JP6523169B2 - Polymer, polymer composition and liquid crystal alignment film for horizontal electric field drive type liquid crystal display device - Google Patents

Description

  The present invention relates to a novel polymer, a composition containing the polymer, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device using the polymer, and a method for producing a substrate having the alignment film. Furthermore, the present invention relates to a novel method for producing a liquid crystal display element excellent in burn-in characteristics.

  Liquid crystal display devices are known as light-weight, thin and low power consumption display devices, and in recent years they have achieved remarkable development such as being used for large-sized television applications. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes. And in a liquid crystal display element, the organic film which consists of organic materials is used as a liquid crystal aligning film so that a liquid crystal may be in a desired orientation state between board | substrates.

  That is, the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate holding the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to control the pretilt angle of the liquid crystal, in addition to the function of aligning the liquid crystal in a fixed direction such as a direction parallel to the substrate. The ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) in such a liquid crystal alignment film is given by performing an alignment process on the organic film constituting the liquid crystal alignment film.

  A rubbing method is conventionally known as an alignment treatment method of a liquid crystal alignment film for imparting alignment controllability. In the rubbing method, the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate is rubbed with a cloth of cotton, nylon, polyester, or the like in a certain direction (rubbing) in the rubbing direction (rubbing direction) It is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystal, it has been used in the conventional liquid crystal display device manufacturing process. And as an organic film used for a liquid crystal aligning film, the organic film of the polyimide system excellent in reliability, such as heat resistance, and an electrical property has been mainly selected.

  However, in the rubbing method in which the surface of the liquid crystal alignment film made of polyimide or the like is rubbed, generation of dust or static electricity may be a problem. In addition, due to the recent increase in resolution of liquid crystal surface elements and irregularities due to electrodes on corresponding substrates and switching active elements for driving liquid crystals, the surface of the liquid crystal alignment film can not be rubbed uniformly with a cloth, and is uniform. In some cases, alignment of the liquid crystal can not be realized.

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

  There are various methods for the light alignment method, but the anisotropy is formed in the organic film constituting the liquid crystal alignment film by the linearly polarized light or the collimated light, and the liquid crystal is aligned according to the anisotropy.

  As a main photoalignment method, a decomposition type photoalignment method is known. For example, polarized ultraviolet light is irradiated to a polyimide film, and anisotropic decomposition is caused by utilizing the polarization direction dependency of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide left without being decomposed (see, for example, Patent Document 1).

  In addition, photocrosslinking and photoisomerization photoalignment methods are also known. For example, using polyvinyl cinnamate, it is irradiated with polarized ultraviolet light to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). When a side chain type polymer having azobenzene in the side chain is used, it is irradiated with polarized ultraviolet light to cause an isomerization reaction in the azobenzene moiety of the side chain parallel to the polarized light, and the liquid crystal in the direction orthogonal to the polarization direction. Align (see, for example, Non-Patent Document 2).

  As in the above example, in the alignment processing method of the liquid crystal alignment film by the photo alignment method, rubbing is unnecessary, and there is no concern of generation of dust or static electricity. And an orientation process can be given also to the substrate of a liquid crystal display element with the unevenness in the surface, and it becomes a method of an orientation process of a liquid crystal aligning film suitable for an industrial production process.

Patent No. 3893659

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

  As described above, the photoalignment method eliminates the rubbing step itself as compared with the rubbing method conventionally used industrially as an alignment treatment method of liquid crystal display elements, and therefore has a great advantage. Then, as compared with the rubbing method in which the alignment control ability is substantially constant by rubbing, in the photo alignment method, the irradiation control amount of polarized light can be changed to control the alignment control ability. However, in the photoalignment method, when it is intended to realize the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be realized. .

  For example, in the decomposition-type photoalignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes. Become. Also, in the case of dimerization type or photoisomerization type photoalignment method, it may be necessary to irradiate a large amount of ultraviolet light of several J (joule) to several tens J. Furthermore, in the case of the photocrosslinking type or the photoisomerization type photoalignment method, the heat stability and light stability of the alignment of the liquid crystal are inferior, so that the problem of the occurrence of alignment failure and display burn-in when used as a liquid crystal display element was there. In particular, in a liquid crystal display element driven by a lateral electric field drive, liquid crystal molecules are switched in-plane, so misalignment of the liquid crystal after liquid crystal drive tends to occur, and display burn-in due to AC drive is considered as a major issue.

  Therefore, in the photoalignment method, realization of high efficiency of alignment processing and realization of stable liquid crystal alignment is required, and a liquid crystal alignment film or liquid crystal that can highly efficiently impart high alignment control ability to a liquid crystal alignment film Alignment agents are required.

The present invention provides a substrate having a liquid crystal alignment film for a liquid crystal display element for a transverse electric field drive type liquid crystal display element, to which a high efficiency and orientation controllability is imparted and which has excellent sticking characteristics, and a transverse electric field drive type liquid crystal display element having the substrate. With the goal.
Another object of the present invention is to provide a lateral electric field drive type liquid crystal device having an improved voltage holding ratio and a liquid crystal alignment film for the device, in addition to the above object.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining in order to achieve the said subject.
<1> A photosensitive side chain polymer exhibiting liquid crystallinity in a predetermined temperature range, which is represented by the following formula (0)

[Wherein, A and B are each independently a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -Or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Represents CH-, and when the number of X is 2, X may be the same or different;
P and Q are each independently selected from the group consisting of 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- or -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is attached is an aromatic ring, When the number of P is 2 or more, P may be the same or different, and when the number of Q is 2 or more, Q may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
G is a group represented by the following formulas (G-1), (G-2), (G-3) and (G-4)

(Wherein the broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R ^50, they are identical or different from each other) T is an integer of 1 to 7, J is O, S, NH or NR ⁵¹ , R ⁵¹ is a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
Is a group selected from
A side chain type polymer further having a side chain represented by

  <2> In the above <1>, the side chain type polymer preferably has a photosensitive side chain which causes photocrosslinking, photoisomerization or light fleece transition.

  In <3> said <1> or <2>, it is good for a side chain type polymer to have any 1 type of photosensitive side chain chosen from the group which consists of following formula (1)-(6).

In the formula, A, B and D are each independently a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- Represents O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents And 2 to 6 different rings are bonded to each other through a bonding group B, and hydrogen atoms bonded to them are each independently -COOR ₀ (wherein, R ₀ is a hydrogen atom or a carbon number of 1 to 4) 5) an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof The hydrogen atoms bonded to each independently are -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Represents CH-, and when the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH- It may be substituted by CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of 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- or -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is attached is an aromatic ring, When the number of P is 2 or more, P may be the same or different, and when the number of Q is 2 or more, Q may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
H and I each independently represent a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

In <4> said <1> or <2>, it is good for a side chain type polymer to have any one kind of photosensitive side chain chosen from the group which consists of following formula (7)-(10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2; m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that n is 0 and B is a single bond).

In <5> said <1> or <2>, it is good for a side chain type polymer to have any 1 type of photosensitive side chain chosen from the group which consists of following formula (11)-(13).
In which A, X, l, m, m1 and R have the same definition as above.

<6> In the above <1> or <2>, the side chain type polymer may have a photosensitive side chain represented by the following formula (14) or (15).
Wherein A, Y ₁ , l, m 1 and m 2 have the same definition as above.

<7> In the above <1> or <2>, the side chain type polymer may have a photosensitive side chain represented by the following formula (16) or (17).
In which A, X, l and m have the same definition as above.

<8> In the above <1> or <2>, the side chain type polymer may have a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q ₁ , q 2, m 1 and m 2 have the same definitions as described above.
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl having 1 to 5 carbon atoms Represents an oxy group.

<9> In the above <1> or <2>, the side chain type polymer preferably has a photosensitive side chain represented by the following formula (20).
Wherein A, Y ₁ , X, l and m have the same definition as above.

<10> In any one of the above <1> to <9>, the side chain type polymer has any one kind of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31) Is good.
In which A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof And the hydrogen atoms bonded to them may be each independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing group A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12 and m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In the above, the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a.

  <11> A polymer composition comprising (A) the side chain type polymer according to any one of the above <1> to <10> and (B) an organic solvent.

  <12> In the above <11>, the polymer composition further has one primary amino group in the (C) molecule and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is aliphatic carbonized It may contain an amine compound bonded to a hydrogen group or a nonaromatic cyclic hydrocarbon group.

<13> In the above <12>, the component (C) is a compound 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).

<14> A step of applying the composition of any of the above <11> to <13> onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and a step of heating the coating film obtained in [III] [II];
A method of manufacturing a substrate having the liquid crystal alignment film, wherein a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which an alignment control ability is imparted by obtaining

<15> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by the method of the above <14>.
<16> A lateral electric field drive liquid crystal display device having the substrate of <15>.

<17> a step of preparing a substrate (first substrate) of the above <15>;
[I '] A step of applying the polymer composition of any of the above <11> to <13> onto a second substrate to form a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet light; and a step of heating the coating film obtained in [III ′] [II ′];
Obtaining a liquid crystal alignment film provided with alignment controllability by having a liquid crystal alignment film having the liquid crystal alignment film; and [IV] a liquid crystal alignment film of the first and second substrates via liquid crystal Arranging the first and second substrates so as to face each other to obtain a liquid crystal display element;
A method of manufacturing a liquid crystal display element, wherein a transverse electric field drive type liquid crystal display element is obtained by having

  <18> A transverse electric field drive liquid crystal display device manufactured by the above <17>.

According to the present invention, there is provided a substrate having a liquid crystal alignment film for a liquid crystal display element for a transverse electric field drive type liquid crystal display element, to which a high efficiency and orientation controllability is imparted and the sticking characteristic is excellent. Can.
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention has high orientation controllability, display characteristics are not impaired even if it is continuously driven for a long time.
Further, according to the present invention, in addition to the above effects, a lateral electric field drive type liquid crystal device having an improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface and a liquid crystal alignment film for the device. Can be provided.

It is a figure of an example which illustrates the introduction process of anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention typically, and is an anisotropic introduced using the crosslinkable organic group for the photosensitive side chain. It is a figure in case sex is small. It is a figure of an example which illustrates the introduction process of anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention typically, and is an anisotropic introduced using the crosslinkable organic group for the photosensitive side chain. It is a figure in case sex is large. It is a figure of an example which illustrates the introduction process of anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention typically, is introduce | transduced using the organic group which raise | generates a fleece transfer or isomerization to a photosensitive side chain. It is a figure in the case where the said anisotropy is small. It is a figure of an example which illustrates the introduction process of anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention typically, is introduce | transduced using the organic group which raise | generates a fleece transfer or isomerization to a photosensitive side chain. It is a figure in the case where the carried out anisotropy is large.

As a result of intensive researches, the inventor has obtained the following findings and completed the present invention.
The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer (hereinafter, also simply referred to as a side chain type polymer) capable of exhibiting liquid crystallinity, and the polymer composition The coating film obtained using a substance is a film having a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. This coating film is not subjected to rubbing treatment, and is subjected to alignment treatment by polarized light irradiation. Then, after irradiation with polarized light, through the process of heating the side chain type polymer film, a coating film (hereinafter also referred to as a liquid crystal alignment film) to which an alignment control ability is imparted is obtained. At this time, the slight anisotropy developed by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is efficiently reoriented by self-organization. As a result, highly efficient alignment processing can be realized as a liquid crystal alignment film, and a liquid crystal alignment film to which high alignment control ability is imparted can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
<Method of Manufacturing Substrate Having Liquid Crystal Alignment Film> and <Method of Manufacturing Liquid Crystal Display Device>
The method for producing a substrate having a liquid crystal alignment film of the present invention is
[I] (A) A photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and further having a side chain represented by the above formula (0), B) a step of applying a polymer composition containing an organic solvent onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and a step of heating the coating film obtained in [III] [II];
Have.
By the above-described steps, it is possible to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device to which an alignment control ability is imparted, and to obtain a substrate having the liquid crystal alignment film.

In addition to the obtained substrate (first substrate), a transverse electric field drive liquid crystal display element can be obtained by preparing a second substrate.
The second substrate uses the substrate having no conductive film for driving a horizontal electric field instead of the substrate having a conductive film for driving a horizontal electric field, except that the step [I] to [III] (for driving a horizontal electric field In order to use a substrate having no conductive film, for convenience, in the present application, steps [I '] to [III'] may be used to provide a liquid crystal alignment film to which alignment control ability is imparted. Two substrates can be obtained.

The manufacturing method of the lateral electric field drive type liquid crystal display device is
[IV] a step of obtaining a liquid crystal display element by opposingly arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other via liquid crystal;
Have. Thereby, a transverse electric field drive type liquid crystal display device can be obtained.

Hereinafter, each process of [I]-[III] which the manufacturing method of this invention has, and [IV] is demonstrated.
<Step [I]>
In the step [I], a photosensitive side-chain type polymer which exhibits liquid crystallinity in a predetermined temperature range on a substrate having a conductive film for driving a lateral electric field, and is represented by the above formula (0) A side chain type polymer further having a side chain, an organic solvent, and optionally, one primary amino group in the molecule and a nitrogen-containing aromatic heterocycle, and the primary amino group is aliphatic carbonized A polymer composition containing an amine compound bonded to a hydrogen group or a non-aromatic cyclic hydrocarbon group is applied to form a coating.

<Board>
The substrate is not particularly limited, but in the case where the liquid crystal display device to be produced is of a transmission type, it is preferable to use a substrate with high transparency. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
In addition, an opaque substrate such as a silicon wafer can be used in consideration of application to a reflective liquid crystal display device.

<Conductive film for horizontal electric field drive>
The substrate has a conductive film for driving a lateral electric field.
As the conductive film, when the liquid crystal display element is of a transmission type, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), and the like can be mentioned, but it is not limited thereto.
In the case of a reflective liquid crystal display element, examples of the conductive film include materials such as aluminum that reflect light, but the present invention is not limited thereto.
A conventionally known method can be used as a method of forming a conductive film on a substrate.

<Polymer composition>
The polymer composition is applied on a substrate having a conductive film for driving a transverse electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention comprises (A) a photosensitive side-chain type polymer exhibiting liquid crystallinity in a predetermined temperature range; (B) an organic solvent; (C) having one primary amino group in the molecule and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group being bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group Containing amine compounds.

<< (A) Side chain type polymer >>
The component (A) is a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and further has a side chain represented by the above formula (0).
The side chain type polymer (A) is preferably reacted with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 100 ° C. to 300 ° C.
The side chain polymer (A) preferably has a photosensitive side chain that responds to light in the wavelength range of 250 nm to 400 nm.
The side chain polymer (A) preferably has a mesogenic group because it exhibits liquid crystallinity in a temperature range of 100 ° C. to 300 ° C.

  The side chain polymer (A) has a photosensitive main chain bonded to the main chain, and can be sensitive to light to cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement. The structure of the side chain having photosensitivity is not particularly limited, but a structure that responds to light to cause a crosslinking reaction or a light fleece dislocation is desirable, and one that causes a crosslinking reaction is more desirable. In this case, even when exposed to external stress such as heat, the realized orientation controllability can be stably maintained for a long time. The structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, when the side chain type polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

  (A) The side chain type polymer gives a liquid crystal alignment film with high reliability such as voltage holding ratio (VHR) by having a group represented by the above formula (0). This is because when the liquid crystal alignment film is formed, the group represented by the above formula (0) acts like a crosslinking agent, thereby improving the film density and reducing the elution of ionic impurities into the liquid crystal. It is considered to be for.

  The structure of the polymer has, for example, a main chain and a side chain linked thereto, and the side chain is a tip with a mesogenic component such as biphenyl group, terphenyl group, phenylcyclohexyl group, phenylbenzoate group, azobenzene group, etc. And a main chain and a side chain connected to the main chain, and the side chain also serves as a mesogenic component, and It can be made a structure having a phenyl benzoate group which undergoes light fleece rearrangement reaction.

  More specific examples of the structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as vinyl, maleimide, norbornene and the like and siloxane, a group represented by the above formula (0), and a compound represented by the following formula (1) It is preferable that it is a structure which has a side chain which consists of at least 1 sort (s) of 6).

In the formula, A, B and D are each independently a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- Represents O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents And 2 to 6 different rings are bonded to each other through a bonding group B, and hydrogen atoms bonded to them are each independently -COOR ₀ (wherein, R ₀ is a hydrogen atom or a carbon number of 1 to 4) 5) an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof The hydrogen atoms bonded to each independently are -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Represents CH-, and when the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH- It may be substituted by CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of 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- or -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is attached is an aromatic ring, When the number of P is 2 or more, P may be the same or different, and when the number of Q is 2 or more, Q may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
H and I each independently represent a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

The side chain is preferably any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2; m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that n is 0 and B is a single bond).

The side chain is preferably any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In which A, X, l, m, m1 and R have the same definition as above.

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
Wherein A, Y ₁ , l, m 1 and m 2 have the same definition as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In which A, X, l and m have the same definition as above.

Further, the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q ₁ , q 2, m 1 and m 2 have the same definitions as described above.
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl having 1 to 5 carbon atoms Represents an oxy group.

The side chain is preferably a photosensitive side chain represented by the following formula (20).
Wherein A, Y ₁ , X, l and m have the same definition as above.

The (A) side chain type polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof And the hydrogen atoms bonded to them may be each independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing group A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12 and m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In the above, the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a.

<< Production of photosensitive side chain type polymer >>
The photosensitive side chain type polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the photosensitive side chain and the liquid crystalline side chain monomer.

[Monomer Having a Side Chain Represented by Formula (0)]
More specific examples of the monomer having a side chain represented by the above formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide It is preferable that it is a structure which has a side chain represented by said polymerizable group comprised from at least 1 sort (s) selected from the group which consists of radically polymerizable groups, such as norbornene, and siloxane, and the said Formula (0).

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

  Specific examples of the monomer having thiirane include those in which the epoxy structure of the above-mentioned monomer having an epoxy group is replaced with thiirane, and the like.

  As a monomer which has aziridine, specifically, what the epoxy structure of the monomer which has the said epoxy group replaced by aziridine or 1-methyl aziridine etc. is mentioned, for example.

  As a monomer which has oxetane group, the (meth) acrylic acid ester which has oxetane group etc. can be mentioned, for example. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (acryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyl oxetane, 2- (acryloyly) Oxymethyl) -4-trifluoromethyl oxetane are preferable, 3- (methacryloyloxy) -3-ethyl - oxetane, 3- (acryloyloxy-methyl) -3-ethyl - oxetane, and the like.

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

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

  Among the above, from the viewpoint of availability etc., a monomer having an epoxy group and a monomer having an oxetane group are preferable, and a monomer having an epoxy group is more preferable. Among them, glycidyl (meth) acrylate is preferable from the viewpoint of availability.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.
As a photoreactive group which a side chain has, the following structure and its derivative are preferable.

  More specific examples of the photoreactive side chain monomer include radically polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and the like And a photosensitive side chain composed of at least one selected from the group consisting of at least one selected from the group consisting of siloxanes and siloxanes, and at least one of the above formulas (1) to (6), preferably, for example, A photosensitive side chain comprising at least one of (1) to (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), a photosensitivity represented by the above formula (14) or (15) Side chain, photosensitive side chain represented by the above formula (16) or (17), photosensitive side chain represented by the above formula (18) or (19), photosensitivity represented by the above formula (20) Have sex side chains The structure is preferably

The present application is directed to novel compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and / or liquid crystalline side chain monomers, and the following formulas (12) to (17) Provided are compounds (12) to (17) represented by
In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; And 0 and 1; and Py each represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. Also, v represents 1 or 2.

[Liquid crystalline side chain monomer]
The liquid crystalline side chain monomer is a monomer capable of causing the polymer derived from the monomer to exhibit liquid crystallinity and forming the mesogenic group at the side chain site of the polymer.
Even if it is a group which becomes a mesogen structure alone, such as biphenyl and phenyl benzoate, as a mesogen group which a side chain has, even if it is a group which becomes a mesogen structure by side bonds hydrogen bond like a benzoic acid etc. Good. As a mesogen group which a side chain has, the following structures are preferable.

  More specific examples of liquid crystalline side chain monomers include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and the like It is preferable that it is a structure which has a side chain which consists of a polymerizable group comprised from at least 1 sort (s) selected from the group which consists of siloxanes, and at least 1 sort (s) of said Formula (21)-(31).

  The side chain type polymer (A) can be obtained by the polymerization reaction of the above-mentioned photoreactive side chain monomer exhibiting liquid crystallinity. In addition, it may be obtained by copolymerization of a photoreactive side chain monomer that does not express liquid crystallinity with a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity with a liquid crystal side chain monomer it can. Furthermore, it can be copolymerized with other monomers as long as the ability to develop liquid crystallinity is not impaired.

Other monomers include, for example, commercially available monomers capable of radical polymerization.
Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

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

  As an acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

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

  Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.

  Examples of maleimide compounds include maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide.

  The content of the side chain represented by the formula (0) in the side chain type polymer of the present invention is preferably 0.1 mol% to 20 mol% from the viewpoint of the improvement of reliability and the influence on the liquid crystal alignment. 0.5 mol%-10 mol% are more preferable, and 1 mol%-5 mol% are still more preferable.

  The content of the photoreactive side chain in the side chain type polymer of the present invention is preferably 20 mol% to 99.9 mol%, more preferably 30 mol% to 95 mol%, from the viewpoint of liquid crystal alignment. More preferred is mole% to 90 mole%.

  The content of the liquid crystalline side chain in the side chain type polymer of the present invention is preferably 80 mol% or less, more preferably 10 mol% to 70 mol%, and 20 mol% to 60 mol% from the viewpoint of liquid crystal alignment. Is more preferred.

  The side chain type polymer of the present invention may contain other side chains other than the side chain represented by the above formula (0), the photoreactive side chain and the liquid crystalline side chain. The content thereof is the remaining part when the total content of the side chain, the photoreactive side chain and the liquid crystalline side chain represented by the above formula (0) is less than 100%.

  It does not specifically limit about the manufacturing method of the side chain type | mold polymer of this Embodiment, The general-purpose method carried out industrially can be utilized. Specifically, it can be produced by cationic polymerization, radical polymerization or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

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

A radical thermal polymerization initiator is a compound which generates a radical by heating above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide etc., dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide etc), peroxy ketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethyl cyclohexene San acid-tert-amyl ester etc., persulfates (potassium persulfate, sodium persulfate, ammonium persulfate etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) Azobisisobutyronitrile etc.). One of such radical thermal polymerization initiators may be used alone, or two or more thereof may be used in combination.

The radical photopolymerization initiator is not particularly limited as long as it is a compound which initiates radical polymerization by light irradiation. Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate 4, 4'-di (t-butylperoxy carbonyl) benzophenone, 3,4,4'-tri (t-butyl peroxy carbonyl) benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2- (4'- methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) 4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di ( Ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloro) Methyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3 '-Carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimi Azole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'- Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3 -(2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2, 4-cyclopentadi -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2 -(3-Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1,3-benzothiol Tetrazole -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

  The organic solvent used for the polymerization reaction of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the produced polymer can be dissolved. The example is given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide Γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropyle Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy And -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent in which the polymer | macromolecule to produce | generate is not dissolved, it may be mixed and used for the above-mentioned organic solvent in the range which the produced | generated polymer | macromolecule does not precipitate.
In addition, since oxygen in the organic solvent causes inhibition of the polymerization reaction in radical polymerization, it is preferable to use an organic solvent that has been degassed as much as possible.

  Although the polymerization temperature in the case of radical polymerization can select any temperature of 30 degreeC-150 degreeC, Preferably it is the range of 50 degreeC-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a polymer of high molecular weight, if the concentration is too high the viscosity of the reaction solution will be too high and uniform stirring will be difficult The monomer concentration is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer decreases when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer increases when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. At the time of polymerization, various monomer components, solvents, initiators and the like can be added.

[Collection of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent and It is sufficient to precipitate the coalescence. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer precipitated by charging in a poor solvent can be recovered by filtration and then dried at normal temperature or under heating under normal pressure or reduced pressure. In addition, when the precipitated and recovered polymer is redissolved in an organic solvent and the operation of reprecipitating and recovering is repeated twice to 10 times, impurities in the polymer can be reduced. As a poor solvent in this case, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more poor solvents selected from these, because the efficiency of purification is further improved.

  The molecular weight of the (A) side chain type polymer of the present invention is measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the resulting coating film, the workability at the time of coating film formation, and the uniformity of the coating film. The weight average molecular weight is preferably 2,000 to 1,000,000, and more preferably 5,000 to 200,000.

[Preparation of Polymer Composition]
It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, it is preferable that the polymer composition used for this invention is prepared as a solution which the resin component for forming a resin film melt | dissolved in the organic solvent. Here, the resin component is a resin component containing the photosensitive side chain type polymer capable of exhibiting the liquid crystallinity described above. At that time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the above-mentioned resin component may be a photosensitive side-chain type polymer capable of expressing all the liquid crystallinity described above, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers other than them may be mixed in the range. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
Such other polymers include, for example, poly (meth) acrylates, polyamic acids, polyimides, and the like, and examples include polymers that are not photosensitive side-chain polymers that can exhibit liquid crystallinity.

<Amine compound>
The polymer composition used in the present invention has a specific amine compound, specifically, one primary amino group in the molecule and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is a fat. It is preferable to have an amine compound bonded to a group hydrocarbon group or a non-aromatic cyclic hydrocarbon group. By containing such an amine compound, when forming a liquid crystal alignment film, it is possible to reduce the elution of ionic impurities and to promote the cross-linking reaction of the group represented by the above formula (0), which is more durable. Liquid crystal alignment film can be obtained.

  The specific amine compound is not particularly limited as long as the polymer composition used in the present invention produces the following effects i) and / or ii) when the liquid crystal alignment film is formed. i) adsorbs ionic impurities in the liquid crystal at the interface of the liquid crystal alignment film, and / or ii) exerts an improved voltage holding ratio.

  The amount of the specific amine compound is not particularly limited as long as the above effects are exhibited, but 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention It is preferably in parts by mass.

  As a specific example of the aliphatic hydrocarbon group, a linear alkylene group, an alkylene group having a branched structure, a divalent hydrocarbon group having an unsaturated bond and the like can be mentioned. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.

  Specific examples of the divalent non-aromatic cyclic hydrocarbon group include 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, cycloicosane ring, tricycloeicosan ring, tricyclococosan ring, bicycloheptane ring, Examples include decahydronaphthalene ring, norbornene ring, adamantane ring and the like. The ring is preferably a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and still more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound is represented by the following Formula [20a], Formula [20b] and Formula [20c] (wherein, Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms) It is preferable that it is an aromatic cyclic hydrocarbon containing at least one, preferably 1 to 4 structures selected from the group consisting of

  Specifically, 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, benzoline ring, chinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a hetero atom.

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

Preferred Y ₁₁ in the formula A- [1] is a divalent organic group having one selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms It is good. The non-aromatic cyclic hydrocarbon group can include the above-mentioned structures. Y ₁₁ is more preferably an 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 And 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.

Further, -CH _2-in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group which is included in Y ₁₁ and is not adjacent to an amino group is -O-, -NH-, -CO-O- , -O-CO -, - CO -NH -, - NH-CO -, - CO -, - S -, - S (O) 2 -, - CF 2 -, - C (CF 3) 2 -, - _{C (CH 3) 2 -,} - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 -O And may be substituted with a divalent cyclic hydrocarbon group or a heterocyclic ring. Further, a hydrogen atom bonded to any carbon atom is a linear or branched alkylene 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, It may be replaced by a hydroxyl group.

  Specific examples of the divalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene 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, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane Rings, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclococosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like.

  In addition, specific examples of the divalent heterocyclic ring include 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, chinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring And acridine rings.

Y ₁₂ in Formula A- [1] is a nitrogen-containing aromatic heterocycle, and as described above, at least one member selected from the group consisting of Formula [20a], Formula [20b], and Formula [20c] It is preferable that it is an aromatic cyclic hydrocarbon containing the structure of As a specific example, the above-mentioned structure can be mentioned. Among them, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazole ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring And phenazine ring and phthalazine ring are preferable.

In addition, from the viewpoint of easiness of electrostatic interaction such as salt formation and hydrogen bond between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide, Y ₁₁ is a group represented by Y ₁₂ [20a], It is preferable to be bonded to a substituent that is not adjacent to [20b] and the formula [20c].
Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y ₁₂ of the formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, sulfur It may contain heteroatoms such as atoms and nitrogen atoms.

A preferred combination of Y ₁₁ and Y ₁₂ in the formula A- [1] is that Y ₁₁ is a group consisting of a C 1-20 aliphatic hydrocarbon group and a C 3-20 non-aromatic cyclic hydrocarbon group And 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, and Y ₁₂ is a divalent organic group having one type selected from And 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 ₁₂ may have a substituent of a halogen atom and / or an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom May be contained.
Further preferable amine compounds are those represented by the following formula A- [2] (wherein, Y ₁₃ is a C 1 to C 10 divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y ₁₄ Is a single bond, or -O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19 carbon atoms, and the total of carbon atoms of Y ₁₃ and Y ₁₄ Is 1 to 20. Y ₁₅ is a nitrogen-containing aromatic heterocycle.) It is an amine compound represented by

Y ₁₃ in the 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 a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclotetradecane ring, cyclohexadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosan ring, tri And a cycloeicosan ring, a tricyclococosan ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like. More preferably, it is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Examples thereof include a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring and an 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 which is contained in Y ₁₃ and is not adjacent to an amino group is -O-, -NH-, -CO-O-,- O-CO -, - CO- NH -, - NH-CO -, - CO -, - S -, - S (O) 2 -, - CF 2 -, - C (CF 3) 2 -, - C ( _{CH 3) 2 -, - Si} (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 -O-, It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring. Further, a hydrogen atom bonded to any carbon atom is 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, It may be replaced by a hydroxyl group. The cyclic hydrocarbon group and the heterocycle as used herein are as defined in Y ₁₁ in Formula A- [1].

Y ₁₄ in the formula A- [2] is a single bond, or a -O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19 carbon atoms. This C1-C19 bivalent organic group is a bivalent organic group which has 1-19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. Specific examples of such Y ₁₄ are given below.

For example, a single bond, -O-, -NH-, -S-, -SO _2- , a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, _{-NH-CO -, - CO -} , - CF 2 -, - C (CF 3) 2 -, - CH (OH) -, - C (CH 3) 2 -, - Si (CH 3) 2 -, - _{O-Si (CH 3) 2} -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane Ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring , Anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine Ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinolin ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, Phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring and the like. Two or more of these may be contained as Y ₁₄ .

Specific examples including such two or _{more, -NH-CH 2 -, -} NH-C 2 H 4 -, - NH-C 3 H 6 -, - NH-C 4 H 8 -, - S-CH 2 _{-, - S-C 2 H} 4 -, - S-C 3 H 6 -, - S-C 4 H 8 -, - O-CH 2 -, - O-C 2 H 4 -, - O-C 3 _{H 6 -, - O-C} 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) -, - S-C 2 H _{4 -CH (CH 3) -,} - S-C 3 H 6 -CH (CH 3) -, - S-C 4 H 8 -CH (CH 3) -, - O-CH 3 -CH (CH 3) —, —O—C ₂ H ₄ —CH (CH ₃ ) —, —O—C ₃ H ₆ —CH (CH ₃ ) —, —O—C 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 heterocycle, and is the same as the definition of Y _{12 in} Formula A- [1]. Specific examples may include the same structure as Y ₁₂ described above. Among them, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazole ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring And phenazine ring or phthalazine ring is preferred.

In addition, from the viewpoint of ease of electrostatic interaction such as salt formation or hydrogen bonding between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the specific polyimide, Y ₁₄ is a group represented by Y ₁₅ [20a], It is preferable to bond to a carbon atom not adjacent to [20b] or the formula [20c].
Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is Y ₁₅ of the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom or a sulfur atom And a hetero atom such as a nitrogen atom.

A preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y ₁₄ is a single bond or 1 carbon atom To 10 linear or branched alkylene groups, -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 -, - S-C 2 H 4 -, - S-C 3 H 6 -, - S-C 4 H 8 -, - O-CH 2 -, - O-C _{2 H 4 -, - O-} C 3 H 6 -, - O-C 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) -, _{-S-C 2 H 4 -CH (} CH 3) -, - S-C 3 H 6 -CH (CH 3) -, - S-C 4 H 8 -CH (CH 3) -, - O-CH 3 _{-CH (CH 3) -, -} O-C 2 H 4 -CH (CH 3) -, - O-C 3 H 6 -CH (CH 3) -, - O-C 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, Clopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, Fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzo And an imidazole 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 ₁₅ may have a substituent of a halogen atom and / or an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom May be contained.

A more preferable combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Ring, cycloheptane ring, norbornene ring, or adamantane ring, and Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-,- O-CO -, - CO- NH -, - NH-CO -, - CO -, - S -, - S (O) 2 -, - CH (OH) -, - NH-CH 2 -, - S- _{CH 2 -, - O-CH} 2 -, - O-C 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 , Cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, a benzene ring, a naphthalene ring, tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, phenanthrene ring, or phenalene ring, Y ₁₅ is a 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 It is a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent of a halogen atom and / or an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom May be contained.

A further preferable combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, or A cyclohexane ring, Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH- , -NH-CO -, - CO -, - CH (OH) -, - NH-CH 2 -, - S-CH 2 -, - O-CH 2 -, - NH-CO-CH 2 -, - CO _{-CH 2 -, - CO-NH} -CH 2 -, - NH-CH 2 -CH (CH 3) -, - S-CH 2 -CH (CH 3) -, - O-CH 3 -CH (CH 3 _{) -, - NH-CO-} CH 2 -CH (CH 3) -, - CH (OH) -CH _{-, - 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 A tetrahydronaphthalene ring, fluorene ring, or an anthracene ring, Y ₁₅ 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, or It is a benzimidazole ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent of a halogen atom and / or an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom May be contained.

A particularly preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring or a cyclohexane ring, and Y ₁₄ is , Single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH)-, benzene ring, naphthalene ring, fluorene ring, or anthracene And 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 substituent of a halogen atom and / or an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom May be contained.

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

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

<Organic solvent>
The organic solvent used for the polymer composition used for this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. The example is given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Can be mentioned. These may be used alone or in combination.

  The polymer composition used in the present invention may contain components other than the components (A), (B) and (C). Examples thereof include solvents and compounds for improving film thickness uniformity and surface smoothness when a polymer composition is applied, compounds for improving adhesion between a liquid crystal alignment film and a substrate, etc. Not limited to this.

The following may be mentioned as specific examples of the solvent (poor solvent) for improving the film thickness uniformity and the surface smoothness.
For example, isopropyl alcohol, methoxymethyl pentanol, 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 monoacetate Isopropyl 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, dipro Glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexyl, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. The solvent etc. which have surface tension are mentioned.

  These poor solvents may be used alone or in combination of two or more. When a solvent as described above is used, it is preferably 5% by mass to 80% by mass of the whole solvent, and more preferably, so as not to significantly reduce the solubility of the whole solvent contained in the polymer composition. Is 20% by mass to 60% by mass.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include fluorine-based surfactants, silicone-based surfactants and nonion-based surfactants.
More specifically, for example, F-Top (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafuck (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431. (Sumitomo 3M Co., Ltd.), Asahi Guard (registered trademark) AG 710 (Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC Seimi Chemical Co., Ltd.) and the like. Be The proportion of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 100 parts by mass of the resin component contained in the polymer composition. It is a mass part.

As a specific example of a compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, the functional silane containing compound etc. which are shown next are mentioned.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl tri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned.

  Furthermore, in addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film, the following addition of phenoplast-based and epoxy group-containing compounds is carried out for the purpose of preventing the deterioration of the electrical characteristics due to backlight when forming the liquid crystal display element. Agents may be included in the polymer composition. Specific phenoplast-based additives are shown below, but are not limited to this structure.

  Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4 4'-diaminodiphenylmethane and the like.

  When using the compound which improves adhesiveness with a board | substrate, it is preferable that the usage-amount is 0.1 mass part-30 mass parts with respect to 100 mass parts of the resin component contained in a polymer composition. And more preferably 1 part by mass to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxy ketones, and amino-substituted ones Aromatic 2-hydroxy ketone (2-hydroxy benzophenone, mono- or di-p- (dimethylamino) 2-hydroxy benzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoyl methylene-3) -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-Methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-Methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) )) 3-Methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Futoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p) -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocumarin and the like.
Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl bis coumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal.

  In the polymer composition, in addition to those described above, a dielectric or a conductive substance, for the purpose of changing the electric properties such as the dielectric constant and the conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired. Furthermore, a crosslinkable compound may be added for the purpose of enhancing the hardness and the degree of compactness of the film when forming a liquid crystal alignment film.

The method of apply | coating the polymer composition mentioned above on the board | substrate which has a conductive film for horizontal electric field drive is not specifically limited.
The coating method is generally industrially performed by screen printing, offset printing, flexographic printing, an inkjet method or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotation coating method) or a spray method, and these may be used according to the purpose.

After the polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, it is heated to 50 to 200 ° C., preferably 50 to 50 ° C., by a heating means such as a hot plate, a heat circulating oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° C. to obtain a coating. The drying temperature at this time is preferably lower than the liquid crystal phase development temperature of the side chain type polymer.
If the thickness of the coating film is too thick, the power consumption of the liquid crystal display device will be disadvantageous. If it is too thin, the reliability of the liquid crystal display device may be reduced, preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate in which the coating film was formed to room temperature before the following [II] process after a [I] process.

<Step [II]>
At a process [II], the ultraviolet-ray which polarized to the coating film obtained at the process [I] is irradiated. In the case where the film surface of the coating film is irradiated with polarized ultraviolet light, the substrate is irradiated with ultraviolet light polarized through a polarizing plate from a certain direction. As ultraviolet rays to be used, ultraviolet rays in the wavelength range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected via a filter or the like depending on the type of coating film used. Then, for example, ultraviolet rays in the wavelength range of 290 nm to 400 nm can be selected and used so that a photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high pressure mercury lamp can be used.

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

<Step [III]>
In step [III], the coating film irradiated with ultraviolet light polarized in step [II] is heated. By heating, the coating film can be provided with orientation controllability.
Heating can be performed using a heating means such as a hot plate, a heat circulating oven, or an IR (infrared) oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.

The heating temperature is preferably within a temperature range at which the side chain polymer exhibits liquid crystallinity (hereinafter, referred to as liquid crystal development temperature). In the case of a thin film surface such as a coating, it is expected that the liquid crystal expression temperature of the coating surface is lower than the liquid crystal expression temperature when the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is observed in bulk. Ru. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal development temperature of the coating film surface. That is, the temperature range of the heating temperature after the polarized ultraviolet irradiation is a temperature 10 ° C. lower than the upper limit of the liquid crystal temperature range, with the temperature 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer used It is preferable that it is the temperature of the range which makes an upper limit. When the heating temperature is lower than the above temperature range, the effect of the heat of anisotropy on the coating film tends to be insufficient, and when the heating temperature is higher than the above temperature range, the state of the coating film Tend to be close to the isotropic liquid state (isotropic phase), in which case it may be difficult to reorient in one direction due to self-assembly.
The liquid crystal development temperature is higher than the glass transition temperature (Tg) at which the phase transition occurs from the solid phase to the liquid phase from the side chain type polymer or coating film surface, and from the liquid crystal phase to the isotropic phase (isotropic phase). The temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

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

  By having the above steps, in the production method of the present invention, highly efficient introduction of anisotropy into the coating film can be realized. And a substrate with a liquid crystal aligning film can be manufactured with high efficiency.

<Step [IV]>
In the [IV] step, similarly to the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a lateral electric field obtained in [III], in the above [I ′] to [III ′] The obtained liquid crystal alignment film-provided substrate (second substrate) having no conductive film is disposed opposite to each other with the liquid crystal alignment films facing each other via liquid crystal, and the liquid crystal cell is formed by a known method. It is a process of producing and producing a horizontal electric field drive type liquid crystal display element. In the steps [I '] to [III'], in place of the substrate having the conductive film for driving a horizontal electric field in step [I], a substrate having no conductive film for driving the horizontal electric field was used, It can carry out similarly to process [I]-[III]. Since the difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the conductive film described above, the description of steps [I '] to [III'] is omitted. Do.

  If an example of preparation of a liquid crystal cell or a liquid crystal display element is given, the above-mentioned 1st and 2nd board | substrates are prepared, a spacer is sprayed on the liquid crystal aligning film of one board | substrate, and the liquid crystal aligning film surface becomes inside. Thus, the other substrate is attached and the liquid crystal is injected under reduced pressure and sealed, or after the liquid crystal is dropped on the liquid crystal alignment film surface to which the spacer is dispersed, the substrate is attached and sealed. , Etc. can be illustrated. At this time, it is preferable to use a substrate having an electrode-like structure for driving a horizontal electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The spacer diameter determines the distance between the pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a coated substrate of the present invention, a polymer composition is coated on a substrate to form a coated film, and then polarized ultraviolet light is irradiated. Next, heating is performed to realize introduction of highly efficient anisotropy to the side chain type polymer film, and a liquid crystal alignment film-provided substrate having the ability to control the alignment of liquid crystal is manufactured.
In the coating used in the present invention, the principle of molecular reorientation induced by self-organization based on photoreaction and liquid crystallinity of side chains is used to realize highly efficient introduction of anisotropy to the coating. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain type polymer, after forming a coating on the substrate using the side chain type polymer, polarized ultraviolet light is After irradiation and heating, a liquid crystal display element is formed.

  Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is a first embodiment, and a structure having a photofleece rearrangement group or a group causing an isomerization as a photoreactive group An embodiment using a side chain type polymer is described as a second embodiment.

  FIG. 1 schematically shows anisotropic introduction processing in a method for producing a liquid crystal alignment film using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. FIG. 8 is a diagram of an example described in FIG. FIG. 1 (a) is a view schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 1 (b) is a view schematically showing the state of the side chain type polymer film after irradiation with polarized light 1 (c) schematically shows the state of the side chain type polymer film after heating, and in particular, when the introduced anisotropy is small, that is, In 1 form, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process is in the range of 1%-15% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 2 schematically shows anisotropic introduction processing in a method for producing a liquid crystal alignment film using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. FIG. 8 is a diagram of an example described in FIG. FIG. 2 (a) is a view schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 2 (b) is a view schematically showing the state of the side chain type polymer film after irradiation with polarized light FIG. 2 (c) is a view schematically showing the state of the side chain type polymer film after heating, and in particular, when the introduced anisotropy is large, that is, In 1 form, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process is in the range of 15%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 3 shows a side chain type polymer having a structure having a photofleece rearrangement group represented by the above-mentioned formula (18) or a photoisomerizable group as a photoreactive group in the second embodiment of the present invention. It is a figure of an example which illustrates typically introduction processing of anisotropy in a manufacturing method of a used liquid crystal aligning film. FIG. 3 (a) is a view schematically showing the state of the side chain type polymer film before irradiation with polarized light, and FIG. 3 (b) is a view schematically showing the state of the side chain type polymer film after irradiation with polarized light FIG. 3 (c) is a view schematically showing the state of the side chain type polymer film after heating, and in particular, in the case where the introduced anisotropy is small, that is, FIG. In 2 aspect, it is a schematic diagram in case the ultraviolet irradiation amount of a process [II] is in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 4: manufacture of the liquid crystal aligning film using the side chain type | mold polymer of the structure which has a light fleece dislocation group represented by said Formula (19) as a photoreactive group in 2nd form in this invention. It is a figure of an example which illustrates introduction processing of anisotropy in a method typically. FIG. 4A is a view schematically showing the state of the side chain type polymer film before polarized light irradiation, and FIG. 4B is a view schematically showing the state of the side chain type polymer film after polarized light irradiation FIG. 4C is a view schematically showing the state of the side chain type polymer film after heating, and in particular, in the case where the introduced anisotropy is large, that is, the fourth aspect of the present invention. In 2 aspect, it is a schematic diagram in case the ultraviolet irradiation amount of a process [II] is in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  In the first embodiment of the present invention, the ultraviolet irradiation dose in the step [II] is in the range of 1% to 15% of the ultraviolet irradiation dose maximizing ΔA in the anisotropic introduction treatment to the coating film. In the case, first, the coating film 1 is formed on the substrate. As shown to Fig.1 (a), in the coating film 1 formed on the board | substrate, it has a structure where the side chain 2 arranges at random. According to the random arrangement of the side chains 2 of the coating 1, the mesogen components and photosensitive groups of the side chains 2 are also randomly oriented, and the coating 1 is isotropic.

  In the first embodiment of the present invention, the ultraviolet irradiation dose in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation dose maximizing ΔA in the anisotropic introduction treatment to the coating film. In the case, first, the coating film 3 is formed on the substrate. As shown to Fig.2 (a), in the coating film 3 formed on the board | substrate, it has a structure where the side chain 4 arranges at random. According to the random arrangement of the side chains 4 of the coating 3, the mesogen components and photosensitive groups of the side chains 4 are also randomly oriented, and the coating 2 is isotropic.

  In the second embodiment of the present invention, a side chain type of a structure having a light fleece rearrangement group represented by the photoisomerizable group or the above-mentioned formula (18) in the anisotropic introduction treatment to a coating film. In the case of using a liquid crystal alignment film using a polymer, when the ultraviolet radiation dose in the step [II] is in the range of 1% to 70% of the ultraviolet radiation dose that maximizes ΔA, first, on the substrate To form a coating film 5. As shown to Fig.3 (a), in the coating film 5 formed on the board | substrate, it has a structure where the side chain 6 arranges at random. According to the random arrangement of the side chain 6 of the coating film 5, the mesogen component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

  In the second embodiment of the present invention, a liquid crystal alignment using a side chain polymer having a structure having an optical fleece dislocation group, represented by the above-mentioned formula (19), by anisotropic introduction treatment to a coating film. In the case of using a film, when the ultraviolet radiation dose in the step [II] is in the range of 1% to 70% of the ultraviolet radiation dose that maximizes ΔA, first, the coating film 7 is formed on the substrate . As shown to Fig.4 (a), in the coating film 7 formed on the board | substrate, it has a structure where the side chain 8 arranges at random. According to the random arrangement of the side chains 8 of the coating film 7, the mesogen components and photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

  In the first embodiment of the present embodiment, the isotropic coating film 1 is applied to the case where the ultraviolet radiation dose in the step [II] is in the range of 1% to 15% of the ultraviolet radiation dose that maximizes ΔA. It emits polarized ultraviolet light. Then, as shown in FIG. 1 (b), the photosensitive group of the side chain 2a having the photosensitive group in the side chain 2 arranged in the direction parallel to the polarization direction of the ultraviolet light is preferentially a dimerization reaction etc. Causes a light reaction. As a result, the density of the photoreactive side chains 2a becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, the coating film 1 is given a very small anisotropy.

  In the first embodiment of the present embodiment, the isotropic coating film 3 is used in the case where the ultraviolet radiation dose in the step [II] is in the range of 15% to 70% of the ultraviolet radiation dose that maximizes ΔA. It emits polarized ultraviolet light. Then, as shown in FIG. 2 (b), the photosensitive group of the side chain 4a having the photosensitive group of the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet light is preferentially a dimerization reaction etc. Causes a light reaction. As a result, the density of the photoreactive side chains 4a increases in the polarization direction of the irradiated ultraviolet light, and as a result, the coating film 3 is given a small anisotropy.

  In the second embodiment of the present embodiment, using a liquid crystal alignment film using a photoisomerizable group or a side chain polymer having a structure having a light fleece rearrangement group represented by the above-mentioned formula (18), In the case where the ultraviolet ray irradiation amount in the step [II] is in the range of 1% to 15% of the ultraviolet ray irradiation amount which makes ΔA maximum, the polarized ultraviolet ray is irradiated to this isotropic coating film 5. Then, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 arranged in the direction parallel to the polarization direction of the ultraviolet light is preferentially a light fleece dislocation etc. Causes a light reaction. As a result, the density of the photoreactive side chains 6a becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, the coating film 5 is given a very small anisotropy.

  In the second embodiment of the present embodiment, using a coating film using a side chain polymer having a structure having a light fleece rearrangement group represented by the above-mentioned formula (19), the ultraviolet radiation dose in the step [II] In the case where the film thickness is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes .DELTA.A, the isotropic coated film 7 is irradiated with polarized ultraviolet light. Then, as shown in FIG. 4B, the photosensitive group of the side chain 8a having the photosensitive group of the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet light is preferentially a light fleece dislocation etc. Causes a light reaction. As a result, the density of the photoreactive side chains 8a increases in the polarization direction of the irradiated ultraviolet light, and as a result, the coating film 7 is given a small anisotropy.

  Next, in the first embodiment of the present invention, the coating film 1 after polarized light irradiation in the case where the ultraviolet radiation dose in the step [II] is in the range of 1% to 15% of the ultraviolet radiation dose maximizing ΔA. Heat to make it into a liquid crystal state. Then, as shown in FIG. 1 (c), in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet light is very small, this crosslinking reaction site acts as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light becomes higher than the liquid crystallinity in the parallel direction, and self-organization is performed in the direction parallel to the polarization direction of the irradiated ultraviolet light to reorient the side chain 2 containing the mesogen component. As a result, the very small anisotropy of the coating 1 induced by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating 1.

  Similarly, in the first embodiment of the present embodiment, the coating film after polarized light irradiation in the case where the ultraviolet irradiation dose in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation dose maximizing ΔA. 3. Heat to 3 liquid crystal state. Then, as shown in FIG. 2C, in the side chain type polymer film 3, the amount of the generated crosslinking reaction is different between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. Therefore, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet light, and the side chains 4 containing the mesogenic component are reoriented. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 3.

  Similarly, in the second embodiment of the present embodiment, a coating film using a side chain type polymer having a structure having a photofleece rearrangement group, which is represented by the photoisomerizable group or the above-mentioned formula (18) is used. In the case where the ultraviolet irradiation dose in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation dose maximizing ΔA, the coating film 5 after the polarized light irradiation is heated to be in a liquid crystal state. Then, as shown in FIG. 3C, in the coating film 5, the amount of the generated light-fleece dislocation reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. In this case, since the liquid crystal alignment force of the light fleece dislocation generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, self-organization is performed in the direction perpendicular to the polarization direction of the irradiated ultraviolet light The side chain 6 containing the mesogenic component is reoriented. As a result, the very small anisotropy of the coating 5 induced by the light fleece rearrangement reaction is amplified by heat, and a greater anisotropy is imparted to the coating 5.

  Similarly, in the second embodiment of the present embodiment, a coating film using a side chain type polymer having a structure having a light fleece rearrangement group represented by the above-mentioned formula (19) is used. In the case where the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount which maximizes ΔA, the coating film 7 after the polarized light irradiation is heated to be in a liquid crystal state. Then, as shown in FIG. 4C, in the side chain type polymer film 7, the amount of generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. . Since the anchoring force of the optical fleece dislocation body 8 (a) is stronger than that of the side chain 8 before the dislocation, when a certain amount or more of the optical fleece dislocation body is generated, self-organization is performed in a direction parallel to the polarization direction of the irradiated ultraviolet light. The side chains 8 containing the mesogenic component are reoriented. As a result, the small anisotropy of the coating 7 induced by the light fleece rearrangement reaction is amplified by heat, and a greater anisotropy is imparted to the coating 7.

  Accordingly, the coating film used in the method of the present invention is a liquid crystal alignment film having high efficiency of introducing anisotropy and having excellent alignment controllability by sequentially irradiating the coating film with polarized ultraviolet light and heating treatment. can do.

  And in the coating film used for the method of this invention, the irradiation amount of the polarized ultraviolet light to a coating film and the heating temperature in heat processing are optimized. Thereby, highly efficient introduction of anisotropy to the coating can be realized.

  The irradiation amount of polarized ultraviolet light most suitable for introducing highly efficient anisotropy to the coating film used in the present invention is that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction or light fleece rearrangement reaction in the coating film It corresponds to the irradiation amount of polarized ultraviolet light which optimizes the amount. When the coating film used in the present invention is irradiated with polarized ultraviolet light, the photocrosslinking reaction, photoisomerization reaction, or light fleece rearrangement reaction does not result in a sufficient amount of photoreaction if there are few photosensitive groups on the side chain. . In that case, sufficient self-organization does not progress even if it heats after that. On the other hand, in the coating film used in the present invention, as a result of irradiating the polarized ultraviolet light to the structure having the photocrosslinkable group, if the photosensitive group of the crosslinkable side chain becomes excessive, the crosslink reaction between the side chains It will be progressing too much. In that case, the resulting film may become rigid and interfere with the progress of self-organization by subsequent heating. In the coating film used in the present invention, as a result of irradiation of ultraviolet light polarized to the structure having a light fleece rearrangement group, if the photosensitive group of the side chain which undergoes light fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Would be too low. In that case, the liquid crystallinity of the resulting film may also be reduced, which may impede the progress of self-assembly due to subsequent heating. Furthermore, in the case of irradiating polarized ultraviolet light to a structure having a light fleece rearrangement group, if the irradiation amount of ultraviolet light is too large, the side chain type polymer is photolyzed, and the subsequent heating prevents the progress of the self-organization. It can be

  Therefore, in the coating film used in the present invention, the optimum amount of photocrosslinking reaction, photoisomerization reaction, or light fleece rearrangement reaction of the photosensitive group in the side chain by irradiation of polarized ultraviolet light is the side chain type polymer film It is preferable to make it 0.1 to 40 mol% of the photosensitive group which it has, and it is more preferable to make it 0.1 to 20 mol%. By setting the amount of photoreactive side-chain photosensitive groups in such a range, the self-assembly in the subsequent heat treatment efficiently proceeds, and highly efficient formation of anisotropy in the film is possible. Become.

  In the coating used in the method of the present invention, the photocrosslinking reaction or photoisomerization reaction of the photosensitive group, or the light fleece rearrangement reaction in the side chain of the side chain type polymer film is performed by optimizing the irradiation amount of polarized ultraviolet light. Optimize the amount of And, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy to the coating film used in the present invention is realized. In that case, the amount of polarized ultraviolet light can be determined based on the evaluation of the ultraviolet absorption of the coating used in the present invention.

  That is, with respect to the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption in the vertical direction are measured after the irradiation with polarized ultraviolet light. From the measurement results of the ultraviolet absorption, ΔA which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the perpendicular direction in the coating film is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light to realize it are determined. In the manufacturing method of the present invention, a preferable amount of polarized ultraviolet light to be irradiated in the production of a liquid crystal alignment film can be determined based on the polarized ultraviolet irradiation amount to realize this ΔAmax.

  In the production method of the present invention, the irradiation amount of the polarized ultraviolet light to the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet light to realize ΔAmax, 1% to More preferably, it is in the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light for realizing ΔAmax is 0. 4 of the entire photosensitive group possessed by the side chain type polymer film. It corresponds to the amount of polarized ultraviolet light to be photocrosslinked by 1 mol% to 20 mol%.

  From the above, in the production method of the present invention, in order to realize introduction of highly efficient anisotropy to the coating film, the above-mentioned suitable heating temperature is set based on the liquid crystal temperature range of the side chain type polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100 ° C. to 200 ° C., it is desirable to set the heating temperature after polarized ultraviolet irradiation to 90 ° C. to 190 ° C. As a result, greater anisotropy is imparted to the coating used in the present invention.

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

  As described above, the substrate for a lateral electric field drive type liquid crystal display device manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display device having the substrate becomes excellent in reliability and has a large screen and high definition. It can be suitably used for the liquid crystal television of

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

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

MA1 and M2 were synthesized as follows, respectively. That is, MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).
G1 was synthesized by the synthesis method described in Synthesis Example 1 below.
GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether) and additive T1 (3-aminomethylpyridine) used were commercially available.

Synthesis Example 1
Synthesis of specified glycidyl compound (G1)

To a solution of carboxylic acid derivative (MA2) (18.4 g, 60 mmol) in THF (tetrahydrofuran) (184 g), (COCl) ₂ (Ogizalyl chloride) (11.4 g, 90 mmol) and DMF (dimethylformamide) 2 Add dropwise and let react for 2 hours at room temperature. The solution was concentrated and the resulting solid was dissolved in THF (350 g). This solution was added dropwise to a THF solution (88 g) of glycidol (8.89 g, 120 mmol) and triethylamine (13.4 g, 132 mmol) over 1 hour, and allowed to react 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, the crude product was obtained by concentration. The obtained crude product was subjected to silica gel chromatography using ethyl acetate and hexane to obtain G1 as a white solid. (Yield: 14.9 g, 69%).

Glycidyl derivative (G1):
¹ H-NMR (CDCl ₃ , δ ppm): 8.01 (d, 2 H), 7.01 (d, 2 H), 6.01 (s, 1 H), 5.56 (s, 1 H), 4.65 -4.61 (m, 1 H), 4.18-4.12 (m, 3 H), 4.02 (t, 2 H), 3.36-3.32 (m, 1 H), 2.9 1-2 .89 (m, 1 H), 2.74-2.72 (m, 1 H), 1.95 to 1.94 (m, 3 H), 1.86 to 1.79 (m, 2 H), 1.76 -1.69 (m, 2H), 1.57-1.44 (m, 4H).

Synthesis Example 2
Synthesis of specific oxetane compound (G2)

  Carboxylic acid derivative (M2) (21.4 g, 70 mmol), dimethylaminopyridine (0.85 g, 7 mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (14, 8 g, 77 mmol) in THF To a (tetrahydrofuran) solution (107 g) was added 3-ethyl-3-oxetanemethanol (8.58 g, 73.5 mmol), and allowed to react at room temperature for 18 hours. Thereafter, the precipitated insolubles were removed by filtration, ethyl acetate (500 g) was added, and the mixture was washed three times with water (200 g) and dried over magnesium sulfate. After magnesium sulfate was removed by filtration, concentration was performed to obtain G2 (yield 27.3 g, 96%) as a colorless liquid.

Oxetane Compound (G2):
¹ H-NMR (CDCl ₃ , δ ppm): 7.97 (d, 2 H), 6.91 (d, 2 H), 6. 10 (s, 1 H), 5.55 (s, 1 H), 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, 4 H), 1.76-1.69 (m, 2 H), 1.57-1.43 (m, 4 H), 0.97 (t, 3 H).

Synthesis Example 3
Synthesis of Specific Oxetane Compound (G3) The following oxetane compounds (G3) were synthesized in the same manner as in the above synthesis example.

Oxetane Compound (G3):
¹ H-NMR (CDCl ₃ , δ ppm): 7.98 (d, 2 H), 6. 90 (d, 2 H), 6. 10 (s, 1 H), 5.55 (s, 1 H), 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).

In addition, abbreviations of reagents used in this example are shown below.
(Organic solvent)
THF: tetrahydrofuran.
NMP: N-methyl-2-pyrrolidone.
BC: butyl cellosolve.
(Polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile.

<Polymer Synthesis Example 1>
After dissolving MA1 (9.67 g, 29.1 mmol) and GMA (0.13 g, 0.9 mmol) in THF (56.3 g) and degassing with a diaphragm pump, AIBN (0.15 g, 3 mmol) ) Was added and degassed again. After this, reaction was carried out at 60 ° C. for 12 hours to obtain a polymer solution of methacrylate. The polymer solution was added dropwise to diethyl ether (1000 ml) and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder P1.

<Polymer Synthesis Examples 2 to 6>
The composition shown in Table 1 was synthesized using the same method as in Polymer Synthesis Example 1.

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

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

Control Polymer Synthesis Example 1
MA1 (9.97 g, 30 mmol) was dissolved in THF (57.5 g) and degassed with a diaphragm pump, and then AIBN (0.15 g, 3 mmol) was added to carry out degassing again. After this, reaction was carried out at 60 ° C. for 12 hours to obtain a polymer solution of methacrylate. The polymer solution was added dropwise to diethyl ether (1000 ml) and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder CP1.

Control Polymer Synthesis Example 2
Methacrylate polymer powder CP2 using the same method as control 1 with the composition of MA1 (5.9 g, 18 mmol), MA2 (3.7 g, 12 mmol), THF (55.5 g), AIBN (0.15 g, 3 mmol) I got

<Control 1 and 2>
The liquid crystal aligning agent B1 of the control 1 was obtained by the method similar to Example 1 using CP1. Similarly, CP2 was used to obtain a liquid crystal aligning agent B2 of Control 2.

<< Preparation of liquid crystal cell >>
Using the liquid crystal aligning agent A1 obtained in Example 1, a liquid crystal cell was produced in the following procedure. The substrate used was a glass substrate of 30 mm × 40 mm in size and 0.7 mm in thickness, and on which a comb-like pixel electrode formed by patterning an ITO film was disposed.

  The pixel electrode had a comb-like shape formed by arranging a plurality of V-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element was 10 μm, and the distance between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent V-shaped electrode elements in the central portion, the shape of each pixel is not rectangular but in the central portion like the electrode elements. It has a shape resembling a bold, bold letter.

  Each pixel is divided up and down at its central bending portion, and has a first region above the bending portion and a second region below the bending portion. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode elements of the pixel electrode are formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel The electrode elements of the pixel electrode were formed to form an angle (clockwise) of -15 [deg.]. That is, in the first area and the second area of each pixel, the directions of rotational movement (in-plane switching) in the plane of the substrate of the liquid crystal induced by voltage application between the pixel electrode and the counter electrode are mutually different. It was configured to be in the opposite direction.

The liquid crystal aligning agent A1 obtained in Example 1 was spin-coated on the prepared electrode-equipped substrate. Subsequently, it dried for 90 seconds with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the coated film surface was irradiated with ultraviolet light of 313 nm at 20 mJ / cm ² through a polarizing plate and then heated on a hot 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 with a height of 4 μm in which an electrode is not formed as an opposing substrate, and an orientation process was performed. A sealing agent (XN-1500T, manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Next, the other substrate was pasted so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. Liquid crystal MLC-2041 (manufactured by Merck & Co., Ltd.) is injected into this empty cell by a pressure reduction injection method, the injection port is sealed, and a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element is obtained. Obtained.

  The liquid crystal aligning agents A2 to A12 obtained in Examples 2 to 12 were similarly used in liquid crystal aligning agents B1 and B2 obtained in Controls 1 and 2 to prepare liquid crystal cells.

<< Voltage Holding Ratio (VHR) Evaluation >>
Using the liquid crystal cell manufactured above, a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C., the voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as the voltage holding ratio (VHR1) . Further, an AC voltage of 16 Vpp was applied at a frequency of 30 Hz for 168 hours in a constant temperature environment of 70 ° C. for the measured cell. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. The obtained cell was measured under the same conditions as VHR1, and how much the voltage could be held was calculated as a voltage holding ratio (VHR2). In addition, the voltage holding ratio measuring apparatus VHR-1 made from Toyo Technica Co., Ltd. was used for the measurement of a voltage holding ratio.

  The VHR results are shown in Table 3 together with the compositions of the liquid crystal aligning agents of the example and the control.

  It can be seen from Table 3 that, in Examples 1 to 12, by copolymerizing a monomer having an epoxy group, VHR1 is improved as compared with Controls 1 and 2 which do not copolymerize. Moreover, it turns out that the result of VHR2 is favorable by adding the additive T1 in Examples 5-8, 11 and 12 further.

<Afterimage evaluation>
The liquid crystal cell for IPS mode prepared in Examples 1 to 8 is placed between two polarizing plates disposed so that the polarization axes are orthogonal to each other, and the backlight is turned on in the state of no voltage application, and transmitted light The arrangement angle of the liquid crystal cell was adjusted so as to minimize the brightness of. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the pixel is the darkest to the angle at which the first region is the dark is calculated as the initial alignment azimuth angle.
Then, in a 60 ° C. oven, an alternating voltage of 16 V _PP at frequency 30 Hz was applied for 168 hours. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. After leaving, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuth before and after AC drive was calculated as the angle Δ (deg.).
The same measurement was performed in the other examples.

As a result, in all the examples, the angle Δ was 0.1 or less.
The side chain type polymer film exhibiting liquid crystallinity is irradiated with ultraviolet light, and then heated in the liquid crystal expression temperature range, so that the liquid crystal alignment ability is highly efficiently imparted to the whole polymer by self-organization, or long-term Almost no deviation in the orientation was observed even after AC driving.

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

Claims (7)

It is a photosensitive side-chain type polymer which exhibits liquid crystallinity in a predetermined temperature range, which is represented by the following formula (0)

[Wherein, A and B are each independently a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -Or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be replaced by a halogen group;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Represents CH-, and when the number of X is 2, X may be the same or different;
P and Q are each independently selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof Group, provided that when X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q to which -CH = CH- is attached is an aromatic ring;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
G is a group represented by the following formulas (G-1), (G-2), (G-3) and (G-4)

(Wherein the broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R ^50, they are identical or different from each other) T is an integer of 1 to 7, J is O, S, NH or NR ⁵¹ , R ⁵¹ is a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)
Is a group selected from
A side chain type polymer having a side chain represented by and a side chain represented by the following formula (9) ,
A side chain type polymer having a main chain composed of at least one selected from the group consisting of (meth) acrylate, itaconate, fumarate, maleate and vinyl .

(Wherein, 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 = Represents CH-, and when the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2;
R represents a hydroxy group). Following formulas (21) to (31)
(In the formula,
A and B are each independently a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or- Represents O-CO-CH = CH-;
Y ₃ is a group selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof And the hydrogen atoms bonded to them may be each independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing group A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12 and m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26) In the above, the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And an alkyl group or an alkyloxy group;
Z _{1, Z 2} is a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 - represents a)
The side chain type polymer according to claim 1 having any one liquid crystalline side chain selected from the group consisting of

  A polymer composition comprising (A) the side chain type polymer according to claim 1 or 2 and (B) an organic solvent.   The polymer composition further has one primary amino group in the (C) molecule and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is an aliphatic hydrocarbon group or a non-aromatic cyclic group. The composition according to claim 3, comprising an amine compound bound to a hydrocarbon group. The component (C) is represented by the following formula A- [1] (wherein, Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is nitrogen-containing) 5. The composition according to claim 4, which is an amine compound represented by (a) hetero ring.

[I] a step of applying the composition according to any one of claims 3 to 5 on a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and a step of heating the coating film obtained in [III] [II];
A method of manufacturing a substrate having the liquid crystal alignment film, wherein a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which an alignment control ability is imparted by obtaining Preparing a substrate (first substrate) manufactured by the manufacturing method according to claim 6;
[I '] a step of applying the polymer composition according to any one of claims 3 to 5 on a second substrate to form a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet light; and a step of heating the coating film obtained in [III ′] [II ′];
Obtaining a second substrate having the liquid crystal alignment film by obtaining a liquid crystal alignment film to which alignment control ability is imparted; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal Arranging the first and second substrates so that the films face each other to obtain a liquid crystal display element;
A method of manufacturing a liquid crystal display element, wherein a transverse electric field drive type liquid crystal display element is obtained by having

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