KR102290811B1 - Polymer, polymer composition, and liquid crystal alignment film for horizontal-electric-field drive-type liquid crystal display element - Google Patents

Abstract

[식 중, G 는, 하기 식 (G-1), (G-2), (G-3) 및 (G-4) (식 중, 파선은 결합손을 나타내고, R⁵⁰ 은 수소 원자, 할로겐 원자, 탄소수 1 ∼ 3 의 알킬기, 페닐기에서 선택되는 기를 나타내고, R⁵⁰ 이 복수 있는 경우에는 서로 동일해도 되고 상이해도 되고, J 는 O, S, NH 또는 NR⁵¹ 을 나타내고, R⁵¹ 은 탄소수 1 ∼ 3 의 알킬기 및 페닐기에서 선택되는 기를 나타낸다) 에서 선택되는 기이다] 으로 나타내는 측사슬을 추가로 갖는 측사슬형 고분자에 의해, 상기 과제를 해결한다.

The present invention provides a transverse electric field driving type liquid crystal display element which is highly efficient, has orientation controllability, and is excellent in burn-in characteristics. This invention is a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, The following formula (0)

[Wherein, G is the following formulas (G-1), (G-2), (G-3) and (G-4) (wherein, a broken line represents a bond, R ⁵⁰ is a hydrogen atom, a halogen represents an atom, a group selected from 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, J represents O, S, NH or NR ⁵¹ , R ⁵¹ represents 1 to C 1 The said subject is solved by the side chain type polymer|macromolecule which has a side chain further represented by] which is group selected from) which shows the group chosen from the alkyl group of 3 and a phenyl group.

Description

Polymer, polymer composition, and liquid crystal alignment film for a transverse electric field driving type liquid crystal display device {POLYMER, POLYMER COMPOSITION, AND LIQUID CRYSTAL ALIGNMENT FILM FOR HORIZONTAL-ELECTRIC-FIELD DRIVE-TYPE LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to a novel polymer, the composition containing the said polymer, the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements using the same, and the manufacturing method of the board|substrate which has this alignment film. Further, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent burn-in properties.

BACKGROUND ART A liquid crystal display element is known as a light-weight, thin, and low-power display device, and in recent years it is used for a large-size television use, and has 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, a liquid crystal aligning film is provided in the surface in contact with the liquid crystal of the board|substrate which clamps a liquid crystal as a structural member of a liquid crystal display element, and is playing 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.

Conventionally, the rubbing method is known as an orientation processing method of the liquid crystal aligning film for providing orientation control ability. 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 This rubbing method has been used in the conventional manufacturing process of a liquid crystal display element, since the alignment state of a relatively stable liquid crystal can be implement|achieved easily. 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 an electrical characteristic has been mainly selected.

However, as for the rubbing method which rubs the surface of the liquid crystal aligning film which consists of polyimide etc., generation|occurrence|production of dust generation or 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 with 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, polyvinyl cinnamate is used, polarized ultraviolet light is irradiated, and a dimerization reaction (crosslinking reaction) is generated at the double bond portion of two side chains parallel to polarization. And a liquid crystal is orientated in the direction orthogonal to a polarization direction (for example, refer nonpatent literature 1.) Moreover, when using the side chain type polymer|macromolecule which has azobenzene in a side chain, it irradiates a polarization|polarized-light ultraviolet-ray, and polarization and An isomerization reaction is generated in the azobenzene moiety of a parallel side chain, and a liquid crystal is orientated in the direction orthogonal to a polarization direction (for example, refer nonpatent literature 2).

As in the above example, rubbing is not required in the orientation processing method of the liquid crystal aligning film by a photo-alignment method, 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 orientation treatment method 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 does not require a rubbing process itself compared with the rubbing method conventionally used industrially as an orientation processing method of a liquid crystal display element, Therefore, it has a 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 trying to realize the same degree of alignment control ability as in the case of the rubbing method, the irradiation amount of a large amount of polarized light may be required, or stable alignment of the liquid crystal may not be realized.

For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp having an output of 500 W for 60 minutes. becomes necessary Moreover, also in the case of the photo-alignment method of a dimerization type|mold or a photoisomerization type|mold, the ultraviolet irradiation of a large amount of about several J (joules) - 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 the 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 burn-in generate|occur|produced. In particular, in a liquid crystal display device of a transverse electric field drive type, since liquid crystal molecules are switched in-plane, misalignment of the liquid crystal after liquid crystal drive occurs easily, and display burn-in resulting from AC drive is a major 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 the high orientation control ability to a liquid crystal aligning film efficiently are calculated|required.

An object of this invention is to provide the board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements which is provided with orientation control ability with high efficiency and is excellent in burn-in characteristics, and the transverse electric field drive type liquid crystal display element which has this board|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> As a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, following formula (0)

[Formula 1]

[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-;

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 the 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, and the number of P At the time, P may be the same or different, and when the number of Q becomes 2 or more, Q may be same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

When l1 is 1, 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)

It is a group selected from

A side chain-type polymer further having a side chain represented by .

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

In <3> said <1> or <2>, it is good for side chain type polymer|macromolecule 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 the 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, and the number of P At the time, P may be the same or different, and when the number of Q becomes 2 or more, Q may be same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

In <4> said <1> or <2>, it is good for side chain type polymer|macromolecule to have 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 an integer of 1 to 12;

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

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

[Formula 4]

In <5> said <1> or <2>, it is good for side chain type polymer|macromolecule to have 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, m1 and R have the same definitions as above.

[Formula 5]

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

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

[Formula 6]

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

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

[Formula 7]

In <8> said <1> or <2>, it is good for side chain type polymer|macromolecule to have a photosensitive side chain represented by following formula (18) or (19).

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

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

[Formula 8]

In <9> said <1> or <2>, it is good for side chain type polymer|macromolecule to have 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 9]

In any one of <10> said <1>-<9>, it is good for 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 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, 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;

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, 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 10]

<11> (A) Side chain type polymer|macromolecule in any one of said <1>-<10>, and (B) organic solvent are contained, The polymer composition characterized by the above-mentioned.

<12> The polymer composition according to the above <11>, wherein the polymer composition further has (C) one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. It is good to contain the amine compound that is being used.

<13> In the above <12>, component (C) is _{a divalent organic group having the following formula A-[1] (wherein Y 11} is an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y ₁₂ is It is preferably an amine compound represented by a nitrogen-containing aromatic heterocyclic ring.

[Formula 11]

<14> A step of applying the composition in any one of <11> to <13> 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] The 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 method of <15> said <14>.

A transverse electric field drive type liquid crystal display element which has the board|substrate of <16> said <15>.

<17> Step of preparing the substrate (first substrate) of the above <15>;

[I'] A process of forming a coating film by applying the polymer composition in any one of <11> to <13> above on a second substrate;

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

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

The process of obtaining the 2nd board|substrate which has the 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 correspond 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.

<18> Transverse electric field driving type liquid crystal display device manufactured according to <17>.

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 burn-in 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.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure of one example demonstrating typically the anisotropy introduction|transduction process in the manufacturing method of the liquid crystal aligning film used for this invention, a crosslinkable organic group is used for a photosensitive side chain, and introduce|transduced anisotropy is small. It is a drawing of the case.
It is a figure of one example demonstrating typically the anisotropy introduction|transduction process in the manufacturing method of the liquid crystal aligning film used for this invention, a crosslinkable organic group is used for a photosensitive side chain, and the introduce|transduced anisotropy is large. It is a drawing of the case.
3 : is a figure of one example explaining typically the anisotropic introduction|transduction process in the manufacturing method of the liquid crystal aligning film used for this invention, The organic group which raise|generates a fleece transition or isomerization in a photosensitive side chain is used, and introduce|transduced It is a diagram in the case of small anisotropy.
4 : is a figure of one example explaining typically the anisotropic introduction|transduction process in the manufacturing method of the liquid crystal aligning film used for this invention, The organic group which raise|generates a fleece transition or isomerization in a photosensitive side chain is used, and introduce|transduced It is a diagram in the case of large anisotropy.

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 manufacturing method of this invention has a photosensitive side chain type polymer|macromolecule (henceforth simply called side chain type polymer|macromolecule) which can express liquid crystallinity, The coating film obtained using the said polymer composition is It is a film|membrane which has photosensitive side chain type polymer|macromolecule which can express liquid crystallinity. It orientation-processes by polarized light irradiation, without giving a rubbing process to this coating film. And it becomes the 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 small anisotropy expressed by polarized light irradiation becomes a driving force, and liquid crystalline side chain type polymer|macromolecule itself reorient|orients efficiently 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) A photosensitive side chain type polymer which expresses liquid crystallinity in a predetermined temperature range, The side chain type polymer|macromolecule which further has a side chain represented by said Formula (0), and

(B) organic solvent

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

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

[III] The 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] (conductive film for transverse electric field drive) except that a substrate not having a transverse electric field drive film is used instead of a substrate having a transverse electric field drive conductive film In order to use the board|substrate which does not have, for convenience, in this application, by using the process [I'] - [III']), the 2nd board|substrate which has a liquid crystal aligning film to which the orientation control ability was provided can be obtained by using there is.

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 driving 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], on the board|substrate which has an electrically conductive film for transverse electric field drive, 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. 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 A coating film is formed by applying the polymer composition containing it.

<substrate>

Although it does not specifically limit 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, it does not specifically limit, A glass substrate, or plastic substrates, such as an acrylic substrate and a polycarbonate substrate, etc. can be used.

Moreover, in consideration of application to a reflection type 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), IZO (Indium Zinc Oxide: Indium Zinc Oxide), and the like when the liquid crystal display element is a transmissive film.

Moreover, in the case of a reflective 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 an electrically 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>>

(A) A component is photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined|prescribed temperature range, Comprising: It further has a side chain represented by the said Formula (0).

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

(A) The side chain which has photosensitivity has couple|bonded with the principal chain, and (A) side chain type polymer|macromolecule can raise|generate a crosslinking reaction, an isomerization reaction, or an optical Fris dislocation in response 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 photosensitive side chain type polymer|macromolecule 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 the 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 because the elution of the ionic impurity to a liquid crystal is reduced.

The polymer structure has, for example, a main chain and a side chain bonded thereto, and the side chain is a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group; , has a structure having a photosensitive group that reacts with light and undergoes a crosslinking reaction or isomerization reaction bonded to the tip portion, 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 a structure having a phenylbenzoate group.

More specific examples of the structure of the photosensitive side chain polymer capable of expressing liquid crystallinity include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, 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, and a group represented by the formula (0), in the following formulas (1) to (6) It is preferable that it is a structure which has a side chain which consists of at least 1 type.

[Formula 12]

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 the 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, and the number of P At the time, P may be the same or different, and when the number of Q becomes 2 or more, Q may be same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

When l1 is 1, 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 an integer of 1 to 12;

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

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

[Formula 13]

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, m1 and R have the same definitions as above.

[Formula 14]

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 , l, m1 and m2 have the same definitions as above.

[Formula 15]

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 16]

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 17]

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 18]

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 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, 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;

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, 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 19]

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

The photosensitive side chain type polymer|macromolecule which can express said liquid crystal property 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)]

More specific examples of the monomer having a side chain represented by the formula (0) include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, It is preferable that it is a structure which has a polymeric group comprised by at least 1 sort(s) chosen from the group which consists of radical polymerizable groups, such as maleimide 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 glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether. Compounds such as these are mentioned, 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 in 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.

[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 20]

More specific examples of the photoreactive side chain monomer include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. A photosensitive side chain comprising at least one polymerizable group selected from the group consisting of a radical polymerizable group and siloxane, and at least one of the formulas (1) to (6), preferably, 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 is a photoreactive and/or liquid crystalline side chain monomer, It is novel compound (1) - (11) represented by the following formulas (1) - (11); And it is represented by the following formulas (12) - (17) Compounds (12) to (17) are provided.

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

[Formula 21]

[Formula 22]

[Formula 23]

[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 may contribute to become a mesogenic structure independently, such as biphenyl and phenyl benzoate, and may also 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 24]

More specific examples of the liquid crystalline side chain monomer include hydrocarbon, (meth)acrylate, itaconate, 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 sort(s) chosen from the group which consists of a radical polymerizable group and siloxane, and a side chain which consists of at least 1 sort(s) in said Formula (21)-(31).

(A) Side chain type polymer|macromolecule can be obtained by the polymerization reaction of the photoreactive side chain monomer which expresses the above-mentioned liquid crystallinity. Moreover, it can obtain by the copolymerization of the photoreactive side chain monomer which does not express liquid crystallinity, and a liquid crystalline side chain monomer, or the copolymerization of the photoreactive side chain monomer which expresses liquid crystallinity, and a liquid crystalline side chain monomer. Moreover, it can copolymerize with other monomers 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.

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

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 acrylic 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 rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- and propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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.

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

From the point of 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% is more preferable.

From the point of 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 % is more preferable.

The side chain type polymer|macromolecule of this invention may contain other side chains other than the side chain shown by said Formula (0), a photoreactive side chain, and a liquid crystalline side chain. 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, and a liquid crystalline side chain 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 for 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 more than decomposition temperature. 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 peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), and sulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) can be heard 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 ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2- Ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin Ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4-dimethylamino Isoamyl benzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 2'-Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s- Triazine, 4-[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-dimethylaminostyryl)benz Oxazole, 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'-tetrakis (4 -Ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcar Bazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)- phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di (t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl- 3H-Benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1- (2-benzoyl)ethanone etc. are mentioned. 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, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate , ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, 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 and 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, mixing with the organic solvent mentioned above in the range in which the produced|generated polymer|macromolecule does not precipitate.

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 high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. The concentration is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. The reaction initial stage can be performed at high concentration, and an organic solvent can be added after that.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer becomes small, and when it is small, the molecular weight of the obtained polymer becomes large, so the ratio of the radical initiator is 0.1 with respect to the monomer to be polymerized It is preferable that they are mol% - 10 mol%. In addition, at the time of polymerization, various monomer components, a solvent, an initiator, etc. can also be added.

[Recovery of polymer]

What is necessary is just to inject|throw-in the reaction solution to a poor solvent, and to precipitate these polymers, 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. . Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can be heard 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, when 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 reduced. 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 5000-20000.

[Preparation of polymer composition]

It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, it is preferable that the polymer composition used for this invention is prepared as a solution in which the resin component for forming a resin film was melt|dissolved in the organic solvent. Here, the resin component is a resin component containing the photosensitive side chain type polymer|macromolecule which can express the liquid crystal demonstrated already demonstrated. 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 all can express the liquid crystallinity mentioned above 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 those 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 for such another polymer.

<Amine compound>

The polymer composition used in the present invention is a specific amine compound, specifically, has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, It is preferable to have an amine compound present. 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

A specific amine compound will not be specifically limited if the following effect i) and/or ii) are exhibited when the polymer composition used for this invention forms a liquid crystal aligning film. 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.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. Preferably carbon number of an aliphatic hydrocarbon group is 1-20, More preferably, it is 1-15, More preferably, it is 1-10.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosan ring, tricycloeicosane ring , a tricyclodecic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. Preferably it is a C3-C20 ring, More preferably, it is a C3-C15 ring, More preferably, it is a C3-C10 ring non-aromatic cyclic hydrocarbon group.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound is a 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 structure selected from, and preferably 1 to 4 structures.

[Formula 25]

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 a substituent containing a hetero atom in the carbon atom of these nitrogen-containing aromatic heterocyclic rings.

A more preferable amine compound is represented by the following formula A-[1] ( _{wherein Y 11} is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring) Preferably, it is an amine compound. In the formula A-[1], Y ₁₂ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

[Formula 26]

_{Preferably, Y 11} in the formula A-[1] is a divalent organic group having one selected from a C1-C20 aliphatic hydrocarbon group and a C3-C20 non-aromatic cyclic hydrocarbon group. Examples of the non-aromatic cyclic hydrocarbon group include the structures described above. Y ₁₁ is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclo an undecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, an adamantane ring, etc. are mentioned. Y ₁₁ is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, _{-CH 2} - in the arbitrary aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group included in _{Y 11} and not adjacent to the amino group is -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, divalent ring It may be substituted by a type hydrocarbon group or a heterocyclic ring. In addition, even if the hydrogen atom bonded to an arbitrary carbon atom is substituted with a C1-C20 linear or branched alkylene group, a cyclic hydrocarbon group, a C1-C10 fluorine-containing alkyl group, a heterocyclic ring, a fluorine atom, or a hydroxyl group do.

Specific examples of the divalent cyclic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a cyclopropane ring, a cyclobutane Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring , cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosan ring, tricycloeicosane ring, tricyclodecane ring, bicycloheptane ring, decahydronaphthalene ring, norbor a nene ring, an adamantane ring, etc. are mentioned.

Moreover, as a specific example of a bivalent heterocyclic ring, 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, carbazole Ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenantrol and a lean ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring.

_{Y 12} in Formula A-[1] is a nitrogen-containing aromatic heterocyclic ring, and as above-mentioned, at least 1 selected from the group which consists of Formula [20a], Formula [20b], and Formula [20c] It is preferably an aromatic cyclic hydrocarbon containing a structure. As the specific example, the structure mentioned above is mentioned. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a quinoxaline ring, An azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, and a phthalazine ring are preferable.

Further, in view of ease of electrostatic interaction, such as salt formation, or hydrogen bonding to the nitrogen-containing aromatic heterocyclic ring, and in particular polyimide carboxyl group, Y ₁₁ is formula [20a], equation [20b] is contained in Y _12, And it is preferable to couple|bond with the substituent which is not mutually adjacent to Formula [20c].

_{In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 12} of Formula A-[1] may have a halogen atom and/or a substituent of an organic group, The organic group may be heterocyclic, such as an oxygen atom, a sulfur atom, and a nitrogen atom. You may contain an atom.

A preferable combination of _{Y 11} and Y _{12 in} the formula A-[1] is one selected from the _{group consisting of Y 11} being an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. is a divalent organic group having, Y ₁₂ is, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 12} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

In a more preferred amine compound is the formula A- [2] (the following equation, Y ₁₃ is a second aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having a carbon number of valence 1 ~ 10, Y ₁₄ is a single bond, or - O-, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms, and the total of carbon atoms in _{Y 13} and Y _{14 is 1 to 20. Y 15} is nitrogen It is an amine compound represented by the containing aromatic heterocyclic ring.).

[Formula 27]

_{Y 13} in Formula A-[2] is a C1-C10 divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. , cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclo and the like. More preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclounde A kane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring are mentioned. Especially preferably, it is a C1-C10 linear or branched alkylene group.

_{-CH 2} - in any aliphatic hydrocarbon group not adjacent to the amino group or non-aromatic cyclic hydrocarbon group included in Y ₁₃ is -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ - , -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, divalent cyclic hydrocarbon It may be substituted by group or heterocyclic ring. The hydrogen atom bonded to any carbon atom may be substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or a hydroxyl group. . The cyclic hydrocarbon group and heterocyclic ring as used herein have the same definitions as those described for _{Y 11 in Formula A-[1].}

_{Y 14} in Formula A-[2] is a single bond or -O-, -NH-, -S-, -SO ₂ -, or a C1-C19 divalent organic group. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y ₁₄ are given below.

For example, a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, - O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring , cyclooctadecane ring, cyclononadecane ring, cycloicosan ring, tricycloeicosane ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring , naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, Benzimidazole ring, benzoimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, A piperazine ring, a piperidine ring, a dioxane ring, a morpholine ring, etc. are mentioned. As ₁₄ Y, it may contain two or more of them.

Specific examples including two or more of these include -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ - , -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, - CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH -C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H ₈ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH(CH ₃ ) -, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH) -CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, -CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH( CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH) ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, and the like.

_{Y 15} in Formula A-[2] is a nitrogen-containing aromatic heterocyclic ring, and is the same as the definition _{of Y 12 in Formula A-[1].} As a specific example, there may be mentioned the same structure as the above-mentioned Y _12. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a quinoxaline ring, An azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring is preferred.

In addition, nitrogen containing in terms of ease of electrostatic interaction, such as salt formation or hydrogen bond of the aromatic heterocyclic rings and in particular polyimide carboxyl group, Y ₁₄ is an expression that includes the Y ₁₅ [20a], formula [20b] or It is preferable to couple|bond with the carbon atom which is not mutually adjacent to Formula [20c].

_{In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y 15} in Formula A-[2] may have a halogen atom and/or a substituent of an organic group, and the organic group is a hetero atom, such as an oxygen atom, a sulfur atom, and a nitrogen atom. may contain.

A preferable combination _{of Y 13} , Y ₁₄ and Y _{15 in} the formula A-[2] is that _{Y 13} is a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring; , Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO -, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, - Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, -CH(OH)-, -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, - OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ - , -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH -CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )- , -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H8-CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH(CH ₃ )-, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O- CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ -CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ - CH(CH ₃ )-, -NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, -CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH) )-C ₄ H ₈ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)- CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N (CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, Y ₁₅ is, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benz an imidazole ring, a benzoimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A more preferable combination _{of Y 13} , Y ₁₄ and Y _{15 in} the formula A-[2] is that _{Y 13} is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, or a cyclopentane ring. , a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring, Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO -O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CH(OH)-, -NH-CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -OC ₂ H ₄ -, -NH-CO-CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ -, -NH -CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ ) -, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH (CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene a ring, a fluorene ring, an anthracene ring, a phenanthrene ring, or a phenalene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrida a gin ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring . In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A more preferable combination _{of Y 13} , Y ₁₄ and Y _{15 in} the formula A-[2] is that _{Y 13} is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, or a cyclopentane ring. , or a cyclohexane ring, Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH -, -NH-CO-, -CO-, -CH(OH)-, -NH-CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -NH-CO-CH ₂ -, - CO-CH ₂ -, -CO-NH-CH ₂ -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, - CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO -, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring , benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, or anthracene ring, Y ₁₅ is, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring , a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A particularly preferable combination _{of Y 13} , Y ₁₄ and Y _{15 in} the formula A-[2] _{is, Y 13} is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, Y ₁₄ valence, single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH(OH)-, benzene ring, naphthalene ring, fluorene ring , or an anthracene ring, and Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. In addition, _{the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y 15} may have a halogen atom and/or a substituent of an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

As a specific example of the specific amine compound of (B) component of this invention, the compound of M1-M156 is mentioned.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

As a more preferable compound, M6-M8, M10, M16-M21, M31-M36, M40-M45, M47-M57, M59-M63, M68, M69, M72-M82, M95-M98, M100-M103, M108- M125, M128-M137, M139-M143, M149-M156 are mentioned. More preferably, M6-M8, M16-M20, M32-M36, M40, M41, M44, M49-M54, M59-M62, M68, M69, M75-M82, M100-M103, M108-M112, M114-M116, M118 to M121, M125, M134 to M136, M139, M140, M143, M150, M152 to M156.

<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 and may be mixed and used.

The polymer composition used for this invention may contain components other than said (A), (B), and (C) component. Although the solvent and compound which improve the film-thickness uniformity and surface smoothness at the time of apply|coating a polymer composition as the example, 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 acetate, methyl pyruvate, ethyl pyruvate, 3-methoxymethyl propionate, 3-ethoxy methyl ethyl propionate , 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-monoethyl Low levels of 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 surface tension, etc. can be heard

One type may be sufficient as these poor solvents, and multiple types may be mixed and used for them. 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, a silicone type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Corporation), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Semi-Chemicals) ) 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-ureapropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, 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 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 34]

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, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylamino methyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like are exemplified.

When using the compound which improves the adhesiveness of 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 resin components 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.

As an additive, a photosensitizer can also be used. 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, benzan Tron, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methyl Benzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxa) Zoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzo Oxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-(p- Fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene) ), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoinalkylether, N-alkylated phthalone, acetophenoneketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolidine, merocumarin, and the like.

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

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 dielectric constant and electroconductivity of a liquid crystal aligning film, when it is set as a dielectric material and an electrically-conductive substance, and also 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), a spray method, etc., You may use these according to the objective.

After the polymer composition is applied on the substrate having a conductive film for driving a transverse electric field, it is 50 to 200° C., preferably 50 to 150° C. by a 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 to 150 nm.

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

The irradiation amount of the polarized ultraviolet rays depends on the coating film to be used. The amount of irradiation is the amount of polarized ultraviolet light that achieves the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet light in the coating film and the ultraviolet absorbance in the perpendicular direction. 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 which polarized in process [II] was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

Heating can use heating means, such as a hot plate, a heat circulation type oven, or an IR (infrared) type|mold 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 thin film surface like a coating film, it is expected that the liquid crystal expression temperature of the coating film surface 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, as for heating temperature, it is more preferable that it exists in the temperature range of the liquid-crystal expression temperature of the surface of a coating film. That is, the temperature range of the heating temperature after polarization ultraviolet irradiation is a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer to be used as the lower limit, and 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 an upper limit. 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 the surface of the coating film undergoes a phase transition from the solid phase to the liquid crystal phase, and the isotropic phase transition temperature causing the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase). (Tiso) refers to the temperature below.

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 with a liquid crystal aligning film can be manufactured with high efficiency.

<Process [IV]>

[IV] The process has a 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], and the electrically conductive film obtained by said [I'] - [III'] similarly. A liquid crystal cell is prepared by a known method by arranging a substrate (second substrate) with a liquid crystal aligning film, which is not present, to face each other through a liquid crystal so that both liquid crystal aligning films face each other, and a transverse electric field driving type liquid crystal display device is manufactured. it is fair Further, in the steps [I'] to [III'], in the step [I], instead of the substrate having the conductive film for driving the lateral electric field, a substrate without the conductive film for driving the lateral electric field was used, except that the substrate was used in 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 manufacturing a liquid crystal cell or a liquid crystal display element, the above-mentioned first and second substrates are prepared, a spacer is dispersed on the liquid crystal aligning film of one side of the substrate, the liquid crystal aligning film surface is inside, and another After bonding the one side board|substrate, the method of injecting a liquid crystal under reduced pressure and sealing, or the method of sealing a board|substrate, after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. can be exemplified. 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, and more preferably 2 µm to 10 µm. The spacer diameter determines the distance between the pair of substrates that sandwich 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, it irradiates polarized ultraviolet-ray. Next, by heating, highly efficient anisotropic introduction to a side chain type polymer film is implement|achieved, and the board|substrate with a 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 into 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 a side chain polymer, a coating film is formed on a substrate using a side chain polymer, then irradiated with polarized ultraviolet rays, After heating, a liquid crystal display element is manufactured.

Hereinafter, embodiment using side chain type polymer|macromolecule of the structure which has group which raise|generates an optical Fries rearrangement group or isomerization as a 1st form and photoreactive group for embodiment using side chain type polymer|macromolecule of the structure which has a photocrosslinkable group as a photoreactive group will be described as a second form.

BRIEF DESCRIPTION OF THE DRAWINGS In the 1st aspect in this invention, the anisotropic introduction process in the manufacturing method of the liquid crystal aligning film using the side chain type polymer|macromolecule of the structure which has a photocrosslinkable group as a photoreactive group is demonstrated typically It is one example drawing. Fig. 1 (a) is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, and Fig. 1 (b) is a diagram schematically showing the state of the side chain polymer film after polarized light irradiation, Fig. 1 (c) is a figure which shows typically the state of the side chain type polymer film after heating, and especially when introduce|transduced anisotropy is small, ie, in the 1st aspect of this invention, WHEREIN: In the 1st aspect of this invention, the ultraviolet irradiation amount of [II] process is ΔA It is a schematic diagram in the case of being in the range of 1% - 15% of the ultraviolet irradiation amount which maximizes.

2 is a 1st aspect in this invention. WHEREIN: The anisotropic introduction process in the manufacturing method of the liquid crystal aligning film using the side chain type polymer|macromolecule of the structure which has a photocrosslinkable group as a photoreactive group is demonstrated typically It is one example drawing. Fig.2 (a) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, Fig.2 (b) is a figure which shows typically the state of the side chain type polymer film|membrane after polarized light irradiation, FIG. (c) is a figure which shows typically the state of the side chain type polymer film after heating, and especially when introduce|transduced anisotropy is large, ie, in the 1st aspect of this invention, WHEREIN: The ultraviolet irradiation amount of [II] process is ΔA It is a schematic diagram in the case of being in the range of 15% - 70% of the ultraviolet irradiation amount which maximizes.

FIG. 3 : is a 2nd aspect in this invention. WHEREIN: Liquid crystal aligning film using side chain type polymer|macromolecule of the structure which is a photoisomerization group as a photoreactive group, or is represented by Formula (18) mentioned above, and has an optical Fries potential group. It is a figure of one example which schematically demonstrates the anisotropic introduction|transduction process in the manufacturing method. Fig. 3 (a) is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, and Fig. 3 (b) is a diagram schematically showing the state of the side chain polymer film after polarized light irradiation, Fig. 3 (c) is a figure which shows typically the state of the side chain type polymer film after heating, especially when the introduced anisotropy is small, ie, in the 2nd aspect of this invention, WHEREIN: The ultraviolet irradiation amount of the [II] process is ΔA It is a schematic diagram in the case of being in the range of 1% - 70% of the ultraviolet irradiation amount which maximizes.

4 : in the 2nd aspect in this invention. WHEREIN: In the manufacturing method of the liquid crystal aligning film using the side chain type polymer|macromolecule of the structure which has an optical Fries potential group represented by Formula (19) mentioned above as a photoreactive group. It is a figure of one example which schematically demonstrates the anisotropic introduction|transduction process of . Fig.4 (a) is a figure which shows typically the state of the side chain type polymer film before polarized light irradiation, Fig.4 (b) is a figure which shows typically the state of the side chain type polymer film after polarized light irradiation, Fig. 4 (c) is a figure which shows typically the state of the side chain type polymer film after heating, and especially when the introduced anisotropy is large, ie, in the 2nd aspect of this invention, WHEREIN: The ultraviolet irradiation amount of the [II] process is ΔA It is a schematic diagram in the case of being in the range of 1% - 70% of the ultraviolet irradiation amount which maximizes.

In the first aspect of the present invention, in the anisotropic introduction treatment into the coating film, when the ultraviolet irradiation amount in step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, first, the substrate A coating film 1 is formed on it. As shown to Fig.1 (a), in the coating film 1 formed on the board|substrate, it has the structure which the side chain 2 arranges at random. According to the random arrangement|sequence of the side chain 2 of the coating film 1, the mesogenic component of the side chain 2 and the photosensitive group are orientating at random, and the coating film 1 is isotropic.

In the first aspect of the present invention, in the anisotropic introduction treatment into the coating film, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount for maximizing ΔA, first, the substrate A coating film 3 is formed on it. As shown to Fig.2 (a), in the coating film 3 formed on the board|substrate, it has the structure which the side chain 4 arranges at random. According to the random arrangement of the side chain 4 of the coating film 3, the mesogenic component and the photosensitive group of the side chain 4 are orientating at random, and the coating film 2 is isotropic.

2nd aspect in this invention WHEREIN: Liquid crystal using side chain type polymer|macromolecule of the structure which is a photoisomerism group, or is represented by Formula (18) mentioned above by the anisotropic introduction|transduction process to a coating film, and has an optical Fries potential group. In the case of using an alignment film, when the ultraviolet irradiation amount in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation amount for maximizing ΔA, the coating film 5 is first formed on the substrate. As shown to Fig.3 (a), in the coating film 5 formed on the board|substrate, it has the structure which the side chain 6 arranges at random. According to the random arrangement|sequence of the side chain 6 of the coating film 5, the mesogenic component of the side chain 6 and the photosensitive group are orientating at random, and the side chain type polymer film 5 is isotropic.

2nd aspect in this invention WHEREIN: When using the liquid crystal aligning film using the side chain type polymer|macromolecule of the structure which has an optical Fries potential group represented by Formula (19) mentioned above by the anisotropic introduction process to a coating film, WHEREIN: When the ultraviolet irradiation amount of step [II] exists in the range of 1% - 70% of the ultraviolet irradiation amount which maximizes (DELTA)A, the coating film 7 is first formed on a board|substrate. As shown to Fig.4 (a), in the coating film 7 formed on the board|substrate, it has the structure which the side chain 8 arranges at random. According to the random arrangement of the side chain 8 of the coating film 7, the mesogenic component and the photosensitive group of the side chain 8 are orientating at random, and the coating film 7 is isotropic.

In the first embodiment of the present embodiment, when the ultraviolet irradiation amount in step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the ultraviolet ray polarized with respect to this isotropic coating film 1 investigate Then, as shown in FIG. 1(b), the photosensitive group of the side chain 2a having a photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as a dimerization reaction. causes As a result, the density of the side chain 2a which carried out the photoreaction becomes slightly high in the polarization direction of an irradiation ultraviolet-ray, and very small anisotropy is provided to the coating film 1 as a result.

In the first embodiment of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount for maximizing ΔA, the ultraviolet ray polarized with respect to the isotropic coating film 3 investigate Then, as shown in Fig. 2(b), the photosensitive group of the side chain 4a having a photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as a dimerization reaction. causes As a result, the density of the side chain 4a which performed photoreaction becomes high in the polarization direction of an irradiation ultraviolet-ray, and small anisotropy is provided to the coating film 3 as a result.

In the 2nd aspect of this embodiment, using the liquid crystal aligning film using the side chain type polymer|macromolecule of a structure which is a photoisomerism group or is represented by Formula (18) mentioned above and has an optical Fries potential group, the ultraviolet irradiation amount of the [II] process When it exists in the range of 1% - 15% of the ultraviolet-ray irradiation amount which maximizes (DELTA)A, the ultraviolet-ray which polarized with respect to this isotropic coating film 5 is irradiated. Then, as shown in Fig. 3(b), the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as an optical Fleece dislocation. causes As a result, the density of the side chain 6a which performed photoreaction becomes slightly high in the polarization direction of an irradiation ultraviolet-ray, and very small anisotropy is provided to the coating film 5 as a result.

In the 2nd aspect of this embodiment, the ultraviolet irradiation amount of the [II] process maximizes (DELTA)A using the coating film using the side chain type polymer|macromolecule of the structure which has an optical Fries potential group, which is represented by Formula (19) mentioned above and has an optical Fries potential group. When it exists in 1 % - 70% of the range of the ultraviolet irradiation amount to do WHEREIN: The ultraviolet-ray which polarized with respect to this isotropic coating film 7 is irradiated. Then, as shown in Fig. 4(b), the photosensitive group of the side chain 8a having a photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as an optical Fleece dislocation. causes As a result, the density of the side chain 8a which performed photoreaction becomes high in the polarization direction of an irradiation ultraviolet-ray, and small anisotropy is provided to the coating film 7 as a result.

Next, in the first embodiment of the present embodiment, when the ultraviolet irradiation amount in step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount for maximizing ΔA, the coating film 1 after polarized light irradiation is heated, liquid crystal state. Then, as shown in FIG.1(c), in the coating film 1, the quantity of the crosslinking reaction which generate|occur|produced differs between the direction parallel to the polarization direction of an irradiation ultraviolet-ray, and a direction perpendicular|vertical. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet light is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity of the polarization direction of an irradiation ultraviolet-ray and the perpendicular|vertical direction becomes higher than the liquid crystallinity of a parallel direction, the side chain 2 containing a mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of an irradiation ultraviolet-ray. . As a result, the very small anisotropy of the coating film 1 caused by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 1 .

Similarly, in the first embodiment of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount for maximizing ΔA, the coating film 3 after polarized light irradiation is heated, liquid crystal state. Then, as shown to FIG.2(c), in the side chain type polymer film 3, the quantity of the crosslinking reaction which generate|occur|produced differs between the direction parallel to the polarization direction of an irradiation ultraviolet-ray, and the perpendicular|vertical direction. Therefore, it self-organizes in the direction parallel to the polarization direction of an irradiation ultraviolet-ray, and the side chain 4 containing a mesogenic component is reorientated. As a result, the small anisotropy of the coating film 3 caused by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 3 .

Similarly, in the 2nd aspect of this embodiment, it is a photoisomerism group, or it is an ultraviolet-ray of [II] process using the coating film using the side chain type polymer|macromolecule of the structure which is represented by Formula (18) mentioned above and has an optical Fries potential group. When an irradiation amount exists in 1% - 70% of the range of the ultraviolet irradiation amount which maximizes (DELTA)A, the coating film 5 after polarized light irradiation is heated and it is set as a liquid-crystal state. Then, as shown in FIG.3(c), in the coating film 5, the amount of the optical Fries dislocation reaction which generate|occur|produced differs between the direction parallel to the polarization direction of an irradiation ultraviolet-ray, and a direction perpendicular|vertical. In this case, since the liquid crystal orientation force of the optical fleece potential body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet ray is stronger than the liquid crystal orientation force of the side chain before the reaction, it self-organizes in a direction perpendicular to the polarization direction of the irradiated ultraviolet ray to form a mesogenic component The side chain (6) comprising As a result, the very small anisotropy of the coating film 5 caused by the optical Fris dislocation reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 5 .

Similarly, in the 2nd aspect of this embodiment, using the coating film using the side chain type polymer|macromolecule of the structure which has an optical Fries potential group represented by Formula (19) mentioned above, the ultraviolet irradiation amount of [II] process is ΔA When it exists in 1% - 70% of the range of the ultraviolet irradiation amount made into the maximum WHEREIN: The coating film 7 after polarization|polarized-light irradiation is heated and it is set as a liquid-crystal state. Then, as shown to FIG.4(c), in the side chain type polymer film 7, the quantity of the optical Fries dislocation reaction which generate|occur|produced differs between the direction parallel to the polarization direction of an irradiation ultraviolet-ray, and the direction perpendicular|vertical. Since the anchoring force of the optical fleece dislocation body 8(a) is stronger than that of the side chain 8 before the dislocation, when a certain amount or more of the optical fleece dislocation body is generated, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet light to form a mesogenic component The containing side chain (8) is reorientated. As a result, the small anisotropy of the coating film 7 caused by the optical Fris dislocation reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 7 .

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

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

The amount of polarized ultraviolet light that is optimal for highly efficient anisotropy introduction into the coating film used in the present invention is that of the 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 amount of irradiation. 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 for this invention, as a result of irradiating the ultraviolet-ray which polarized with respect to the structure which has a photocrosslinkable group, when the photosensitive group of the side chain to crosslink reacts excessively, the crosslinking reaction between side chains will advance too much. In that case, the obtained film|membrane becomes rigid, and it may interfere with advancing of 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 the case of irradiating a polarized ultraviolet ray to a structure having an optical Fris dislocation group, if the irradiation amount of ultraviolet ray 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. there is.

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 Fris relocation reaction by irradiation of polarized ultraviolet light is the amount of the photosensitive group of the side chain type polymer film. It is preferable to set it as 0.1 mol% - 40 mol%, and it is more preferable to set it as 0.1 mol% - 20 mol%. By 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, the quantity of the photocrosslinking reaction of the photosensitive group in the side chain of a side chain type polymer film, a photoisomerization reaction, or an optical Fries rearrangement reaction by optimization of the irradiation amount of the ultraviolet-ray which polarized Optimize. And the anisotropic introduction|transduction to the coating film used for this invention which is highly efficient with heat processing after that 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 polarization|polarized-light ultraviolet irradiation, and the ultraviolet absorption of the perpendicular|vertical direction are measured, respectively. From the measurement result of ultraviolet absorption, (DELTA)A which is the difference between the ultraviolet absorbance of the direction parallel to the polarization direction of the ultraviolet-ray which polarized in the coating film, and the ultraviolet absorbance of the perpendicular|vertical direction is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays 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 ultraviolet-ray which polarized in 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 make the irradiation amount of the polarized ultraviolet-ray with respect to the coating film used for this invention into 1% - 70% of the amount of polarized ultraviolet-ray which implement|achieves ΔAmax, and 1% to 50% It is more preferable to set it as within the range. The coating film used for this invention WHEREIN: The irradiation amount of the polarization 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 It corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

From the above, in the manufacturing method of this invention, in order to implement|achieve highly efficient anisotropic introduction to a coating film, it is good to determine the suitable 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 the temperature of the heating 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 and high quality liquid crystal television, etc. can be used readily.

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

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 respectively synthesize|combined as follows. 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 for GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether), and additive T1 (3-aminomethylpyridine), a commercially available thing was used.

[Formula 35]

<Synthesis Example 1>

Synthesis of specific glycidyl compound (G1)

[Formula 36]

To 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 (dimethyl formamide) was added dropwise, and reacted at room temperature for 2 hours. The solution was concentrated and the obtained individual was dissolved with THF (350 g). This solution was dripped at the THF solution (88g) of glycidol (8.89g, 120 mmol) and triethylamine (13.4g, 132 mmol) 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. Silica gel chromatography was performed for the obtained crude substance using ethyl acetate and hexane, and G1 was obtained as a white solid. (Amount: 14.9 g, 69%).

Glycidyl derivative (G1):

<Synthesis Example 2>

Synthesis of specific oxetane compound (G2)

[Formula 37]

Carboxylic acid derivative (M2) (21.4 g, 70 mmol), dimethylaminopyridine (0.85 g, 7 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (14,8 g, To a THF (tetrahydrofuran) solution (107 g) of 77 mmol) was added 3-ethyl-3-oxetanemethanol (8.58 g, 73.5 mmol), and the mixture was reacted at room temperature for 18 hours. Then, the precipitated insoluble matter was removed by filtration, and after adding ethyl acetate (500g), it wash|cleaned 3 times with water (200g), and dried over magnesium sulfate. After removing magnesium sulfate by filtration, G2 (amount 27.3 g, yield 96%) was obtained as a colorless liquid by concentrating.

Oxetane compound (G2):

<Synthesis Example 3>

Synthesis of specific oxetane compound (G3)

In the same manner as in the above synthesis example, the following oxetane compound (G3) was synthesized.

[Formula 38]

Oxetane compound (G3):

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.

(Polymerization Initiator)

AIBN: 2,2'-azobisisobutyronitrile.

<Polymer Synthesis Example 1>

MA1 (9.67 g, 29.1 mmol) and GMA (0.13 g, 0.9 mmol) were dissolved in THF (56.3 g) and degassed with a diaphragm pump, then AIBN (0.15 g, 3 mmol) was added and degassed again. did. Then, it was made to react at 60 degreeC for 12 hours, and the polymer solution of methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (1000 ml), and the obtained precipitate was filtered. This deposit was wash|cleaned with diethyl ether, it was made to dry under reduced pressure in 40 degreeC oven, and the methacrylate polymer powder P1 was obtained.

<Polymer Synthesis Examples 2 to 6>

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

<Example 1>

NMP (54.0 g) was added to the methacrylate polymer powder P1 (6.0 g) obtained in polymer synthesis 1, and stirred at room temperature for 5 hours to dissolve it. To this solution, BC (40.0 g) was added and stirred to obtain a polymer solution A1. This polymer solution was made into the liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

<Examples 2 to 12>

The composition shown in Table 2 was adjusted using the method similar to Example 1, and liquid crystal aligning agents A2-A12 of Examples 2-12 were obtained.

<Control polymer synthesis example 1>

After dissolving MA1 (9.97 g, 30 mmol) in THF (57.5 g) and deaeration with a diaphragm pump, AIBN (0.15 g, 3 mmol) was added thereto and deaeration was performed again. Then, it was made to react at 60 degreeC for 12 hours, and the polymer solution of methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (1000 ml), and the obtained precipitate was filtered. This deposit was wash|cleaned with diethyl ether, it dried under reduced pressure in 40 degreeC oven, and obtained methacrylate polymer powder CP1.

<Control polymer synthesis example 2>

Using the same method as in Control 1 with the composition of MA1 (5.9 g, 18 mmol), MA2 (3.7 g, 12 mmol), THF (55.5 g), and AIBN (0.15 g, 3 mmol), methacrylate polymer powder CP2 got

<Controls 1 and 2>

Liquid crystal aligning agent B1 of the control 1 was obtained by the method similar to Example 1 using CP1. Similarly, liquid crystal aligning agent B2 of the control 2 was obtained using CP2.

<<Preparation of liquid crystal cell>>

The liquid crystal cell was manufactured in the procedure as shown below using liquid crystal aligning agent A1 obtained in Example 1. The substrate was a glass substrate having a size of 30 mm x 40 mm, a thickness of 0.7 mm, and a comb-tooth-shaped pixel electrode formed by patterning an ITO film was used.

The pixel electrode had the comb-tooth-like shape comprised by arranging two or more "<"-shaped electrode elements in which the center part was bent. The width in the transverse direction of each electrode element was 10 mu m, and the distance between the electrode elements was 20 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but a thick, curved shape in the central part similarly to the electrode element. It has a shape resembling the letter 'K'.

Each pixel was divided|segmented up and down with the bent part in the center as a boundary, and had the 1st area|region above the bending|flexion part, and the 2nd area|region below. Comparing the 1st area|region and 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them was found to be different. That is, based on the alignment treatment direction of the liquid crystal alignment film to be described later, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of +15° (clockwise), and in the second region of the pixel, the pixel electrode The electrode elements were formed so as to form an angle (clockwise) of -15°. That is, in the first region and the second region of each pixel, the directions of the rotational operation (in-plane switching) in the substrate plane of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode are opposite to each other. was structured to be

Liquid crystal aligning agent A1 obtained in Example 1 was spin-coated to the prepared said board|substrate with an electrode. Then, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Then, after 20 mJ/cm<2> of 313 nm ultraviolet-rays were irradiated to the coating-film surface through a polarizing plate, it heated for 10 minutes with a 150 degreeC hotplate, and obtained the board|substrate with a liquid crystal aligning film. Moreover, it orientation-processed by forming a coating film similarly also to the glass substrate which has a columnar spacer with a height of 4 micrometers in which the electrode is not formed as a counter board|substrate. The sealing compound (XN-1500T by Kyoritsu Chemical) was printed on the liquid crystal aligning film of one board|substrate. Then, after bonding the other board|substrate so that a liquid crystal aligning film surface faced and an orientation direction might be set to 0 degree, and it bonded together, the sealing compound was thermosetted and the empty cell was manufactured. Liquid crystal MLC-2041 (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 provided with the structure of IPS(In-Planes Switching) mode liquid crystal display element was obtained.

Liquid crystal cell was similarly manufactured for liquid crystal aligning agent A2 - A12 obtained in Examples 2-12 using liquid crystal aligning agent B1, B2 obtained by Controls 1 and 2.

<<Evaluation of voltage retention (VHR)>>

Using the liquid crystal cell prepared above, a voltage of 5 V was applied for 60 μs under a temperature of 70° C., the voltage after 16.67 ms was measured, and how much the voltage was maintained was calculated as the voltage retention (VHR1). Furthermore, the AC voltage of 16Vpp was applied to the measured cell in the constant temperature environment of 70 degreeC at the frequency of 30 Hz for 168 hours. 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. The obtained cell was measured under the same conditions as VHR1, and how much voltage was maintained was calculated as voltage retention (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 is shown in Table 3 with the composition of the liquid crystal aligning agent of an Example and a control.

Table 3 shows that in Examples 1-12, VHR1 improves by copolymerizing the monomer which has an epoxy group compared with Controls 1 and 2 which do not copolymerize. Moreover, in Examples 5-8, 11 and 12, it turns out that the result of VHR2 is favorable by adding additive T1 further.

<Afterimage evaluation>

The liquid crystal cell for IPS mode prepared in Examples 1 to 8 is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the backlight is turned on in a state where no voltage is applied, and the liquid crystal cell is arranged so that the luminance of the transmitted light is the smallest. The angle was adjusted. And the rotation angle when the liquid crystal cell was 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.

Next, in 60 degreeC oven, the alternating voltage of 16V _{PP was applied at the frequency of 30 Hz for 168 hours.} 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.

By heating in a liquid crystal expression temperature range after irradiating an ultraviolet-ray to the side chain type polymer film which expresses liquid crystallinity, it is because liquid crystal orientation ability is provided with high efficiency in the whole polymer by self-organization, or shift of orientation orientation even after long-term AC drive was hardly observed.

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

Claims (18)

As a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a predetermined temperature range, 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-;
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 the 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 l1 and l2 are both 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)

(Wherein, the 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)
It is a group selected from
Side chain polymer|macromolecule which has a side chain represented by and a side chain represented by following formula (9).

(wherein A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O -CO-CH=CH- represents;
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 the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2;
R represents a hydroxyl group) The method of claim 1,
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, 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;
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, and an alkyl group , or an alkyloxy group;
Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -)
A side chain type polymer having any one kind of liquid crystalline side chain selected from the group consisting of.

(A) The polymer composition containing the side chain type polymer|macromolecule of Claim 1, and (B) an organic solvent. 4. The method of claim 3,
The polymer composition further comprises (C) 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. 5. The method of claim 4,
The component (C) is represented by the following formula A-[1] ( _{wherein Y 11} is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring) A composition that is an amine compound.

[I] A step of applying the composition according to any one of claims 3 to 5 on a 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] The 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 6. A transverse electric field drive type liquid crystal display element which has the board|substrate of Claim 7. [I] A step of applying the composition according to any one of claims 3 to 5 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] The process of heating the coating film obtained in [II];
The process of obtaining the 1st 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;
[I'] A process of applying the polymer composition according to any one of claims 3 to 5 on a second substrate to form a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet rays; and
[III'] A step of heating the coating film obtained in [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 the said 1st and 2nd board|substrate so that the liquid crystal aligning film of a said 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. A transverse electric field driving type liquid crystal display device manufactured by the method according to claim 9. delete delete delete delete delete delete delete delete

Images