KR102324573B1 - Polymer composition and liquid crystal alignment film for transverse electric field driving liquid crystal display element - Google Patents

Abstract

This invention is [I] (A) It is photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, It has a side chain represented by Formula (0), A nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane A polymer composition containing a side chain polymer further having a side chain (a) having a group selected from the group, and (B) an organic solvent, and the composition is applied on a substrate having a conductive film for driving a transverse electric field, The manufacturing method of the board|substrate which has a liquid crystal aligning film which has the process of forming a coating film, the process of irradiating the ultraviolet-ray which polarized to the obtained coating film, and the process of heating the obtained coating film is provided. By this polymer composition and a transverse electric field drive type liquid crystal display element, orientation control ability is provided with high efficiency, and the liquid crystal aligning film excellent in exposure characteristics is provided.

Description

A polymer composition and a liquid crystal aligning film for a transverse electric field driving type liquid crystal display element TECHNICAL FIELD

The present invention relates to a novel polymer composition, a liquid crystal aligning film for a transverse electric field driving type liquid crystal display element using the same, and a method for producing a substrate having the alignment film. Furthermore, it is related with the novel method for manufacturing the liquid crystal display element excellent in exposure characteristics.

BACKGROUND ART Liquid crystal display elements are known as light-weight, thin, and low-power display devices, and in recent years they have been used for large-sized televisions, and have achieved remarkable development. A liquid crystal display element clamps a liquid crystal layer with a pair of transparent board|substrates provided with an electrode, and is comprised, for example. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates.

That is, the liquid crystal aligning film is a structural member of a liquid crystal display element, it is formed in the surface in contact with the liquid crystal of the board|substrate which clamps a liquid crystal, and plays the role of orientating a liquid crystal in a fixed direction between the board|substrates. And in addition to the role of orientating a liquid crystal in fixed directions, such as a direction parallel to a board|substrate, for example, the role of controlling the pretilt angle of a liquid crystal may be calculated|required by a liquid crystal aligning film. The ability to control the orientation of a liquid crystal in such a liquid crystal aligning film (it is hereafter called orientation control ability.) is provided by orientation-processing with respect to the organic film which comprises a liquid crystal aligning film.

As an orientation processing method of the liquid crystal aligning film for providing orientation control ability, the rubbing method is conventionally known. The rubbing method refers to rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing direction), and rubbing direction (rubbing direction) A method of aligning liquid crystals with Since this rubbing method can implement|achieve the orientation state of a relatively stable liquid crystal easily, it has been used in the manufacturing process of the conventional liquid crystal display element. And as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and electrical characteristic has been mainly selected.

However, as for the rubbing method of rubbing the surface of the liquid crystal aligning film which consists of polyimide etc., generation|occurrence|production of dust and static electricity may become a problem. In addition, due to the recent increase in precision of liquid crystal display elements and irregularities due to the electrodes on the corresponding substrates or the switching active elements for driving liquid crystals, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment can be realized. There were cases where there was no

Then, as another orientation processing method of the liquid crystal aligning film which does not rub, the photo-alignment method is examined actively.

Although there are various methods in the photo-alignment method, anisotropy is formed in the organic film which comprises a liquid crystal aligning film by linearly polarized light or collimated light, and a liquid crystal is orientated according to the anisotropy.

As a main photo-alignment method, the decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is generated using the polarization direction dependence of the ultraviolet absorption of the molecular structure. And it is made to orientate a liquid crystal by the polyimide which remained without decomposition|disassembly (for example, refer patent document 1).

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

As in the above example, in the orientation processing method of the liquid crystal aligning film by a photo-alignment method, rubbing is made unnecessary, and there is no possibility of generation|occurrence|production of dust and static electricity. And it can orientation-process also to the board|substrate of the liquid crystal display element with an unevenness|corrugation on the surface, and it becomes the method of the orientation treatment of the liquid crystal aligning film suitable for an industrial production process.

Japanese Patent Publication No. 3893659

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

As mentioned above, the photo-alignment method makes the rubbing process itself unnecessary compared with the rubbing method which has been conventionally used industrially as an orientation processing method of a liquid crystal display element, Therefore, it is equipped with the big advantage. And compared with the rubbing method in which orientation controllability becomes substantially constant by rubbing, by the photo-alignment method, the irradiation amount of the polarized light can be changed and orientation controllability can be controlled. However, in the photo-alignment method, when it is intended to realize the same degree of alignment control ability as in the case of the rubbing method, a large amount of polarized light irradiation is required, or stable alignment of the liquid crystal cannot 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 having an output of 500 W for 60 minutes. will be needed Moreover, also in the case of the photo-alignment method of a dimerization type|mold or a photoisomerization type|mold, the ultraviolet irradiation of the large quantity of about several J (joule) - several tens of J may be required. Moreover, in the case of the photo-alignment method of a photocrosslinking type or a photoisomerization type, since thermal stability and light stability of liquid crystal orientation were inferior, when it was set as a liquid crystal display element, there existed a problem that orientation defect and display exposure generate|occur|produced. In particular, in a liquid crystal display element of a transverse electric field drive type, since liquid crystal molecules are switched in-plane, the orientation shift of the liquid crystal after liquid crystal drive is easy to occur, and display exposure resulting from AC drive becomes a big problem.

Therefore, in the photo-alignment method, high efficiency improvement of an orientation process and realization of the stable liquid-crystal orientation are calculated|required, and the liquid crystal aligning film and liquid crystal aligning agent which can provide high orientation control ability with respect to a liquid crystal aligning film with high efficiency are calculated|required.

An object of the present invention is to provide a substrate having a liquid crystal aligning film for a transverse electric field driving type liquid crystal display element, which is highly efficient in orientation controllability and excellent in exposure characteristics, and a transverse electric field driving type liquid crystal display element having the substrate.

Moreover, in addition to the said objective, the objective of this invention is providing the lateral electric field drive type liquid crystal element which has an improved voltage retention, and the liquid crystal aligning film for this element.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining in order to achieve the said subject.

<1> [I] (A) As a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, following formula (0)

[Formula 1]

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

S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the halogen group;

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

X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and the number of X becomes 2, X may be same or different;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; , when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

G is the following formula (G-1), (G-2), (G-3) and (G-4)

[Formula 2]

(Wherein, a broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and ^{when there are two or more R 50} , they may be the same or different from each other, and t is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group);

A side chain polymer having a side chain represented by

(B) organic solvent

A polymer composition containing

In <2> said <1>, it is good for (A) component to have a photosensitive side chain which raise|generates photocrosslinking, photoisomerization, or optical fleece transition.

In <3> said <1>, it is good for (A) component to have any 1 type of photosensitive side chain chosen from the group which consists of following formula (1)-(6).

[Formula 3]

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

S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the halogen group;

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

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or 2 to 6 identical or different selected from their substituents A ring is a group formed by bonding through a bonding group B, and the hydrogen atoms bonded thereto are each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a hydrogen atom bonded thereto may be each independently _{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 CH- is represented and the number of X becomes 2, X may be same or different;

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

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

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; , when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

<4> What has any 1 type of liquid crystalline side chain in any one of said <1>-<3> WHEREIN: (A) component is chosen from the group which consists of following formula (21)-(31) good.

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

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to each hydrogen atom to be used may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

l represents an integer of 1 to 12, m represents an integer of 0 to 2, with the proviso that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In , the sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1 to 3;

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

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

[Formula 4]

<5> The composition according to any one of <1> to <4>, wherein the composition further contains, as component (D), an alkoxysilyl group and a compound having a urea structure in which both 1-position and 3-position are substituted good.

<6> process of apply|coating the polymer composition in any one of said <1>-<5> on the board|substrate which has an electrically conductive film for transverse electric field drive, and forming a coating film;

[II] The process of irradiating the polarized ultraviolet-ray to the coating film obtained in [I]; And

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

The manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which orientation control ability was provided by having.

The board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by the manufacturing method as described in <7> said <6>.

A transverse electric field drive type liquid crystal display element which has the board|substrate of <8> said <7>.

<9> Step of preparing the substrate (first substrate) of <7> above;

[I'] The process of apply|coating the polymer composition in any one of said <1>-<5> on a 2nd board|substrate, and forming a coating film;

[II'] The process of irradiating the polarized ultraviolet-ray to the coating film obtained by [I'];

and

[III'] The process of heating the coating film obtained by [II'];

The process of obtaining the 2nd board|substrate which has this liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; And

[IV] The process of opposingly arrange|positioning a 1st and 2nd board|substrate so that the liquid crystal aligning film of a 1st and 2nd board|substrate may oppose through a liquid crystal, and obtaining a liquid crystal display element;

The manufacturing method of the liquid crystal display element which obtains a transverse electric field drive type liquid crystal display element by having.

<10> Transverse electric field driving type liquid crystal display device manufactured according to <9>.

<11> Side chain type polymer|macromolecule as described in said <1>.

ADVANTAGE OF THE INVENTION By this invention, orientation control ability is provided with high efficiency, and the board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements excellent in exposure characteristics, and the transverse electric field drive type liquid crystal display element which has this board|substrate can be provided.

Since the lateral electric field drive type liquid crystal display element manufactured by the method of this invention is highly efficient and orientation control ability is provided, even if it drives continuously for a long time, a display characteristic is not impaired.

Moreover, according to this invention, in addition to the said effect, in the liquid crystal aligning film interface, the ionic impurity in a liquid crystal adsorb|sucks, and it can provide the transverse electric field drive type liquid crystal element which has an improved voltage retention, and the liquid crystal aligning film for this element.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor came to complete this invention by obtaining the following knowledge.

The polymer composition used in the production method of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as side chain polymer) capable of expressing liquid crystallinity, and the coating film obtained by using the polymer composition is liquid crystal It is a film|membrane which has photosensitive side chain type polymer|macromolecule which can express. It orientation-processes by polarized light irradiation, without giving a rubbing process to this coating film. And it becomes a coating film (henceforth a liquid crystal aligning film) to which orientation control ability was provided through the process of heating the side chain type polymer film after polarized light irradiation. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and liquid crystalline side chain type polymer|macromolecule itself is efficiently reorientated by self-organization. As a result, as a liquid crystal aligning film, highly efficient orientation processing is implement|achieved, and the liquid crystal aligning film to which high orientation control ability was provided can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<The manufacturing method of the board|substrate which has a liquid crystal aligning film> and <The manufacturing method of a liquid crystal display element>

The manufacturing method of the board|substrate which has a liquid crystal aligning film of this invention,

[I] (A) Side chain type polymer|macromolecule which further has a side chain represented by said Formula (0) as photosensitive side chain type polymer|macromolecule which expresses liquid crystal in a predetermined temperature range, and

(B) organic solvent

A step of forming a coating film by coating a polymer composition containing

[II] The process of irradiating the polarized ultraviolet-ray to the coating film obtained in [I]; And

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

has

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

Moreover, a transverse electric field drive type liquid crystal display element can be obtained by preparing a 2nd board|substrate other than the board|substrate (1st board|substrate) obtained above.

For the second substrate, the above steps [I] to [III] (the conductive film for the transverse electric field drive) is used in place of the substrate having the transverse electric field drive conductive film, except that a substrate not having the transverse electric field drive conductive film is used. In order to use the board|substrate which does not have, for convenience, in this application, it may abbreviate as process [I'] - [III'] By using), the 2nd board|substrate which has a liquid crystal aligning film to which orientation control ability was provided is obtained can

A method for manufacturing a transverse electric field driving type liquid crystal display device,

[IV] Process of opposingly arrange|positioning the 1st and 2nd board|substrate obtained above so that the liquid crystal aligning film of a 1st and 2nd board|substrate may oppose through a liquid crystal, and obtaining a liquid crystal display element;

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

Hereinafter, each process of [I]-[III] and [IV] which the manufacturing method of this invention has is demonstrated.

<Process [I]>

In process [I], the side which further has a side chain represented by said Formula (0) as photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range on the board|substrate which has an electrically conductive film for a transverse electric field drive. A chain polymer, an organic solvent, and, if desired, an amine compound having one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group and further, if desired, as component (D), a polymer composition containing a compound having a urea structure in which an alkoxysilyl group is substituted at both 1-position and 3-position is applied to form a coating film.

<substrate>

Although limitation in particular is not carried out about a board|substrate, When the liquid crystal display element manufactured is a transmissive type, it is preferable that a board|substrate with high transparency is used. In that case, limitation in particular is not carried out, Plastic substrates, such as a glass substrate or an acrylic substrate and a polycarbonate board|substrate, etc. can be used.

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

<Conductive film for lateral electric field drive>

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

Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: Indium Tin Oxide) and IZO (Indium Zinc Oxide: Indium Zinc Oxide) when the liquid crystal display element is a transmissive film.

Moreover, in the case of a reflection type liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, it is not limited to these.

A conventionally well-known method can be used for the method of forming a conductive film on a board|substrate.

<Polymer composition>

A polymer composition is apply|coated on the board|substrate which has the electrically conductive film for lateral electric field drive, especially on the electrically conductive film.

The polymer composition used for the manufacturing method of this invention is (A) a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range; (B) an organic solvent; And, if desired, (C) in a molecule|numerator It contains an amine compound having one primary amino group and a nitrogen-containing aromatic heterocyclic ring, and wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

<<(A) side chain type polymer>>

Component (A) is a photosensitive side chain polymer that expresses liquid crystallinity in a predetermined temperature range, has a side chain represented by the formula (0), and is selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group It further has a side chain (a) which has group used as it.

(A) It is good that side chain type polymer|macromolecule reacts with the light of the wavelength range of 250 nm - 400 nm, and shows liquid crystallinity in the temperature range of 100 degreeC - 300 degreeC.

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

(A) In order that side chain type polymer|macromolecule may show liquid crystallinity in the temperature range of 100 degreeC - 300 degreeC, it is preferable to have a mesogenic group.

(A) A side chain polymer|macromolecule has the side chain which has photosensitivity couple|bonded with the main chain, and can generate|occur|produce a crosslinking reaction, an isomerization reaction, or an optical Fris dislocation by sensitizing to light. Although the structure of the side chain which has photosensitivity is not specifically limited, The structure which responds to light and raise|generates a crosslinking reaction or an optical Fries dislocation is preferable, and it is more preferable to raise a crosslinking reaction. In this case, even when exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. Although the structure of the photosensitive side chain type polymer film which can express liquid crystallinity will not be specifically limited if such a characteristic is satisfy|filled, It is preferable to have a rigid mesogenic component in a side chain structure. In this case, when the side chain type polymer|macromolecule is used as a liquid crystal aligning film, stable liquid-crystal orientation can be obtained.

(A) Side chain type polymer|macromolecule provides reliable liquid crystal aligning films, such as voltage retention (VHR), by having group represented by said Formula (0). When this is set as a liquid crystal aligning film, when group represented by said Formula (0) acts like a crosslinking agent, a film density improves and it is thought that it is because the elution of the ionic impurity with respect to a liquid crystal is reduced.

Moreover, (A) side chain type polymer|macromolecule further improves reliability, such as voltage retention (VHR), by having a side chain (a) which has group chosen from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. can This is considered to be because these groups trap ionic impurities.

The polymer structure has, for example, a main chain and a side chain bonded thereto, and the side chain is a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group; It has a structure having a photosensitive group bonded to the tip portion that undergoes a crosslinking reaction or an isomerization reaction in response to light, a main chain and a side chain bonded thereto, the side chain also serves as a mesogenic component, and also an optical Fris rearrangement reaction It can be set as the structure which has a phenyl benzoate group.

More specific examples of the structure of the photosensitive side chain polymer film capable of expressing liquid crystallinity include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as vinyl, maleimide, norbornene, and siloxane, a group represented by the formula (0), and at least one of the following formulas (1) to (6) It is preferable that it is a structure which has a side chain which consists of 1 type.

[Formula 5]

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

S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the halogen group;

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

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded thereto are each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group may be substituted;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a hydrogen atom bonded thereto is each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

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

one of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; When is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

It is good that a side chain is any 1 type of photosensitive side chain chosen from the group which consists of following formula (7) - (10).

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

l represents the integer of 1-12;

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

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

[Formula 6]

It is good that a side chain is any 1 type of photosensitive side chain chosen from the group which consists of following formula (11)-(13).

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

[Formula 7]

It is good that a side chain is a photosensitive side chain represented by following formula (14) or (15).

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

[Formula 8]

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

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

[Formula 9]

Moreover, it is good that a side chain is a photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms.

[Formula 10]

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

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

[Formula 11]

Moreover, it is good for (A) side chain type polymer|macromolecule to have any 1 type of liquid crystalline side chain chosen from the group which consists of following formula (21)-(31).

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

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms may each independently be _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero a 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;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, with the proviso that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In , the sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1 to 3;

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

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

[Formula 12]

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

The photosensitive side chain type polymer|macromolecule which can express said liquid crystallinity can be obtained by superposing|polymerizing the photoreactive side chain monomer and liquid crystalline side chain monomer which have said photosensitive side chain.

[The monomer which has a side chain represented by Formula (0)]

As a more specific example of the monomer which has a side chain represented by said Formula (0), Hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, (alpha)-methylene-gamma-butyrolactone, styrene, vinyl, maleate It is preferable that it is a structure which has the polymeric group comprised by at least 1 sort(s) chosen from the group which consists of radically polymerizable groups, such as mid and norbornene, and siloxane, and the side chain shown by said Formula (0).

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

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

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

As a monomer which has an oxetane group, (meth)acrylic acid ester etc. which have an oxetane group are mentioned, for example. Among such monomers, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3 -(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoro Romethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl) Oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoro Methyloxetane is preferable, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl- oxetane, etc. are mentioned.

As a monomer which has a thietane group, the monomer by which the oxetane group of the monomer which has an oxetane group was substituted by the thietane group is preferable, for example.

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

Among the above, the monomer which has an epoxy group, and the monomer which has an oxetane group from points, such as availability, are preferable, and the monomer which has an epoxy group is more preferable. Especially, the point of availability to glycidyl (meth)acrylate is preferable.

[Monomer having a side chain (a)]

The polymer which is (A) component of this application further has a side chain (a) which has group chosen from a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. By containing such a side chain (a), when it is set as a liquid crystal aligning film, while reducing the elution of an ionic impurity, it is because it is for promoting the crosslinking reaction of group represented by said Formula (0), or more durable liquid crystal An alignment film can be obtained. In order to manufacture the polymer which has a side chain (a), what is necessary is just to copolymerize the monomer which has a side chain (a).

As a monomer which has such a side chain (a), a hydrocarbon, (meth)acrylate, itaconate, a fumarate, a maleate, (alpha)-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. It is preferable that it is a structure which has a polymeric group comprised by at least 1 sort(s) selected from the group which consists of a radical polymerizable group and siloxane, and has a side chain which has a nitrogen-containing aromatic heterocyclic group, an amide group, and a urethane group. NH of the amide group and the urethane group may or may not be substituted. As a substituent in the case of being substituted, an alkyl group, the protecting group of an amino group, a benzyl group, etc. are mentioned.

The nitrogen-containing aromatic heterocyclic ring is a structure selected from the group consisting of the following formulas [20a], [20b] and [20c] ( _{wherein Z 2} is a linear or branched alkyl group having 1 to 5 carbon atoms) It is good that it is an aromatic cyclic hydrocarbon containing at least 1 piece, preferably 1~4 pieces.

[Formula 13]

Specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, thiadia Sole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinoc A saline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, etc. are mentioned. Moreover, you may have the substituent containing a hetero atom in the carbon atom of these nitrogen-containing aromatic heterocyclic rings.

Of these, for example, a pyridine ring is preferable.

Among such monomers, specific examples of the monomer having a nitrogen-containing aromatic heterocyclic group include, for example, 2-(2-pyridylcarbonyloxy)ethyl(meth)acrylate, 2-(3-pyridylcarbonyloxy) Ethyl (meth)acrylate, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, etc. are mentioned.

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

[Photoreactive Side Chain Monomer]

A photoreactive side chain monomer is a monomer which can form the polymer|macromolecule which has a photosensitive side chain in the side chain site|part of a polymer|macromolecule, when polymer|macromolecule is formed.

As a photoreactive group which a side chain has, the following structure and its derivative(s) are preferable.

[Formula 14]

More specific examples of the photoreactive side chain monomer include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene A photosensitive side chain which consists of a polymeric group comprised by at least 1 type selected from the group which consists of a radically polymerizable group and siloxane, and at least 1 type in said Formula (1)-(6) Preferably, for example, said Formula ( The photosensitive side chain which consists of at least 1 type of 7)-(10), the photosensitive side chain which consists of at least 1 type of said Formula (11)-(13), the photosensitive side chain represented by said Formula (14) or (15), It is preferable that it is a structure which has the photosensitive side chain represented by the photosensitive side chain represented by said Formula (16) or (17), the photosensitive side chain represented by said Formula (18) or (19), and said Formula (20).

This application provides novel compounds (1)-(11) represented by the following formulas (1)-(11) as a photoreactive side chain monomer.

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1 represents; and Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.

[Formula 15]

[Formula 16]

[Liquid crystalline side chain monomer]

A liquid crystalline side chain monomer is a monomer which polymer|macromolecule derived from the monomer expresses liquid crystallinity, and the polymer can form a mesogenic group in a side chain site|part.

As a mesogenic group which a side chain has, it is group used as mesogenic structure independently, such as biphenyl and phenyl benzoate, or it may contribute to become a mesogenic structure by hydrogen bonding of side chains like benzoic acid. As a mesogenic group which a side chain has, the following structure is preferable.

[Formula 17]

As a more specific example of a liquid crystalline side chain monomer, hydrocarbon, (meth)acrylate, itaconate, a fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. It is preferable that it is a structure which has a polymeric group comprised by at least 1 type selected from the group which consists of a radically polymerizable group and siloxane, and the side chain which consists of at least 1 type in said Formula (21)-(31).

(A) Side chain type polymer|macromolecule is obtained by the copolymerization reaction of the monomer which has the photoreactive side chain monomer which expresses above-mentioned liquid crystallinity, the monomer which has a side chain represented by said Formula (0), and a side chain (a) can Moreover, copolymerization of the monomer which has a photoreactive side chain monomer which does not express liquid crystallinity, a liquid crystalline side chain monomer, and the monomer which has a side chain represented by said Formula (0), and a side chain (a), and liquid crystallinity are expressed It can obtain by copolymerization of the monomer which has a photoreactive side chain monomer to say, a liquid crystalline side chain monomer, and the monomer which has a side chain represented by said Formula (0), and a side chain (a). Moreover, it can copolymerize with another monomer in the range which does not impair liquid crystalline expression ability.

Examples of the other monomer include an industrially available monomer capable of a radical polymerization reaction.

As a specific example of another monomer, an unsaturated carboxylic acid, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned.

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, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, and the like.

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

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

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

As for content of the side chain represented by Formula (0) in side chain type polymer|macromolecule of this invention, 0.1 mol% - 20 mol% are preferable and 0.5 mol% is a point similar to the influence with respect to a reliability improvement and liquid-crystal orientation. -10 mol% is more preferable, and 1 mol% - 5 mol% are still more preferable.

From the point similar to liquid-crystal orientation, 20 mol% - 99.9 mol% are preferable, as for content of the photoreactive side chain in side chain type polymer|macromolecule of this invention, 30 mol% - 95 mol% are more preferable, 40 mol % - 90 mol% are more preferable.

From the point similar to liquid-crystal orientation, 80 mol% or less is preferable, as for content of the liquid crystalline side chain in side chain type polymer|macromolecule of this invention, 10 mol% - 70 mol% are more preferable, 20 mol% - 60 mol% mol% is more preferable.

20 mol% or less is preferable and, as for content of the side chain (a) in side chain type polymer|macromolecule of this invention, from the point like an influence on a reliability improvement and liquid-crystal orientation, 10 mol% or less is more preferable, 5 mol% or less is more preferable.

The side chain type polymer|macromolecule of this invention may contain other side chains other than the side chain represented by said Formula (0), a photoreactive side chain, a liquid crystalline side chain, and a side chain (a). The content is the remaining part, when the sum total of content of the side chain shown by said Formula (0), a photoreactive side chain, a liquid crystalline side chain, and a side chain (a) does not reach 100 %.

It does not specifically limit about the manufacturing method of side chain type polymer|macromolecule of this embodiment, The general-purpose method handled industrially can be used. Specifically, it can manufacture by cationic polymerization using the vinyl group of a liquid crystalline side chain monomer or a photoreactive side chain monomer, radical polymerization, and anionic polymerization. Among these, radical polymerization is especially preferable from a viewpoint of the easiness of reaction control, etc.

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

A radical thermal polymerization initiator is a compound which generate|occur|produces a radical by heating to decomposition temperature or more. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides ( Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxide, etc.) oxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates compounds (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) can Such a radical thermal polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more type.

A radical photoinitiator will not be specifically limited if it is a compound which starts radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioxanthone. , 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, iso Propylbenzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4 -Dimethylaminobenzoic acid isoamyl, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl) reyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) -s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)- 5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostiazine Lyl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o- Chlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra kiss (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-Biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n- dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1- yl)-phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl) Benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3 '-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3 -Methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene) -1-(2-benzoyl)ethanone and the like. These compounds may be used independently and may be used in mixture of 2 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.

It will not specifically limit, if the produced|generated polymer|macromolecule melt|dissolves as an organic solvent used for the polymerization reaction of the photosensitive side chain type polymer|macromolecule which can express liquid crystallinity. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, Pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene Glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl- 3-Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutylpropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide , 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropana Mead etc. are mentioned.

These organic solvents may be used independently or may be mixed and used. Moreover, even if it is a solvent which does not dissolve the produced|generated polymer|macromolecule, you may use it in the range in which the produced|generated polymer|macromolecule does not precipitate, mixing with the organic solvent mentioned above.

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

Although the polymerization temperature at the time of radical polymerization can select the arbitrary temperature of 30 degreeC - 150 degreeC, Preferably it is the range of 50 degreeC - 100 degreeC. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Preferably they are 1 mass % - 50 mass %, More preferably, they are 5 mass % - 30 mass %. The reaction initial stage can be performed at high concentration, and an organic solvent can be added after that.

In the radical polymerization reaction described above, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer becomes large. It is preferable that it is -10 mol%. Moreover, in the case of polymerization, various monomer components, a solvent, an initiator, etc. can also be added.

[Recovery of polymer]

When collect|recovering the produced|generated polymer|macromolecule from the reaction solution of the photosensitive side chain type polymer|macromolecule which was obtained by the reaction mentioned above and can express liquid crystallinity, the reaction solution is thrown into a poor solvent, and these polymers are should be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can The polymer charged and precipitated in the poor solvent can be collected by filtration, and then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, if the polymer which carried out precipitation collection|recovery is made to dissolve again in an organic solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons, and the use of three or more types of poor solvents selected from these is preferable because the efficiency of purification further increases.

The molecular weight of the (A) side chain polymer of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the obtained coating film, workability at the time of coating film formation, and the uniformity of the coating film are considered. 2000-1000000 are preferable, More preferably, it is 5000-100000.

[Preparation of polymer composition]

It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing the photosensitive side chain type polymer|macromolecule which can express already demonstrated liquid crystal. In that case, as for content of a resin component, 1 mass % - 20 mass % are preferable, More preferably, they are 3 mass % - 15 mass %, Especially preferably, they are 3 mass % - 10 mass %.

The polymer composition of this embodiment WHEREIN: Although the photosensitive side chain type polymer|macromolecule which can express the liquid crystallinity mentioned above all may be sufficient as the resin component mentioned above, in the range which does not impair liquid-crystal expression ability and photosensitive performance, other than them. of other polymers may be mixed. In that case, content of the other polymer in a resin component is 0.5 mass % - 80 mass %, Preferably they are 1 mass % - 50 mass %.

The polymer etc. which are not the photosensitive side chain type polymer|macromolecule which consist of poly(meth)acrylate, a polyamic acid, a polyimide, etc., and can express liquid crystallinity are mentioned, for example as such another polymer.

<(C) amine compound>

The polymer composition used in the present invention has a specific amine compound as component (C), specifically, one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is an aliphatic hydrocarbon group or a non-aromatic group. It may have an amine compound bonded to a cyclic hydrocarbon group. Such a compound is described as (B) component in WO2008/013285 publication. By containing such an amine compound, when it is set as a liquid crystal aligning film, while reducing the elution of an ionic impurity, it is because it accelerates|stimulates the crosslinking reaction of group represented by said Formula (0), or a more durable liquid crystal aligning film is obtained can

When the polymer composition used for this invention forms a liquid crystal aligning film, a specific amine compound will not be specifically limited if it exhibits the following effect i) and/or ii). i) adsorb|sucks the ionic impurity in a liquid crystal in the liquid crystal aligning film interface, and/or ii) exhibits the improved voltage retention.

Although the quantity of a specific amine compound will not be specifically limited if the said effect is exhibited, It is 0.01-10 mass parts in 100 mass parts of polymer compositions used for this invention, It is good that it is preferably 0.1-5 mass parts.

<(D) component>

(D)component contained in the liquid crystal aligning agent of this invention is an alkoxysilyl group, and the compound (henceforth a compound D) which has the urea structure by which both 1-position and 3-position were substituted.

If the compound has a urea structure in which one or more alkoxysilyl groups are substituted with one or more 1-position and 3-positions in the compound, other structures are not particularly limited, but from the viewpoint of availability, the following formula ( The compound represented by d) is one of the preferable examples.

[Formula 18]

In the formula, X ¹⁰² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, R ¹⁰² is a hydrogen atom or an alkyl group, and n is 2 In the above case, R ¹⁰² together with other R ¹⁰² may be alkylene or, when n is 1 to 6, may also be bonded ^{to X 102 to form a ring structure together with X 102 ,} and L is a carbon number of 2 to 20 represents alkylene, and R ¹⁰³ and R ¹⁰⁴ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and q is a natural number of 1 to 3.

^{Examples of R 103} and R ¹⁰⁴ in the formula (d) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl each independently, but availability of raw materials and reactivity methyl or ethyl is preferable in terms of

Although C2-C20 alkylene is mentioned as L in Formula (d), From the point of availability of a raw material, trimethylene is preferable.

As q in Formula (d), 2 or 3 is preferable and 3 is especially preferable.

As n in Formula (d), 1, 2 or 3 are preferable and 1 or 2 is especially preferable.

One aspect of the compound of component (D) is ^{compound (2-1), wherein X 102} is a divalent organic ^{group, R 102} is a hydrogen atom, and L is trimethylene.

[Formula 19]

The compound represented by such Formula (2-1) is obtained by making diamine react with 2.05 equivalent amount of trialkoxy silyl propyl isocyanate.

[Formula 20]

As X in the compound represented by Formula (2-1), Preferably it is a structure chosen from the following structural formula.

[Formula 21]

One aspect of the compound of component (D) ^{is the compound (2-2) in which X 102} is a divalent organic group, R ¹⁰² is one to form alkylene, and L is trimethylene.

[Formula 22]

The compound represented by such a formula (2-2) is obtained by making 2.05 equivalent amount of trialkoxysilylpropyl isocyanate react with the cyclic compound containing two NH.

[Formula 23]

As X in the compound represented by Formula (2-2), Preferably it is a structure chosen from the following structural formula. Also, for convenience, the nitrogen atom in the ring is included in the description.

[Formula 24]

One aspect of the compound of component (D) is a compound in which X ¹⁰² is a divalent organic ^{group, one of R 102} is a hydrogen atom, the other is ^{also bonded to X 102} to form a ring, and L is trimethylene (2-3) is.

[Formula 25]

The compound represented by such Formula (2-3) is obtained by making diamine react with 2.05 equivalent amount of trialkoxy silyl propyl isocyanate.

As X in the compound represented by Formula (2-3), Preferably it is a structure chosen from the following structural formula. Also, for convenience, the nitrogen atom in the ring is included in the description.

[Formula 26]

One aspect of the compound of component (D) is ^{compound (2-4) in which X 102} is a trivalent organic ^{group, R 102} is a hydrogen atom, and L is trimethylene.

[Formula 27]

The compound represented by such Formula (2-4) is obtained by making a triamine compound react with 3.05 equivalent amount of trialkoxy silyl propyl isocyanate.

[Formula 28]

As X in the compound represented by Formula (2-4), Preferably it is a structure chosen from the following structural formula.

[Formula 29]

One aspect of the compound of component (D) is ^{compound (2-5), wherein X 102} is a monovalent organic ^{group, R 102} is a hydrogen atom, and L is trimethylene.

[Formula 30]

The compound represented by such formula (2-5) is obtained by making 1.05 equivalent amount of trialkoxy silyl propyl isocyanate react with a monoamine compound.

[Formula 31]

As X in the compound represented by Formula (2-5), Preferably it is a structure chosen from the following structural formula.

[Formula 32]

One aspect of the compound of component (D) is the ^{compound (2-6) wherein X 102} is a monovalent organic group, R ¹⁰² is ^{bonded to X 102} to form a ring, and L is trimethylene.

[Formula 33]

The compound represented by such a formula (2-6) is obtained by making 1.05 equivalent amount of trialkoxysilylpropyl isocyanate react with the cyclic compound containing one NH.

[Formula 34]

As X in the compound represented by Formula (2-6), Preferably it is a structure chosen from the following structural formula. Also, for convenience, the nitrogen atom in the ring is included in the description.

[Formula 35]

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

The reaction solvent is not particularly limited as long as it is inert to the reaction, and for example, hydrocarbons such as hexane, cyclohexane, benzene, and toluene; halogen-based hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; diethyl Ethers, such as ether, diisopropyl ether, 1, 4- dioxane, tetrahydrofuran; Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Nitriles, such as acetonitrile and propionitrile; Ethyl acetate, Carboxylic acid esters such as ethyl propionate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Nitrogen-containing aprotic polar solvents; Sulfur-containing aprotic polar solvents, such as dimethyl sulfoxide and sulfolane; Pyridines, such as pyridine and picoline, etc. are mentioned. These solvents may be used independently or may mix and use 2 or more types of these. Preferably, they are toluene, acetonitrile, ethyl acetate, and tetrahydrofuran, More preferably, they are acetonitrile and tetrahydrofuran.

Although the usage-amount (reaction density|concentration) of a solvent is not specifically limited, You may react without using a solvent, Moreover, when using a solvent, you may use 0.1-100 mass times of solvent with respect to an isocyanate compound. Preferably it is 0.5-30 mass times, More preferably, it is 1-10 mass times.

Although the reaction temperature is not specifically limited, For example, it is -90 - 150 degreeC, Preferably it is -30 - 100 degreeC, More preferably, it is 0 degreeC - 80 degreeC.

Reaction time is 0.05 to 200 hours normally, Preferably it is 0.5 to 100 hours.

A catalyst may be added to shorten the reaction time, and examples thereof include dibutyltin dilaurate, dioctyltin bis(isooctylthioglycolic acid ester), dibutyltin bis(isooctylthioglycolic acid ester), dibutyl organotin compounds such as tin diacetate; triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, and N-methylmor Pauline, 1,4-diazabicyclo-2.2.2-octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene amines such as amines; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; Titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; bismuth Bismuth compounds, such as tris(2-ethylhexanoate); Quaternary ammonium salt, etc. are mentioned. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, it is preferable that these catalysts are liquid or melt|dissolve in a reaction solvent.

When adding the catalyst, the catalyst may be used in an amount of 0.005 wt % to 100 wt %, preferably 0.05 wt % to 10 wt %, more preferably with respect to the total amount (mass) of the compound having an isocyanate group. 0.1 wt% to 5 wt%. If an organotin compound, a titanium compound, and a bismuth-type compound are used as a catalyst, Preferably it is 0.005 wt% - 0.1 wt% of copper.

This reaction can be performed under normal pressure or pressurization, and a batch type or a continuous type may be sufficient as it.

As a specific example of preferable (D)component, the compound represented by any one of S1 - S4 is mentioned.

[Formula 36]

(D) When there are too many compounds of a component, liquid-crystal orientation or a pretilt angle will be affected, and when there are too few, the effect of this invention will not be acquired. Therefore, 0.1-20 mass % is preferable with respect to the polymer of (A) component, and, as for the addition amount of the compound of (D)component, 1-10 mass % is more preferable.

<Organic solvent>

The organic solvent used for the polymer composition used for this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. The specific example is given below.

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

The polymer composition used for this invention may contain components other than said (A), (B), and (C) component. As the example, although the solvent and compound which improve film thickness uniformity and surface smoothness at the time of apply|coating a polymer composition, the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate are mentioned, It is not limited to this.

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

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n -octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethyl propionate, 3-ethoxy methyl propionate Ethyl, 3-methoxyethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2 -Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. Solvents with low surface tension, etc. can be heard

These poor solvents may be used by one type or in mixture of multiple types. When using the solvent as mentioned above, it is preferable that it is 5 mass % - 80 mass % of the whole solvent so that the solubility of the whole solvent contained in a polymer composition may not be reduced remarkably, More preferably, 20 They are mass % - 60 mass %.

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

More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by Sumitomo 3M), AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Corporation), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) ) and the like. To [ the usage ratio of these surfactant / 100 mass parts of resin components contained in a polymer composition ], Preferably they are 0.01 mass part - 2 mass parts, More preferably, they are 0.01 mass part - 1 mass part.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane etc. are mentioned.

Moreover, in addition to the improvement of the adhesiveness of a board|substrate and a liquid crystal aligning film, for the purpose of preventing the fall of the electrical property by the backlight when a liquid crystal display element is comprised, etc., the additive of the following phenoplast type|system|group and an epoxy group containing compound is a polymer composition You may contain it in. Although a specific phenoplast type additive is shown below, it is not limited to this structure.

[Formula 37]

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

When using the compound which improves adhesiveness with a board|substrate, it is preferable that the usage-amount is 0.1 mass part - 30 mass parts with respect to 100 mass parts of the resin component contained in a polymer composition, More preferably, 1 mass part - 20 mass parts is wealth When the usage-amount is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino. substituted, aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, Benzanthrone, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3 -Methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoyl Methylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naph Tooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3- Methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- nitroacenaphthene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone) ), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocumarin, and the like.

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

In the polymer composition, if it is the range in which the effect of this invention is not impaired other than what was mentioned above, for the purpose of changing electrical properties, such as the dielectric constant and electroconductivity of a liquid crystal aligning film, when it is set as a dielectric material and an electrically-conductive material, furthermore, a liquid crystal aligning film You may add a crosslinking|crosslinked compound for the purpose of raising the hardness and density of the film|membrane.

The method of apply|coating the above-mentioned polymer composition on the board|substrate which has the electrically conductive film for lateral electric field drive is not specifically limited.

As for the coating method, industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method (rotary coating method), the spray method, etc., You may use these according to the objective.

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

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, preferably 5 nm to 300 nm, more preferably 10 nm ∼150 nm.

Moreover, it is also possible to set the process of cooling the board|substrate with a coating film to room temperature after the [I] process before the subsequent [II] process.

<Process [II]>

In process [II], the ultraviolet-ray which polarized to the coating film obtained by process [I] is irradiated. When irradiating the polarized ultraviolet-ray to the film surface of a coating film, the polarized ultraviolet-ray is irradiated through a polarizing plate from a fixed direction with respect to a board|substrate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter etc. according to the kind of coating film to be used. And, for example, in order to selectively cause a photocrosslinking reaction, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

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

<Process [III]>

In process [III], the coating film to which the ultraviolet-ray polarized in process [II] was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

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

It is preferable that heating temperature exists in the temperature range of the temperature (henceforth liquid crystal expression temperature) at which side chain type polymer|macromolecule expresses liquid crystallinity. In the case of the surface of a thin film like a coating film, it is expected that the liquid crystal expression temperature of the surface of a coating film is lower than the liquid crystal expression temperature at the time of observing the photosensitive side chain type polymer|macromolecule which can express liquid crystal in bulk. For this reason, it is more preferable that heating temperature exists in the temperature range of the liquid-crystal expression temperature of the coating-film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet light is 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer to be used as the lower limit, and the upper limit is the temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is a temperature in the range made into When the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy by heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the coating film state is in an isotropic liquid state (isotropic phase). ), and in this case, it may be difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is above the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and isotropic phase transition causing the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase) Temperature (Tiso) refers to the temperature below the temperature.

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

By having the above process, in the manufacturing method of this invention, highly efficient and anisotropic introduction to a coating film can be implement|achieved. And the board|substrate in which the liquid crystal aligning film was formed can be manufactured with high efficiency.

<Process [IV]>

[IV] Process has a conductive film obtained in [I'] - [III'] similarly to the board|substrate (1st board|substrate) which has a liquid crystal aligning film on the electrically conductive film for transverse electric field drive obtained by [III]. A step of arranging a substrate (second substrate) provided with a liquid crystal aligning film that does not have a liquid crystal aligning film therebetween through a liquid crystal so that both liquid crystal aligning films face each other, producing a liquid crystal cell by a known method, and producing a transverse electric field driving type liquid crystal display element am. In addition, in step [I'] to [III'], in step [I], instead of the substrate having the conductive film for lateral electric field drive, a substrate not having the lateral electric field drive film was used, and the process [ It can carry out similarly to I]-[III]. Since the only difference between the steps [I] to [III] and the steps [I'] to [III'] is the presence or absence of the above-described conductive film, the description of the steps [I'] to [III'] is omitted.

To give an example of the production of a liquid crystal cell or a liquid crystal display element, prepare the above-mentioned first and second substrates, spread a spacer on the liquid crystal aligning film of one substrate, make the liquid crystal aligning film surface inside, and The method of bonding one side board|substrate and sealing by pressure-reducing injection and sealing of a liquid crystal, or the method of bonding a board|substrate and sealing after dripping a liquid crystal to the liquid crystal aligning film surface which spread|dispersed the spacer, etc. can be illustrated. have. In this case, it is preferable to use a substrate having an electrode having a structure similar to that of a comb for lateral electric field driving as the substrate on one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, more preferably 2 µm to 10 µm. The diameter of this spacer determines the distance between the pair of substrates holding the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate to form a coating film, polarized ultraviolet-ray is irradiated. Next, by heating, highly efficient anisotropic introduction|transduction with respect to a side chain type polymer film is implement|achieved, and the board|substrate with the liquid crystal aligning film provided with the orientation control ability of a liquid crystal is manufactured.

In the coating film used for this invention, highly efficient anisotropic introduction to a coating film is implement|achieved using the principle of molecular reorientation caused by the self-organization based on the photoreaction of a side chain and liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, a coating film is formed on the substrate using the side chain polymer, then irradiated with polarized ultraviolet light, and then, After heating, a liquid crystal display element is manufactured.

Therefore, the coating film used for the method of this invention can be set as the liquid-crystal aligning film excellent in orientation control ability by introducing anisotropy with high efficiency by performing irradiation of the ultraviolet-ray polarized to a coating film, and heat processing sequentially.

And in the coating film used for the method of this invention, the irradiation amount of the ultraviolet-ray which polarized to a coating film, and the heating temperature in heat processing are optimized. Thereby, highly efficient and anisotropic introduction|transduction to a coating film can be implement|achieved.

The amount of polarized ultraviolet light that is optimal for the introduction of highly efficient anisotropy to the coating film used in the present invention is polarized ultraviolet light that optimizes the amount of photosensitive group photocrosslinking reaction, photoisomerization reaction, or optical Fris dislocation reaction in the coating film. corresponding to the dose of As a result of irradiating the ultraviolet-ray which polarized with respect to the coating film used for this invention, when there are few photosensitive groups of the side chain which a photocrosslinking reaction, a photoisomerization reaction, or an optical Fries rearrangement reaction, it will not become a sufficient photoreaction amount. In that case, even if it heats after that, sufficient self-organization does not advance. On the other hand, in the coating film used in the present invention, when polarized ultraviolet rays are irradiated with respect to the structure having a photocrosslinkable group, when the photosensitive groups of the side chains to be crosslinked are excessive, the crosslinking reaction between the side chains will proceed too much. In that case, the obtained film|membrane becomes rigid, and it may interfere with advancing of the self-organization by subsequent heating. Moreover, in the coating film used for this invention, when polarized ultraviolet-ray is irradiated with respect to the structure which has an optical Fries potential group, when the photosensitive group of the side chain which reacts optical Fries potential becomes excessive, the liquid crystal property of a coating film will fall too much. . In that case, the liquid crystallinity of the film|membrane obtained also falls, and it may become a hindrance of advancing of the self-assembly by subsequent heating. In addition, when polarized ultraviolet light is irradiated to a structure having an optical Fris dislocation group, if the irradiation amount of ultraviolet light is too large, the side chain polymer is photodecomposed, and there is a case where the progress of self-organization by subsequent heating is hindered. have.

Therefore, in the coating film used in the present invention, the optimal amount in which the photosensitive group of the side chain undergoes a photocrosslinking reaction, a photoisomerization reaction, or an optical Fries potential reaction by irradiation of polarized ultraviolet light is the amount of the photosensitive group possessed by the side chain type polymer film. It is preferable to set it as 0.1 mol% - 40 mol%, and it is more preferable to set it as 0.1 mol% - 20 mol%. By making the quantity of the photosensitive group of the side chain which photoreacts into such a range, self-organization in subsequent heat processing advances efficiently, and highly efficient anisotropic formation in a film|membrane is attained.

In the coating film used for the method of this invention, by optimization of the irradiation amount of the polarized ultraviolet-ray, the amount of the photocrosslinking reaction and photoisomerization reaction of the photosensitive group in the side chain of a side chain type polymer film, or an optical Fris rearrangement reaction to optimize And the anisotropic introduction|transduction with respect to the coating film used for this invention which is high efficiency and is combined with subsequent heat processing is implement|achieved. In that case, about the quantity of a preferable polarization|polarized-light ultraviolet-ray, it is possible to implement based on evaluation of the ultraviolet absorption of the coating film used for this invention.

That is, about the coating film used for this invention, the ultraviolet absorption of the direction parallel to the polarization direction of the polarized ultraviolet-ray after polarized-ultraviolet irradiation and the ultraviolet absorption of the perpendicular direction are respectively measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the perpendicular direction, in the coating film is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays that realize it are calculated. In the manufacturing method of this invention, on the basis of the polarization|polarized-light ultraviolet irradiation amount which implement|achieves this (DELTA)Amax, the amount of the polarized-light ultraviolet-ray of the preferable quantity irradiated in manufacture of a liquid crystal aligning film can be determined.

In the manufacturing method of this invention, it is preferable to carry out the irradiation amount of the polarized ultraviolet-ray to the coating film used for this invention in 1% - 70% of the amount of the polarized ultraviolet-ray which implement|achieves ΔAmax, and 1% to 50% It is more preferable to set it within the range of The coating film used for this invention WHEREIN: The irradiation amount of the polarization|polarized-light ultraviolet-ray within the range of 1% - 50% of the quantity of the polarization|polarized-light ultraviolet-ray which implement|achieves (DELTA)Amax is 0.1 mol% - 20 mol of the whole photosensitive group which the side chain type polymer film has. % corresponds to the quantity of the polarization|polarized-light ultraviolet-ray which carries out a photocrosslinking reaction.

From the above, in the manufacturing method of this invention, in order to implement|achieve highly efficient anisotropic introduction with respect to a coating film, it is good to determine the preferable heating temperature as mentioned above on the basis of the liquid crystal temperature range of the side chain type polymer|macromolecule as a reference. . Therefore, for example, when the liquid crystal temperature range of side chain type polymer|macromolecule used for this invention is 100 degreeC - 200 degreeC, it is preferable to make heating temperature after polarization|polarized-light ultraviolet irradiation into 90 degreeC - 190 degreeC. By doing in this way, larger anisotropy is provided in the coating film used for this invention.

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

As described above, the substrate for a transverse electric field driving type liquid crystal display element manufactured by the method of the present invention or a transverse electric field driving type liquid crystal display element having the substrate has excellent reliability, and is suitable for a large screen, high-definition liquid crystal television, etc. Available.

Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to the Example.

Example

GMA, HBAGE, G1, and additive T1 are shown below as methacrylic monomers MA1 and MA2 used in Examples, and monomers having an epoxy side chain.

In addition, MA1 and MA2 were synthesize|combined as follows, respectively. That is, MA1 was synthesize|combined by the synthesis method described in patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Unexamined-Japanese-Patent No. 9-118717).

G1 was synthesized by the synthesis method described in Synthesis Example 1 below.

As GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether), and additive T1 (3-aminomethylpyridine), a commercially available thing was used.

[Formula 38]

<Synthesis Example 1>

Synthesis of specific glycidyl compound (C1)

[Formula 39]

In a THF (tetrahydrofuran) solution (184 g) of a carboxylic acid derivative (MA2) (18.4 g, 60 mmol), (COCl) ₂ (oxalyl chloride) (11.4 g, 90 mmol) and DMF (dimethylformamide) ) was added dropwise and reacted at room temperature for 2 hours. The individual obtained by concentrating this solution was dissolved with THF (350 g). This solution was dripped at the THF solution (88g) of glycidol (8.89g, 120mmol) and triethylamine (13.4g, 132mmol) over 1 hour, and it was made to react for 18 hours. Then, ethyl acetate (500 g) was added, and the organic phase was washed 3 times with water (300 g), and dried over magnesium sulfate. After removing magnesium sulfate by filtration, the crude substance was obtained by concentrating. The obtained crude product was subjected to silica gel chromatography using ethyl acetate and hexane to obtain C1 as a white solid. (Amount: 14.9 g, 69%).

Glycidyl derivative (C1):

<Synthesis Example 2>

Synthesis of compound A1

[Formula 40]

In a 1 L 4 neck flask, compound [A] (63.42 g, 287 mmol), compound [B] (50.00 g, 406 mmol), EDC (N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride) (93.43 g, 487 mmol), DMAP (4-dimethylaminopyridine) (4.96 g, 40.6 mmol), and THF (500 g) were added, and reaction was carried out at 23°C. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, distilled water (3L) was poured into the reaction solution, ethyl acetate (1L) was added, and liquid separation operation removed the water layer. Thereafter, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried over magnesium sulfate. Then, 86.3g of compound [A1] was obtained as an oily compound by filtration and solvent distillation with an evaporator (yield 92%).

<Synthesis Example 3>

Synthesis of compound A2

[Formula 41]

15.00 g of 1-methylpiperazine and 120 g of toluene were poured into a 500 ml four-neck flask, and a solution obtained by diluting 24.40 g of 2-isocyanatoethyl methacrylate with 30 g of toluene was diluted at 5° C. in 50 minutes. After dripping over time, it stirred at room temperature for 3 hours. Next, after adjusting the reaction liquid to about half the weight by concentrating the reaction liquid under reduced pressure with an evaporator, 75 g of heptane was added. Subsequently, the precipitated crystals were filtered by suction under reduced pressure by stirring at 5°C for a while, and then dried under reduced pressure to obtain 33.26 g of compound [A2] (yield: 87%, appearance: white crystals).

<Synthesis Example 4>

Synthesis of compound A3

[Formula 42]

Carboxylic acid derivative [MA2] (86.39 g, 282 mmol), compound [C] (50.00 g, 310 mmol), EDC (64.87 g, 338 mmol), DMAP (3.45 g, 28.2 mmol), THF (900 g) was added and the reaction was carried out at 23 °C. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, the reaction solution was poured into distilled water (4L), ethyl acetate (1L) was added, and the water layer was removed by liquid separation operation. Thereafter, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried over magnesium sulfate. Then, 121.7 g of compounds [A3] were obtained as an oily compound by filtration and solvent distillation with an evaporator (yield 96%).

<Synthesis Example 5>

Synthesis of compound A4

[Formula 43]

Carboxylic acid derivative [MA2] (69.17 g, 286 mmol), compound [D] (50.00 g, 248 mmol), EDC (51.95 g, 271 mmol), DMAP (2.76 g, 22.58 mmol), THF (700 g) was added and the reaction was carried out at 23 °C. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, the reaction solution was poured into distilled water (4L), ethyl acetate (1L) was added, and the water layer was removed by liquid separation operation. Thereafter, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried over magnesium sulfate. Then, 100.9 g of compounds [A4] were obtained as an oily compound by filtration and solvent distillation with an evaporator (yield 91%).

In addition, the abbreviation of the reagent used in this Example is shown below.

(organic solvent)

THF: tetrahydrofuran.

NMP: N-methyl-2-pyrrolidone.

BC: Butyl cellosolve.

PB: propylene glycol monobutyl ether

(Polymerization Initiator)

AIBN: 2,2'-azobisisobutyronitrile.

<Synthesis of compound S1>

[Formula 44]

20.00 g of 4,4'- diaminodiphenylamine and THF 300g were poured into a 2L 4-necked flask, and the solution which diluted 50.90 g of triethoxysilyl propyl isocyanate with THF 100g under ice-cooling stirring was 30 After dripping over minutes, it stirred at room temperature for 18 hours. Then, the reaction liquid was concentrated under reduced pressure, and about half amount of THF was distilled off. Next, after adding 720 g of acetonitrile at room temperature and stirring for 30 minutes, it stirred at 5 degreeC for a while. The crystals thus precipitated were filtered under reduced pressure and dried under reduced pressure to obtain 60.70 g of compound S1 (yield: 87%, appearance: white solid).

<Synthesis of compound S2>

[Formula 45]

1,4-diaminobenzene 4.00g and THF 60g were poured into a 300 mL four neck flask, and the solution which diluted 18.76g of triethoxysilyl propyl isocyanate with THF 20g under ice-cooling stirring over 1.5 hours After dripping, it stirred at room temperature for 18 hours. Thereafter, the crystals precipitated in the reaction solution were filtered under reduced pressure, and this was transferred to another 300 ml four-necked flask. Next, after adding 100 g of acetonitrile to this, it stirred at room temperature for a while. The crystal slurry thus obtained was filtered under reduced pressure and dried under reduced pressure to obtain 18.98 g of compound S2 (yield: 85%, appearance: white solid).

<Polymer Synthesis Example 11>

MA1 (3.98 g), MA2 (5.51 g), GMA (0.04 g), and A1 (0.07 g) were dissolved in THF (40.0 g), degassed with a diaphragm pump, and then AIBN (0.24 g) was added. Degassing was performed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (300 ml), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P11.

<Polymer Synthesis Examples 12 to 21>

The composition shown in Table 1 was synthesize|combined using the method similar to polymer synthesis example 11.

<Example 11>

N-ethyl-2-pyrrolidone (NEP) (5.1 g) was added to the methacrylate polymer powder P11 (0.4 g) obtained in polymer synthesis 11, and stirred at room temperature for 1 hour to dissolve. Polymer solution T11 was obtained by adding and stirring PB (4.5g) to this solution. This polymer solution was set as the liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

<Examples 12 to 25>

The liquid crystal aligning agent was adjusted for the composition shown in Table 2 using the method similar to Example 11, and liquid crystal aligning agents T12-T25 of Examples 12-25 were obtained.

<Control polymer synthesis example 1>

After dissolving M1 (3.98 g) and M2 (5.51 g) in THF (40.0 g) and deaeration with a diaphragm pump, AIBN (0.24 g) was added and deaeration was performed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (300 ml), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder CP1.

<Control polymer synthesis examples 2 to 4>

The compositions shown in Table 3 were synthesized using the same method as in Control Polymer Synthesis Example 1.

<Control 11>

To the methacrylate polymer powder CP1 (0.4 g) obtained in Control Polymer Synthesis Example 1, NEP (5.1 g) was added, and the mixture was dissolved by stirring at room temperature for 1 hour. Polymer solution CT11 was obtained by adding and stirring PB (4.5g) to this solution. This polymer solution was set as the liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

<Controls 12 to 16>

Liquid crystal aligning agent was adjusted for the composition shown in Table 4 using the method similar to control 11, and liquid crystal aligning agent CT12-CT16 of Controls 12-16 was obtained.

<Production of liquid crystal cell>

After filtering the liquid crystal aligning agent (T11) obtained in Example 11 with a 0.45 micrometer filter, it spin-coated on the glass substrate with a transparent electrode, and after drying for 90 second on a 70 degreeC hotplate, a liquid crystal aligning film with a film thickness of 100 nm has formed Then, after 15 mJ/cm<2> of 313 nm ultraviolet-ray was irradiated to the coating-film surface through a polarizing plate, it heated for 10 minutes with a 140 degreeC hotplate, and obtained the board|substrate with a liquid crystal aligning film. Prepare two substrates on which such a liquid crystal aligning film is formed, and after installing a 6 μm spacer on the liquid crystal aligning film surface of one substrate, combine the two substrates so that the rubbing directions of the two substrates are parallel, leaving the liquid crystal injection port around the periphery was sealed, and an empty cell having a cell gap of 4 µm was produced. Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell by which the liquid crystal was parallel-aligned was obtained.

The liquid crystal cell was produced similarly using liquid crystal aligning agents T12-T25 obtained in Examples 12-25, and liquid crystal aligning agents CT11-CT16 obtained by the controls 11-16.

<Afterimage evaluation>

The liquid crystal cell for IPS mode prepared above is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the backlight is turned on with no voltage applied, and the arrangement angle of the liquid crystal cell is adjusted so that the luminance of the transmitted light is the smallest. did. And the rotation angle when the liquid crystal cell is rotated from the angle at which the 2nd area|region of a pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as an initial stage orientation azimuth. Then, from among the 60 ℃ oven was 168 hours is (印加) an alternating-current voltage of 16 V _PP at the frequency 30 Hz. Then, it was set as the state made short between the pixel electrode of a liquid crystal cell, and a counter electrode, and it was left to stand at room temperature as it is for 1 hour. After leaving it to stand, the orientation azimuth was measured similarly, and the difference of orientation azimuth before and behind an alternating current drive was computed as angle (DELTA)(deg.). Measurements were also made in the same manner in other Examples. As a result, in all Examples, the angle Δ was 0.1 or less. After irradiating an ultraviolet-ray to the side chain type polymer film which expresses liquid crystallinity, by heating in the liquid crystal expression temperature range, it is because the liquid crystal orientation ability is provided with high efficiency in the whole polymer by self-organization, or the orientation orientation even after long-term AC drive. No deviation was observed.

＜VHR evaluation＞

Evaluation of VHR applied the voltage of 1V to the obtained liquid crystal cell under the temperature of 70 degreeC for 60 microseconds, measured the voltage 16.67 ms later, and calculated how much the voltage was maintained as voltage retention. . After VHR1 and VHR1 measurement for VHR measured immediately after liquid crystal cell manufacture, VHR measured after performing aging on a backlight for 1 week was made into VHR2. In addition, voltage retention measuring apparatus VHR-1 by the Toyo Technica company was used for the measurement of voltage retention.

The result of VHR of Examples 11-25 and the liquid crystal aligning agent of Controls 11-16 is shown in Table 5.

From Table 5, it can be seen that in Examples 11 to 25, VHR1 is improved by copolymerizing both the monomer having an epoxy group and the monomer having an amide group, compared with Controls 11 to 16 in which the monomer having an amide group is not copolymerized. . Moreover, the fall of VHR(VHR2) by backlight aging is also suppressed.

Claims (11)

(A) It is a polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, and has a photosensitive side chain whose main chain is derived from (meth)acrylate, following formula (0)
(Wherein, A and B are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH- is represented;
S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted with a halogen group;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and the number of X becomes 2, X may be same or different;
P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; , when X is -CH=CH-CO-O- or -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When both l1 and l2 are 0 and T is a single bond, A also represents a single bond;
When l1 is 1 and T is a single bond, B also represents a single bond;
G is the following formula (G-1), (G-2), (G-3) and (G-4)
(Wherein, a broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and ^{when there are two or more R 50} , they may be the same or different from each other, and t is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group))
A side chain (a) having a group selected from a side chain represented by , a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, and the following formula (9) (wherein A and X have the same definitions as above, and R represents a hydroxyl group, l represents an integer of 1 to 12, and m represents an integer of 0 to 2);
(B) organic solvent
A polymer composition containing

The method of claim 1,
(A) The polymer composition in which a component has a photosensitive side chain which raise|generates photocrosslinking, photoisomerization, or optical fleece transition. The method of claim 1,
(A) The component has the following formulas (21) to (31) (wherein A and B have the same definitions as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to each hydrogen atom to be used may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, nitrogen-containing A heterocyclic ring, a C5-C8 alicyclic hydrocarbon group, a C1-C12 alkyl group, or a C1-C12 alkoxy group is represented;
As for q1 and q2, one is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, with the proviso that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In , the sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group or an alkyloxy represents a group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N- or -CF ₂ -) further having any one liquid crystalline side chain selected from the group consisting of polymer composition.

The method of claim 1,
Further, as component (D), the polymer composition further contains a compound having an alkoxysilyl group and a urea structure in which both 1-position and 3-position are substituted. [I] A step of applying the composition according to any one of claims 1 to 4 on a substrate having a conductive film for lateral electric field drive to form a coating film;
[II] The process of irradiating the polarized ultraviolet-ray to the coating film obtained in [I]; And
[III] Process of heating the coating film obtained in [II];
The manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which orientation control ability was provided by having. The board|substrate which has the liquid crystal aligning film for lateral electric field drive type liquid crystal display elements manufactured by the method of Claim 5. A transverse electric field drive type liquid crystal display element which has the board|substrate of Claim 6. [I] A step of applying the composition according to any one of claims 1 to 4 on a first substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] The process of irradiating the polarized ultraviolet-ray to the coating film obtained in [I]; And
[III] Process of heating the coating film obtained in [II];
The process of preparing the 1st board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for lateral electric field drive type liquid crystal display elements to which orientation control ability was provided by having;
[I'] The process of apply|coating the polymer composition in any one of Claims 1-4 on a 2nd board|substrate, and forming a coating film;
[II'] The process of irradiating the polarized ultraviolet-ray to the coating film obtained by [I'];
and
[III'] The process of heating the coating film obtained by [II'];
The process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; And
[IV] The process of opposingly arrange|positioning a said 1st and 2nd board|substrate and obtaining a liquid crystal display element so that the liquid crystal aligning film of a said 1st and 2nd board|substrate may oppose through a liquid crystal;
The manufacturing method of the liquid crystal display element which obtains a transverse electric field drive type liquid crystal display element by having. A transverse electric field driving type liquid crystal display device manufactured by the method according to claim 8. It expresses liquid crystallinity in a predetermined temperature range, It is a polymer|macromolecule which has a photosensitive side chain whose main chain is derived from (meth)acrylate, following formula (0)
(Wherein, A and B are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH- is represented;
S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted with a halogen group;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and the number of X becomes 2, X may be same or different;
P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; , when X is -CH=CH-CO-O- or -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When both l1 and l2 are 0 and T is a single bond, A also represents a single bond;
When l1 is 1 and T is a single bond, B also represents a single bond;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein, the broken line represents a bond, R ⁵⁰ represents a hydrogen atom, a halogen atom, and 1 carbon atom) to 3 represents a group selected from an alkyl group and a phenyl group, and ^{when there are a plurality of R 50} , they may be the same or different from each other, t is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group))
A side chain represented by
a side chain (a) having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, and
Photosensitivity represented by the following formula (9) (wherein A and X have the same definitions as above, R represents a hydroxy group, l represents an integer of 1 to 12, and m represents an integer of 0 to 2) Polymers with side chains.

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