KR20170082560A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

According to the present invention, there is provided a liquid crystal alignment film for a liquid crystal display device in which 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 excellent in burning property, and a liquid crystal alignment film for a liquid crystal display / RTI > (A) a photosensitive side-chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative, and at least two kinds of diamine compounds , And (C) an organic solvent. The present invention also provides a liquid crystal alignment film comprising a step of coating the composition on a substrate having a conductive film for transverse electric field driving to form a coating film, a step of irradiating the obtained coating film with polarized ultraviolet rays, and a step of heating the obtained coating film The present invention relates to a method of manufacturing a substrate.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a novel polymer composition (liquid crystal aligning agent), a liquid crystal alignment film for a transverse electric field driven liquid crystal display element 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 has recently achieved remarkable development, such as being used in a large-sized television application. 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 a surface of the substrate holding the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. 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 the liquid crystal alignment film (hereinafter, referred to as orientation control ability) is given 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 left 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 polarized ultraviolet rays are irradiated to generate a dimerization reaction (crosslinking reaction) at the double bond portions of two side chains parallel to the polarized 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 described above, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, there is no need of rubbing and there is no risk of generation of oscillation or static electricity. The substrate of the liquid crystal display element having the irregularities on the surface can be subjected to the alignment treatment, and the liquid crystal alignment film is suitable for the 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, in order to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of polarized light is required to be irradiated, and stable alignment of the liquid crystal may not be realized in some cases.

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. In addition, even in the case of the diminution type or the photo-isomerization type photo-alignment method, a large amount of ultraviolet light irradiation of several tens to several tens J may be required. Further, in the case of the photo-crosslinking or photo-isomerization photo-alignment method, there is a fear that the alignment failure and the display burn-in may occur when the liquid crystal display device is used as the liquid crystal display device because the thermal stability and the light stability of the orientation of the liquid crystal are deteriorated . 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 aligning agent capable of realizing high alignment control ability to a liquid crystal alignment film with high efficiency are required.

The present invention relates to a novel polymer composition which imparts 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 transversal electric field driven liquid crystal display device using the same, 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) at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative, a polymer produced by using at least two kinds of diamine compounds, 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> A polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and at least two diamine compounds in the component <1>, wherein the component (B) It is preferably a polymer having a structure represented by formula (Y2-1).

[Chemical Formula 1]

(Wherein Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding portion of Z ₃ and the benzene ring is a single bond, Ester bond, urea bond or amide bond).

<3> The polymer of component (B) as described in <1> or <2> above is preferably a polyurea obtained by polymerizing a diisocyanate component and a diamine component.

(4) The polyurea polyimide precursor as described in (1) or (2) above, wherein the polymer of component (B) is obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative and a diamine component.

<5> The polymer according to <1> or <2>, wherein the polymer of component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.

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

(B) a polyurea polyimide prepared by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound followed by imidization, and

(C) an organic solvent

&Lt; / RTI &gt;

<7> In the above-mentioned <6>, it is preferable that the component (B) has a structure represented by the formula (Y2-1) as a structure derived from a diamine.

(2)

(Wherein Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding portion of Z ₃ and the benzene ring is a single bond, Ester bond, urea bond or amide bond).

<8> In any one of <1> to <7>, it is preferable that the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate.

<9> The photosensitive resin composition according to <1>, wherein the component (A) has a photosensitive side chain which causes photo crosslinking, photoisomerization, or optical free electric potential.

<10> It is preferable that in any one of the above items <1> to <9>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

(3)

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 the hydrogen atoms bonded to the rings are 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 bonding to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- 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.

<11> The liquid crystal display panel according to any one of <1> to <10>, wherein the component (A) has one kind of 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 4]

<12> [I] A process for forming a coating film by coating any one of the compositions <1> to <11> on a substrate having a conductive film for transverse electric field drive;

[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.

<13> 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 <12>.

&Lt; 14 &gt; A transverse electric field driving type liquid crystal display element having the substrate of [13].

<15> preparing a substrate (first substrate) of the above <13>;

[I '] a step of coating a polymer composition of any one of <1> to <11> on a second substrate 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 face each other through the liquid crystal to obtain a liquid crystal display element;

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

<16> A transverse electric field driving type liquid crystal display device manufactured by the above <15>.

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 is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even if the liquid crystal display device is continuously driven for a long time.

In the present invention, by including the above-mentioned polymer as the component (B) in the polymer composition, it is possible to provide a transverse electric field driving type liquid crystal device having excellent voltage holding ratio even by low temperature firing and a liquid crystal alignment film for the device.

In addition, in the present invention, by including the polymer 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, a voltage holding ratio higher than that of a polyacrylate based alignment film alone can be obtained at low temperature firing.

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, a slight anisotropy expressed by polarized light irradiation becomes a driving force, and the liquid crystalline side-chain type polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment can be realized as a liquid crystal alignment film, and a liquid crystal alignment film having high alignment control ability can be obtained.

In addition, in the polymer composition of the present invention, in addition to the side chain type polymer as the component (A) and the organic solvent as the component (C), at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative And a polymer produced by using two or more kinds of diamine compounds. Thus, it was unexpected that the voltage retention ratio of the liquid crystal alignment film was remarkably improved even at low temperature firing. In particular, the use of a specific polymer as the component (B) has increased its 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 intended to be bound by the present invention).

In addition, in the polymer composition of the present invention, in addition to the side chain type polymer as the component (A) and the organic solvent as the component (C), the diisocyanate compound, the tetracarboxylic acid derivative, , Followed by imidation. The polyurea polyimide according to the present invention is a polyurea polyimide. Thus, it was unexpected that the voltage retention ratio of the liquid crystal alignment film was remarkably improved even at low temperature firing. 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 intended to be bound by the present invention).

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

&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 process of the present invention is a polymeric composition comprising: (A) a photosensitive side chain polymer which exhibits liquid crystallinity at a predetermined temperature range; (B) at least one compound selected from a diisocyanate component and a tetracarboxylic acid derivative A polymer prepared by using two or more kinds of diamine compounds, and (C) an organic solvent.

(A) a photosensitive side-chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a diisocyanate compound, and a tetracarboxylic acid derivative , A polyurea polyimide prepared by polymerization reaction of a diamine compound and then imidation, 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) has a mesogen group because it exhibits liquid crystallinity in a temperature range of 100 占 폚 to 300 占 폚.

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 maintained stably for a long period of time. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable 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 main chain and a side chain bonded to the main chain, and a structure having a side chain thereof also as a mesogen component, Or a structure having a phenylbenzoate group that undergoes a free-space potential 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 5]

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 the hydrogen atoms bonded to the rings are 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 bonding to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- 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 6]

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.

(7)

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 8]

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 9]

The side chain may be 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 10]

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.

(11)

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 -.

[Chemical Formula 12]

<< 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 refers to 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.

[Chemical Formula 13]

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) A photosensitive side chain comprising at least one of the above-mentioned formulas (7) to (10), a photosensitive side chain comprising at least one of the above-mentioned formulas (11) to (13), the photosensitive side chain represented by the formula (14) , A photosensitive side chain represented by the formula (16) or (17), a photosensitive side chain represented by the formula (18) or (19) and a photosensitive side chain represented by the formula (20).

[Liquid crystalline side chain monomer]

The liquid crystalline side chain monomer refers to a monomer in which the polymer derived from the monomer exhibits 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 14]

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-purpose method that 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, di-lauroyl peroxide, etc.), peroxyketal (dibutyl peroxide, (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 (such as azobisisobutyronitrile and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile) . 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' -trimethoxystyryl) -4,6-bis -Dimethoxystyryl) -4,6-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 , 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis 2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3'- (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl Phenyl) titanium, 3,3 ', 4,4'-tetramethyluronium hexafluorophosphate, bis (5-2,4-cyclopentadien-1-yl) , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, (Tert-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) Benzophenone, 2- (3-methyl-3H-benzothiazol-2-yl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'- Ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl- (Thiazol-2 (3H) -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-methoxypropionic 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 that has been deaerated 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 too 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 too 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 proportion of the radical polymerization initiator is larger than that of the monomer, the molecular weight of the obtained polymer becomes smaller and, if it is smaller, the molecular weight of the obtained polymer becomes larger. 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) 2,000 to 2,000,000, and more preferably 5,000 to 150,000. Alternatively, the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 200,000.

<< Component (B) >>

The polymer composition for use in the present invention has, as the component (B), a polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and at least two diamine compounds. The polymer of the component (B) is a polyimide precursor prepared by using a polyurea, a diisocyanate component and a tetracarboxylic acid derivative prepared by using a diisocyanate component and a diamine component, and a polyisocyanate component, a diisocyanate component, a tetracarboxylic acid A polyurea polyimide precursor prepared using an acid derivative and a diamine component, that is, a copolymer of a polyurea and a polyimide precursor.

In the second aspect of the present invention, the polymer composition used in the present invention is produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound as the component (B), and then imidizing And a polyurea polyimide.

<<< 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 phenyl 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 the diisocyanate components, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferable from the viewpoints of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is preferable from the standpoint of availability, polymerization reactivity, More preferable.

<< Tetracarboxylic acid derivatives >>

As the tetracarboxylic acid derivative as a raw material of the component (B), for example, the following tetracarboxylic acid dianhydride can be mentioned.

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.

These tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters and tetracarboxylic acid dicarboxylic acid diesters can be used either individually or in combination of two or more types, depending on the properties such as liquid crystal alignability, voltage holding characteristics, Type or more.

<<< 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 (4-aminophenyl) decane, 1,8-bis (4-aminophenyl) octane, 1,9- Bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,8-bis (4-aminophenoxy) pentane, (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di (4-aminophenoxy) decane, Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) Phenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di 1,1-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4 Bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] butane, Bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- Bis [4- (4-aminophenoxy) phenoxy] decane, and 1,10-bis [4- (4-aminophenoxy) phenoxy] decane.

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

[Chemical Formula 15]

(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.

[Chemical Formula 16]

(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.

[Chemical Formula 17]

(Wherein m is an integer of 1 to 10)

When the diamine compound further has a nitrogen atom in the middle of the two amino groups, the nitrogen atom present in the middle of the two amino groups may be bonded to carbonyl or may be bonded to two or more benzene rings as a single bond Is preferable because it can prevent salt formation with the component (A).

The preferred diamine component as a raw material for the component (B) is, for example, a diamine having a structure represented by the following formula (Y2-1).

[Chemical Formula 18]

In formula (Y2-1)

Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding portion of Z ₃ and the benzene ring is a single bond, an ether bond, Urea bond or amide bond.

Specific examples of the formula (Y2-1) include the following formulas (Y2-2) to (Y2-9).

[Chemical Formula 19]

In the formula (Y2-7) and (Y2-8), R ₁₃ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, since the number of carbon atoms is too large, the deterioration of the liquid crystal alignment property, a hydrogen atom, a methyl group or an ethyl group .

In terms of liquid crystal alignment, roneun Y _2, formula (Y2-2), (Y2-3), (Y2-5) is preferable, and a particularly preferred formula (Y2-2) or a group represented by the formula (Y2-5).

To introduce the structure represented by the formula (Y2-1) into the polymer as the component (B), a diamine having a structure represented by the formula (Y2-1) may be used in the production of the polymer as the component (B).

Examples of such diamines include 4,4'-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 1,3-bis Bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis 4-aminophenyl) octane, 1,9-bis (4-aminophenyl) Bis (4-aminophenoxy) pentane, 1, 1-bis (4-aminophenoxy) Bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) (4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate Di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane- Di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy) Phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis Bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- Phenoxy] decane, N, N'-bis (4-aminophenethyl) urea, and the like.

(Y2-1) in the polymer of the component (B) is preferably from 15 to 90 mol%, more preferably from 40 to 85 mol%, based on the total structural units derived from the diamine More preferable.

The diamine component in the component (B) is used in combination of two or more kinds in accordance with the characteristics such as the liquid crystal alignment property, the voltage holding property, and the accumulated charge when the liquid crystal alignment film is used. The mixing ratio at that time is not limited. However, in order to exhibit the effect of improving the voltage holding ratio by mixing two or more kinds of diamines, the content ratio of each diamine is preferably from 10 to 90 mol %, More preferably from 15 to 85 mol%. When three or more diamines are mixed, at least two diamines are mixed so as to be in the range of 10 to 90 mol% based on the total structural units derived from diamine, and then the total amount of nails is 100 mol% It is preferable to mix such portion so that one or more other diamines are occupied. At that time, the kind of the diamine is not limited as long as it is two or more, but it is preferably six or less in consideration of economic factors and the like.

The molecular weight of the polymer of the component (B) is preferably in the range of, for example, 1, 2, 3, 4, 5, 6, It is preferably 5,000 to 1,000,000, more preferably 10,000 to 200,000.

In order to obtain the polymer of the component (B) by the polymerization reaction of at least one member selected from the respective raw material diisocyanate component and the tetracarboxylic acid derivative with the diamine component, a known synthetic method may be used. Generally, it is a method of reacting at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent. The reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is advantageous in that it proceeds comparatively easily in an organic solvent and does not produce any by-products.

The organic solvent used for the reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is not particularly limited as long as the resulting polymer 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. Also, even when the solvent does not dissolve the polyurea, it may be mixed with the solvent in the range where the produced polymer of component (B) is not precipitated.

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.

In the reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent, a solution prepared by dispersing or dissolving a diamine component in an organic solvent is stirred, and a diisocyanate component and a tetracarboxylic acid derivative Or a method of dispersing or dissolving at least one selected from the group consisting of a diisocyanate component and a tetracarboxylic acid derivative in an organic solvent or a method in which a diamine component is added to a solution in which at least one selected from a diisocyanate component and a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent And a method of alternately adding at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component. Any of these methods may be used. When at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative or a diamine component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, individually or sequentially, May be mixed and reacted to form a high molecular weight material.

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 too high, 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 too high and it becomes difficult to perform uniform stirring. The total concentration in the reaction solution of at least one member selected from an isocyanate component and a tetracarboxylic acid derivative and the diamine component 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 of the polymer as the component (B), the ratio of the total number of moles of at least one member selected from the diisocyanate component and the tetracarboxylic acid derivative to the total number of moles of the diamine component is preferably 0.8 to 1.2. As with the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polymer.

In the case of recovering the resulting polymer from the reaction solution of the polymer as the component (B), 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 polymer resin and polyurea as the component (B) are, for example, polymers having a repeating unit represented by the following formula [1].

[Chemical Formula 20]

(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 polyimide precursor is, for example, a polymer having a repeating unit represented by the following formula [2].

[Chemical Formula 21]

In formula [2], A ₃ is each independently a tetravalent organic group, and A ₂ is each independently a divalent organic group. R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; each of C ₁ to C ₂ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, And an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the alkyl group for R ₁₁ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- . From the viewpoint of easy imidization by heating, R &lt; ₁₁ &gt; is preferably a hydrogen atom or a methyl group.

The polyurea polyimide precursor is, for example, a polymer having a repeating unit represented by the formula [1] and a repeating unit represented by the formula [2].

Here, the molar ratio of the tetracarboxylic acid derivative to the diisocyanate in the polyurea polyimide precursor is preferably 99: 1 to 1:99.

The polyurea polyimide is obtained by ring closure of the above polyurea polyamic acid or polyurea polyamic acid ester. The closed rate (also referred to as the imidization rate) of the amide acid group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

As a method for imidizing a polyurea polyamic acid or a polyurea polyamic acid ester, a method of imidizing a solution of a polyimide precursor as it is, or a method of adding a catalyst to a solution of a polyurea polyamic acid or a polyurea polyamic acid ester And the like.

When the polyurea polyamic acid or the polyurea polyamic acid ester is thermally imidized in the solution, the temperature is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C. When water generated by the imidization reaction is removed out of the system It is preferable to conduct it.

The catalyst imidation of a polyurea polyamic acid or a polyurea polyamic acid ester is carried out by adding a basic catalyst and an acid anhydride to a solution of a polyurea polyamic acid or a polyurea polyamic acid ester and heating the solution at a temperature of -20 DEG C to 250 DEG C, Deg.] C to 180 [deg.] C. The amount of the basic catalyst is 0.5 to 30 parts by weight, preferably 2 to 20 parts by weight, and the amount of the acid anhydride is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Of these, pyridine is preferable because it has a basicity suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the produced polyurea polyimide is recovered from the reaction solution of polyurea polyamic acid or polyurea polyamic acid ester or polyurea polyimide, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. Further, when the polymer precipitated and recovered is redissolved in a solvent, and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

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) Is 1, the component (A) is 0.01 to 0.99, more preferably 0.1 to 0.9, and still more preferably 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 surface-active agent.

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 in adhesion between the substrate and the liquid crystal alignment film, in order to prevent deterioration of the electrical characteristics due to the backlight when the liquid crystal display element is constituted, additives such as the following phenoplast series or epoxy group- It may be contained in the composition. Specific phenoplast-based additives are shown below, but are not limited to these structures.

[Chemical Formula 22]

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.

In the case of using a compound improving the adhesiveness with the substrate, 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-methylbenzooxazoline, 2- Methyl-beta-naphthooxazoline, 2- (4-biphenoylmethylene) -3-methyl- beta -naphthooxazoline, 2- (p- fluorobenzoylmethylene) Nitro- aniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroceaphthene), (2 - [(m-hydroxy- (2-naphthalene-2-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid , 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin, and the like.

Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketokmarine, 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.

[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 for use in the present invention can improve the adhesion between the above-described component (A), the component (B) and the solvent or compound for improving the uniformity of the film thickness or the surface smoothness described above or the liquid crystal alignment film and the substrate A compound or the like is dissolved in an organic solvent. The total content of the components (A) and (B) is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, and particularly preferably from 3% to be.

In the polymer composition of the present embodiment, other polymers may be mixed in addition to the components (A) and (B) within a range that does not impair the liquid crystal developing ability and photosensitive performance. 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.

&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) at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative, a polymer produced by using at least two kinds of diamine compounds, and

(C) an organic solvent

A step of applying a polymer composition 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.

In a second aspect of the present invention, a method of manufacturing a substrate having a liquid crystal alignment film of the present invention comprises:

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

(B) a polyurea polyimide prepared by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound followed by imidization, and

(C) an organic solvent

A step of applying a polymer composition 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 as described above so as to oppose each other so that the liquid crystal alignment layers of the first and second substrates face each other through the liquid crystal to obtain a liquid crystal display element;

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

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

&Lt; Process [I] &gt;

In the step [I], a photosensitive side-chain type polymer which exhibits liquid crystallinity in a predetermined temperature range, a polymer of component (B), and a polymer composition containing an organic solvent are laminated on a substrate having a conductive film for transversal- To form a coating film.

<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.

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

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

&Lt; Process [II] &gt;

In the process [II], polarized ultraviolet rays are irradiated to the coating film obtained in the process [I]. When polarized ultraviolet rays are irradiated on the film surface of the coated film, polarized ultraviolet rays are irradiated to the substrate from a certain direction through a polarizer. As ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selectively used so as to cause a photo-crosslinking reaction selectively. 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 to realize the maximum value of DELTA A (hereinafter also referred to as DELTA Amax), 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 Is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

&Lt; Process [III] &gt;

In the step [III], the coated film irradiated with polarized ultraviolet rays in the 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, the coating film is in an isotropic liquid state (isotropic phase) In this case, it may become difficult to reorient in one direction by self-organization.

In addition, the liquid crystal display temperature is preferably not lower than the glass transition temperature (Tg) at which the surface of the side chain type polymer or the coating film changes from solid to liquid crystal phase, and isotropic phase transition 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;

The step [IV] includes a step of preparing a substrate (first substrate) having a liquid crystal alignment film on a conductive film for driving a transversal electric field obtained in [III] (Second substrate) on which a liquid crystal alignment film having no liquid crystal alignment film is placed is opposed to the liquid crystal alignment film through the liquid crystal so as to face each other, and a liquid crystal cell is manufactured by a known method to produce a transverse electric field driven liquid crystal display element Process. 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.

For example, the above-described first and second substrates 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 room is bonded and a liquid crystal is injected at a reduced pressure to seal the liquid crystal or a method in which a liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is dispersed and then the substrate is bonded and sealed For example. 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 photocrosslinking 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.

Further, as to the photo-alignment method using a side chain type polymer having a structure which has a group causing a photo-crosslinkable group, a light-free electric charge group or an isomerization as a photoreactive group, WO2014 / 054785 (the contents of which are incorporated herein by reference in their entirety Which is hereby incorporated by reference in its entirety.

Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film having anisotropy introduced at high efficiency and excellent in orientation control capability, 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 photosensitive groups in the side chain that undergoes photo-crosslinking reaction, photoisomerization reaction, or light- In that case, sufficient self-organization does not proceed even after heating. On the other hand, as a coating film used in the present invention, a structure having a photocrosslinkable group is irradiated with polarized ultraviolet rays. 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 too much. In such a case, the obtained film becomes rigid, which may interfere with the progress of self-organization by subsequent heating. Further, as a coating film used in the present invention, polarized ultraviolet rays are irradiated to a structure having a light-free stress period, and as a result, when the photosensitive group of the side chain which reacts to the light-free potential is 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. In the case of irradiating a polarized ultraviolet ray to a structure having a light-free stress period, if the irradiation amount of ultraviolet light is too large, the side-chain type polymer is photodegraded and the progress of self-organization by heating after that is hindered 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 DELTA Amax realized in the coating film used in the present invention (DELTA Amax) and the irradiation amount of the polarized ultraviolet ray to realize it 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 ray realizing the DELTA Amx.

In the production method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of the polarized ultraviolet ray realizing DELTA Amma, And more preferably within the range. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray in the range of 1% to 50% of the amount of the polarized ultraviolet ray realizing DELTA Amma is preferably 0.1 mol% to 20 mol% of the entire photosensitive unit of the side- Is subjected to a 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, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100 ° C to 200 ° C, it is preferable to set the temperature for heating after the polarized ultraviolet irradiation 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;

(23)

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

MA2 was synthesized by the synthetic method described in the patent document (JP-A-9-118717).

HBAGE was purchased from Nippon Hoso KK.

A1 was synthesized by a synthesis method described in Patent Document (WO2014-054785).

<Diisocyanate Component>

ISO: isophorone diisocyanate

DI-1: Isophorone diisocyanate

DI-2: Diphenylmethane-4,4'-diisocyanate

DI-3: 1,4-Phenylene diisocyanate

DI-4: Tolylene 2,4-diisocyanate

&Lt; Diamine component &gt;

DDM: 4,4'-diaminodiphenylmethane

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

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

DA-2MG: 1,3-bis (4-aminophenoxy) ethane

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

p-PDA: p-phenylenediamine

DADPA: 4,4'-diaminodiphenylamine

&Lt; EMI ID =

&Lt; Tetracarboxylic acid dianhydride &gt;

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

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

GBL:? -Butyrolactone

<Polymerization Initiator>

AIBN: 2,2'-azobisisobutyronitrile

[Test I]

Using the above-described components, raw materials, an organic solvent, a polymerization initiator and the like, a polymer composition was prepared and evaluated as follows.

&Lt; Methacrylate polymer Synthesis Example 1 &gt;

MA1 (5.3 g) and MA2 (19.6 g) were dissolved in THF (101.3 g) and degassed with a diaphragm pump. Then, AIBN (0.39 g) was added and degassed again. Thereafter, reaction was carried out at 60 DEG C for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40 DEG C to obtain a methacrylate polymer powder MP1.

&Lt; Methacrylate polymer Synthesis Examples 2 and 3 &gt;

The composition shown in Table 1 was synthesized using the same method as in the methacrylate polymer Synthesis Example 1.

&Lt; Polyamic acid Synthesis Example 1 &gt;

As the diamine component, DDM (4.76 g) and Me-DADPA (1.28 g) were dissolved in 75.9 g of NMP and BODA (7.35 g) as an acid dianhydride component was added thereto at room temperature. To obtain a solution having a concentration of 15 wt% of polyamic acid (PAA-1).

&Lt; Polyamic acid Synthesis Examples 2 and 3 &gt;

The composition shown in Table 2 was synthesized using the same method as Polyamic acid Synthesis Example 1.

<Polyurea Synthesis Example 1>

As the diamine component, DDM (4.76 g) and Me-DADPA (1.28 g) were dissolved in 71.2 g of NMP and ISO (6.53 g) as a diisocyanate was added thereto at room temperature. Urea (PU-1) at a concentration of 15 wt%.

&Lt; Polyurea Synthesis Examples 2 to 4 &gt;

The composition shown in Table 3 was synthesized using the same method as Polyamic acid Synthesis Example 1.

&Lt; Polyurea-amic acid Synthesis Example 1 &gt;

As the diamine component, DMP (5.35 g), Me-DADPA (0.32 g) and Me-4APhA (0.22 g) were dissolved in 76.8 g of NMP and ISO 6,53 g as diisocyanate was added at room temperature to give 1 Then, TDA (4.32 g) was added as acid dianhydride at room temperature and reacted at 60 ° C. for 18 hours to obtain a solution of 15 wt% of polyurea-amic acid (PUPAA-1).

&Lt; Polyurea-amic acid Synthesis Examples 2 and 3 &gt;

The composition shown in Table 4 was synthesized using the same method as Polyamic acid Synthesis Example 1.

 (Example 1)

NMP (2.35 g) was added to 0.1 g of the methacrylate polymer powder (MP1) obtained in Synthesis Example 1 of the methacrylate polymer and stirred for 30 minutes to obtain a methacrylate polymer solution. 2.8 g of polyamic acid solution (PAA-1) and GBL (5.25 g) were added thereto, followed by stirring at room temperature for 1 hour. 5.5 g of BCS was added to this solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid concentration of 3.5 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 2 to 7 and Comparative Examples 1 to 9)

The polymer solutions of Examples 2 to 7 were obtained in the same manner as in Example 1, with the compositions shown in Table 5. Controls 1 to 9 were also adjusted in the same manner.

[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-like pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of <-like electrode elements bent at the center portion. The width of each of the electrode elements in the short direction was 10 mu m and the interval between the electrode elements was 20 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of <-like electrode elements bent at the center portion, the shape of each pixel is not rectangular, It was shaped like a letter 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 formed in different directions. 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 direction of the rotation operation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other Respectively.

The liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the prepared substrate having the electrode. 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 surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 15 mJ / cm 2 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 columnar spacers 4 占 퐉 in height, on which electrodes were not formed as opposing substrates, and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was bonded to the liquid crystal alignment film so that the alignment direction was 0 °, and the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) 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 device.

A liquid crystal cell was prepared in the same manner as in A1 for the liquid crystal aligning agents (A2 to A7) obtained in Examples 2 to 7 and the liquid crystal aligning agents (C1 to C9) obtained in Controls 1 to 9.

(Evaluation of voltage holding ratio (VHR)) [

In the evaluation of VHR, a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 70 캜, and a voltage after 16.67 ms was measured, and to what extent the voltage could be maintained was calculated as a 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 results are shown in Table 6 below.

As shown in Table 6, in Examples 1 to 7 according to the present invention, when the same methacrylic polymer was used, it was found that the voltage holding ratio (VHR) was higher than that of Comparative Example.

[Test II]

Using the above-described components, raw materials, an organic solvent, a polymerization initiator and the like, a polymer composition was prepared and evaluated as follows.

&Lt; Methacrylate polymer Synthesis Example 11 &gt;

After MA1 (6.65 g, 20.0 mmol) and MA2 (24.51 g, 80.0 mmol) were dissolved in THF (181.2 g) and degassed with a diaphragm pump and replaced with nitrogen, AIBN (0.82 g, 5.0 mmol ) Was added, degassed again, and nitrogen substitution was carried out. Thereafter, the reaction was carried out at 50 DEG C for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (5000 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 MP11.

&Lt; Methacrylate polymer Synthesis Example 12 &gt;

MA1 (5.3 g), MA2 (19.6 g), HBAGE (0.34 g) and Al (0.18 g) were dissolved in THF (102.6 g) and degassed with a diaphragm pump to carry out nitrogen substitution. ) Was added, degassed again, and nitrogen substitution was carried out. Thereafter, reaction was carried out at 60 DEG C for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40 DEG C to obtain a methacrylate polymer powder MP12.

&Lt; Synthesis of polyurea-based polymer &

&Lt; Synthesis Example 11 &

DA-2MG (1.47 g, 6.0 mmol), DA8 (0.79 g, 2.0 mmol) and DADPA (0.39 g, 2.0 mmol) were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen- , And 24.4 g of NMP were added. DI-1 (2.18 g, 9.8 mmol) was added under stirring in a nitrogen atmosphere, NMP was added so that the solid content concentration became 15 mass%, and the mixture was stirred at 50 캜 for 15 hours To obtain a polymer solution (11). The polymer had a number average molecular weight of 7,100 and a weight average molecular weight of 13,400.

&Lt; Synthesis Example 12 &

DA-2MG (1.47 g, 6.0 mmol), DA8 (0.79 g, 2.0 mmol), Me-4APhA (0.33 g, 2.0 mmol) were added to a 100 ml four- necked flask equipped with a stirrer and a nitrogen- (2.18 g, 9.8 mmol) was added while stirring under a nitrogen atmosphere, NMP was added so that the solid concentration became 15% by mass, and the mixture was stirred at 50 占 폚 for 15 hours Followed by stirring to obtain a polymer solution (12). The polymer had a number average molecular weight of 4,800 and a weight average molecular weight of 8,100.

&Lt; Synthesis Example 13 &

DA-2MG (1.47 g, 6.0 mmol), DADPA (0.39 g, 2.0 mmol), Me-4APhA (0.33 g, 2.0 mmol) were added to a 100 ml four- necked flask equipped with a stirrer and a nitrogen- (2.18 g, 9.8 mmol) was added under stirring in a nitrogen atmosphere while stirring. Further, NMP was added so that the solid concentration became 15% by mass, and the mixture was stirred at 50 占 폚 for 15 hours Followed by stirring to obtain a polymer solution (13). The polymer had a number average molecular weight of 10,300 and a weight average molecular weight of 22,000.

&Lt; Synthesis Example 14 &

DA-2MG (2.15 g, 8.8 mmol) and DADPA (0.46 g, 2.2 mmol) were placed in a 100-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 25.4 g of NMP was added, DI-1 (2.40 g, 10.8 mmol) was added with stirring, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution (14). The polymer had a number average molecular weight of 14,300 and a weight average molecular weight of 29,700.

&Lt; Synthesis Example 15 &

DA-2MG (2.15 g, 8.8 mmol) and DA8 (0.87 g, 2.2 mmol) were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 27.6 g of NMP was added, DI-1 (2.40 g, 10.8 mmol) was added with stirring, NMP was added so that the solid concentration became 15% by mass, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution (15). The polymer had a number average molecular weight of 6500 and a weight average molecular weight of 11,900.

&Lt; Synthesis Example 16 &

DA-2MG (2.15 g, 8.8 mmol) and Me-4APhA (0.31 g, 2.2 mmol) were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, DI-1 (2.40 g, 10.8 mmol) was added with stirring under the atmosphere, NMP was added so that the solid content concentration became 15 mass%, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution (16). The polymer had a number average molecular weight of 9,700 and a weight average molecular weight of 19,500.

&Lt; Synthesis Example 17 &

DA-2MG (2.15 g, 8.8 mmol) and DDM (0.43 g, 2.2 mmol) were taken in a 100-ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 27.6 g of NMP was added, DI-1 (2.40 g, 10.8 mmol) was added with stirring, NMP was added so that the solid concentration became 15% by mass, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution (17). The polymer had a number average molecular weight of 13,700 and a weight average molecular weight of 32,400.

&Lt; Synthesis Example 18 &

DA-2MG (2.93 g, 12.0 mmol) and BAPU (0.89 g, 3.0 mmol) were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 37.6 g of NMP was added, DI-1 (3.27 g, 14.7 mmol) was added with stirring, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution 18. The polymer had a number average molecular weight of 11,300 and a weight average molecular weight of 25,400.

&Lt; Synthesis Example 19 &

DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, Under stirring, DI-1 (2.13 g, 9.6 mmol) was added with stirring, and the mixture was stirred at 25 占 폚 for 3 hours. Thereafter, DI-2 (0.51 g, 2.0 mmol) was added, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at 50 캜 for 15 hours to obtain a polymer solution (19). This polymer had a number average molecular weight of 13,500 and a weight average molecular weight of 33,100.

&Lt; Synthesis Example 20 &

DDM (1.90 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 28.1 g of NMP was added, DI-1 (2.13 g, 9.6 mmol) was added with stirring, and the mixture was stirred at 25 占 폚 for 3 hours. Thereafter, DI-3 (0.32 g, 2.0 mmol) was added, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a polymer solution 20. The polymer had a number average molecular weight of 8,600 and a weight average molecular weight of 18,200.

&Lt; Synthesis Example 21 &

DA-2MG (2.34 g, 9.6 mmol) and Me-DADPA (0.51 g, 2.4 mmol) were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, Under stirring, DI-1 (2.13 g, 9.6 mmol) was added with stirring, and the mixture was stirred at 25 占 폚 for 3 hours. Thereafter, DI-4 (0.32 g, 2.0 mmol) was added, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at 50 캜 for 15 hours to obtain a polymer solution 21. The polymer had a number average molecular weight of 11,800 and a weight average molecular weight of 25,300.

The composition of the polymer thus obtained is shown in Table 11.

(Example 11)

6.4 g of the polyurea polymer solution, polymer (11), 3.98 g of NMP and 10.5 g of GBL were added to 0.12 g of the methacrylic acid polymer (MP11) obtained in the above Synthesis Example 1, followed by stirring at room temperature for 3 hours. Further, 9.0 g of BCS was added to this solution, and the mixture was stirred at room temperature for 3 hours to obtain a polymer solution (A11) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 12 to 22, Controls 11 to 12)

The polymer solutions of Examples 12 to 22 were obtained in the same manner as in Example 11, with the compositions shown in Table 12. Controls 11 through 12 were also adjusted in the same manner.

[Production of liquid crystal cell]

Using each liquid crystal alignment treatment agent, a liquid crystal cell was produced as follows. 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-like pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of <-like electrode elements bent at the center portion. The width of each of the electrode elements in the short direction was 10 mu m and the interval between the electrode elements was 20 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of <-like electrode elements bent at the center portion, the shape of each pixel is not rectangular, It has 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 formed in different directions. That is, in the first region of the pixel, the electrode elements of the pixel electrode are formed so as to form an angle of + 15 degrees (clockwise rotation) in the direction of orientation of the liquid crystal alignment film, And the electrode elements were formed so as to form an angle (clockwise rotation) of -15 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation operation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other Respectively.

The liquid crystal alignment treatment agent was filtered with a filter having a size of 1.0 탆, and then spin-coated on the substrate having the electrode. 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 coating film surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 20 mJ / cm 2, and then heated on a hot plate at 140 캜 for 20 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, which had no electrode as an opposing substrate, and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was bonded to the liquid crystal alignment film so that the alignment direction was 0 °, and the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display device.

(Observation of Orientation)

A liquid crystal cell was prepared by the above-mentioned method. Thereafter, the polarizing plate was observed through a polarizing microscope in a Cross-Nicol state. When the liquid crystal cell was rotated and turned to a black display state, a good state was defined as a state in which no luminescent spot or orientation defect was present, and a case where there was a luminescent spot or alignment defect was represented by X. Table 12 shows the results of heating the liquid crystal cell to the isotropic (isotropic) temperature region of the liquid crystal and observing in the same manner.

(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 占 폚 and measuring the holding voltage of the liquid crystal cell after 1667 ms. VHR1 was taken as the initial value, and the value measured after giving the stress for one week by the LED backlight was taken as VHR2.

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 results are shown in Table 13 below.

As shown in Table 13, in Examples 11 to 22 according to the present invention, it was found that the voltage holding ratio (VHR) was higher than that of the control by including the component (B).

[Test III]

Using the above-described components, raw materials, an organic solvent, a polymerization initiator and the like, a polymer composition was prepared and evaluated as follows.

&Lt; Methacrylate polymer synthesis example 31 &gt;

MA1 (5.3 g), MA2 (19.6 g), HBAGE (0.34 g) and Al (0.18 g) were dissolved in THF (102.6 g) and degassed with a diaphragm pump. And then degassed again. Thereafter, reaction was carried out at 60 DEG C for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder MP31.

&Lt; Polyurea-amic acid Synthesis Example 31 &gt;

As the diamine component, DMP (5.35 g), Me-DADPA (0.32 g) and Me-4APhA (0.22 g) were dissolved in 76.8 g of NMP and ISO 6,53 g as diisocyanate was added at room temperature to give 1 Then, TDA (4.32 g) was added as an acid anhydride at room temperature and reacted at 60 ° C for 18 hours to obtain a solution of polyurea-amic acid (PUPAA-31) at a concentration of 15 wt%.

&Lt; Polyurea-amic acid Synthesis Example 32 &gt;

As the diamine component, DMP (5.35 g), Me-DADPA (0.32 g) and Me-4APhA (0.22 g) were dissolved in 76.8 g of NMP and ISO 6,53 g as diisocyanate was added at room temperature to give 1 Then, BODA (1.93 g) was added as an acid anhydride at room temperature, followed by reaction at 60 ° C for 1 hour. Thereafter, additional acid anhydride TDA (2.14 g) was added and reacted for 18 hours to obtain a solution having a concentration of polyurea-amic acid (PUPAA-32) of 15 wt%.

&Lt; Polyurea-imide Synthesis Example 31 &gt;

NMP (50 g) was added to a solution (PUPAA-1, 30 g) having a concentration of 15 wt% obtained in Synthesis Example 1 of polyurea-amic acid to dilute the solution to a concentration of 6 wt%, acetic anhydride (6.42 g) and pyridine (2.49 g) were added. The mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C to obtain a polyurea-imide powder. The imidization rate of this polyurea-imide was 96%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI31) having a concentration of 15 wt%.

&Lt; Polyurea-imide Synthesis Example 32 &gt;

NMP (50 g) was added to a solution (PUPAA-22, 30 g) having a concentration of 15 wt% obtained in Synthesis Example 2 of polyurea-amic acid to dilute the solution to a concentration of 6 wt%, acetic anhydride (6.42 g) and pyridine (2.49 g) were added. The mixture was stirred at room temperature for 30 minutes and then reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C to obtain a polyurea-imide powder. The imidization rate of the polyurea-imide was 73%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI32) having a concentration of 15 wt%.

(Example 31)

NMP (2.35 g) was added to 0.1 g of the methacrylate polymer powder (MP1) obtained in Synthesis Example 1 of the methacrylate polymer and stirred for 30 minutes to obtain a methacrylate polymer solution. 2.8 g of a polyurea-imide solution (PUPI-21) and GBL (5.25 g) were added thereto, followed by stirring at room temperature for 1 hour. BCS (5.5 g) was further added to this solution and stirred at room temperature for 1 hour to obtain a polymer solution (A31) having a solid concentration of 3.5 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 32 to 34)

The polymer solutions (A32 to A34) of Examples 32 to 34 were obtained in the same manner as in Example 31 using the compositions shown in Table 21.

[Production of liquid crystal cell]

Using the liquid crystal aligning agent (A31) obtained in Example 31, 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-like pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of <-like electrode elements bent at the center portion. The width of each of the electrode elements in the short direction was 10 mu m and the interval between the electrode elements was 20 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of <-like electrode elements bent at the center portion, the shape of each pixel is not rectangular, It was shaped like a letter 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 formed in different directions. That is, in the first region of the pixel, the electrode elements of the pixel electrode are formed so as to form an angle of + 15 degrees (clockwise rotation) in the direction of orientation of the liquid crystal alignment film, And the electrode elements were formed so as to form an angle (clockwise rotation) of -15 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation operation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other Respectively.

The liquid crystal aligning agent (A31) obtained in Example 31 was spin-coated on the prepared substrate having the electrode. 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 surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 15 mJ / cm 2 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, which had no electrode as a counter substrate, and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was bonded to the liquid crystal alignment film so that the alignment direction was 0 °, and the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) 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 device.

The liquid crystal aligning agents (A32 to A34) obtained in Examples 32 to 34 were also prepared in the same manner as in A31.

(Evaluation of voltage holding ratio (VHR)) [

The VHR was evaluated by applying a voltage of 1 V to the obtained liquid crystal cell at a temperature of 70 캜, measuring the voltage after 1000 ms, and calculating the voltage holding ratio. The initial voltage holding ratio measured after the production of the liquid crystal cell was taken as VHR1, and the voltage holding ratio measured after performing the backlight aging test after 1 week was taken as VHR2.

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 results are shown in Table 22 below.

As shown in Table 22, in all of Examples 31 to 34 according to the present invention, the initial voltage holding ratio (VHR1) and the voltage holding ratio (VHR2) after backlight aging are high. It can be seen that the voltage holding ratios of Examples 31, 32 and 34 are further improved than those of Example 33 using PUPAA 31 which is the same as PUPAA1.

Claims (16)

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative, a polymer produced by using at least two kinds of diamine compounds, and
(C) an organic solvent. The method according to claim 1,
(B) is a polymer produced by using at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and at least two kinds of diamine compounds, wherein the structure derived from a diamine is represented by the formula (Y2-1) &Lt; / RTI &gt; structure.
[Chemical Formula 1]

(Wherein Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding portion of Z ₃ and the benzene ring is a single bond, Ester bond, urea bond or amide bond). 3. The method according to claim 1 or 2,
Wherein the polymer of component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component. 3. The method according to claim 1 or 2,
Wherein the polymer of component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. 3. The method according to claim 1 or 2,
Wherein the polymer of component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component. (A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) a polyurea polyimide prepared by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound followed by imidization, and
(C) an organic solvent. The method according to claim 6,
(B) has a structure represented by the formula (Y2-1) as a structure derived from a diamine.
(2)

(Wherein Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bonding portion of Z ₃ and the benzene ring is a single bond, Ester bond, urea bond or amide bond). 8. The method according to any one of claims 1 to 7,
Wherein the diisocyanate component is an aromatic diisocyanate and / or an aliphatic diisocyanate. 9. The method according to any one of claims 1 to 8,
(A) has a photosensitive side chain that causes photo-crosslinking, photoisomerization, or light-free potential. 10. The method according to any one of claims 1 to 9,
(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 the hydrogen atoms bonded to the rings are 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 bonding to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- 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.
&Lt; / RTI &gt; wherein the composition has any one of the photosensitive side chains selected from the group consisting of &lt; RTI ID = 0.0 &gt;
(3)

11. The method according to any one of claims 1 to 10,
(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 4]

[I] a step of coating the composition described in any one of claims 1 to 11 on a substrate having a conductive film for transverse electric field driving 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 a transverse electric field driving type manufactured by the method according to claim 12. 13. A transverse electric field driving type liquid crystal display element having the substrate according to claim 13. Preparing a substrate (first substrate) according to claim 13;
[I '] a step of applying a polymer composition according to any one of claims 1 to 11 on a second substrate 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 arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates face 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 15.