may be dispersed or dissolved in an organic solvent to stir the solution. The diisocyanate component may be added or dispersed or dissolved in an organic solvent. Alternatively, A method of adding a diamine component to a solution in which an isocyanate component is dispersed or dissolved in an organic solvent, and a method of alternately adding a diisocyanate component and a diamine component. Any of these methods may be used. When the diisocyanate component or the diamine component is composed of a plurality of compounds, they may be reacted in advance in a mixed state, or they may be sequentially reacted individually, or a low molecular weight substance reacted individually may be mixed and reacted to form a high molecular weight substance .

The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, but is preferably in the range of -5 DEG C to 100 DEG C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to perform uniform stirring. The total concentration of the isocyanate component and the diamine component in the reaction solution is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyurea, the ratio of the total number of moles of the diisocyanate component to the total number of moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyurea.

When the produced polyurea is recovered from the reaction solution of polyurea, the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by pouring into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, by repeating the operation of redissolving the polymer recovered and recovered in the organic solvent and re-precipitating and recovering the polymer solution 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

Such a polyurea is, for example, a polymer having a repeating unit represented by the following formula [1].

(33)

(In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different. )

In the above formula [1], A ₁ and A ₂ may each be a polymer having the same repeating unit, or may be a polymer having repeating units having a structure in which plural kinds of A ₁ or A ₂ are different from each other.

In the above formula [1], A ₁ is a group derived from a diisocyanate component as a raw material. A ₂ is a group derived from a diamine component as a raw material.

According to a preferred embodiment of the present invention, A ₁ is preferably a group derived from the preferred diisocyanate component exemplified above. As A ₂ , a group derived from the preferred diamine component exemplified above is preferable.

The polyurea to be used in the present invention is preferably obtained from a diamine and a diisocyanate, but it is preferable to use a tetracarboxylic acid dianhydride, a tetracarboxylic acid derivative, a tricarboxylic acid derivative, a dicarboxylic acid derivative and the like in combination with a diisocyanate May be obtained by using a small amount of a compound having two or more reaction sites with the amino group of the same diamine component. Such an embodiment is included in the scope of the present invention as long as the effect of the present invention is not impaired.

Here, the compound having two or more reaction sites with the amino group of the diamine component preferably means a carboxylic acid derivative having two or more carboxylic acid moieties capable of generating a carboxyl group capable of reacting with an amine group and / or an anhydride thereof For example, a tetracarboxylic acid derivative and / or an anhydride thereof, a tricarboxylic acid derivative and / or an anhydride thereof, a dicarboxylic acid derivative and / or an anhydride thereof. Such a carboxylic acid derivative having two or more carboxylic acid moieties and / or anhydrides thereof includes those in which a carboxylic acid moiety forms a carboxylic acid salt, a carboxylic acid anhydride, a carboxylic acid ester, or the like , For example, tetracarboxylic acid dianhydride, tetracarboxylic acid dialkyl ester, tetracarboxylic acid dialkyl ester dichloride, and the like. Here, when a compound having two or more reaction sites with the amino group of the diamine component is used, the ratio of the compound to the diisocyanate is preferably from 99: 1 to 0: 100 in terms of the molar ratio.

The amount of the "compound having two or more reaction sites with the amino group of the diamine component" is preferably such that the ratio of the total number of moles of the compound having two or more reaction points with the amino group of the diamine component to the number of moles of the diisocyanate , An amount of about 0.8 to 1.2, and preferably an amount of about 0.9 to 1.1. As with the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polymer.

Examples of the tetracarboxylic acid derivative and / or anhydride thereof include the following tetracarboxylic acid dianhydrides.

Examples of the tetracarboxylic acid dianhydride having an alicyclic or aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,4,5-pentane Tetracarboxylic acid dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride , 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tet Lacarboxylic acid dianhydride, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-2 anhydride, hexacyclo [6.6.0.1 ^{2 , 7.0, 3,6} .1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11,12-2 anhydride, 3,4- Carboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride and the like.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid Acid anhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3 ', 4 (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, bis A tetracarboxylic acid dianhydride, a tetracarboxylic acid dianhydride, a 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and the like.

The above-mentioned tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties of the liquid crystal alignment film to be formed, such as liquid crystal aligning property, voltage holding property, and accumulated charge.

As the tetracarboxylic acid component which is a raw material of the component (B), a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl diester dichloride may be used. Further, when the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester which is a polyimide precursor. The tetracarboxylic acid dialkyl ester that can be used is not particularly limited and includes, for example, aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.

Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, 1,2,4,5-pentanetetracarboxylic acid dialkyl ester, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, Ester, 3 , 3 ', 4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene -1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-di alkyl esters, cycloalkyl hexahydro ^{[6.6.0.1 2,7 .0 3,6 .1 9,14 .0} 10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11, 12-dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, and the like.

Specific examples of the aromatic tetracarboxylic acid dialkyl ester include dialkyl pyromellitic acid ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyl Tetracarboxylic acid dialkyl ester, 2,3,3 ', 4'-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ' Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5, Naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like.

Examples of the tetracarboxylic acid diester dichloride include diester dichloride obtained by converting the carboxyl group of the tetracarboxylic acid dialkyl ester into a chlorocarbonyl group by a known method.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid , 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid , 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclo Hexane dicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane- Dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-dicarboxylic acid, However, only tandicarboxylic acid, 4,8-di Small-l, 3 Ah, and the like adamantan-dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,3-adamantane acetic acid 2, camphor acid.

Examples of the aromatic dicarboxylic acid include aliphatic dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, , Tetramethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, Dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylene dicarboxylic acid , 4,4'-terphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid Dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4, 4'-diphenyl ether dicarboxylic acid, , 4'-stilbenedicarboxylic acid, 4,4'-tolandicarboxylic acid, 4,4'-carbonyl 2-benzoic acid, 4,4'- Dicarboxylic acid, dicarboxylic acid, 4,4'-diphenylsulfide dicarboxylic acid, p-phenylene diacetic acid, 3,3'-p-phenylenedipropionic acid, 4,4 '- [(4,4' - (oxydi-p-phenylene)] diphopropionic acid, 4,4 ' - dicarboxylic acids such as [4,4 '- (oxydip-phenylene)] 2-butyric acid, (isopropylidenediphenyldiphenyldioxy) 2-butyric acid and bis (p-carboxyphenyl) .

Examples of the dicarboxylic acid having a heterocyclic ring include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2 Phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole- An aliphatic dicarboxylic acid such as 2,3-pyridine dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4- Acid, 3,5-pyridine dicarboxylic acid, and the like.

The various dicarboxylic acids may be acid dihalides or anhydrous structures. These dicarboxylic acids are preferably dicarboxylic acids capable of imparting a linear polyamide, which is preferable in maintaining the orientation properties of the liquid crystal molecules. Among them, terephthalic acid, isoterephthalic acid, 1,4-cyclohexane dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-di Diphenyl propane dicarboxylic acid, 4,4'-diphenyl hexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propane dicarboxylic acid, 4,4'-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid, or an acid dihalide, etc. These compounds are preferably used in the presence of an isomer The dicarboxylic acids to be used in the present invention are not limited to the above-mentioned exemplified compounds.

These tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, tetracarboxylic acid diester dichlorides, dicarboxylic acids and dicarboxylic acid halides are used as liquid crystal aligning films for liquid crystal alignment properties, voltage holding characteristics, One kind or two or more kinds can be used in combination.

Tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride, tetracarboxylic dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dichloride, dicarboxylic acid or dicarboxylic acid halide and the like are allowed to coexist with the isocyanate compound to react with the diamine component, In order to obtain a polymer as a component, a known synthetic method can be used. In general, the tetracarboxylic acid dianhydride or its derivative and the diamine component are reacted in an organic solvent. The reaction of the tetracarboxylic acid dianhydride with the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and does not produce any by-products.

According to a preferred embodiment of the present invention, in the polymer composition according to the present invention, the blending ratio (by mass) of the above-mentioned components (A) and (B) (A) is from 0.01 to 0.99, more preferably from 0.1 to 0.9, and still more preferably from 0.2 to 0.5.

<< (C) Organic solvent >>

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent dissolving the resin component. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, But are not limited to, hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol- Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Propylene 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 Methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). Examples thereof include, but are not limited to, a solvent or a compound that improves film thickness uniformity or surface smoothness when the polymer composition is applied, a compound that improves adhesion between the liquid crystal alignment film and the substrate, and the like.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Hexane, n-pentane, n-octane, diethyl ether, n-pentane, n-pentane, n-pentane, But are not limited to, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy- Propane Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, And a solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

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

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic-based surfactant.

More specifically, for example, EFTA (registered trademark) 301, EF303, EF352 (manufactured by Tohchem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seiyam Chemical Co., Ltd.), FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Kagaku), Surflon (registered trademark) ) And the like. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and the like.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, 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- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

In addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film, in order to prevent deterioration of the electric characteristics due to the backlight when the liquid crystal display device is constituted, additives such as phenolplast or epoxy group- . Specific phenoplast-based additives are shown below, but are not limited to these structures.

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Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl 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-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound improving the adhesion with a substrate is used, the amount of the compound used is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition Mass part. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

As an additive, a photosensitizer may be used. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- Substituted aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di- p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thiosantone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- Benzothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- (? -Naphthoylmethylene) -3-methyl-? -Naphthothiazoline, 2- Methyl-beta-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl- beta -naphthothiazoline), oxazoline (2-benzoylmethylene- Zolin, 2- (? -Naphthoylmethylene) -3- 2- (4-biphenoylmethylene) -3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3 Methyl-β-naphthooxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphtho Nitro- aniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroceaphthene), (2 - [(m-hydroxy-p- (2-naphthalene-2-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, Acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolydine, merocoumarin, and the like.

Preferred are aromatic 2-hydroxy ketones (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

The polymer composition may contain, in addition to the above-described ones, a dielectric substance or a conductive substance, or a liquid crystal alignment film, for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, A cross-linking 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 a coating method, a method generally carried out by screen printing, offset printing, flexographic printing, inkjet printing or the like is generally used. Examples of other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spray method, and the like, depending on the purpose.

After the polymer composition is applied onto the substrate having a conductive film for transversal electric field driving, it is heated to 50 to 200 DEG C, preferably 50 to 150 DEG C, by heating means such as a hot plate, a heat circulation type oven or an IR The solvent can be evaporated at &lt; RTI ID = 0.0 &gt; 20 C &lt; / RTI &gt; The drying temperature at this time is preferably lower than the liquid crystal phase temperature of the side chain type polymer.

If the thickness of the coating film is excessively large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. If the thickness of the coating film is excessively thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 nm to 300 nm, 10 nm to 150 nm.

It is also possible to form a step of cooling the substrate on which the coated film is formed to the room temperature after the step [I] and before the subsequent step [II].

&Lt; Process [II] &gt;

In the step [II], the coated film obtained in the step [I] is irradiated with polarized ultraviolet rays. When polarized ultraviolet rays are irradiated to the film surface of the coated film, polarized ultraviolet rays are irradiated to the substrate through a polarizing plate from a certain direction. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm may be selected and used so as to selectively cause photo-crosslinking reaction. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The irradiation dose is the amount of the polarized ultraviolet ray realizing the maximum value of? A (hereinafter also referred to as? A max) which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction in the coating film , More preferably within a range of 1% to 50%, and more preferably within a range of 1% to 50%.

&Lt; Process [III] &gt;

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

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

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

In addition, the liquid crystal display temperature is higher than the glass transition temperature (Tg) at which the side chain type polymer or the surface of the coating film undergoes phase transition from the solid phase to the liquid crystal phase, and isotropic phase transition from the liquid crystal phase to the isotropic phase (isotropic phase) Refers to the temperature below the temperature (Tiso).

By the above process, the production method of the present invention can realize introduction of anisotropy into the coating film with high efficiency. Then, a substrate having a liquid crystal alignment film adhered thereto can be produced with high efficiency.

&Lt; Process [IV] &gt;

[Step IV] is a step of preparing a substrate (first substrate) having a liquid crystal alignment film on a conductive film for driving a transverse electric field obtained in [III] (Second substrate) on which a liquid crystal alignment film having no liquid crystal alignment film is disposed is opposed so that both liquid crystal alignment films are opposed to each other with a liquid crystal interposed therebetween to manufacture a liquid crystal cell by a known method, . It is to be noted that the steps [I '] to [III'] are the same as the steps [I '] to [III'] except that a substrate having no conductive film for transversal field driving is used instead of the substrate having a conductive film for driving a transversal electric field, I] to [III]. Since the difference between the steps [I] to [III] and the steps [I '] to [III'] is only the existence of the conductive film described above, the description of the steps [I '] to [III'] is omitted.

In order to prepare a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, the spacer is scattered on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a substrate of a single chamber is bonded and a liquid crystal is injected under reduced pressure to seal the substrate or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which spacers are dispersed, Can be exemplified. At this time, it is preferable to use a substrate having electrodes of a structure like a comb-like driving electrode for lateral electric field driving on one side of the substrate. The diameter of the spacer at this time is preferably 1 mu m to 30 mu m, more preferably 2 mu m to 10 mu m. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a substrate with a coating film of the present invention, a polarizing ultraviolet ray is irradiated after coating a polymer composition on a substrate to form a coating film. Subsequently, by heating, introduction of high-efficiency anisotropy into the side-chain type polymer membrane is realized, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.

In the coating film used in the present invention, the introduction of highly efficient anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by the self-organization based on the light reaction of side chains and liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group on a side chain type polymer, a coating film is formed on a substrate by using a side chain type polymer, then irradiated with polarized ultraviolet rays, After heating, a liquid crystal display element is manufactured.

Hereinafter, embodiments using side-chain polymers having a structure having a photocrosslinkable group as the photoreactive group will be described as first embodiment, embodiments using the side-chain polymer having a structure having a group causing a photo- Will be referred to as a second embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view for explaining an introduction process of anisotropy in a process for producing a liquid crystal alignment film using a side chain type polymer having a photo-crosslinkable group as a photo-reactive group in the first aspect of the present invention Fig. Fig. 1 (a) is a diagram schematically showing the state of a side-chain type polymer membrane before irradiation with polarized light, Fig. 1 (b) is a diagram schematically showing the state of a side- (c) is a diagram schematically showing the state of the side chain type polymer membrane after heating. In particular, when the introduced anisotropy is small, that is, in the first aspect of the present invention, Is within the range of 1% to 15% of the ultraviolet radiation dose to maximize the exposure dose.

2 schematically illustrates introduction of anisotropy in the process for producing a liquid crystal alignment film using a side chain type polymer having a photo-crosslinkable group as a photo-reactive group in the first aspect of the present invention Fig. Fig. 2 (a) is a diagram schematically showing the state of the side-chain type polymer film before polarization irradiation, Fig. 2 (b) is a diagram schematically showing the state of the side- (c) is a diagram schematically showing the state of the side chain type polymer membrane after heating. Specifically, in the case where the introduced anisotropy is large, that is, in the first embodiment of the present invention, Is within a range of 15% to 70% of the ultraviolet radiation amount for maximizing the ultraviolet radiation dose.

Fig. 3 is a graph showing the relationship between the photo-reactive group and the liquid crystal alignment layer using the side-chain type polymer having a structure having the light-free stress period represented by the above-mentioned formula (18) Fig. 8 is an example diagram schematically illustrating an introduction process of anisotropy in the manufacturing method of the present invention. Fig. 3 (a) is a diagram schematically showing the state of the side-chain polymer film before the polarized light irradiation, Fig. 3 (b) is a diagram schematically showing the state of the side- (c) is a diagram schematically showing the state of the side chain type polymer membrane after heating. Specifically, when the introduced anisotropy is small, that is, in the second embodiment of the present invention, the ultraviolet radiation amount in the step [II] Is within the range of 1% to 70% of the ultraviolet radiation dose for maximizing the irradiation dose.

Fig. 4 is a graph showing the results of evaluation of the method for producing a liquid crystal alignment layer using a side chain type polymer having a structure having a light-free stress period represented by the above-mentioned formula (19) as a photoreactive group in the second aspect of the present invention Fig. 2 is a view showing an example of a process of introducing anisotropy of the present invention. 4A is a diagram schematically showing the state of the side chain type polymer film before the polarized light irradiation, FIG. 4B is a diagram schematically showing the state of the side chain type polymer film after the polarized light irradiation, and FIG. 4 (c) is a diagram schematically showing the state of the side-chain type polymer membrane after heating. Specifically, when the introduced anisotropy is large, that is, in the second embodiment of the present invention, Is within the range of 1% to 70% of the ultraviolet radiation dose for maximizing the irradiation dose.

In the first aspect of the present invention, when the anisotropy is introduced into the coating film and the amount of ultraviolet radiation in the step [II] is within the range of 1% to 15% of the amount of ultraviolet radiation that maximizes the amount of ΔA, The coating film 1 is formed. As shown in Fig. 1 (a), the coating film 1 formed on a substrate has a structure in which the side chains 2 are randomly arranged. The mesogenic component of the side chain 2 and the photosensitive pigment are randomly oriented in accordance with the random arrangement of the side chains 2 of the coating film 1 and the coating film 1 is isotropic.

In the first aspect of the present invention, when the anisotropy is introduced into the coating film and the amount of ultraviolet irradiation in the step [II] is within the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes? A, A coating film (3) is formed on a substrate. As shown in Fig. 2 (a), the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. The mesogen component of the side chain 4 and the photosensitive pigment are randomly oriented in accordance with the random arrangement of the side chains 4 of the coating film 3 and the coating film 2 is isotropic.

In the second mode of the present invention, the process of introducing anisotropy into the coating film is preferably a process for producing a liquid crystal cell using a photo-isomerizable group or a liquid crystal using a side-chain polymer having a structure having a light- When an ultraviolet ray irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet ray irradiation amount which maximizes the? A in the case of using the alignment film, the coating film 5 is first formed on the substrate. As shown in Fig. 3 (a), the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. The mesogenic component of the side chain 6 and the photosensitive airgel are randomly oriented in accordance with the random arrangement of the side chains 6 of the coating film 5 and the side chain type polymer membranes 5 are isotropic.

In the second embodiment of the present invention, when a liquid crystal alignment film using a side chain type polymer having a structure having a light-free stress period represented by the above-described formula (19) is used in anisotropic introduction processing into a coating film When the ultraviolet ray irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet ray irradiation amount which maximizes the? A, the coating film 7 is first formed on the substrate. As shown in Fig. 4 (a), the coating film 7 formed on the substrate has a structure in which the side chains 8 are randomly arranged. The mesogenic component of the side chain 8 and the photosensitive pigment are randomly oriented in accordance with the random arrangement of the side chains 8 of the coating film 7 and the coating film 7 is isotropic.

In the first embodiment, when the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes DELTA A, the isotropic coating film (1) . Then, as shown in Fig. 1 (b), among the side chains 2 arranged in the direction parallel to the polarization direction of the ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group is preferentially photoreaction such as dimerization reaction Cause. As a result, the density of the side chain 2a subjected to the photoreaction slightly increases in the polarization direction of the irradiated ultraviolet ray, and consequently very small anisotropy is imparted to the coating film 1.

In the first embodiment, when the amount of ultraviolet irradiation in the step [II] is within the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes DELTA A, the isotropic coating film (3) . Then, as shown in Fig. 2 (b), among the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet rays, the photosensitive group of the side chain 4a having the photosensitive group is preferentially photoreaction such as dimerization reaction Cause. As a result, the density of the side chain 4a that undergoes the photoreaction becomes higher in the polarization direction of the irradiated ultraviolet ray, and consequently, the coating film 3 is given a small anisotropy.

In the second embodiment, a liquid crystal alignment layer using a photo-isomerizable group or a side-chain polymer having a structure having a light-free stress period represented by the above-mentioned formula (18) Polarized ultraviolet ray is irradiated to the isotropic coating film 5 in the range of 1% to 70% of the ultraviolet ray irradiation amount which maximizes? A. Then, as shown in Fig. 3 (b), among the side chains 6 arranged in the 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 a light- Cause. As a result, the density of the side chain 6a that has undergone the photoreaction slightly increases in the polarization direction of the irradiated ultraviolet ray, and consequently very small anisotropy is imparted to the coating film 5.

In the second embodiment, the coating film using the side-chain type polymer having a structure having the light-free stress period represented by the above-mentioned formula (19) is used so that the amount of ultraviolet irradiation in the step [II] Polarized ultraviolet rays are irradiated to the isotropic coating film 7 in the range of 1% to 70% of the ultraviolet ray irradiation amount to be applied. Then, as shown in Fig. 4 (b), among the side chains 8 arranged in the direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 8a having a photosensitive group preferentially undergoes a photoreaction such as a light- Cause. As a result, the density of the side chain 8a that has undergone the photoreaction becomes higher in the polarization direction of the irradiated ultraviolet ray, and consequently, the coating film 7 is given a small anisotropy.

Next, in the first embodiment, in the case where the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes DELTA A, the coated film 1 after the irradiation with polarized light is heated, Liquid crystal state. Then, as shown in Fig. 1 (c), in the coated film 1, the amount of the crosslinking reaction generated is different between the direction parallel to the polarizing direction of the irradiating ultraviolet ray and the direction perpendicular to the polarizing direction of the irradiating ultraviolet ray. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, the crosslinking reaction site acts as a plasticizer. Therefore, the liquid crystal property in the direction parallel to the polarization direction of the irradiating ultraviolet ray becomes higher than the liquid crystallinity in the parallel direction, and the side chains 2 containing the mesogen component are self-organized in a direction parallel to the polarization direction of the irradiated ultraviolet ray . As a result, the very small anisotropy of the coating film 1 caused by the photo-crosslinking reaction is amplified by the heat, and a greater anisotropy is imparted to the coating film 1.

Likewise, in the first embodiment, in the case where the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes? A, the coated film 3 after the polarized light irradiation is heated, Liquid crystal state. Then, as shown in Fig. 2 (c), in the side-chain polymer film 3, the amount of the cross-linking reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular thereto. Therefore, the side chains 4 containing the mesogen component are self-organizing in the direction parallel to the polarization direction of the irradiating ultraviolet rays, and the side chains 4 are rearranged. As a result, the small anisotropy of the coating film 3 caused by the photo-crosslinking reaction is amplified by the heat, and a greater anisotropy is imparted to the coating film 3.

Likewise, in the second embodiment of the present invention, a coating film using a photo-isomerizable group or a side-chain polymer having a structure represented by the above-described formula (18) having a light- When the irradiation amount is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes DELTA A, the coated film 5 after the irradiation of polarized light is heated to a liquid crystal state. Then, as shown in Fig. 3 (c), in the coating film 5, the amount of the light-free potential reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction. In this case, since the liquid crystal aligning force of the light-free positively charged substance generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet ray is stronger than the liquid crystal aligning force of the side chain before the reaction, it self-aligns in the direction perpendicular to the polarization direction of the irradiated ultraviolet ray, The side chain 6 including the side chain 6 is rearranged. As a result, the very small anisotropy of the coating film 5 caused by the light-free-potential reaction is amplified by the heat and a greater anisotropy is imparted to the coating film 5.

Likewise, in the second embodiment, the coating film using the side-chain type polymer having a structure having the light-free stress period represented by the above-mentioned formula (19) is used so that the ultraviolet irradiation amount in the step [II] The coating film 7 after the irradiation with polarized light is heated to a liquid crystal state when the ultraviolet ray irradiation amount is within the range of 1% to 70% of the maximum irradiation amount. Then, as shown in Fig. 4 (c), in the side-chain polymer film 7, the amount of the light-free potential reaction generated varies between directions parallel to the polarization direction of the irradiated ultraviolet ray and directions perpendicular thereto. Since the anchoring force of the light-free electric potential element 8 (a) is stronger than that of the side chain 8 before the electric potential, when a certain amount or more of the light-free electric potential elements are generated, the organic compound is magnetized in a direction parallel to the polarization direction of the irradiated ultraviolet light, And the side chain 8 containing it is rearranged. As a result, the small anisotropy of the coating film 7 caused by the light-free-potential reaction is amplified by the heat, and a larger anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can introduce anisotropy with high efficiency and can provide a liquid crystal alignment film excellent in orientation control ability by sequentially irradiating the coating film with polarized ultraviolet light and heat treatment.

In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film and the heating temperature in the heating treatment are optimized. Thus, introduction of anisotropy into the coating film, which is highly efficient, can be realized.

The irradiation amount of the polarized ultraviolet ray which is most suitable for introduction of high efficiency anisotropy into the coating film to be used in the present invention is not particularly limited as long as the amount of the polarized ultraviolet ray which optimizes the amount of the photosensitive group to react with the light crosslinking reaction or the optical isomerization reaction, Corresponds to dose. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, a sufficient photoreaction amount can not be obtained when the number of the photosensitive groups in the side chains which are subjected to the photo-crosslinking reaction, the photoisomerization reaction or the light- In that case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, the structure having the photo-crosslinkable group is irradiated with polarized ultraviolet rays, and as a result, when the photosensitive group of the side chain to be crosslinked becomes excessive, the cross-linking reaction between the side chains becomes excessive. In such a case, the obtained film becomes rigid, which may interfere with the progress of self-organization by subsequent heating. In the coating film used in the present invention, the polarizing ultraviolet rays are irradiated to the structure having the light-free electric potential, and as a result, when the photosensitive group of the side chain reacting with the light-free electric potential becomes excessive, the liquid crystallinity of the coating film is excessively lowered. In such a case, the liquid crystallinity of the obtained film is also lowered, which may interfere with the progress of self-organization by the subsequent heating. Further, in the case of irradiating polarized ultraviolet rays to a structure having a light-free prismatic phase, if the irradiation amount of ultraviolet light is excessively large, there is a case where the side-chain type polymer is photodegraded and the progress of self- have.

Therefore, in the coating film used in the present invention, the optimum amount of photo-crosslinking reaction, photoisomerization reaction, or light-free potential reaction of the photosensitive group of the side chain by irradiation with polarized ultraviolet light is preferably such that the photosensitive group of the side chain- Is preferably 0.1 mol% to 40 mol%, and more preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the photoreactive side chain within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and it becomes possible to form anisotropy with high efficiency in the film.

In the coating film used in the method of the present invention, by optimizing the amount of irradiation of polarized ultraviolet rays, the amount of photo-crosslinking reaction, optical isomerization reaction, or optical free-electric potential reaction of the photosensitive group in the side chain of the side- Optimize. In addition to the subsequent heat treatment, introduction of anisotropy into the coating film used in the present invention, which is highly efficient, is realized. In this case, the amount of the polarized ultraviolet ray to be suitably applied can be evaluated on the basis of the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, ultraviolet absorption in a direction parallel to the polarization direction of polarized ultraviolet rays after irradiation with polarized ultraviolet light, and ultraviolet absorption in a perpendicular direction are respectively measured. From the measurement results of ultraviolet absorption, ΔA which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction in the coating film is evaluated. Then, the maximum value? A max of? A realized in the coating film used in the present invention and the irradiation amount of the polarized ultraviolet ray for realizing the maximum value are obtained. In the production method of the present invention, the amount of polarized ultraviolet ray to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of irradiated polarized ultraviolet light that realizes this? A max.

In the production method of the present invention, the amount of irradiated polarized ultraviolet rays to the coating film used in the present invention is preferably within a range of 1% to 70% of the amount of polarized ultraviolet ray realizing DELTA Amax, preferably 1% to 50% And more preferably within the range of &lt; RTI ID = 0.0 &gt; In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray within the range of 1% to 50% of the amount of the polarized ultraviolet ray realizing DELTA Amax is preferably 0.1 mol% to 20 mol% % To the amount of polarized ultraviolet rays subjected to photo-crosslinking reaction.

From the above, in the production method of the present invention, it is preferable to set the above-mentioned suitable heating temperature based on the liquid crystal temperature range of the side chain type polymer in order to realize introduction of high efficiency anisotropy into the coating film. Therefore, for example, in the case where the liquid crystal temperature range of the side chain type polymer used in the present invention is 100 ° C to 200 ° C, it is preferable to set the heating temperature after irradiation with the polarized ultraviolet ray to 90 ° C to 190 ° C. By doing so, a greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the substrate for a transverse electric field driving type liquid crystal display element manufactured by the method of the present invention or the transverse electric field driving type liquid crystal display element having the substrate has excellent reliability and is suitable for a large- Can be used to make.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to the Examples.

Example

The abbreviations used in the examples are as follows.

&Lt; Methacrylate monomer &gt;

(35)

MA1 was synthesized by the synthetic method described in the patent document (WO2011-084546).

MA2 was synthesized by the synthetic method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).

<Diisocyanate Component>

ISO1: tolylene 2,4-diisocyanate

ISO2: Isophorone diisocyanate

&Lt; Diamine component &gt;

Me-4APhA: N-methyl-2- (4-aminophenyl) ethylamine

DA-1MG: bis (4-aminophenoxy) methane

DA-2MG: 1,2-bis (4-aminophenoxy) ethane

DA-3MG: 1,3-bis (4-aminophenoxy) propane

BAPU: 1,3-bis [2- (4-aminophenyl) ethyl] urea

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

3 AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzoic acid amide

DADPA: 4,4'-diaminodiphenylamine

Me-DADPA: 4,4'-diaminodiphenyl (N-methyl) amine

(36)

&Lt; Tetracarboxylic acid dianhydride &gt;

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid 1,2: 3,4 2 anhydride

PMDA: pyromellitic acid dianhydride

TDA: 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

BODA: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride

BDAM: 1,2,4,5-pentanetetracarboxylic acid dianhydride

BDA: 1,2,3,4-butanetetracarboxylic acid dianhydride

(37)

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

<Polymerization Initiator>

AIBN: 2,2'-azobisisobutyronitrile

&Lt; Synthesis Example 1: Methacrylate polymer solution &gt;

After MAI (2.99 g, 9.0 mmol) and MA2 (1.83 g, 6.0 mmol) were dissolved in THF (44.57 g) and deaerated with a diaphragm pump, AIBN (0.12 g, 0.5 mmol) Degassed. Thereafter, the reaction was carried out at 50 DEG C for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (500 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder.

To 4.0 g of the obtained powder was added 36.0 g of NMP and the mixture was stirred at room temperature for 3 hours. To obtain a methacrylate polymer solution (M1) having a solid concentration of 10.0 wt%. At the end of the stirring, the polymer was completely dissolved.

&Lt; Synthesis Example 2: Polyurea &gt;

As a diamine component, 1.50 g of Me-4 APhA was dissolved in 12.77 g of NMP, 1.68 g of ISO1 as a diisocyanate component was added thereto at room temperature, and the mixture was reacted at 60 DEG C for 18 hours to obtain a polyurea (PU- 20 wt% solution was obtained.

&Lt; Synthesis Examples 3 to 10: Polyurea &gt;

The polyurea solutions of Synthesis Examples 3 to 10 were synthesized in the same manner as in Synthesis Example 2 (polyurea) in the composition shown in Table 1.

&Lt; Synthesis Example 11: Polyamic acid &gt;

A solution of polyamic acid (PAA-1) at a concentration of 20 wt% was obtained by reacting 1.88 g of CBDA as a tetracarboxylic acid dianhydride component and 2.98 g of BAPU as a diamine component in 19.4 g of NMP at room temperature for 18 hours. &Lt; / RTI &gt;

Table 1:

&Lt; Synthesis Example 12: Polyurea polyamic acid &gt;

As a diamine component, 1.99 g of DADPA was dissolved in 16.55 g of NMP, 1.55 g of ISO2 as a diisocyanate component was added thereto at room temperature, and after stirring for 1 hour, 0.59 g of PMDA was added as an acid anhydride component And further reacted at room temperature for 6 hours to obtain a solution having a concentration of polyurea-amic acid (PUA-1) of 20 wt%.

&Lt; Synthesis Examples 13 to 21: Polyurea polyamic acid &gt;

The polyurea-amic acid solutions of Synthesis Examples 13 to 21 were synthesized in the same manner as in Synthesis Example 12 of polyurea-amic acid in the composition shown in Table 2.

Table 2:

(Example 1)

3.0 g of the polyurea solution (PU-1) was added to 3.0 g of the methacrylate polymer solution (M1) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 1 hour. 4.0 g of BCS and 5.0 g of NMP were further added to this solution and stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid concentration of 6.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 2 to 9 and Comparative Examples 1 and 2)

The polymer solutions of Examples 2 to 9 were obtained in the same manner as in Example 1, with the compositions shown in Table 3. Also, Comparative Examples 1 and 2 were adjusted in the same manner.

Table 3:

(Example 10)

3.5 g of a polyurea-amic acid solution (PUA-1) was added to 3.0 g of the methacrylate polymer solution (M1) obtained in the methacrylic synthesis example 1, and the mixture was stirred at room temperature for 1 hour. To this solution, 6.7 g of BCS and 3.5 g of NMP were added and stirred at room temperature for 1 hour to obtain a polymer solution (A10) having a solid concentration of 6.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 11 to 19)

The polymer solutions of Examples 11 to 20 were obtained in the same manner as in Example 10, with the compositions shown in Table 4.

Table 4:

[Production of liquid crystal cell]

Using the liquid crystal aligning agent (A1) obtained in Example 1, the liquid crystal cell was produced in the following order. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm and provided with a comb-shaped pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements having a bent central portion. The width of each electrode element in the short direction was 10 占 퐉, and the interval between the electrode elements was 20 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not rectangular, It had a shape resembling the character of the letter. Each pixel is divided into upper and lower portions with the central bent portion as a boundary, and has a first region on the upper side and a second region on the lower side of the bent portion. When the first region and the second region of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first region and the second region are different from each other. In other words, when the alignment treatment direction of a liquid crystal alignment film to be described later is taken as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle of + 15 ° (clockwise) in the first region of the pixel, And the electrode elements were formed so as to form an angle of -15 DEG (clockwise direction). That is, in the first region and the second region of each pixel, the directions of rotation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other .

The liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the prepared electrode-adhered substrate. Subsequently, the substrate was dried with a hot plate at 70 DEG C for 90 seconds to form a liquid crystal alignment film having a thickness of 100 nm. Subsequently, the coated film was irradiated with 5 mJ / cm 2 of 313 nm ultraviolet rays through a polarizing plate, and then heated on a hot plate at 140 캜 for 10 minutes to obtain a substrate with a liquid crystal alignment film attached thereto. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and alignment treatment was carried out. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, the other substrate was bonded so that the orientation direction of the liquid crystal alignment film face was 0 °, and then the sealant was thermally cured to manufacture empty cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into this empty cell by a vacuum injection method and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

The liquid crystal aligning agents (A2 to A19) obtained in Examples 2 to 19 were also prepared in the same manner as in A1.

(Evaluation of voltage holding ratio (VHR)) [

The VHR was evaluated by applying a voltage of 5 V for 60 seconds to the obtained liquid crystal cell at a temperature of 70 캜, measuring the voltage after 1667 ms, and calculating the voltage holding ratio to calculate the voltage holding ratio.

For the measurement of the voltage holding ratio, a voltage holding ratio measuring apparatus VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

The liquid crystal aligning agent (B1) obtained in Comparative Example 1 was used to produce a liquid crystal cell in the same manner as in the case of using the liquid crystal aligning agent (A1) described above, and VHR was evaluated by the same method.

The results are shown in Tables 5 and 6 below.

Table 5:

Table 6:

As shown in Tables 5 and 6, in Examples 1 to 19 according to the present invention, the voltage holding ratio (VHR) was higher than that of Comparative Example 1 in which the component (A) .

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

Claims (18)

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) polyurea, and
(C) an organic solvent
&Lt; / RTI &gt; The method according to claim 1,
(A) has a photosensitive side chain that causes photo-crosslinking, photoisomerization, or light-free transition. 3. The method according to claim 1 or 2,
Wherein the polyurea of component (B) is obtained by polymerizing a diisocyanate component and a diamine component. 3. The method according to claim 1 or 2,
Wherein the polyurea of component (B) is obtained by polymerizing a diisocyanate component, a carboxylic acid derivative having two or more carboxylic acid moieties and / or an anhydride thereof, and a diamine component. The method according to claim 3 or 4,
Wherein the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate. 6. The method according to any one of claims 1 to 5,
(A) is represented by the following formulas (1) to (6)
(Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO -O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
Cou is 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 , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are one in one and zero in the other;
q3 is 0 or 1;
P and Q are each independently a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof; , When X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring and the number of P is 2 or more , The P groups may be the same or different and when Q is 2 or more, the Q groups may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B is also a single bond when T is a single bond;
H and I are each independently selected from divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and combinations thereof.
Wherein the photosensitive side chain is selected from the group consisting of the following.
[Chemical Formula 1]

6. The method according to any one of claims 1 to 5,
(A) is represented by the following formulas (7) to (10)
(Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO -O-, or -O-CO-CH = CH-;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;
n is an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ )
Wherein the photosensitive side chain is selected from the group consisting of the following.
(2)

6. The method according to any one of claims 1 to 5,
(A) is represented by the following formulas (11) to (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-;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
1 represents an integer of 1 to 12; m represents an integer of 0 to 2; and m2 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (wherein R ₀ 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms, or a hydroxyl group or an alkyl group having 1 to 6 carbon atoms Lt; / RTI &gt; alkoxy group)
Wherein the photosensitive side chain is selected from the group consisting of the following.
(3)

6. The method according to any one of claims 1 to 5,
(A) is a compound represented by the following formula (14) or (15)
(Wherein A independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- Or -O-CO-CH = CH-;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
1 represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
&Lt; / RTI &gt;
[Chemical Formula 4]

6. The method according to any one of claims 1 to 5,
(A) is a compound represented by the following formula (16) or (17)
(Wherein A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- CO-CH = CH-;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
1 represents an integer of 1 to 12, and m represents an integer of 0 to 2)
&Lt; / RTI &gt;
[Chemical Formula 5]

6. The method according to any one of claims 1 to 5,
(A) is a compound represented by the following formula (18) or (19)
(Wherein, A, B are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -, or -O-CO-CH = CH-;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are one in one and zero in the other;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms )
&Lt; / RTI &gt;
[Chemical Formula 6]

6. The method according to any one of claims 1 to 5,
(A) is a compound represented by the following formula (20)
(Wherein A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- or -O -CO-CH = CH-;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And each of the hydrogen atoms bonded to them is independently -COOR ₀ (wherein 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, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- when the number of X's is 2, X's may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
&Lt; / RTI &gt;
(7)

13. The method according to any one of claims 1 to 12,
(A) is represented by the following formulas (21) to (31)
(Wherein A and B have the same definitions as above;
Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, 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 represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
q1 and q2 are one in one and zero in the other;
m represents an integer of 0 to 2, provided that the sum of all m in the formulas (23) to (24) is 2 or more, and the formulas (25) to (26) , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, , Or an alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH═N-, -CF ₂ -
Wherein the liquid crystalline side chain is at least one kind selected from the group consisting of a liquid crystalline side chain and a liquid crystalline side chain.
[Chemical Formula 8]

[I] a step of coating the composition described in any one of claims 1 to 13 on a substrate having a conductive film for driving a transverse electric field to form a coated film;
[II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and
[III] a step of heating the coating film obtained in [II];
To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted. A substrate having a liquid crystal alignment film for a liquid crystal display device of the lateral electric field type manufactured by the method according to claim 14. A transverse electric field driving type liquid crystal display element having the substrate according to claim 15. Preparing a substrate (first substrate) according to claim 15;
[I '] on the second substrate
(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) polyurea, and
(C) an organic solvent
To form a coating film;
Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; and
Heating the coating film obtained in [III '] [II'];
To obtain a liquid crystal alignment film having the alignment control ability, thereby obtaining a second substrate having the liquid crystal alignment film; and
[IV] a step of opposing the first and second substrates so that the liquid crystal alignment layers of the first and second substrates are opposed to each other through the liquid crystal to obtain a liquid crystal display element;
To obtain a transverse electric field driven liquid crystal display element. A transverse electric field driving type liquid crystal display element manufactured by the method according to claim 17.

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