TWI637044B - Polymer, polymer composition, and liquid crystal alignment film for horizontal electric field drive type liquid crystal display element - Google Patents

Abstract

The present invention provides a lateral electric field drive type liquid crystal display element that is highly efficient, imparts alignment control ability, and has excellent afterimage characteristics. The present invention is a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and further has the following formula (0) [wherein G is the following formula (G-1), (G- 2), (G-3) and (G-4) (where the dotted line is a bonding bond, and R ^{50 is a group selected} from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group. When there are a plurality of R ⁵⁰ , they may be the same or different from each other, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group) The side chain type polymer represented by the side chain] can solve the above problems.

Description

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

The present invention relates to a novel polymer, a composition containing the polymer, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element using the same, and a method for manufacturing a substrate having the alignment film. Furthermore, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent afterimage characteristics.

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices. In recent years, they have been used for large-scale television applications, and have developed dramatically. The liquid crystal display element includes, for example, a liquid crystal layer supported by a transparent pair of substrates including electrodes. Meanwhile, in a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film in such a manner that liquid crystal is in a desired alignment state between substrates.

That is, the liquid crystal alignment film is a constituent member of a liquid crystal display element, and is formed on a liquid crystal interface between a substrate supporting liquid crystal and a role of orienting the liquid crystal in a certain direction between the substrates. In addition, in the liquid crystal alignment film, in addition to orienting the liquid crystal in a certain direction such as parallel to the substrate, etc. In addition to the alignment function, there are cases where the pre-tilt function of the liquid crystal is sought to be controlled. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystals (hereinafter, referred to as an alignment control ability) is provided by performing an alignment treatment on an organic film constituting the liquid crystal alignment film.

Alignment of liquid crystal alignment film for giving alignment control ability The processing method is known from the conventional friction method. The rubbing method refers to rubbing (friction) the surface of an organic film such as polyvinyl alcohol, polyimide, or polyimide on a substrate with a cloth such as cotton, nylon, polyester, or the like in a certain direction. (Friction direction) A method for aligning liquid crystals. This rubbing method can be used in a conventional manufacturing process of a liquid crystal display element because a relatively stable liquid crystal alignment state can be easily achieved. As for the organic film used for the liquid crystal alignment film, a polyfluorene-based organic film having excellent reliability such as heat resistance or excellent electrical characteristics is mainly selected.

However, a liquid crystal alignment film made of polyimide or the like is rubbed. The friction method on the surface has the problem of generating dust or static electricity. In addition, in recent years, due to the high definition of the liquid crystal display element or the unevenness caused by the electrodes on the substrate or the switching active element for liquid crystal driving, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment cannot be achieved. situation.

Therefore, as a liquid crystal alignment film that does not undergo rubbing, Alignment processing methods, popular reviews of light alignment methods.

Although there are various methods of light alignment, The collimated light forms an anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal is aligned according to the anisotropy.

The main photo-alignment method is known as decomposed photo-alignment law. For example, the polyimide film is irradiated with polarized ultraviolet light, and the polarization dependence of the ultraviolet light absorption by the molecular structure produces decomposition in different directions. The liquid crystal is aligned by polyimide remaining without being decomposed (see, for example, Patent Document 1).

In addition, the photo-alignment method of a photo-crosslinking type or a photo-isomerization type is also A known. For example, using polyvinyl cinnamate and irradiating polarized ultraviolet light, a dimerization reaction (crosslinking reaction) occurs in the double bond portion of the two side chains parallel to the polarized light. The liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, Non-Patent Document 1). When a side-chain polymer having azobenzene in the side chain is used, polarized ultraviolet light is irradiated, an isomerization reaction occurs in the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the direction of the polarized light. (For example, Non-Patent Document 2 is used as a reference.)

As in the above example, the alignment processing method of the liquid crystal alignment film by the photo-alignment method does not require friction and there is no concern about dust generation or static electricity. Moreover, even a substrate of a liquid crystal display element having an uneven surface can be subjected to an alignment treatment, which is an alignment treatment method for a liquid crystal alignment film with a better industrial production process.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992)

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000)

As described above, the photo-alignment method does not require a rubbing step as compared with the conventional industrial rubbing method, which is an alignment processing method for liquid crystal display elements, and therefore has a great advantage. In contrast to the friction method, in which the alignment control ability is almost constant due to friction, in the optical alignment method, the irradiation amount of polarized light can be changed to control the alignment control ability. However, in the case of the photo-alignment method, in order to realize the alignment control ability on the level of the contract with the friction method, there is a case where a large amount of polarized light irradiation is required, and stable liquid crystal alignment cannot be achieved.

For example, the decomposition-type photo-alignment method described in the above-mentioned Patent Document 1 requires that the polyimide film be irradiated with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, etc., which requires a long and large amount of ultraviolet irradiation. In addition, in the case of a dimerization-type or photo-isomerization-type photo-alignment method, there may be a case where a large amount of ultraviolet rays of several J (Joule) to several tens J are required to be irradiated. Furthermore, in the case of a photo-alignment method of a photo-crosslinking type or a photo-isomerization type, there is a problem of poor alignment or image sticking when a liquid crystal display element is manufactured due to poor thermal stability or light stability of liquid crystal alignment. In particular, in a liquid crystal display element driven by a transverse electric field, in order to switch liquid crystal molecules in a plane, alignment misalignment of the liquid crystal after liquid crystal driving and display sticking caused by AC driving are easily caused.

Therefore, in the optical alignment method, the high efficiency of the alignment process is pursued. The realization of stabilized or stabilized liquid crystal alignment pursues a liquid crystal alignment film or a liquid crystal alignment agent that can provide a liquid crystal alignment film with efficient and high alignment control ability.

The present invention is to provide A substrate for a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element having excellent force and afterimage characteristics and a transverse electric field drive type liquid crystal display element having the substrate are intended.

Moreover, the objective of this invention is to provide the horizontal electric field drive type liquid crystal element which has a high voltage maintenance factor in addition to the said objective, and the liquid crystal aligning film used for this element.

In order to achieve the above-mentioned problems, the present inventors endeavored to review the results and completed the following inventions.

1. A side chain polymer, which is a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and further has a side chain represented by the following formula (0),

[In the formula, A and B are independent and represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-; S is an alkyl group having 1 to 12 carbon atoms, and hydrogen atoms bonded to them may be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl groups, hydrogen atoms bonded to them may be substituted with halogen groups; X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same or different from each other; P and Q are independent, and are composed of divalent benzene ring and naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbons, and groups selected from their combination; but X is -CH = CH-CO-O-,- When O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring. When the number of P is 2 or more, P may be the same or different from each other. When the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are 0, A is a single bond when T is a single bond; when l1 is 1, T is a single bond B is also a single bond; G is the following formula (G-1), (G-2), (G-3), and (G-4)

(In the formula, the dotted line is a bonding bond, R ^{50 is a group selected} from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group. When there are a plurality of R ⁵⁰ , they may be the same or different from each other. , T is an integer from 1 to 7, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is a group selected from an alkyl group and a phenyl group having 1 to 3 carbon atoms)

Selected base].

2. The side chain polymer according to the above 1, which has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photo-Fryce rearrangement.

3. The side chain polymer according to 1 or 2 above, which has a photosensitive side chain selected from the group consisting of the following formulae (1) to (6),

(In the formula, A, B, and D are independent of each other, indicating a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- O-, or -O-CO-CH = CH-; S is an alkylene group with 1 to 12 carbon atoms, and hydrogen atoms bonded to them can be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms It is an alkylene group, and the hydrogen atoms bonded to them may be replaced with halogen groups; Y ₁ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and a lipid having 5 to 8 carbon atoms. Rings selected from cyclic hydrocarbons, or the same or different 2 to 6 rings selected from their substituents, are bonded through a bonding group B, and the hydrogen atoms bonded to them are independent of each other , Can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, an alkyl group having 1 to 5 carbon atoms, the carbon atoms or an alkyl group of 1 to 5 substituents; the Y ₂ by the divalent benzene ring, a naphthalene ring, biphenyl ring, a furan ring, a pyrrole ring carbon atoms 5 ~ 8 alicyclic hydrocarbons, and groups selected from their combination, the hydrogen atoms bonded to them are independent, and can be -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms Or an alkyl group having a carbon number of 1 to 5 substituents; R & lt hydroxy, alkoxy having 1 to 6 carbon atoms of the group, or Y ₁ are as defined; X is a single bond, -COO -, - OCO -, - N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same or different from each other Cou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are independent and can be -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms; q1 and q2, one of which is 1, the other is 0; q3 is 0 or 1 ; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof When X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and when the number of P is 2 or more , P can be the same or different from each other, when the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are 0, T is a single A is also a single bond when it is bonded; when l1 is 1, B is also a single bond when T is a single bond; H and I are independent and are composed of a divalent benzene ring, naphthalene ring, and Ring, furan ring, pyrrole ring, and their combinations selected from the group).

4. The side chain polymer according to the above 1 or 2, wherein in the photosensitive side chain formula having any one selected from the group consisting of the following formulae (7) to (10), A, B, and D , Y ₁ , X, Y ₂ and R have the same definitions as above; l is an integer from 1 to 12; m is an integer from 0 to 2; m1 and m2 are integers from 1 to 3; n is an integer from 0 to 12 ( (When n = 0, B is a single bond)

5. The side chain polymer according to 1 or 2 above, which has a photosensitive side chain selected from the group consisting of the following formulae (11) to (13)

(Where A, X, l, m, m1 and R have the same definitions as above)

6. The side chain polymer according to the above 1 or 2, which has a photosensitive side chain represented by the following formula (14) or (15)

(Where A, Y ₁ , 1, m1 and m2 have the same definitions as above)

7. The side chain polymer according to the above 1 or 2, which has a photosensitive side chain represented by the following formula (16) or (17)

(Where A, X, l, and m have the same definitions as above)

8. The side chain polymer according to 1 or 2 above, which Wherein it has a photosensitive side chain represented by the following formula (18) or (19)

(In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definition as above; R ₁ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH -CN, halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons)

9. The side chain polymer according to 1 or 2 above, which has a photosensitive side chain represented by the following formula (20)

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

10.Side-chain high scores as described in any of 1 to 9 above Wherein the liquid crystal side chain has any one selected from the group consisting of the following formulae (21) to (31)

(Wherein A and B have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms And selected groups in the group formed by the combination of them, the hydrogen atoms bonded to them are independent, and can be -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number 1 ~ 5 alkyloxy substitution; R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, Biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; one of q1 and q2 Is 1, the other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more, formula (25) In ~ (26), the total of all m is 1 or more, and m1, m2, and m3 are each independently an integer of 1 to 3. R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, and a monovalent benzene ring. , Naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkyloxy group; Z ₁ and Z ₂ are single bonds, -CO -, -CH ₂ O-, -CH = N-, -CF _2- )

11. A polymer composition characterized by containing (A) the side chain polymer according to any one of 1 to 10 above and (B) an organic solvent.

12. The composition according to 11 above, wherein The polymer composition further contains (C) an amine compound having one primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

13. The composition according to the above 12, wherein the component (C) is 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, Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocyclic ring)

14. A method for manufacturing a substrate having the aforementioned liquid crystal alignment film, characterized by having

[I] a step of forming a coating film by applying the composition described in any one of the above 11 to 13 on a substrate having a conductive film for driving a transverse electric field; [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]; and obtaining a liquid crystal for a transverse electric field drive type liquid crystal display element that provides alignment control ability Alignment film.

15. A substrate comprising a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method described in the above 14.

16. A transverse electric field drive type liquid crystal display device comprising the substrate according to 15 above.

17. A method for manufacturing a liquid crystal display element, characterized by having

The step of preparing the substrate (first substrate) according to the above 15;

[I '] A step of forming a coating film after coating the polymer composition described in any one of 11 to 13 on a second substrate; [II'] irradiating the coating film obtained in [I '] with polarized ultraviolet light Step; and [III '] a step of heating the coating film obtained in [II']; a step of obtaining a liquid crystal alignment film imparting alignment control ability to obtain a second substrate having the liquid crystal alignment film; and [IV] across The liquid crystal is a step of obtaining a liquid crystal display element by facing the liquid crystal alignment films of the first and second substrates and arranging the first and second substrates in opposite directions; and obtaining a transverse electric field driving type liquid crystal display element.

18. A transverse electric field drive type liquid crystal display device, characterized in that it is manufactured by the method described in 17 above.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element that provides alignment control ability with high efficiency and excellent afterimage characteristics, and a transverse electric field drive type liquid crystal display element having the substrate.

The horizontal electric field drive type liquid crystal display element manufactured by the method of the present invention provides alignment control ability with high efficiency, and even if continuously driven for a long time, the display characteristics are not damaged.

In addition, according to the present invention, in addition to the above-mentioned effects, it is possible to provide a transverse electric field drive type liquid crystal element having an improved voltage maintenance rate by adsorbing ionic impurities in the liquid crystal at the interface of the liquid crystal alignment film and a liquid crystal alignment film for the device.

1‧‧‧ side chain polymer film

2, 2a‧‧‧ side chain

3‧‧‧ side chain polymer film

4, 4a‧‧‧ side chain

5‧‧‧ side chain polymer film

6, 6a‧‧‧ side chain

7‧‧‧ side chain polymer film

8, 8a‧‧‧ side chain

[Fig. 1] An example of a mode for explaining the introduction of anisotropy in the method for manufacturing a liquid crystal alignment film used in the present invention, which shows the anisotropy introduced by using a crosslinkable organic group on a photosensitive side chain Illustration for small occasions.

[Fig. 2] An example of a model for explaining the introduction of anisotropy in the method for producing a liquid crystal alignment film used in the present invention, which shows the anisotropy introduced by using a crosslinkable organic group on a photosensitive side chain Illustration for big occasions.

[Fig. 3] A diagram illustrating an example of an introduction process of anisotropy in a method for manufacturing a liquid crystal alignment film used in the present invention, and an organic group that causes Fries rearrangement or isomerization is used for a photosensitive side chain. , And the imported alien This figure shows the case where the directivity is small.

[Fig. 4] An example of a mode for explaining the introduction of anisotropy in the method for producing a liquid crystal alignment film used in the present invention, and an organic group that causes Fries rearrangement or isomerization is used for a photosensitive side chain. And the case where the introduced anisotropy is large.

As a result of diligent research, the inventors obtained the following Knowledge to complete the present invention.

In the production method of the present invention, the polymer composition used is a photosensitive side-chain polymer (hereinafter, also referred to as a side-chain polymer) having a photosensitive property capable of expressing liquid crystallinity. The coating film is a film having a photosensitive side chain polymer that can express liquid crystallinity. This coating film was not subjected to rubbing treatment, but was subjected to alignment treatment by polarized light irradiation. After the polarized light is irradiated, the side-chain polymer film is heated to form a coating film (hereinafter, also referred to as a liquid crystal alignment film) that provides alignment control ability. At this time, a slight anisotropy due to polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently realigned due to self-organization. As a result, as a liquid crystal alignment film, a liquid crystal alignment film that achieves highly efficient alignment processing and is provided with high alignment control ability can be obtained.

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

<Manufacturing method of a substrate with a liquid crystal alignment film> and <Manufacturing method of a liquid crystal display element>

The method for manufacturing a substrate having a liquid crystal alignment film of the present invention is

[I] a side chain polymer containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range and further having a side chain represented by the formula (0); and

(B) Organic solvents

A step of forming a coating film after applying a polymer composition on a substrate having a conductive film for driving a transverse electric field; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] applying [ II] A step of heating the obtained coating film.

Through the above steps, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which alignment control ability is provided can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In addition to the substrate (first substrate) obtained as described above, by preparing a second substrate, a lateral electric field drive type liquid crystal display element can be obtained.

The second substrate is replaced with a substrate having a conductive film for lateral electric field drive, and a substrate without a conductive film for lateral electric field drive is used. By using the above steps [I] to [III] (due to use without a lateral electric field drive) The substrate of the conductive film used is convenient in the present invention, which is also simply referred to as steps [I '] to [III']), and a second substrate of a liquid crystal alignment film having an alignment control capability can be obtained.

A method for manufacturing a lateral electric field-driven liquid crystal display device includes

[IV] Obtained by placing the first and second substrates obtained above with the liquid crystal alignment film facing the first and second substrates facing each other, Steps to the liquid crystal display element. This makes it possible to obtain a lateral electric field-driven liquid crystal display element.

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

<Step [I]>

In step [I], a substrate having a conductive film for driving a transverse electric field is coated with a side-chain polymer containing a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and further has a formula represented by the above formula (0). The side chain type polymer, organic solvent and the molecule having a side chain have a first-order amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned first-order amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic type A polymer composition of a hydrocarbon-based amine compound forms a coating film.

<Substrate>

Although the substrate is not particularly limited, when the manufactured liquid crystal display element is a transmissive type, it is preferable to use a substrate having high transparency. In this case, although not particularly limited, a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used.

In addition, considering the application of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

<Conductive film for driving transverse electric field>

The substrate is a conductive film having a lateral electric field drive.

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

In the case of a reflective liquid crystal display element, a material for reflecting light such as aluminum may be used as the conductive film, but the material is not limited to this.

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

<Polymer composition>

A polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, particularly a conductive film.

The polymer composition used in the production method of the present invention has (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range; (B) an organic solvent; and (C) has One amine compound having a primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

<< (A) side chain polymer >>

The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range and further has a side chain represented by the above formula (0).

(A) It is preferable that the side chain polymer reacts with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

(A) The side chain polymer is preferably a photosensitive side chain that reacts with light in a wavelength range of 250 nm to 400 nm.

(A) The side chain type polymer is displayed at a temperature range of 100 ° C to 300 ° C. Liquid crystallinity is preferred to have a liquid crystal primary group.

(A) The side chain polymer has a photo-sensitive bond to the main chain. The side chain can induce cross-linking reaction, isomerization reaction, or photo-Fryce rearrangement after sensing light. Although the structure of the photosensitive side chain is not particularly limited, a structure that causes cross-linking reaction or light-Fries rearrangement after sensing light is preferable, and a cross-linking reaction is more preferable. In this case, even if exposed to external pressure such as heat, the realized alignment control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer film capable of expressing liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid liquid crystal component. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

(A) A side chain polymer is represented by the following formula (0) It can provide a highly reliable liquid crystal alignment film such as a voltage maintenance ratio (VHR). It is considered that when a liquid crystal alignment film is formed, the film density is increased and the ionic impurities are eluted into the liquid crystal by acting as a crosslinking agent based on the group represented by the formula (0).

The structure of the polymer may have, for example, a main chain and a bond In its side chain, the side chain is a liquid crystal component having biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, and the like, and induced light bonded to the tip. The structure of the photosensitive group that causes a crosslinking reaction or an isomerization reaction later, or has a main chain and a side chain bonded to the side chain. The side chain also becomes a mesogen component and has a photo-Fries rearrangement Structure of phenylbenzoate group.

Photosensitive side chain polymer film that can express liquid crystal More specific examples of the structure include a hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleic acid, α-methylene-γ-butyrolactone, styrene, and vinyl. Esters, maleimide, norbornene, etc., and a main chain composed of at least one selected from the group consisting of siloxanes, a main chain composed of a group represented by the above formula (0), and The structure of the side chain comprised by at least one of the following formulae (1) to (6) is preferable.

In the formula, A, B, and D are independent and represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -, Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to them may be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl groups, hydrogen atoms bonded to them can be replaced with halogen groups; Y ₁ is a valent ring consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and 5 to 8 carbon atoms The selected ring in the formula hydrocarbon, or the same or different 2 to 6 ring selected from their substituents, is a group formed by bonding the bonding group B, and the hydrogen atoms bonded to them are independent of each other. Can be -COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group , an alkyl group having 1 to 5 carbon atoms, the carbon atoms or an alkyl group of 1 to 5 substituents; the Y ₂ by the divalent benzene ring, a naphthalene ring, biphenyl ring, a furan ring, a pyrrole ring, a 5 carbon atoms, ~ 8 alicyclic hydrocarbons, and groups selected from their combination, the hydrogen atoms bonded to them are independent of each other, and can be -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms Or an alkyl group having a carbon number of 1 to 5 substituents; R & lt hydroxy, alkoxy having 1 to 6 carbon atoms of the group, or Y ₁ are as defined; X is a single bond, -COO -, - OCO -, - N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same or different from each other Cou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are independent and can be -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms; q1 and q2, one of which is 1, the other is 0; q3 is 0 or 1 ; P and Q are each independently 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 a combination thereof When X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and when the number of P is 2 or more , P can be the same or different from each other, when the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are 0, T is a single A is also a single bond when it is bonded; when l1 is 1, B is also a single bond when T is a single bond; H and I are independent and are divalent benzene rings, naphthalene rings, biphenyl groups Selected from the group consisting of a ring, a furan ring, a pyrrole ring, and a combination thereof.

It is preferable that the side chain is any one of the photosensitive side chains selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; l is an integer of 1 to 12; m is an integer of 0 to 2; m1 and m2 are integers of 1 to 3 ; N is an integer from 0 to 12 (but when n = 0, B is a single bond).

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

In the formula, A, X, 1, m, m1, and R have the same definitions as described above.

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

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

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

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

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

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

R ₁ is 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 alkyl group having 1 to 5 carbon atoms Oxygen.

The side chain is preferably a photosensitive side chain represented by the following formula (20).

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

The (A) side chain polymer is preferably one having a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31).

In the formula, A and B have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, And the groups selected from the group formed by them, and the hydrogen atoms bonded to them are independent, and can be -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. 5 alkyloxy substitution; R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, Phenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; one of q1 and q2 is 1, the other is 0; l is an integer from 1 to 12, m is an integer from 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, and formula (25) to In (26), the total of all m is 1 or more, and m1, m2, and m3 are each independently an integer of 1 to 3; R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, Naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkyloxy group; Z ₁ and Z ₂ are single bonds, -CO- , -CH ₂ O-, -CH = N-, -CF _2- .

<< Production method of photosensitive side chain polymer >>

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

[Monomer having a side chain represented by Formula (0)]

More specific examples of the aforementioned monomer having a side chain represented by formula (0) Hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleic acid, α-methylene-γ-butyrolactone, styrene, vinyl ester, maleinia A polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups such as amines and norbornenes, and siloxanes, and the structure having the side chain represented by the formula (0) is preferable.

Among such monomers, a monomer having an epoxy group, specifically For example, compounds such as epoxypropyl (meth) acrylate, (3,4-epoxycyclohexyl) meth (meth) acrylate, allyl epoxypropyl ether, etc. Examples include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-vinyl-7-oxabicyclo [4.1.0] heptane , 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

As for the monomer having a thiopropane ring, specifically, examples can be given. As described above, the epoxy structure of the monomer having an epoxy group is substituted with a thiopropane ring and the like.

With respect to the monomer having aziridine, specifically, for example, The epoxy structure of the monomer having an epoxy group is substituted with aziridine or 1-methylaziridine.

As for the monomer having an oxetanyl group, for example, (Meth) acrylic esters of oxetanyl and the like. Among such monomers, 3- (methacryloxymethyl) oxetane, 3- (propenyloxymethyl) oxetane, and 3- (methacrylic acid) (Oxymethyl) -3-ethyl-oxetane, 3- (propenyloxymethyl) -3-ethyl-oxetane, 3- (methacryloxymethyl) Yl) -2-trifluoromethyloxetane, 3- (propenyloxymethyl) -2-trifluoromethyloxetane, 3- (methacrylic acid) Methyl) -2-phenyl-oxetane, 3- (propenyloxymethyl) -2-phenyl-oxetane, 2- (methacryloxymethyl) ) Oxetane, 2- (propenyloxymethyl) oxetane, 2- (methacryloxymethyl) -4-trifluoromethyloxetane, 2 -(Propenyloxymethyl) -4-trifluoromethyloxetane is preferred, and for example, 3- (methacryloxymethyl) -3-ethyl-oxetan Alkanes, 3- (propenyloxymethyl) -3-ethyl-oxetane, and the like.

For monomers with thietane, such as with oxygen The heterocycloalkyl monomer is preferably a monomer substituted with an oxetanyl group and a thietyl group.

In terms of monomers having azetidine, for example, having The oxetanyl monomer is preferably a monomer in which an oxetanyl group is replaced with an azetyl group.

In the above, from the point of availability and the like, The monomer and the monomer having an oxetanyl group are preferable, and the monomer having an epoxy group is more preferable. Among these, from the point of availability, glycidyl (meth) acrylate is preferred.

[Photoreactive side chain monomer]

The photoreactive side chain single system refers to a monomer that can form a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.

The photoreactive group in the side chain preferably has the following structure and its derivative.

More specific examples of the photoreactive side chain monomer include Hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleic acid, α-methylene-γ-butyrolactone, styrene, vinyl ester, maleimide, norbornyl A polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as olefins and siloxanes, a photosensitive side chain composed of at least one selected from the above formulae (1) to (6), For example, a photosensitive side chain composed of at least one of the above formulae (7) to (10), a photosensitive side chain composed of at least one of the above formulas (11) to (13), and the above formula (14) are preferred. ) Or (15), the photosensitive side chain, the photosensitive side chain represented by the formula (16) or (17), the photosensitive side chain represented by the formula (18) or (19), the formula ( The structure of the photosensitive side chain shown in 20) is preferable.

The present invention provides a novel formula represented by the following formulae (1) to (11) The glaze compounds (1) to (11); and the compounds (12) to (17) represented by the following formulae (12) to (17) serve as photoreactive and / or liquid crystal side chain monomers.

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

[Liquid crystal side chain monomer]

Liquid crystal side chain single system means that the polymer derived from this monomer expresses liquid crystal In addition, the polymer can form a monomer of a mesogen at a side chain portion.

The mesogen of the side chain may be a group such as biphenyl or phenylbenzoate, which alone forms a mesogen structure or a side chain such as benzoic acid, and the hydrogen is bonded to each other to form a mesogen structure. The mesogen of the liquid crystal in the side chain preferably has the following structure.

More specific examples of the liquid crystalline side chain monomer include Hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleic acid, α-methylene-γ-butyrolactone, styrene, vinyl ester, maleimide, norbornyl A polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as olefins and siloxanes, and a side chain composed of at least one selected from the above formulae (21) to (31) is preferred. .

(A) The side chain polymer can express the liquid crystal by the light described above. It is obtained by the polymerization reaction of a reactive side chain monomer. In addition, it is possible to copolymerize a photoreactive side chain monomer and a liquid crystalline side chain monomer that do not exhibit liquid crystallinity or to copolymerize a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity. get. Furthermore, it can be copolymerized with other monomers in a range that does not impair the performance of liquid crystal.

Other monomers include, for example, monomers which are commercially available and which can undergo radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

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

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate , 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylic acid Ester, 2-epoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantine Alkyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

For methacrylate compounds, such as methmethacrylate, ethylmethacrylate, isopropylmethacrylate, benzyl Methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-epoxy Methyl ethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantine Alkyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like.

For vinyl compounds, such as vinyl ether, methyl ethyl Alkenyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

In terms of styrene compounds, such as styrene and methylphenethyl Ene, chlorostyrene, bromostyrene, etc.

For maleimide compounds, such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The side chain represented by formula (0) in the side chain polymer of the present invention The content is from the improvement of reliability and the point of influence on the alignment of the liquid crystal, preferably 0.1 mol% to 20 mol%, 0.5 mol% to 10 mol% is better, 1 mol% to 5 mol% Even better.

The content of the photoreactive side chain in the side chain polymer of the present invention The amount of liquid crystal alignment point is preferably 20 mol% to 99.9 mol%, more preferably 30 mol% to 95 mol%, and 40 mol% to 90 mol%.

Content of liquid crystal side chain in side chain polymer of the present invention The amount of liquid crystal alignment point is preferably 80 mol% or less, 10 mol% to 70 mol% is more preferable, and 20 mol% to 60 mol% is more preferable.

The side-chain polymer of the present invention may contain the above-mentioned formula (0) Indicated side chains, side chains other than photo-reactive side chains and liquid crystal side chains. When the content is less than 100% of the total content of the side chain, the photoreactive side chain, and the liquid crystal side chain represented by the formula (0), the remainder thereof.

About the manufacturing method of the side chain polymer of this embodiment The method is not particularly limited, and a common method used in industry can be used. Specifically, it can be produced by cation polymerization, radical polymerization, or anion polymerization using vinyl groups of a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, from the standpoint of ease of reaction control and the like, radical polymerization is particularly preferred.

For the radical polymerization polymerization initiator, free Conventional compounds such as radical polymerization initiators or reversible addition-cracking type chain transfer (RAFT) polymerization reagents.

The radical thermal polymerization initiator is a compound that generates a radical by heating above the decomposition temperature. In terms of such radical thermal polymerization initiators, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diethylfluorenyl peroxides (acetamidine peroxide) , Benzamyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-tert-butyl Base peroxide, dicumyl peroxide, dilaurate peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecane Alkanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexane acid-tert-pentyl ester, etc.), persulfates (potassium persulfate, sodium, ammonium persulfate, etc.), azo compound (azobisisobutyronitrile, and 2,2 '- bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator can be used alone or in combination of two or more.

The free radical photopolymerization initiator starts to be free by light irradiation The polymerized compound is not particularly limited. As such a radical photopolymerization initiator, for example, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl Propyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropanone, 2-hydroxy-2-methyl-4 '-Isopropylpropylbenzene, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diepoxyacetophenone, 2,2-dimethoxy 2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 4,4'-bis (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tris (t-butylperoxycarbonyl) benzophenone, 2 , 4,6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyrene base ) -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-bis (epoxycarbonylmethyl)]- 2,6-bis (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4'-methoxyphenyl) -s- Triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-Carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-(4-epoxycarbonylphenyl) -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'-tetra Phenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2-methyl-2-morpholinopropane) (Fluorenyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- 3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4, 4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) dibenzoyl Ketone, 3,4'-bis (methoxycarbonyl) -4,3'-bis (t-butylperoxy (Carbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H -Benzothiazole-2-fork) -1-naphthalene-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -fork) -1- (2 -Benzamidine) ethyl ketone and the like. These compounds can be used alone or in combination of two or more.

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

Polymerization of photosensitive side chain polymers capable of expressing liquid crystallinity The organic solvent used in the reaction is not particularly limited as long as it is a polymer produced by dissolution. Specific examples thereof include the following.

For example, N, N-dimethylformamide, N, N-dimethylacetamidine Amine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfinium, tetramethylurea, pyridine, dimethylfluorene, hexamethyl Fluorene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone , Methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butylcarbitol, ethylcarbitol, 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, diethylene glycol Propylene 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-methoxybutane Alcohol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butylbutyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, diisobutyl ketone Hexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-epoxy Methyl ethyl propionate, ethyl 3-methoxypropionate, 3-epoxy propionic acid, 3-methoxy propionic acid, 3-methoxy propionic acid propyl ester, 3-methyl Butyl oxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentyl Ketones, 3-methoxy-N, N-dimethylpropaneamide, 3-epoxy-N, N-dimethylpropaneamide, 3-butoxy-N, N-dimethylpropane Amidine and so on.

These organic solvents may be used alone or in combination. and then Even if it is a solvent that does not dissolve the produced polymer, it can be used in a mixture with the above-mentioned organic solvent to the extent that the produced polymer does not precipitate.

Also, in radical polymerization, since the oxygen in the organic solvent hinders the polymerization reaction, it is preferable to use an organic solvent that is capable of degassing as much as possible.

The polymerization temperature during free radical polymerization can be between 30 ℃ ~ 150 ℃ The temperature can be selected arbitrarily, but it is preferably in the range of 50 ° C to 100 ° C. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer with a high molecular weight. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so the monomer concentration is better. It is 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction proceeds at a high concentration in the initial stage, and thereafter, an organic solvent may be added.

In the above-mentioned radical polymerization reaction, a radical polymerization initiator When the ratio of the monomer to the monomer is larger, the molecular weight of the obtained polymer becomes smaller and the molecular weight of the obtained polymer becomes larger. Therefore, the ratio of the radical initiator is 0.1 mol% to 10 mol% relative to the polymerized monomer. Better. During the polymerization, various monomer components, solvents, initiators, and the like may be added.

[Recycling of polymers]

When the reaction solution of the photosensitive side-chain type polymer capable of expressing liquid crystal properties obtained by the above reaction is used to recover the generated polymer, the reaction solution may be poured into a poor solvent to precipitate the polymers. Lean solvent used for precipitation Examples include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, and methyl ethyl. Ether, water, etc. After the polymer precipitated by adding a poor solvent is filtered and recovered, the polymer can be dried at room temperature or heated under normal pressure or reduced pressure. In addition, the polymer recovered by precipitation is redissolved in an organic solvent, and the re-precipitation recovery operation is repeated 2 to 10 times, so that impurities in the polymer can be reduced. Lean solvents at this time, such as alcohols, ketones, hydrocarbons, etc., use of three or more types of lean solvents selected from these can further improve the efficiency of purification, so it is better.

The molecular weight of the (A) side chain polymer of the present invention is obtained by considering In the case of the strength of the coating film, the workability during the formation of the coating film, and the uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2000 to 1,000,000, and more preferably 5000 to 200000.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid in a manner suitable for the formation of a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably a solution prepared by dissolving a resin component for forming a resin film in an organic solvent. Here, the resin component refers to a resin component containing the above-mentioned photosensitive side chain polymer that can express liquid crystallinity. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass.

In the polymer composition of this embodiment, the resin is All of them may be the above-mentioned photosensitive side-chain polymers that can exhibit liquid crystallinity, but other polymers other than them can be mixed without impairing the liquid crystal performance and the range of photosensitive performance. At this time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, and preferably 1% by mass to 50% by mass.

Such other polymers are, for example, polymers of a photosensitive side-chain type polymer composed of poly (meth) acrylate, polyamidic acid, polyamidoimide, or the like and which do not exhibit liquid crystallinity.

<Amine compound>

The polymer composition used in the present invention has a specific amine compound. Specifically, the polymer composition has one primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic group. A cyclic hydrocarbon-based amine compound is preferred. By containing the amine compound, when a liquid crystal alignment film is formed, the elution of ionic impurities is reduced, and the crosslinking reaction of the group represented by the formula (0) is promoted, and a liquid crystal alignment film having higher durability can be obtained.

The specific amine compound is a polymer group used in the present invention When the product forms a liquid crystal alignment film, the following effects i) and / or ii) are achieved, but it is not particularly limited. i) At the interface of the liquid crystal alignment film, ionic impurities in the liquid crystal are adsorbed, and / or ii) the voltage maintenance ratio is increased.

If the amount of a specific amine compound is to achieve the above effect, then It is not particularly limited, and it is preferable that the polymer composition used in the present invention is 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass.

Specific examples of the aliphatic hydrocarbon group include linear alkylene Group, branched structure, alkylene group, divalent hydrocarbon group having unsaturated bond Wait. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include, for example, 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, cyclohexadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, three Cycicocosane ring, tricyclic behenane ring, dicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, etc. The non-aromatic cyclic hydrocarbon group is preferably a ring composed of 3 to 20 carbon atoms, more preferably a ring composed of 3 to 15 carbon atoms, and even more preferably a ring composed of 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound contains at least one, preferably one to four, by the following formula [20a], [20b], and [20c] (wherein Z ₂ is a carbon An aromatic cyclic hydrocarbon having a structure selected from the group consisting of a linear or branched alkyl group of 1 to 5 is preferable.

Specifically, for example, a pyrrole ring, an imidazole ring, an oxazole ring, Thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine Ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, A benzimidazole ring, a phenanthroline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, and the like. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocyclic rings may have a hetero atom-containing substituent.

A preferred 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) Amine compounds are preferred. In Formula A- [1], Y ₁₂ is not particularly limited as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferred Y ₁₁ in the formula A- [1] is preferably a divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the non-aromatic cyclic hydrocarbon group include the structures described above. Y _{11 is more} preferably, for example, aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane Ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y _{11 is} particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, -CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amine group contained in Y ₁₁ may be replaced by -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-, 2 Valent cyclic hydrocarbon or heterocyclic substitution. In addition, a hydrogen atom bonded to an arbitrary carbon atom may be a straight 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. To replace.

Specific examples of the divalent cyclic hydrocarbon group include benzene ring and naphthalene Ring, tetrahydronaphthalene ring, chamomile ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, Cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecanyl ring, cyclohexadecane ring , Cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricyclic eicosane ring, tricyclic behenyl ring, bicycloheptane ring, decahydronaphthalene ring, Norbornene ring, adamantane ring and the like.

Specific examples of the divalent heterocyclic ring include a 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, Pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, lymeline ring, phenanthroline ring, indole ring, quinoxaline ring, Benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like.

In formula A- [1], Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring, and it has a structure containing at least one selected from the group consisting of formula [20a], formula [20b], and formula [20c] as described above. Aromatic cyclic hydrocarbons are preferred. Specific examples thereof include the structure described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline Rings, azepine rings, diazepine rings, naphthyridine rings, phenazine rings, and phthalazine rings are preferred.

From the viewpoint of the ease of the so-called electrostatic interaction between the formation of a nitrogen-containing aromatic heterocyclic ring and a salt of a carboxyl group in a specific polyimide, or hydrogen bonding, Y ₁₁ is bonded to a substance not contained in Y ₁₂ The adjacent substituents of the formula [20a], [20b], and [20c] are preferred.

Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₂ of the formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group may contain an oxygen atom, a sulfur atom, a nitrogen atom, and the like. atom.

The preferred combination of Y ₁₁ and Y ₁₂ in Formula A- [1] is that Y ₁₁ is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Y ₁₂ is a divalent organic group, Y ₁₂ is 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. 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 a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

Further preferred amine compounds are represented by the following formula A- [2] (wherein Y ₁₃ is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, and Y ₁₄ is a single bond, Or -O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19. The total number of carbon atoms in Y ₁₃ and Y ₁₄ is 1 to 20. Y ₁₅ is an amine compound represented by a nitrogen-containing aromatic heterocyclic ring.).

Y ₁₃ in Formula A- [2] is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include straight or branched alkylene groups having 1 to 10 carbon atoms, unsaturated alkylene groups having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, and cyclohexane. Ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring Ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, tricyclic behenane ring, dicycloheptane Ring, decalin ring, norbornene ring, adamantane ring and the like. More preferably, it 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, or a cyclononane ring. , Cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring. Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

-CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amine group contained in Y ₁₃ can be replaced by -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-, 2-valent Cyclic hydrocarbyl or heterocyclic substitution. The hydrogen atom bonded to an arbitrary 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, and a hydroxyl group. Herein, the cyclic hydrocarbon group and the heterocyclic ring have the same definitions as those of Y _{11 in} the formula A- [1].

Y ₁₄ in Formula A- [2] is a single bond or -O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19 carbon atoms. 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, and the like. Specific examples of such Y ₁₄ are as follows.

For example, single bond, -O-, -NH-, -S-, -SO _2- , hydrocarbon group with 1 to 19 carbons, -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, cycloicocosane ring, tricycloicocosane ring, tricyclic behenane ring, bicycloheptane ring, Decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, chamomile 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, benzo An azole ring, a phenanthroline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine Ring, dioxane ring, morpholine ring and the like. Y ₁₄ may contain two or more of these.

Specific examples of the two or more types 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 has the same definition as Y _{12 in} formula A- [1]. As a specific example, the same structure as the above Y ₁₂ can be exemplified. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline A ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring is preferred.

In addition, from the viewpoint of the easiness of the formation of a so-called electrostatic interaction between a nitrogen-containing aromatic heterocyclic ring and a carboxyl group in a specific polyimide, Y ₁₄ contains Y ₁₅ and the formula [20a ], Formula [20b] or Formula [20c] is preferably a bond of non-adjacent carbon atoms.

Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ of formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group may contain an oxygen atom, a sulfur atom, a nitrogen atom, and the like. atom.

The formula A- [2] in Y _13, Y ₁₄ and Y ₁₅ of the preferred composition is, Y ₁₃ is a C 1-4 straight-chain or branched alkylene group having 1 to 10, cyclopropane ring, cyclobutane ring, cyclopentane Ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring , Norbornene ring or adamantane ring, Y ₁₄ is a single bond, linear or branched alkylene group with 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 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-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane Ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring A benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, phenalene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine Azine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or Phthalazine ring. 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 include a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

The formula A- [2] in Y _13, Y _14, and preferably the composition is Y _15, Y ₁₃ is a C 1-4 straight-chain or branched alkylene of 1 to 5, cyclopropane ring, cyclobutane ring, cyclopentane Ring, cyclohexane ring, cycloheptane ring, norbornene ring, or adamantane ring, Y ₁₄ is a single bond, straight or branched alkylene group with 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, chamomile ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, or phenalene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring , Pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring , Or a phthalazine ring. 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 include a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Another preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in 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, and a cyclopentane. Ring or cyclohexane ring, Y ₁₄ is a single bond, linear or branched alkylene group with 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, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, fluorene ring, or an anthracene ring, Y ₁₅ is a pyrrole ring, imidazole , A pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring. 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 include a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A particularly preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in Formula A- [2] is that Y ₁₃ is a linear or branched alkylene group, a cyclobutane ring, or a cyclohexane ring having 1 to 5 carbon atoms, Y ₁₄ is a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH)-, benzene ring, naphthalene ring, fluorene ring, or Anthracene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. 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 include a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Specific examples of the specific amine compound of the component (B) of the present invention include compounds of M1 to M156.

Preferred compounds include, for example, 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. Even better are M6 ~ M8, M16 ~ M20, M32 ~ M36, M40, M41, M44, M49 ~ M54, M59 ~ M62, M68, M69, M75 ~ M82, M100 ~ M103, M108 ~ M112, M114 ~ M116, M118 ~ M121, M125, M134 ~ M136, M139, M140, M143, M150, M152 ~ M156.

<Organic solvent>

The organic solvent used in the polymer composition used in the present invention is a resin The organic solvent in which the components are dissolved is not particularly limited. Specific examples are as follows.

Examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Methylpyrrolidone, N-vinylpyrrolidone, dimethyl fluorene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, 3-methoxy-N, N-di Methylpropanemidamide, 3-epoxy-N, N-dimethylpropanemidamide, 3-butoxy-N, N-dimethylpropanemidamide, 1,3-dimethyl-imidazoline Ketone, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol Methyl ether, 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 Ethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether Ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether. These can be used alone or in combination.

The polymer composition used in the present invention may contain the above (A), Components other than (B) and (C). Examples include solvents or compounds that improve film thickness uniformity or surface smoothness when applying a polymer composition, compounds that improve adhesion between a liquid crystal alignment film and a substrate, and the like, but are not limited thereto.

Solvent to improve the uniformity of film thickness or surface smoothness Specific examples of the agent) are as follows.

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 mono Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Ether, diisobutylene, pentyl acetate, butylbutyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, milk Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-epoxypropionate, ethyl 3-methoxypropionate, 3-epoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-epoxy-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 ether-2- Acetate, dipropylene glycol, 2- (2-epoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate Solvents with low surface tension, such as esters Wait.

These poor solvents may be used in combination of one kind or plural kinds. When using such a solvent, the solubility of the entire solvent contained in the polymer composition is not significantly reduced, and the total solvent is preferably 5% to 80% by mass, and more preferably 20% to 60% by mass.

Examples of compounds that improve the uniformity of the film thickness or the surface smoothness include fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants.

More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Thochem Products.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (Sumitomo 3M) Company), Asahiguard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMI CHEMICAL CO., LTD), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the resin component contained in the polymer composition.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyl Triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxy Silyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl Trimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriamine Ethoxysilane, N-bis (ethylene oxide) -3-aminopropyltrimethoxysilane, N-bis (ethylene oxide) -3-aminopropyltriethoxysilane, and the like.

In addition to improving the adhesion between the substrate and the liquid crystal alignment film, The polymer composition may contain the following phenolic resin-based or epoxy-based compound-containing additives for the purpose of preventing a reduction in electrical characteristics caused by a backlight when constituting a liquid crystal display element. Although a specific phenol resin additive is shown below, it is not limited to this structure.

Specific epoxy-containing compounds, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin dicyclo Oxypropyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ' , N ',-tetraepoxypropyl-4, 4'-diaminodiphenylmethane and the like.

When using a compound that improves adhesion to a substrate, The amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the resin component contained in the polymer composition. If the amount used is less than 0.1 part by mass, the effect of improving adhesion cannot be expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

As an additive, a photosensitizer can also be used. Colorless and triplet sensitizers are preferred.

For photosensitizers, for example, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin, Carbonyl biscoumarin, aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones substituted with amine groups (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2 -Hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphtho) Thiazoline, 2- (β-naphthylmethylene) -3-methylbenzothiazoline, 2- (α-naphthylmethylene) -3-methylbenzothiazoline, 2 -(4-biphenylmethylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylene) -3-methyl-β-naphthothiazoline, 2- ( 4-biphenylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthothiazoline), Oxazoline (2-benzylidenemethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthylmethylidene) -3-methylbenzoxazoline, 2- (α-naphthylmethylene) -3-methylbenzoxazoline, 2- (4-biphenylmethylene) -3-methylbenzooxazoline, 2- (β- Naphthylmethylidene) -3-methyl-β-naphthoxazoline, 2- (4-biphenylmethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6- Trinitroaniline) or nitropanaphthalene (5-nitropanaphthalene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkane Fattylated talon, acetophenone (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene Carboxylic acid), benzopiperan, azoindolezine, miluocoumarin, and the like.

Aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Acetal.

A polymer composition, other than the above, without compromising the present invention For the purpose of changing the electrical characteristics such as the dielectric constant or conductivity of the liquid crystal alignment film, a dielectric body or a conductive substance can be added to further increase the hardness or density of the film when the liquid crystal alignment film is made. Crosslinkable compound.

The method for applying the polymer composition to a substrate having a conductive film for driving a transverse electric field is not particularly limited.

The coating method is generally industrially performed by screen printing, offset printing, flexographic printing, or inkjet. Other coating methods include dipping, roll coating, slit coating, spin (spin coating), or spray coating. Fog method, etc., can be used according to the purpose.

Coating on a substrate with a conductive film for lateral electric field drive After the polymer composition, the coating film can be obtained by evaporating the solvent at a temperature of 50 to 200 ° C, preferably 50 to 150 ° C by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven. The drying temperature at this time is preferably lower than the expression temperature of the liquid crystal phase of the side chain polymer.

If the thickness of the coating film is too thick, it is disadvantageous on the power-consumption surface of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm.

After the [I] step and before the next [II] step, a step of cooling the substrate on which the coating film is formed to room temperature may be provided.

<Step [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the polarizing plate is transmitted through the polarizing plate from a certain direction with respect to the substrate, and the polarized ultraviolet rays are irradiated. For the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select the most appropriate wavelength depending on the type of coating film to be transmitted through a filter or the like. In addition, for example, a method of selectively initiating a photo-crosslinking reaction may be used in a range of 290 nm to 400 nm. As for ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized ultraviolet radiation varies depending on the coating film used. The irradiation amount is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the vertical direction ΔA The maximum value (hereinafter, also referred to as ΔAmax) of the amount of polarized ultraviolet rays is preferably in a range of 1% to 70%, and more preferably in a range of 1% to 50%.

<Step [III]>

In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. After heating, the coating film can be given an alignment control ability.

For heating, heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven can be used. The heating temperature may be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is expressed.

Heating temperature Temperature at which liquid crystallinity is expressed by a side chain polymer (Hereinafter, referred to as the liquid crystal display temperature) is preferably within a temperature range. In the case of a film-like film surface, the liquid crystal presentation temperature on the surface of the coating film is expected to be lower than the liquid crystal presentation temperature when the side-chain type polymer which can express liquid crystallinity is observed in a block shape. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature of the coating film surface. In other words, the temperature range of the heating temperature after the irradiation of polarized ultraviolet light is a lower limit of a temperature lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and a lower temperature of 10 ° C lower than the upper limit of the liquid crystal temperature range. A temperature in the range of the upper limit is preferred. If the heating temperature is lower than the above-mentioned temperature range, the effect of the increase in the directionality of heat in the coating film becomes insufficient, and if the heating temperature is higher than the above-mentioned temperature range, the state of the coating film becomes close to isotropic. The liquid state (isotropic phase) of nature tends to be difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is generated on the surface of the side chain polymer or the coating film. The temperature at which the solid phase phase is transformed into a liquid crystal phase is higher than the glass transition temperature (Tg), and is a temperature below the mean squared phase transformation temperature (Tiso) of the liquid crystal phase to the isotropic phase (isotropic phase).

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

By having the above steps, in the manufacturing method of the present invention, it is possible to achieve efficient introduction of anisotropy into a coating film. In addition, a liquid crystal alignment film substrate can be manufactured efficiently.

<Step [IV]>

[IV] The step is to make the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a transverse electric field obtained in [III] the same as that obtained in [I '] to [III'] above. A liquid crystal alignment film substrate (a second substrate) with a conductive film is arranged opposite to each other with the liquid crystal alignment films interposed therebetween, and a liquid crystal cell is produced by a conventional method to produce a liquid crystal display element driven by a transverse electric field. In addition, steps [I '] to [III'] are the same as in step [I] except that instead of a substrate having a conductive film for lateral electric field drive, a substrate without the conductive film for lateral electric field drive can be used. [I] to [III] are performed in the same manner. Since the difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the above conductive film, the description of steps [I '] to [III'] is omitted.

As an example of the production of a liquid crystal cell or a liquid crystal display element, for example, a method in which the first and second substrates described above are prepared, a spacer is spread on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is inward A method of bonding the other substrate and sealing the liquid crystal after decompression injection, or After the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, a method of sealing the substrate after bonding the substrate, and the like. In this case, the substrate on one side is preferably a substrate having a comb-like electrode for driving a transverse electric field. The spacer diameter at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer is the distance between a pair of substrates holding the liquid crystal layer, that is, determines the thickness of the liquid crystal layer.

The method for producing a coated substrate according to the present invention is to polymerize The composition is applied on a substrate to form a coating film and then irradiated with polarized ultraviolet rays. Next, a liquid crystal alignment film substrate with high-efficiency anisotropy introduced into the side chain polymer film and having an alignment control capability of the liquid crystal is introduced by heating production.

In the coating film used in the present invention, the principle of photoreaction of side chains and molecular realignment caused by self-organization based on liquid crystallinity is used to achieve high-efficiency introduction of anisotropy into the coating film. In the manufacturing method of the present invention, when the side chain polymer has a photocrosslinkable group as a photoreactive group structure, the side chain polymer is used to form a coating film on a substrate, and then irradiated with polarized ultraviolet rays, and then, After heating, a liquid crystal display element was produced.

Hereinafter, a photo-reactive group will be used as the photo-reactivity. An embodiment of a side chain polymer having a base structure is referred to as a first embodiment, and a side chain polymer using a structure having a photo-Fryce rearrangement or isomerization group as a photoreactive group is used. The embodiment will be described as a second embodiment.

FIG. 1 is a liquid crystal composition of a side chain polymer using a structure having a photocrosslinkable group as a photoreactive group in the first aspect of the present invention. The figure which explains an example of the introduction process of anisotropy in the manufacturing method of a film by a pattern. FIG. 1 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, and FIG. 1 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, FIG. 1 (c) is a diagram showing the state of the heated side chain polymer film in a pattern, especially when the introduced anisotropy is small, that is, in the first aspect of the present invention, the ultraviolet radiation in the step [II] A schematic diagram of a case where the amount is within a range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA.

FIG. 2 is a diagram showing a first embodiment of the present invention using light In the method for producing a liquid crystal alignment film of a side chain polymer having a structure in which a crosslinkable group is used as a photoreactive group, a process for introducing anisotropy is explained by way of example. FIG. 2 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, and FIG. 2 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, FIG. 2 (c) is a diagram showing the state of the side-chain polymer film after heating, especially when the introduced anisotropy is large, that is, in the first aspect of the present invention, the ultraviolet rays in the step [II] A schematic diagram of a case where the irradiation amount is in a range of 15% to 70% of the maximum ultraviolet irradiation amount ΔA.

FIG. 3 shows a photoreaction in the second aspect of the present invention. In the method for producing a liquid crystal alignment film having a photo-isomerizable group or a side-chain polymer having a light-Frys rearrangement structure represented by the above formula (18), a method for introducing anisotropy is used to An example of a pattern description. Fig. 3 (a) is a diagram showing the state of the side chain polymer film before polarized light irradiation, and Fig. 3 (b) is a diagram showing the state of the side chain polymer film after polarized light irradiation. FIG. 3 (c) is a diagram showing the state of the side-chain polymer film after heating in a pattern, especially when the introduced anisotropy is small, that is, in the second aspect of the present invention, [II ] A schematic diagram of the case where the ultraviolet irradiation amount in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation amount.

Fig. 4 shows a photoreaction in the second aspect of the present invention. In the method for producing a liquid crystal alignment film using a side chain polymer having a structure having a light-Frys rearrangement group represented by the above formula (19), the introduction of anisotropy is described in an example of a pattern. FIG. 4 (a) is a diagram showing the state of the side chain polymer film before polarized light irradiation, and FIG. 4 (b) is a diagram showing the state of the side chain polymer film after polarized light irradiation, FIG. 4 (c) is a diagram showing the state of the side-chain polymer film after heating, especially when the introduced anisotropy is large, that is, in the second aspect of the present invention, the step [II] A schematic diagram of a case where the amount of ultraviolet irradiation is within a range of 1% to 70% of the maximum amount of ultraviolet irradiation.

In the first aspect of the present invention, an alien is introduced into the coating film For anisotropic treatment, when the amount of ultraviolet irradiation in step [II] is within a range of 1% to 15% of the maximum amount of ultraviolet irradiation, ΔA is first formed on the substrate. As shown in FIG. 1 (a), the coating film 1 formed on the substrate has a structure in which side chains 2 are arranged randomly. Due to the random arrangement of the side chains 2 of the coating film 1, the original liquid crystal components and the photosensitive groups of the side chains 2 are also randomly aligned, and the coating film 1 is isotropic.

In the first aspect of the present invention, an alien is introduced into the coating film In the case of anisotropic treatment, when the amount of ultraviolet irradiation in step [II] is within the range of 15% to 70% of the maximum ultraviolet irradiation, △ A is first applied to the substrate. 上 forms a coating film 3. As shown in FIG. 2 (a), the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. Due to the random arrangement of the side chains 4 of the coating film 3, the mesogen component and the photosensitive group of the side chains 4 are also randomly aligned, and the coating film 2 is isotropic.

In the second aspect of the present invention, an anomaly is introduced into the coating film In the case of anisotropic treatment, in the case of using a side chain polymer liquid crystal alignment film having a light-Fries rearrangement structure represented by the above formula (18) as the photoisomerizable group, the ultraviolet light in the step [II] When the irradiation amount is within a range of 1% to 70% of the maximum ultraviolet irradiation amount, ΔA is first formed on the substrate. As shown in FIG. 3 (a), the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. The side chain 6 of the coating film 5 is randomly arranged, and the original liquid crystal component and the photosensitive group of the side chain 6 are also randomly aligned, and the side chain polymer film 5 is isotropic.

In the second aspect of the present invention, an anomaly is introduced into the coating film In the case of anisotropic treatment, in the case of using a liquid crystal alignment film with a side chain polymer having a structure of a light-Fries rearrangement group represented by the above formula (19), the amount of ultraviolet irradiation in step [II] is such that △ When A is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, a coating film 7 is first formed on the substrate. As shown in FIG. 4 (a), the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. Due to the random arrangement of the side chains 8 of the coating film 7, the original liquid crystal components and the photosensitive groups of the side chains 8 are also randomly aligned, and the coating film 7 is isotropic.

In the first aspect of the present embodiment, the ultraviolet irradiation in the step [II] When the amount is within a range of 1% to 15% of the maximum ultraviolet irradiation amount, ΔA is irradiated with polarized ultraviolet rays to the isotropic coating film 1. in this way Once, as shown in FIG. 1 (b), the photosensitive group of the side chain 2a having a photosensitive group in the side chain 2 aligned in a direction parallel to the polarization direction of the ultraviolet light preferentially generates a photoreaction such as a dimerization reaction. . As a result, the density of the side chains 2a undergoing photoreaction only slightly increased in the direction of polarized light irradiated with ultraviolet rays, and as a result, very little anisotropy was imparted to the coating film 1.

In the first aspect of the present embodiment, the ultraviolet irradiation in the step [II] When the amount is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, ΔA is irradiated with polarized ultraviolet rays to the isotropic coating film 3. In this way, as shown in FIG. 2 (b), the photosensitive group of the side chain 4a having a photosensitive group among the side chains 4 aligned parallel to the polarization direction of the ultraviolet rays preferentially generates light such as a dimerization reaction. reaction. As a result, the density of the side chains 4a undergoing photoreaction becomes higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, a small anisotropy is imparted to the coating film 3.

In the second aspect of this embodiment, a photoisomerizable group or The side chain polymer liquid crystal alignment film having a light-Fries rearrangement structure represented by the above formula (18), the ultraviolet irradiation amount in the step [II] is 1% of the maximum ultraviolet irradiation amount so that △ A is In the range of ~ 15%, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. In this way, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 arranged parallel to the direction of polarization of the ultraviolet rays has a light-Friesian weight preferentially. Wait for the light reaction. As a result, the density of the side chains 6a undergoing photoreaction only slightly increased in the direction of polarized light irradiated with ultraviolet rays, and as a result, very little anisotropy was imparted to the coating film 5.

In the second aspect of the present embodiment, the expression (19) is used In the coating film of a side chain polymer having a light-Fries rearrangement structure, the amount of ultraviolet irradiation in the step [II] is within a range of 1% to 70% of the maximum ultraviolet irradiation amount △ A. In this case, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. In this way, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 aligned in parallel to the polarization direction of the ultraviolet rays preferentially generates a light-Fryes rearrangement. Wait for the light to react. As a result, the density of the side chains 8a undergoing photoreaction becomes higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, a small anisotropy is imparted to the coating film 7.

Next, in the first aspect of the present embodiment, the ultraviolet rays of the step [II] When the linear irradiation amount is within a range of 1% to 15% of the maximum ultraviolet irradiation amount, the coating film 1 after the polarized light irradiation is heated to be in a liquid crystal state. In this way, as shown in FIG. 1 (c), in the coating film 1, the amount of the cross-linking reaction that occurs in a direction parallel to and perpendicular to the polarization direction of the ultraviolet rays is different. In this case, since the amount of the cross-linking reaction occurring in a direction parallel to the direction of polarized light irradiated with ultraviolet rays is very small, the cross-linking reaction site can be used as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the direction of polarized light irradiated with ultraviolet rays is higher than the liquid crystallinity in the parallel direction. After self-organizing in the direction parallel to the direction of polarized light irradiated with ultraviolet rays, the side chain 2 containing the original liquid crystal component is realigned. As a result, the very small anisotropy of the coating film 1 induced by the photo-crosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.

Similarly, in the first aspect of the present embodiment, the ultraviolet rays of the step [II] When the linear irradiation amount is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 after the polarized light irradiation is heated to be in a liquid crystal state. In this way, as shown in FIG. 2 (c), the side chain polymer The film 3 differs in the amount of the cross-linking reaction between the direction parallel to the direction of the polarized light irradiated with ultraviolet rays and the vertical direction. Therefore, the side chain 4 containing the mesogen component is realigned after self-organizing in a direction parallel to the polarization direction of the ultraviolet light. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is increased by heat, and the coating film 3 is given a greater anisotropy.

Similarly, in the second aspect of this embodiment, photoisomerization is used The coating film of a side chain polymer having a light-Frys rearrangement structure represented by the above formula (18), the ultraviolet irradiation amount of the step [II] is equal to the maximum ultraviolet irradiation amount of △ A. In the range of 1% to 70%, the coating film 5 after the polarized light irradiation is heated to be in a liquid crystal state. In this way, as shown in FIG. 3 (c), in the coating film 5, the amount of the generated light-Fries rearrangement reaction differs between a direction parallel to the direction of polarization of the ultraviolet rays and a vertical direction. In this case, since the liquid crystal alignment force of the light-Fryes rearrangement generated perpendicular to the direction of polarized light irradiated with ultraviolet rays is stronger than the liquid crystal alignment force of the side chain before the reaction, self-alignment is performed in a direction perpendicular to the polarized light direction irradiated with ultraviolet rays. After organization, the side chain 6 containing the original mesogen component is realigned. As a result, the very small anisotropy of the coating film 5 induced by the light-Fries rearrangement reaction is amplified by heat, and the coating film 5 is given a larger anisotropy.

Similarly, in the second aspect of the present embodiment, the above formula (19) is used In the coating film of a side chain polymer having a structure with a light-Fryes rearrangement group, the ultraviolet irradiation amount in the step [II] is in a range of 1% to 70% of the maximum ultraviolet irradiation amount △ A. In this case, the coating film 7 after the polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in Figure 4 (c) In general, in the side chain polymer film 7, the amount of the light-Fryes rearrangement reaction generated is different between a direction parallel to the direction of polarization of the ultraviolet rays and a vertical direction. Since the anchoring force of the light-Fryes rearrangement 8 (a) is stronger than the side chain 8 before transposition, a certain amount of light-Fryes rearrangement is generated, and it is parallel to the direction of polarized light irradiated by ultraviolet After self-organization, the side chain 8 containing the mesogen component is realigned. As a result, the small anisotropy of the coating film 7 induced by the light-Frys rearrangement reaction is increased by heat, and the coating film 7 is given a larger anisotropy.

Therefore, the coating film used in the method of the present invention The coating film is irradiated with polarized ultraviolet rays and heat treatment to efficiently introduce anisotropy, and can be used as a liquid crystal alignment film with excellent alignment control ability.

Whereas, the coating film used in the method of the present invention makes the coating film The amount of ultraviolet rays irradiated with polarized light and the heating temperature during the heat treatment are optimized. This makes it possible to efficiently introduce anisotropy into a coating film.

For the highly efficient anisotropy of the coating film used in the present invention Introduced, the most appropriate amount of polarized ultraviolet radiation is the amount of polarized ultraviolet radiation that is most appropriate for the photocrosslinking reaction or photoisomerization reaction, or the light-Fries rearrangement reaction of the photosensitive group in the coating film. the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet light, the number of photosensitive groups in the side chain undergoing the photo-crosslinking reaction, the photo-isomerization reaction, or the photo-Frys rearrangement reaction is insufficient to provide a sufficient photoreaction amount. . At this time, sufficient self-organization is not performed even after heating. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to a structure having a photo-crosslinkable group, an excessive amount of photosensitive groups in a side chain undergoing a crosslinking reaction causes excessive cross-linking between the side chains. should. At this time, the obtained film may become rigid and may hinder the progress of self-organization by subsequent heating. Furthermore, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to a structure having a light-Fryce rearrangement group, if the photosensitive group of the side chain undergoing the light-Fryce rearrangement reaction is excessive, the coating film may be Liquid crystallinity becomes too low. In this case, the liquid crystallinity of the obtained film may also decrease, and the self-organization may be hindered by subsequent heating. Furthermore, when a structure having a light-Fryce rearrangement is irradiated with polarized ultraviolet rays, if the amount of ultraviolet rays is too much, the side chain polymer undergoes photodecomposition, which may hinder the self-organization of subsequent heating.

Therefore, in the coating film used in the present invention, polarized ultraviolet light is used. The most appropriate amount of the photosensitive group in the side chain to undergo photocrosslinking reaction or photoisomerization reaction or photo-Frys rearrangement reaction is 0.1 mol% to 40 mol% is preferred, and 0.1 mol% to 20 mol% is more preferred. By setting the amount of the photosensitive group of the side chain that undergoes the photoreaction to be in such a range, self-organization of the subsequent heat treatment is efficiently performed, and a highly efficient anisotropy can be formed in the film.

The coating film used in the method of the present invention is The amount of external radiation is optimized to optimize the amount of photocrosslinking reaction or photoisomerization reaction or photo-Fryce rearrangement reaction of the photosensitive group in the side chain of the side chain polymer film. In addition, together with the subsequent heat treatment, it is possible to efficiently introduce anisotropy into the coating film used in the present invention. At this time, the amount of the preferred polarized ultraviolet rays can be evaluated based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, each coating film used in the present invention is measured for polarization. After the ultraviolet irradiation, ultraviolet absorption in a direction parallel to the polarization direction of polarized ultraviolet rays and ultraviolet absorption in a vertical direction. From the measurement result of ultraviolet absorption, the difference ΔA between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction in the coating film was evaluated. In addition, in the coating film used in the present invention, the maximum value of ΔA (ΔAmax) achieved and the amount of polarized ultraviolet radiation to achieve it were obtained. In the manufacturing method of the present invention, based on the amount of polarized ultraviolet radiation to achieve the ΔAmax, a preferable amount of polarized ultraviolet light to be irradiated in the manufacture of the liquid crystal alignment film can be determined.

In the manufacturing method of the present invention, it is preferable that the amount of ultraviolet rays used to irradiate the coating film with polarized light used in the present invention be within a range of 1% to 70%, and within a range of 1% to 50%. Better. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays in the range of 1% to 50% of the amount of polarized ultraviolet rays of △ Amax is equivalent to 0.1 mol of the entire photosensitive group of the side chain polymer film. Ear% ~ 20 mole% enter the amount of polarized ultraviolet light that forms a photo-crosslinking reaction.

From the above, in the manufacturing method of the present invention, it is preferable to determine the above-mentioned preferred heating temperature based on the liquid crystal temperature range of the side-chain polymer as the introduction of the highly efficient anisotropy of the coating film. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C to 200 ° C, the heating temperature after irradiation with polarized ultraviolet rays is preferably 90 ° C to 190 ° C. Accordingly, the coating film used in the present invention is provided with greater anisotropy.

Thereby, the liquid crystal display element provided by the present invention External pressure such as heat or heat shows high reliability.

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

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

[Example]

The methacrylic monomers MA1, MA2, GMA, HBAGE, G1, and additive T1 of the monomer having an epoxy-based side chain used in the examples are shown below.

Each of MA1 and M2 was synthesized as follows. That is, MA1 is synthesized according to the synthesis method described in the patent document (WO2011-084546). MA2 is synthesized according to a synthesis method described in a patent document (Japanese Patent Application Laid-Open No. 9-118717).

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

GMA (epoxypropyl methacrylate), HBAGE (hydroxybutyl acrylate epoxypropyl ether), and additive T1 (3-aminomethylpyridine) are commercially available.

<Synthesis example 1>

Synthesis of Specific Glycidyl Ester Compound (G1)

To a solution of carboxylic acid derivative (MA2) (MA2) (18.4 g, 60 mmol) in THF (tetrahydrofuran) (184 g), (COCl) ₂ (grass chloride) (11.4 g, 90 mmol) and DMF (dimethylformamide) were added. Two drops were reacted at room temperature for 2 hours. The solid obtained by concentrating the solution was dissolved in THF (350 g). This solution was dropped into a THF solution (88 g) of glycidyl alcohol (8.89 g, 120 mmol) and triethylamine (13.4 g, 132 mmol), and the solution was dropped for 1 hour and reacted for 18 hours. Thereafter, ethyl acetate (500 g) was added, and the organic phase was washed three times with water (300 g), and dried over magnesium sulfate. After removing magnesium sulfate by filtration, a crude product was obtained by concentration. The obtained crude product was subjected to silica dioxide colloid chromatography using ethyl acetate and hexane to obtain G1 as a white solid. (Yield: 14.9 g, 69%).

Epoxypropyl ester derivative (G1): ¹ H-NMR (CDCl ₃ , δ ppm): 8.01 (d, 2H), 7.01 (d, 2H), 6.01 (s, 1H), 5.56 (s, 1H), 4.65-4.61 (m, 1H), 4.18-4.12 (m, 3H), 4.02 (t, 2H), 3.36-3.32 (m, 1H), 2.91-2.89 (m, 1H), 2.74-2.72 (m, 1H) ), 1.95-1.94 (m, 3H), 1.86-1.79 (m, 2H), 1.76-1.69 (m, 2H), 1.57-1.44 (m, 4H).

<Synthesis example 2> Synthesis of specific oxetane compounds (G2)

Carboxylic acid derivative (M2) (21.4g, 70mmol), dimethyl Aminopyridine (0.85g, 7mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (14, 8g, 77mmol) in THF (tetrahydrofuran) solution ( 107 g), 3-ethyl-3-oxetanemethanol (8.58 g, 73.5 mmol) was added, and the reaction was performed at room temperature for 18 hours. Then, the precipitated insoluble matter was removed by filtration, ethyl acetate (500 g) was added, and then washed three times with water (200 g) and dried over magnesium sulfate. After removing magnesium sulfate by filtration, it was concentrated to obtain G2 as a colorless liquid (yield: 27.3 g, yield: 96%).

Oxetane compound (G2): ¹ H-NMR (CDCl ₃ , δ ppm): 7.97 (d, 2H), 6.91 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.60 (d, 2H), 4.48 (d, 2H), 4.43 (s, 2H), 4.16 (t, 2H), 4.02 (t, 2H), 1.94 (s, 3H), 1.88-1.79 (m, 4H), 1.76-1.69 (m, 2H), 1.57-1.43 (m, 4H), 0.97 (t, 3H).

<Synthesis example 3> Synthesis of specific oxetane compounds (G3)

The following oxetane compound (G3) was synthesized in the same manner as in the above Synthesis Example.

Oxetane compound (G3): ¹ H-NMR (CDCl ₃ , δ ppm): 7.98 (d, 2H), 6.90 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.45 (d, 2H), 4.39 (d, 2H), 4.31 (t, 2H), 4.16 (t, 2H), 4.01 (t, 2H), 4.01 (t, 2H), 3.54-3.50 (m, 4H), 1.87-1.66 (m, 10H) 1.56-1.44 (m, 4H), 0.89 (t, 3H).

The abbreviations of the reagents used in this example are as follows.

(Organic solvents)

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 after degassing with a diaphragm pump, AIBN (0.15 g, 3 mmol) was added and degassed. Thereafter, a reaction was performed at 60 ° C for 12 hours to obtain a methacrylate polymer solution. This polymer solution was dropped to diethyl ether (1000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder P1.

<Polymer Synthesis Examples 2 to 6>

The compositions shown in Table 1 were synthesized by 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 the mixture was dissolved by stirring at room temperature for 5 hours. BC (40.0 g) was added to the solution and stirred to obtain a polymer solution A1. This polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

<Examples 2 to 12>

The composition shown in Table 2 was adjusted using the same method as in Example 1 to obtain liquid crystal alignment agents A2 to A12 of Examples 2 to 12.

<Control Group Polymer Synthesis Example 1>

MA1 (9.97 g, 30 mmol) was dissolved in THF (57.5 g), and after degassing with a diaphragm pump, AIBN (0.15 g, 3 mmol) was added and degassed. Thereafter, a reaction was performed at 60 ° C for 12 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into diethyl ether (1000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder CP1.

<Control Group Polymer Synthesis Example 2>

In the composition of MA1 (5.9g, 18mmol), MA2 (3.7g, 12mmol), THF (55.5g), AIBN (0.15g, 3mmol), the same method as in control group 1 was used to obtain a methacrylate polymer powder CP2.

<Control Groups 1 and 2>

Using CP1, the liquid crystal alignment agent B1 of the control group 1 was obtained in the same manner as in Example 1. Similarly, CP2 was used to obtain the liquid crystal alignment agent B2 of the control group 2.

<< Modulation of liquid crystal cell >>

Using the liquid crystal alignment agent A1 obtained in Example 1, a liquid crystal cell was produced in the following procedure. The substrate is a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm. An ITO film pattern is used. Comb-shaped pixel electrodes.

The pixel electrode has a curved central portion and a zigzag shape. A comb-like shape in which a plurality of electrode elements are aligned. The width in the width direction of each electrode element was 10 μm, and the interval between the electrode elements was 20 μm. The pixel electrode forming each pixel is composed of a plurality of aligned U-shaped electrode elements that are curved at the central portion. Each pixel has a non-rectangular shape and has an approximately bold U-shaped shape that is curved at the central portion in the same manner as the electrode element.

Each pixel is divided into a boundary with a curved portion in the center. The first area on the upper side and the second area on the lower side of the curved portion. Comparing the first area and the second area of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, in the first area of the pixel, the electrode element of the pixel electrode is formed at an angle (clockwise) of + 15 °, and in the second area of the pixel, The field is formed so that the electrode element of the pixel electrode becomes an angle (clockwise) of -15 °. That is, in the first and second areas of each pixel, the directions of rotation of the liquid crystal in the substrate plane (transverse electric field drive) induced by the applied voltage between the pixel electrode and the counter electrode are opposite to each other. Way composition.

The liquid crystal alignment agent A1 obtained in Example 1 was spin-coated on the prepared electrode-attached substrate. Then, it was dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, the coated film surface was irradiated with ultraviolet light at 313 nm and 20 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm without electrodes on the glass substrate as an opposing substrate, and an alignment treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate is bonded so that the liquid crystal alignment film faces each other and the alignment direction becomes 0 °, and then the sealant is thermally hardened to produce an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell using a reduced pressure injection method, and the injection port was closed to obtain a liquid crystal cell having a structure of an IPS (In-Planes Switching) mode liquid crystal display element.

The liquid crystal alignment agent A2 obtained in Examples 2 to 12 A12 uses the liquid crystal alignment agents B1 and B2 obtained in the control groups 1 and 2 to prepare a liquid crystal cell in the same manner.

<< Voltage Maintenance Rate (VHR) Evaluation >>

Using the liquid crystal cell prepared above, a voltage of 5 V and 60 μs was applied at a temperature of 70 ° C., and the voltage after 16.67 ms was measured, and the voltage maintenance rate (VHR1) was calculated as how much the voltage can be maintained. The measured unit cell was further subjected to an AC voltage of 16 Vpp at a frequency of 30 Hz in a constant temperature environment at 70 ° C. for 168 hours. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell are short-circuited, and then left at room temperature for 1 hour. The obtained unit cell was measured under the same conditions as VHR1, and the calculation of how much voltage can be maintained was calculated as the voltage maintenance ratio (VHR2). The voltage maintenance ratio was measured using a voltage maintenance ratio measurement device VHR-1 manufactured by Toyo Corporation.

Examples and composition of the liquid crystal alignment agent of the control group and VHR results are shown in Table 3.

From Table 3, it can be seen that in Examples 1 to 12, by having Compared with the non-copolymerized control groups 1 and 2, the monomers of the oxy group were copolymerized, and VHR1 was increased. It can also be seen that the results of Examples 5 to 8, 11, and 12 were further improved by adding the additive T1 and VHR2.

<Afterimage evaluation>

The IPS-mode liquid crystal cells prepared in Examples 1 to 8 were placed between two polarizing plates arranged perpendicular to the polarization axis, and the backlight was turned on in a state where no voltage was applied to minimize the transmitted light brightness. In this way, the arrangement angle of the liquid crystal cell is adjusted. The rotation angle when the liquid crystal cell is rotated from the darkest angle of the second region of the pixel to the darkest angle of the first region of the pixel. Calculated as the initial alignment azimuth.

Then, in an oven at 60 ° C., an AC voltage of 30 Hz and a 16 V _PP voltage was applied for 168 hours. After that, the pixel electrode and the counter electrode of the liquid crystal cell are in a short-circuited state, and then left at room temperature for 1 hour. After standing, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuths before and after the AC drive was calculated as the angle Δ (deg.).

It measured similarly in other Examples.

As a result, in all the examples, the angle Δ was 0.1 or less.

Since the side-chain polymer film exhibiting liquid crystallinity is irradiated with ultraviolet rays, the liquid crystal is heated in the temperature range of the liquid crystal expression, and due to self-organization, high-efficiency liquid crystal alignment ability is imparted to the entire polymer. Even after long-term AC driving, almost no observation Deviation in orientation.

Claims (11)

A side chain polymer, which is a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and further has a side chain represented by the following formula (0). In formula (0), A and B are independent of each other and represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- O- or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to them may be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl groups, hydrogen atoms bonded to them may be substituted with halogen groups; X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-,- CH = CH-CO-O- or -O-CO-CH = CH-, when the number of X is 2, X may be the same or different from each other; P and Q are independent, and are composed of divalent benzene ring and naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbons, and groups selected from their combination; but X is -CH = CH-CO-O-,- When O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring. When the number of P is 2 or more, P may be the same or different from each other. When the number of Q is 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are 0, A is a single bond when T is a single bond; when l1 is 1, T is a single bond B is also a single bond; G is a group selected from the following formulae (G-1), (G-2), (G-3), and (G-4), In the formulae (G-1), (G-2), (G-3), and (G-4), the dotted line is a bonding bond, and R ⁵⁰ is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. When there are plural R ⁵⁰ groups, they may be the same or different from each other, t is an integer of 1 to 7, J is O, S, NH or NR ⁵¹ , and R ⁵¹ is a carbon number of 1 to An alkyl group selected from 3 and a phenyl group; and a side chain represented by the following formula (2), In formula (2), A, B, and D are independent of each other and represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH- CO-O- or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to them may be replaced with halogen groups; T is a single bond or 1 to carbon number 12 of alkylene, etc. Consists bonded hydrogen atom may be substituted with a halogen group; the Y ₂ by the divalent benzene ring, a naphthalene ring, biphenyl ring, a furan ring, a pyrrole ring, a 5 to 8 carbon atoms, The selected groups in the alicyclic hydrocarbons and their combinations, the hydrogen atoms bonded to them are independent, and can be -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms; R is a hydroxyl group, alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ; Y ₁ is 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 carbons, or the same selected from their substituents Or different 2 to 6 rings are bonded through a bonding group B, and the hydrogen atoms bonded to them are independent and can be -COOR ₀ , -NO ₂ , -CN, -CH = C ( CN) ₂ , -CH = CH-CN, halogen group, carbon number 1 ~ 5 Substituted with an alkyl group or an alkyloxy group having 1 to 5 carbon atoms; and in the formula COOR ₀ , R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; X is a single bond, -COO-, -OCO- , -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O- or -O-CO-CH = CH-, when the number of X is 2, X may be the same as each other Or different; P and Q are independent, and are formed by a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof Selected group in the group; but when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and the number of P is When 2 or more, P may be the same or different from each other; when the number of Q is 2 or more, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, When T is a single bond, A is also a single bond; when l1 is 1, B is also a single bond when T is a single bond. The side chain polymer according to claim 1, which has a photosensitive side chain of the following formula (9), and in the formula (9), A represents a single bond, -O-, -CH _2- , -COO- , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- or -O-CO-CH = CH-; X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O- or -O-CO-CH = CH-, when the number of X is 2, X may be the same or different from each other ; L is an integer of from 1 to 12; m is an integer of 0 to 2; R & lt hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or Y ₁ are as defined; Y ₁ by one of the divalent benzene ring, a naphthalene ring , Biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbons having 5 to 8 carbons, or the same or different 2 to 6 rings selected from their substituents A group formed by bonding of groups B, and the hydrogen atoms bonded to them are independent, and can be -COOR ₀ , -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen Substituted with an alkyl group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; and in the formula COOR ₀ , R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The side chain polymer according to claim 1, which has a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31). In the formulae (21) to (31), A and B have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, and the like The selected groups in the group formed by the combination are independently bonded to their hydrogen atoms, and can be -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons. Oxy group substitution; R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring , Furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; q1 and q2, one of which is 1, and the other One is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more, and formulas (25) to (26) Here, the total of all m is 1 or more, m1, m2, and m3 are each independently 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, Biphenyl ring, furan ring, Nitrogen-containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl groups or alkyloxy groups; Z ₁ and Z ₂ are single bonds, -CO-, -CH ₂ O-, -CH = N -, -CF _2- ; A polymer composition comprising (A) the side chain polymer according to claim 1 and (B) an organic solvent. The composition according to claim 4, wherein the polymer composition further contains (C) one primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amine group is bonded to an aliphatic hydrocarbon group or Non-aromatic cyclic hydrocarbon-based amine compounds. The composition according to claim 5, wherein the component (C) is an amine compound represented by the following formula A- [1]; in the formula A- [1], Y ₁₁ has an aliphatic hydrocarbon group or a non-aromatic group A divalent organic group of a cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring; A method for manufacturing a substrate having the aforementioned liquid crystal alignment film, characterized in that the composition described in any one of claims 4 to 6 is coated on a substrate having a conductive film for driving a transverse electric field by having [I] A step of forming 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]; obtaining a transverse electric field drive that imparts alignment control ability Liquid crystal alignment film for liquid crystal display element. A substrate comprising a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method described in claim 7. A transverse electric field drive type liquid crystal display device having a substrate according to claim 8. A method for manufacturing a liquid crystal display element, which comprises the steps of preparing a substrate (first substrate) described in claim 8; and having [I '] applying any of claims 4 to 6 on a second substrate The step of forming a coating film after the polymer composition according to one item; [II '] a step of irradiating the coating film obtained by [I'] with polarized ultraviolet rays; and [III '] the coating film obtained by [II'] A step of heating; a step of obtaining a liquid crystal alignment film having an alignment control capability to obtain a second substrate having the liquid crystal alignment film; and [IV] facing the liquid crystal alignment films of the first and second substrates through a liquid crystal, A step of obtaining the liquid crystal display element by disposing the first and second substrates, and obtaining a lateral electric field drive type liquid crystal display element. A transverse electric field drive type liquid crystal display device, which is characterized by being manufactured by the method described in claim 10.