JP6676932B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Description

  The present invention relates to a novel polymer composition (liquid crystal alignment agent), a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element using the same, and a method for producing a substrate having the alignment film. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent image sticking characteristics.

  2. Description of the Related Art Liquid crystal display elements are known as light-weight, thin, and low-power-consumption display devices, and have been remarkably developed in recent years, such as being used for large-sized televisions. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display device, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

  That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that sandwiches the liquid crystal, in contact with the liquid crystal, and has a role of aligning the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to have a role of controlling the pretilt angle of the liquid crystal in addition to a role of aligning the liquid crystal in a fixed direction, for example, a direction parallel to the substrate. The ability of such a liquid crystal alignment film to control the alignment of liquid crystal (hereinafter, referred to as alignment control ability) is given by performing an alignment process on an organic film constituting the liquid crystal alignment film.

  A rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth of cotton, nylon, polyester, or the like in a certain direction, and in a rubbing direction (rubbing direction). This 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 a conventional liquid crystal display element manufacturing process. As the organic film used for the liquid crystal alignment film, a polyimide organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.

  However, the rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like sometimes causes problems such as generation of dust and static electricity. In addition, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth due to the recent increase in definition of the liquid crystal display element and unevenness due to the corresponding electrodes on the substrate and switching active elements for driving the liquid crystal. In some cases, liquid crystal alignment could not be realized.

  Therefore, as another alignment treatment method for a liquid crystal alignment film that does not perform rubbing, a photo alignment method has been actively studied.

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

  As a main optical alignment method, a decomposition type optical alignment method is known. In this method, for example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is caused by utilizing the polarization direction dependency of ultraviolet absorption of a molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (for example, see Patent Document 1).

  Further, as other photo-alignment methods, photo-crosslinking type and photo-isomerization type photo alignment methods are also known. In the photo-crosslinking type photo-alignment method, for example, polyvinyl cinnamate is used, and polarized ultraviolet rays are irradiated to cause a dimerization reaction (cross-linking reaction) at a 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 (for example, see Non-Patent Document 1). In the photo-isomerization type photo-alignment method, 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 portion of the side chain parallel to the polarized light, thereby causing polarization. The liquid crystal is aligned in a direction perpendicular to the direction (for example, see Non-Patent Document 2).

  As in the above example, the method for aligning the liquid crystal alignment film by the photo alignment method does not require rubbing, and there is no fear of generating dust or static electricity. Then, an alignment treatment can be performed on a substrate of a liquid crystal display element having an uneven surface, which is a method for an alignment treatment of a liquid crystal alignment film suitable for an industrial production process.

Japanese 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 photo-alignment method has a great advantage because the rubbing process itself is not required as compared with the rubbing method conventionally used industrially as a method of aligning a liquid crystal display element. In contrast to the rubbing method in which the alignment control ability becomes substantially constant by rubbing, in the optical alignment method, the alignment control ability can be controlled by changing the irradiation amount of polarized light. However, the optical alignment method requires a large amount of polarized light irradiation when attempting to achieve the same level of alignment control capability as the rubbing method. There is.

  For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate a polyimide film with ultraviolet light from a high-pressure mercury lamp with a power of 500 W for 60 minutes, and a long and large amount of ultraviolet irradiation is required. Become. Also, in the case of the dimerization type or photoisomerization type photo-alignment method, a large amount of ultraviolet radiation of several J (joules) to several tens J may be required in some cases. Furthermore, in the case of the photo-crosslinking type or photo-isomerization type photo alignment method, thermal stability and light stability of the alignment of the liquid crystal are inferior. was there. In particular, in a horizontal electric field driving type liquid crystal display element, since liquid crystal molecules are switched in a plane, alignment deviation of liquid crystal after liquid crystal driving is apt to occur, and display burn-in caused by AC driving is a major problem.

  Therefore, in the photo-alignment method, high efficiency of the alignment treatment and realization of stable liquid crystal alignment are required, and a liquid crystal alignment film or a liquid crystal capable of providing a high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for an aligning agent.

  The present invention relates to a novel polymer composition which provides a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which is provided with an alignment control ability with high efficiency and is excellent in image sticking properties, and a horizontal electric field drive type liquid crystal display using the same. It is an object of the present invention to provide a liquid crystal alignment film for an element, a substrate having the alignment film, and a horizontal electric field drive type liquid crystal display device having the substrate. It is still another object of the present invention to provide a liquid crystal alignment film having an improved voltage holding ratio even by firing at a low temperature, and a method of manufacturing a substrate having the same.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found the following invention.
<1> (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
(B) a polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound, and then imidizing the polyurea polyimide;
And (C) a polymer composition containing an organic solvent, particularly a polymer composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device.

<2> In the above item <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries transition.
<3> In the above item <1> or <2>, the diisocyanate component may be an aromatic diisocyanate and / or an aliphatic diisocyanate.

式中、Ａ、Ｂ、Ｄはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｓは、炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｔは、単結合または炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｙ_１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ_０（式中、Ｒ_０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｙ_２は、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｒは、ヒドロキシ基、炭素数１〜６のアルコキシ基を表すか、又はＹ_１と同じ定義を表す；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
Ｃｏｕは、クマリン−６−イル基またはクマリン−７−イル基を表し、それらに結合する水素原子はそれぞれ独立に−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
ｑ１とｑ２は、一方が１で他方が０である；
ｑ３は０または１である；
Ｐ及びＱは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である；ただし、Ｘが−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＣＨ＝ＣＨ−である場合、−ＣＨ＝ＣＨ−が結合する側のＰ又はＱは芳香環であり、Ｐの数が２以上となるときは、Ｐ同士は同一でも異なっていてもよく、Ｑの数が２以上となるときは、Ｑ同士は同一でも異なっていてもよい；
ｌ１は０または１である；
ｌ２は０〜２の整数である；
ｌ１とｌ２がともに０であるときは、Ｔが単結合であるときはＡも単結合を表す；
ｌ１が１であるときは、Ｔが単結合であるときはＢも単結合を表す；
Ｈ及びＩは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。 <4> In any one of the above items <1> to <3>, the component (A) may have any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.

Wherein, A, B, D are each independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO- O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto 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 thereto may be replaced by a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a same selected from the substituents thereof; A group in which two to six different rings are bonded via a bonding group B, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 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 a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are each independently —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—. May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are 1 on the one hand and 0 on the other hand;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. Provided that when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; 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;
11 is 0 or 1;
12 is an integer from 0 to 2;
When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

<5> In any one of the above items <1> to <3>, the component (A) may have any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10). Good.
Wherein 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 (however, when n = 0, B is a single bond).

<6> In any one of the above items <1> to <3>, the component (A) may have any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13). Good.
Wherein A, X, 1, m, m1 and R have the same definition as above.

<7> In any one of the above items <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).
Wherein A, Y ₁ , 1, m1 and m2 have the same definition as above.

<8> In any one of the above items <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).
Wherein A, X, l and m have the same definition as above.

<9> In any one of the above items <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definition as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

<10> In any one of the above items <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (20).
Wherein A, Y ₁ , X, l and m have the same definition as above.

<11> In any one of the above items <1> to <10>, the component (A) may have any one type of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
Wherein A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, and a nitrogen-containing group. Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
q1 and q2 are 1 on the one hand and 0 on the other hand;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that, in the formulas (23) to (24), the sum of all m is 2 or more, and the formulas (25) to (26) )), 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 heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms; And represents 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.

<12> [I] a step of applying the composition of any of the above <1> to <11> 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 [III] a step of heating the coating film obtained in [II];
A method for producing a substrate having a liquid crystal alignment film, wherein a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element having an alignment control ability is provided by having the above.

<13> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by the method of <12>.
<14> A horizontal electric field drive type liquid crystal display device having the substrate according to <13>.

<15> a step of preparing the substrate (first substrate) according to <13>;
[I ′] a step of applying the polymer composition according to any one of the above <1> to <13> 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 [III '] a step of heating the coating film obtained in [II'];
Obtaining a second substrate having the liquid crystal alignment film provided with an alignment control ability by having the following: [IV] liquid crystal alignment films of the first and second substrates via liquid crystal Obtaining a liquid crystal display element by arranging the first and second substrates so as to face each other;
A method for manufacturing a liquid crystal display element, wherein a liquid crystal display element is obtained.

  <16> A lateral electric field drive type liquid crystal display device manufactured according to the above <15>.

According to the present invention, there is provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which is provided with an alignment control ability with high efficiency and is excellent in image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can be.
The horizontal electric field driving type liquid crystal display device manufactured by the method of the present invention has an alignment control ability with high efficiency, so that display characteristics are not impaired even when driven continuously for a long time.
Further, in the present invention, a polyurea polyimide produced by polymerizing a diisocyanate compound as a component (B), a tetracarboxylic acid derivative, and a diamine compound and then imidizing the same is contained in the polymer composition. Accordingly, it is possible to provide a lateral electric field driving type liquid crystal element having an excellent voltage holding ratio even by firing at a low temperature and a liquid crystal alignment film for the element.

FIG. 2 is a diagram of one example schematically illustrating an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, wherein a crosslinkable organic group is used in a photosensitive side chain, and an anisotropic introduction is performed. It is a figure in the case where the property is small. FIG. 2 is a diagram of one example schematically illustrating an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, wherein a crosslinkable organic group is used in a photosensitive side chain, and an anisotropic introduction is performed. It is a figure in the case of a large nature. It is a diagram of one example schematically illustrating the introduction of anisotropy in the method for producing a liquid crystal alignment film used in the present invention, using an organic group that causes fleece transfer or isomerization in the photosensitive side chain, introduced It is a figure in the case where the obtained anisotropy is small. It is a diagram of one example schematically illustrating the introduction of anisotropy in the method for producing a liquid crystal alignment film used in the present invention, using an organic group that causes fleece transfer or isomerization in the photosensitive side chain, introduced It is a figure in the case where the obtained anisotropy is large.

The present inventor has earnestly studied and, as a result, 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 polymer capable of exhibiting liquid crystallinity (hereinafter, also simply referred to as a side-chain polymer). The coating film obtained by using the product is a film having a photosensitive side-chain polymer capable of exhibiting liquid crystallinity. This coating film is subjected to an alignment treatment by polarized light irradiation without performing a rubbing treatment. After the polarized light irradiation, the side chain-type polymer film is heated to form a coating film (hereinafter, also referred to as a liquid crystal alignment film) provided with an alignment control ability. At this time, the slight anisotropy developed by the polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently realigned by self-organization. As a result, highly efficient alignment processing is realized as the liquid crystal alignment film, and a liquid crystal alignment film having high alignment control ability can be obtained.

Further, in the polymer composition of the present invention, in addition to the side chain type polymer as the component (A) and the organic solvent as the component (C), a diisocyanate compound as a component (B), a tetracarboxylic acid derivative, It contains a polyurea polyimide produced by polymerizing a diamine compound and then imidizing it. As a result, it was unexpected that the voltage holding ratio of the liquid crystal alignment film was significantly improved even by low-temperature firing. The present inventors have pointed out that these phenomena are caused by the addition of the component (B), and that the components (A) and (B) exert an interaction, thereby achieving a desired effect. (These include the inventor's views on the mechanism of the present invention and do not restrict the present invention.)

<Polymer composition>
The polymer composition of the present invention comprises: (A) a photosensitive side-chain polymer exhibiting liquid crystallinity in a predetermined temperature range; (B) a polymerization reaction of a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound. And a polyurea polyimide produced by imidation; and (C) an organic solvent.

<< (A) side chain type polymer >>
The component (A) is a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range.
(A) It is preferable that the side chain type polymer reacts with light in a wavelength range of 250 nm to 400 nm and shows liquid crystallinity in a temperature range of 100 ° C. to 300 ° C.
(A) The side-chain type polymer preferably has a photosensitive side chain that reacts to light in a wavelength range of 250 nm to 400 nm.
(A) The side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

  (A) In the side chain type polymer, a side chain having photosensitivity is bonded to a main chain, and can cause a crosslinking reaction, an isomerization reaction, or a photo-Fries rearrangement in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction or photo-Fries rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, the realized alignment control ability can be stably maintained for a long period of time even when exposed to external stress such as heat. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as such characteristics are satisfied, but it is preferable that the side chain structure has a rigid mesogen component. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

  The structure of the polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group; Having a structure having a photosensitive group that undergoes a cross-linking reaction or an isomerization reaction in response to light, a main chain and a side chain bonded thereto, and the side chain also serves as a mesogen component, and A structure having a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction can be employed.

式中、Ａ、Ｂ、Ｄはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｓは、炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｔは、単結合または炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｙ_１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ_０（式中、Ｒ_０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｙ_２は、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｒは、ヒドロキシ基、炭素数１〜６のアルコキシ基を表すか、又はＹ_１と同じ定義を表す；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
Ｃｏｕは、クマリン−６−イル基またはクマリン−７−イル基を表し、それらに結合する水素原子はそれぞれ独立に−ＮＯ_２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）_２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
ｑ１とｑ２は、一方が１で他方が０である；
ｑ３は０または１である；
Ｐ及びＱは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である；ただし、Ｘが−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＣＨ＝ＣＨ−である場合、−ＣＨ＝ＣＨ−が結合する側のＰ又はＱは芳香環であり、Ｐの数が２以上となるときは、Ｐ同士は同一でも異なっていてもよく、Ｑの数が２以上となるときは、Ｑ同士は同一でも異なっていてもよい；
ｌ１は０または１である；
ｌ２は０〜２の整数である；
ｌ１とｌ２がともに０であるときは、Ｔが単結合であるときはＡも単結合を表す；
ｌ１が１であるときは、Ｔが単結合であるときはＢも単結合を表す；
Ｈ及びＩは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。 More specific examples of the structure of the photosensitive side chain polymer capable of exhibiting liquid crystal properties include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, and vinyl. Having a main chain composed of at least one member selected from the group consisting of siloxane, a radical polymerizable group such as maleimide and norbornene, and a side chain composed of at least one of the following formulas (1) to (6) It is preferred that

Wherein, A, B, D are each independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO- O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto 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 thereto may be replaced by a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a same selected from the substituents thereof; A group in which two to six different rings are bonded via a bonding group B, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 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 a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are each independently —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—. May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are 1 on the one hand and 0 on the other hand;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. Provided that when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; 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;
11 is 0 or 1;
12 is an integer from 0 to 2;
When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

The side chain is preferably any one of the photosensitive side chains selected from the group consisting of the following formulas (7) to (10).
Wherein A, B, D, Y ₁ , X, Y ₂ and R have the same 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 (however, when n = 0, B is a single bond).

The side chain is preferably any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).
Wherein A, X, 1, m, m1 and R have the same definition as above.

The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).
Wherein A, Y ₁ , 1, m1 and m2 have the same definition as above.

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).
Wherein 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, Y1, q1, q2, m1, and m2 have the same definition as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group 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.

Further, (A) the side chain type polymer preferably has any one type of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
Wherein A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, and a nitrogen-containing group. Represents 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;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that, in the formulas (23) to (24), the sum of all m is 2 or more, and the formulas (25) to (26) )), 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 heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms; And represents 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 method of photosensitive side chain polymer >>
The photosensitive side chain type polymer capable of exhibiting the liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the photosensitive side chain and the liquid crystalline side chain monomer.

[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 site of the polymer when the polymer is formed.
The following structures and derivatives thereof are preferable as the photoreactive group of the side chain.

  More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and the like. And a polymerizable group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7) ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitive 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), and photosensitive represented by the above formula (20) With sex side chains Preferably, the structure is such that:

[Liquid crystalline side chain monomer]
The liquid crystal side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogen group at a side chain site.
The mesogenic group of the side chain may be a group having a mesogenic structure by itself such as biphenyl or phenylbenzoate, or a group having a mesogenic structure by hydrogen bonding between side chains such as benzoic acid. Good. The following structure is preferable as the mesogen group of the side chain.

  More specific examples of the liquid crystalline side chain monomer include a radical polymerizable group such as a hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and the like. The structure preferably has a polymerizable group composed of at least one selected from the group consisting of siloxane and a side chain composed of at least one of the above formulas (21) to (31).

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

Examples of other monomers include, for example, commercially available monomers capable of undergoing a radical polymerization reaction.
Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
As the acrylate 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 methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and 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. (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  The method for producing the side-chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is industrially used can be used. 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 preferred from the viewpoint of easy reaction control.

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

  The radical thermal polymerization initiator is a compound that generates a radical when heated to a temperature higher than the decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (eg, methyl ethyl ketone peroxide, cyclohexanone peroxide), diacyl peroxides (eg, acetyl peroxide, benzoyl peroxide), and hydroperoxides (eg, peroxides). Hydrogen, tert-butylhydroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy-2-ethylcyclohexane) Sannic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl ) Azobisisobutyronitrile). One of these radical thermal polymerization initiators can be used alone, or two or more can be used in combination.

  The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, and 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminoethyl benzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone , 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl ) -S-Triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylamino Coumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bi (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl 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, -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

  The organic solvent used for the polymerization reaction of the photosensitive side-chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the produced polymer is dissolved. Specific examples are 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, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene Glycol 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, trifluoropropyl Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether 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 —N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or as a mixture. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
In addition, since oxygen in an organic solvent causes inhibition of the polymerization reaction in radical polymerization, it is preferable to use a degassed organic solvent as much as possible.

  The polymerization temperature at the time of radical polymerization can be selected from any temperature of 30C to 150C, but is preferably in the range of 50C to 100C. In addition, the reaction can be performed at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, 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, after which an organic solvent can be added.

  In the above-described radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer is small, and when the ratio is small, the molecular weight of the obtained polymer is large. The amount is preferably from 0.1 mol% to 10 mol% based on the monomer to be polymerized. At the time of polymerization, various monomer components, a solvent, an initiator and the like can be added.

[Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side-chain polymer capable of exhibiting liquid crystal properties obtained by the above-described reaction, the reaction solution is poured into a poor solvent, and the weight of the polymer is reduced. What is necessary is just 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 that has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or reduced pressure at normal temperature or by heating. Further, by repeating the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and recovering and recovering the precipitate two to ten times, impurities in the polymer can be reduced. In this case, examples of the poor solvent include alcohols, ketones, and hydrocarbons. It is preferable to use three or more kinds of poor solvents selected from these, because the purification efficiency is further increased.

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

<< (B) component >>
The polymer composition used in the present invention has, as the component (B), a polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound, and then imidizing the polyurea polyimide.

<<<< Diisocyanate component >>>>
Examples of the diisocyanate component which is a raw material of the component (B) include aromatic diisocyanates and aliphatic diisocyanates. Preferred diisocyanate components are aromatic diisocyanates and aliphatic diisocyanates.

  Here, the aromatic diisocyanate means a group in which the R group of the diisocyanate structure (O = C = N-R-N = C = O) includes a structure containing an aromatic ring. In addition, the aliphatic diisocyanate refers to an isocyanate structure in which the R group has a cyclic or acyclic aliphatic structure.

  Specific examples of the aromatic diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (for example, tolylene 2,4-diisocyanate), and 2-methoxybenzene 1,4-diisocyanate. , 2,5-diisocyanate xylenes, 2,2'-bis (4-diisocyanatephenyl) propane, 4,4'-diisocyanate diphenylmethane, 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate Examples include diphenylsulfone, 3,3'-diisocyanic acid diphenylsulfonate, and 2,2'-diisocyanic acid benzophenone. As the aromatic diisocyanate, preferably, tolylene 2,4-diisocyanate is used. Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate. As the aliphatic diisocyanate, preferably, isophorone diisocyanate is used. Of these, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferable from the viewpoint of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferable from the viewpoint of availability, polymerization reactivity, and voltage holding ratio.

<<< Diamine component >>>
Examples of the diamine component which is a raw material of the component (B) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines and diamines containing a urea bond.

  Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine And the like.

  Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene and 1,4-diamino- 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 ′ -Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diamino Tilben, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4- Aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4-amino Phenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6- Diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl Nyl) tetramethyldisiloxane, benzidine, 2,2′-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4 -Aminophenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, bis (4-aminophenoxy) methane, 1,2-bis (4 -Aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) B) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4 -Aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) ) Octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane-1,10-dioate 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) ) Phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- ( 4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.

（式中、Ａｒはベンゼン環またはナフタレン環を表し、Ｒ_１は炭素原子数が１〜５のアルキレン基であり、Ｒ_２は水素原子またはメチル基である。） Examples of the aromatic-aliphatic diamine include a diamine represented by the following formula [DAM].

(In the formula, Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.)

  Specific examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopenty) ) Aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- ( 6-aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

  Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, and 3,6-diaminocarbazole , 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.

  Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples thereof include 1,18-diaminooctadecane and 1,2-bis (3-aminopropoxy) ethane.

  Examples of the urea bond-containing diamine include N, N‘-bis (4-aminophenethyl) urea and the like.

  Further, in the component (B), a diamine having a side chain for vertical alignment may be contained as a diamine component to be polymerized with the diisocyanate component as long as the effects of the present invention are not impaired.

（式中、ｍ、ｎはそれぞれ１から１１の整数であり、ｍ＋ｎは２から１２の整数であり、ｈは１〜３の整数であり、ｊは０から３の整数である。） Further, the diamine component in the component (B) may contain the following diamine.

(In the formula, m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, h is an integer of 1 to 3, and j is an integer of 0 to 3.)

By introducing these diamines, it is advantageous to further improve the voltage holding ratio (VHR) of a liquid crystal display element using a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention. These diamines are preferred from the viewpoint of excellent storage charge reduction effect of such a liquid crystal display element.

（式中、ｍは、１から１０の整数である。） In addition, examples of the diamine component in the component (B) include diaminosiloxanes represented by the following formulas.

(In the formula, m is an integer of 1 to 10.)

When the diamine compound further has a nitrogen atom between the two amino groups, the nitrogen atom present between the two amino groups is bonded to a group selected from a carbonyl and a benzene ring by a single bond. Is preferable in that salt formation with the component (A) can be prevented.

  The diamine component in the component (B) can be used alone or in combination of two or more depending on characteristics such as a liquid crystal alignment property, a voltage holding property, and a stored charge when a liquid crystal alignment film is formed. At that time, the mixing ratio is not limited.

<<< tetracarboxylic acid derivative >>>
Examples of the tetracarboxylic acid derivative as the raw material of the component (B) include tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5-pentanetetracarboxylic Dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3 , 5-Tricarboxycyclopentylacetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, tricyclo [4.2.1. 0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . ^19,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 And naphthalene succinic dianhydride.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'- Benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

  The above-mentioned tetracarboxylic dianhydrides can be used alone or in combination of two or more depending on the properties of the formed liquid crystal alignment film, such as liquid crystal alignment, voltage holding characteristics, and accumulated charge.

Further, as the tetracarboxylic acid derivative which is a raw material of the component (B), tetracarboxylic dialkyl ester or tetracarboxylic dialkyl diester dichloride may be used. When the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester which is a polyimide precursor. The dialkyl tetracarboxylate that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic diesters and aromatic tetracarboxylic dialkyl esters.
Specific examples are given below.

Specific examples of the aliphatic tetracarboxylic diester include 1,2,3,4-cyclobutanetetracarboxylic dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2 2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy- 1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene dialkyl succinate, 1,2,3,4-butanetetracarboxylic dialkyl ester, 1,2,4,5-pentanetetracarboxylic dialkyl ester, bicyclo [ 3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetate dialkyl Ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4 , 7,8-Tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . ^19,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene And succinic dianhydride.

  Specific examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester. Carboxylic acid dialkyl ester, 2,3,3 ', 4'-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ', 4'-benzophenone Tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2 , 3,6,7-naphthalenetetracarboxylic acid Alkyl esters thereof.

  Examples of the tetracarboxylic diester dichloride include a diester dichloride obtained by converting a carboxyl group of the above-described dialkyl tetracarboxylic acid into a chlorocarbonyl group by a known method.

Some of these compounds have isomers, but may be a mixture containing them. Further, two or more compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above exemplified compounds.

  These tetracarboxylic dianhydrides, tetracarboxylic diesters, tetracarboxylic diester dichlorides, etc. may be one or two types depending on the properties of the liquid crystal alignment film, such as liquid crystal alignment, voltage holding characteristics, and accumulated charge. More than one kind can be used together.

  In order to obtain a polyurea polyamic acid or a polyurea polyamic acid ester which is a precursor of the polymer of the component (B) by a polymerization reaction of the diisocyanate component, the tetracarboxylic acid derivative, and the diamine component of each raw material, Synthetic techniques can be used. In general, a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component are reacted in an organic solvent. Such a reaction is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

The organic solvent used for the reaction between the diisocyanate component, the tetracarboxylic acid derivative, and the diamine component is not particularly limited as long as the generated polyureapolyamic acid or polyureapolyamic acid ester can be dissolved.
Specific examples are given below.

  Organic solvents usable herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethyl Urea, pyridine, dimethyl sulfone, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate , Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether Ethylene glycol 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, tri Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxyp Pionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3 -Ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like. These may be used alone or as a mixture. Furthermore, even if the solvent does not dissolve polyurea, it may be mixed with the above solvent and used as long as the generated polyurea does not precipitate.

  In addition, since water in the organic solvent causes inhibition of the polymerization reaction, it is preferable to use a dehydrated organic solvent as much as possible.

  When reacting a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component in an organic solvent, a solution obtained by dispersing or dissolving the diamine component in the organic solvent is stirred, and the diisocyanate component is dispersed as it is or in the organic solvent. Alternatively, a method of adding the compound by dissolving and adding the tetracarboxylic acid derivative as it is or dispersing or dissolving it in an organic solvent, and conversely dispersing or dissolving the diisocyanate component and the tetracarboxylic acid derivative in the organic solvent And a method of adding a diamine component to the solution, and any of these methods may be used. When the diisocyanate component, the tetracarboxylic acid derivative, or the diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be individually reacted. The molecular weights may be mixed and reacted to form high molecular weights.

  The polymerization temperature at this time can be selected from any temperature from -20 ° C to 150 ° C, but is preferably from -5 ° C to 100 ° C. In addition, the reaction can be performed at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the diisocyanate component, the tetracarboxylic acid derivative, and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, after which an organic solvent can be added.

  In the polymerization reaction of the polyurea polyamic acid, the ratio of the total mole number of the diisocyanate component and the tetracarboxylic acid derivative to the total mole number of the diamine component is preferably 0.8 to 1.2. As in the ordinary polycondensation reaction, the molecular weight of the generated polyureapolyamic acid or polyureapolyamic acid ester increases as the molar ratio approaches 1.0.

  When recovering the generated polyurea polyamic acid or polyurea polyamic acid ester from the reaction solution, the reaction solution may be poured into a poor solvent to cause precipitation. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. After the polymer that has been put into a poor solvent and precipitated is collected by filtration, it can be dried at normal temperature or under reduced pressure at normal temperature or under normal pressure. Further, by repeating the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and recovering and recovering the precipitate 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons. It is preferable to use three or more kinds of poor solvents selected from these, because the purification efficiency is further increased.

（式［１］中、Ａ_１は２価の有機基であり、Ａ_２は２価の有機基であり、Ｃ_１及びＣ_２は水素原子又は炭素数１〜３のアルキル基であり、それぞれ同じであっても異なってもよい。） Such polyurea polyamic acid or polyurea polyamic acid ester is, for example, a polymer having a repeating unit represented by the following formula [1] and a repeating unit represented by the following formula [2].

(In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and It may be the same or different.)

In the above formula [1], a polymer in which A ₁ and A ₂ are each one kind and have the same repeating unit may be used, or a polymer in which A ₁ and A ₂ are plural kinds and have repeating units of different structures. May be.

In the above formula [1], A ₁ is a group derived from a diisocyanate component as a raw material. Moreover, A ₂ is a group derived from a diamine component as a raw material.

式［２］において、Ａ_３は、それぞれ独立して４価の有機基であり、Ａ_２はそれぞれ独立して２価の有機基である。Ｒ_１１は、水素原子、又は炭素数１〜５のアルキル基であり、Ｃ_１〜Ｃ_２はそれぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、又は炭素数２〜１０のアルキニル基である。

In the formula [2], A ₃ is each independently a tetravalent organic group, and A ₂ is each independently a divalent organic group. R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and C _{1 to} C ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, It is an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the above alkyl group for R ₁₁ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and an n-pentyl group. And the like. From the viewpoint of ease of imidization by heating, R ₁₁ is preferably a hydrogen atom or a methyl group.

According to a preferred embodiment of the present invention, A ₁ is preferably a group derived from the above-mentioned preferred diisocyanate component. Further, as A ₂ are groups derived from the preferred diamine components listed above are preferred. Further, A ₃ is preferably a group derived from the above-mentioned preferable tetracarboxylic acid derivative and / or anhydride thereof.

  Here, the molar ratio of the tetracarboxylic acid derivative to the diisocyanate is preferably from 99: 1 to 1:99.

  The polyurea polyimide is obtained by ring-closing the above polyurea polyamic acid or polyurea polyamic acid ester. The cyclization rate of the amic acid group (also referred to as imidation rate) does not necessarily need to be 100%, and can be arbitrarily adjusted according to the application and purpose.

  Examples of the method for imidizing the polyurea polyamic acid or the polyurea polyamic acid ester include thermal imidization in which a solution of a polyimide precursor is directly heated or catalytic imidization in which a catalyst is added to a solution of a polyurea polyamic acid or a polyurea polyamic acid ester. .

  The temperature at which the polyurea polyamic acid or polyurea polyamic acid ester is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., while removing water generated by the imidation reaction out of the system. It is preferable to do so.

  Catalytic imidation of polyurea polyamic acid or polyurea polyamic acid ester is performed by adding a basic catalyst and an acid anhydride to a solution of polyurea polyamic acid or polyurea polyamic acid ester, and adding -20 ° C to 250 ° C, preferably 0 ° C to It can be performed by stirring at 180 ° C. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times the mole of the amic acid group, and the amount of the acid anhydride is 1 to 50 times the mole of the amic acid group. Preferably it is 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for causing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because purification after the reaction is easy. The imidation rate by the catalytic imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

  When recovering the generated polyurea polyimide from the reaction solution of polyurea polyamic acid, polyurea polyamic acid ester, or polyurea polyimide, the reaction solution may be put into a solvent to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. After the polymer that has been put into the solvent and precipitated is collected by filtration, it can be dried at normal temperature or under reduced pressure at normal temperature or under normal pressure. Further, by repeating the operation of re-dissolving the precipitated and recovered polymer in a solvent and re-precipitating and recovering it two to ten times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. It is preferable to use three or more solvents selected from these, because purification efficiency is further increased.

  The molecular weight of the polyurea polyimide of the component (B) is determined by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, workability in forming the liquid crystal alignment film, and uniformity of the liquid crystal alignment film. The average molecular weight is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 150,000.

  According to a preferred embodiment of the present invention, in the polymerization composition according to the present invention, the mixing ratio (by mass) of the component (A) and the component (B) is the total (the sum of the components (A) and (B)). ) Is 1, the component (A) is 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.5.

<< (C) Organic solvent >>
The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as the organic solvent dissolves the resin component. Specific examples are 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, 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. Is mentioned. These may be used alone or as a mixture.

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

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.
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 Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 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, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-butyl lactate, isoamyl lactate, etc. Solvents having a surface tension are exemplified.

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

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
More specifically, for example, F-top (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) and the like. Can be The use ratio of these surfactants is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition. Parts by weight.

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

Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, the following phenoplasts or epoxy group-containing compounds are added for the purpose of preventing a decrease in electric characteristics due to a backlight when a liquid crystal display element is formed. The agent may be contained 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-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4 4'-diaminodiphenylmethane and the like.

  When a compound that improves the adhesion to the substrate is used, the amount used is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. And more preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected. If the amount exceeds 30 parts by mass, the orientation of the liquid crystal may be deteriorated.

A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino-substituted , Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3) -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-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-naphthooxazoline, 2- (β-naphthoylmethylene) -3-methylbenzooxazoline, 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-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol , And 9-anthracene carboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Preferably, aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

  The polymer composition, in addition to those described above, as long as the effects of the present invention are not impaired, for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, a dielectric or conductive substance, Further, a crosslinkable compound may be added for the purpose of increasing the hardness and the density of the liquid crystal alignment film.

[Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention includes the components (A) and (B) described above, a solvent and a compound for improving the film thickness uniformity and surface smoothness, and the adhesion between the liquid crystal alignment film and the substrate. It is preferable to prepare a solution in which a compound or the like for improving the property is dissolved in an organic solvent. Here, the total content of the components (A) and (B) 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. is there.

In the polymer composition of the present embodiment, other than the component (A) and the component (B), other polymers may be mixed in a range that does not impair the liquid crystal expression ability and the photosensitive performance. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
Examples of such another polymer include a polymer made of poly (meth) acrylate, polyamic acid, polyimide, or the like, which is not a photosensitive side-chain polymer capable of exhibiting liquid crystallinity.

<Method for Manufacturing Substrate Having Liquid Crystal Alignment Film> and <Method for Manufacturing Liquid Crystal Display Element>
The method for producing a substrate having a liquid crystal alignment film of the present invention,
[I] (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
(B) a polyurea polyimide produced by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound and then imidizing the same; and (C) a polymer composition containing an organic solvent. Applying an object 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 [III] a step of heating the coating film obtained in [II];
Having.
Through the above steps, a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element having an alignment control ability can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In addition, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field driving type liquid crystal display element can be obtained.
As the second substrate, a substrate having no conductive film for driving a lateral electric field is used instead of a substrate having a conductive film for driving a lateral electric field. Since a substrate having no conductive film is used, for convenience, in the present application, the steps [I ′] to [III ′] may be abbreviated) to provide a liquid crystal alignment film having an alignment control ability. Two substrates can be obtained.

The manufacturing method of the lateral electric field driving type liquid crystal display element is as follows.
[IV] a step of obtaining the liquid crystal display element by 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 the liquid crystal;
Having. Thereby, a lateral electric field drive type liquid crystal display element can be obtained.

Hereinafter, each of the steps [I] to [III] and [IV] of the production method of the present invention will be described.
<Step [I]>
In the step [I], a polymer composition containing a photosensitive side-chain polymer exhibiting liquid crystallinity in a predetermined temperature range, polyurea, and an organic solvent on a substrate having a conductive film for driving an in-plane electric field To form a coating film.

<Substrate>
The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is of a transmission type, it is preferable to use a substrate having high transparency. In that case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
Further, an opaque substrate such as a silicon wafer can be used in consideration of application to a reflection type liquid crystal display element.

<Conductive film for driving a horizontal electric field>
The substrate has a conductive film for driving a lateral electric field.
When the liquid crystal display element is of a transmission type, examples of the conductive film include ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). However, the conductive film is not limited thereto.
In the case of a reflective liquid crystal display element, a light-reflective material such as aluminum can be used as the conductive film, but the conductive film is not limited thereto.
As a method for forming the conductive film on the substrate, a conventionally known method can be used.

The method for applying the above-described polymer composition onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
The method of application is industrially generally 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 (rotational coating method), and a spray method, and these may be used according to the purpose.

After applying the polymer composition on a substrate having a conductive film for driving a horizontal electric field, the polymer composition is heated to 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. The coating can be obtained by evaporating the solvent at 150 ° C. The drying temperature at this time is preferably lower than the liquid crystal phase onset temperature of the side chain type polymer.
If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, the thickness is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
It is also possible to provide a step of cooling the substrate on which the coating film is formed to room temperature after the step [I] and before the subsequent step [II].

<Step [II]>
In the step [II], the coating film obtained in the step [I] is irradiated with polarized ultraviolet light. When irradiating polarized ultraviolet light to the film surface of the coating film, the substrate is irradiated with polarized ultraviolet light from a certain direction via a polarizing plate. As an ultraviolet ray to be used, an ultraviolet ray having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected via a filter or the like depending on the type of the coating film to be used. Then, for example, ultraviolet rays having a wavelength in the 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 the polarized ultraviolet light depends on the coating film used. The irradiation amount is a polarized ultraviolet ray which realizes a maximum value of ΔA (hereinafter, also referred to as ΔAmax) which is a difference between the ultraviolet ray absorbance in a direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet ray absorbance in a perpendicular direction in the coating film. Is preferably in the range of 1% to 70% of the amount, and more preferably in the range of 1% to 50%.

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

The heating temperature is preferably within a temperature range of a temperature at which the side chain type polymer exhibits liquid crystallinity (hereinafter, referred to as a liquid crystallinity manifestation temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature of the coating film surface is lower than the liquid crystal expression temperature when a photosensitive side-chain polymer capable of expressing liquid crystal is observed in bulk. is expected. For this reason, the heating temperature is more preferably within the temperature range of the temperature at which liquid crystallinity develops on the coating film surface. That is, the temperature range of the heating temperature after the irradiation of the polarized ultraviolet rays is a lower limit of 10 ° C. lower than the lower limit of the temperature range of the liquid crystallinity manifestation temperature of the side chain polymer to be used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that the temperature be in a range having the temperature as the upper limit. When the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, it may be difficult to reorient in one direction due to self-organization.
The liquid crystallinity development temperature is equal to or higher than the glass transition temperature (Tg) at which the side chain type polymer or the surface of the coating film undergoes a phase transition from a solid phase to a liquid crystal phase, and from the liquid crystal phase to an isotropic phase (isotropic phase). At or below the isotropic phase transition temperature (Tiso) at which a phase transition occurs.

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

<Step [IV]>
In the [IV] step, the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a lateral electric field, obtained in [III], and the above [I '] to [III'] The obtained substrate with a liquid crystal alignment film (second substrate) having no conductive film is disposed so as to be opposed to both liquid crystal alignment films via liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of fabricating a horizontal electric field drive type liquid crystal display element. Steps [I ′] to [III ′] were performed in the same manner as in step [I] except that a substrate having no horizontal electric field driving conductive film was used instead of the substrate having the horizontal electric field driving conductive film. It can be performed in the same manner as in steps [I] to [III]. The difference between the steps [I] to [III] and the steps [I '] to [III'] is only the presence or absence of the above-described conductive film, and thus the description of the steps [I '] to [III'] is omitted. I do.

  To give an example of manufacturing a liquid crystal cell or a liquid crystal display element, the above-described first and second substrates are prepared, spacers are scattered on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is on the inside. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which spacers are scattered, and then the substrate is bonded and sealed. , Etc. can be exemplified. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a lateral 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. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

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

  Hereinafter, the first embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group, a structure having a photo-fleece rearrangement group or a group causing an isomerization as a photoreactive group will be described. An embodiment using the side chain type polymer will be described as a second embodiment.

  FIG. 1 schematically shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. FIG. 3 is a diagram of one example described in FIG. FIG. 1A is a diagram schematically showing a state of the side chain type polymer film before irradiation with polarized light, and FIG. 1B is a diagram schematically showing a state of the side chain type polymer film after irradiation with polarized light. FIG. 1 (c) is a view schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is small, that is, in the case of the present invention. FIG. 7 is a schematic view showing the case where the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes ΔA in the first embodiment.

  FIG. 2 is a schematic view showing an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. FIG. 3 is a diagram of one example described in FIG. FIG. 2A is a diagram schematically illustrating a state of the side-chain type polymer film before irradiation with polarized light, and FIG. 2B is a diagram schematically illustrating a state of the side-chain type polymer film after irradiation with polarized light. FIG. 2C is a view schematically showing the state of the side-chain type polymer film after heating, and particularly when the introduced anisotropy is large, that is, the second embodiment of the present invention. FIG. 7 is a schematic diagram in the case of Embodiment 1, in which the amount of ultraviolet irradiation in the step [II] is in the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes ΔA.

  FIG. 3 shows a side chain type polymer having a photoisomerizable group as a photoreactive group or a photo-fleece rearrangement group represented by the above formula (18) in the second embodiment of the present invention. FIG. 7 is a diagram of one example schematically illustrating an anisotropic introduction process in a method for producing a used liquid crystal alignment film. FIG. 3A is a diagram schematically illustrating a state of the side-chain type polymer film before polarized light irradiation, and FIG. 3B is a diagram schematically illustrating a state of the side-chain type polymer film after polarized light irradiation. FIG. 3 (c) is a view schematically showing the state of the side chain type polymer film after heating, and particularly when the introduced anisotropy is small, that is, in the case of the present invention. FIG. 9 is a schematic diagram in the case of the second embodiment, in which the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA.

  FIG. 4 shows the production of a liquid crystal alignment film using a side chain polymer having a photo-fleece rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically anisotropic introduction processing in a method. FIG. 4A is a diagram schematically illustrating a state of the side-chain type polymer film before irradiation with polarized light, and FIG. 4B is a diagram schematically illustrating a state of the side-chain type polymer film after irradiation with polarized light. FIG. 4 (c) is a view schematically showing the state of the side chain type polymer film after heating. In particular, when the introduced anisotropy is large, that is, in the case of the present invention, FIG. 9 is a schematic diagram in the case of the second embodiment, in which the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA.

  In the first embodiment of the present invention, in the treatment for introducing anisotropy into the coating film, the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes ΔA. In this case, first, the coating film 1 is formed on the substrate. As shown in FIG. 1A, a coating film 1 formed on a substrate has a structure in which side chains 2 are randomly arranged. According to the random arrangement of the side chains 2 of the coating 1, the mesogen component and the photosensitive group of the side chains 2 are also randomly oriented, and the coating 1 is isotropic.

  In the first embodiment of the present invention, in the treatment for introducing anisotropy into the coating film, the amount of ultraviolet irradiation in the step [II] is in the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes ΔA. In this case, first, the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogen component and the photosensitive group of the side chain 4 are also randomly oriented, and the coating film 2 is isotropic.

  In the second embodiment of the present invention, the side chain type of a structure having a photoisomerizable group or a photo-fleece rearrangement group represented by the above formula (18) by the treatment for introducing anisotropy into a coating film. In the case where the liquid crystal alignment film using a polymer is used, when the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, first, Then, a coating film 5 is formed. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. According to the random arrangement of the side chains 6 of the coating film 5, the mesogen component and the photosensitive group of the side chains 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

  In the second embodiment of the present invention, in the process of introducing anisotropy into a coating film, a liquid crystal alignment using a side-chain polymer having a structure having a photo-fleece rearrangement group and represented by the above formula (19). In the case where the film is used, when the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, first, the coating film 7 is formed on the substrate. . As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the coating 7, the mesogen component and the photosensitive group of the side chains 8 are also randomly oriented, and the coating 7 is isotropic.

  In the first embodiment of the present invention, when the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes ΔA, the isotropic coating film 1 On the other hand, polarized ultraviolet light is irradiated. Then, as shown in FIG. 1B, the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially undergoes a dimerization reaction or the like. Causes a light reaction. As a result, the density of the photo-reacted side chains 2a slightly increases 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 invention, when the amount of ultraviolet irradiation in the step [II] is within the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, the isotropic coating film 3 On the other hand, polarized ultraviolet light is irradiated. Then, as shown in FIG. 2B, the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially undergoes a dimerization reaction or the like. Causes a light reaction. As a result, the density of the photo-reacted side chains 4a increases in the polarization direction of the irradiation ultraviolet light, and as a result, the coating film 3 is given a small anisotropy.

  In the second embodiment of the present invention, using a liquid crystal alignment film using a photoisomerizable group or a side chain type polymer having a structure having a photo-fleece rearrangement group represented by the above formula (18), In the case where the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet light. Then, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially undergoes photo-fries rearrangement or the like. Causes a light reaction. As a result, the density of the photo-reacted side chains 6a slightly increases in the polarization direction of the irradiation ultraviolet light, and as a result, the coating film 5 is provided with a very small anisotropy.

  In the second embodiment of the present invention, using a coating film using a side chain polymer having a structure having a photo-fleece rearrangement group represented by the above formula (19), the amount of ultraviolet irradiation in the step [II] Is within the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, the isotropic coating film 7 is irradiated with polarized ultraviolet light. Then, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially undergoes photo-fries rearrangement or the like. Causes a light reaction. As a result, the density of the photo-reacted side chains 8a increases in the polarization direction of the irradiation ultraviolet light, and as a result, the coating film 7 is given a small anisotropy.

  Next, in the first embodiment of the present invention, when the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes ΔA, the coating film 1 after the irradiation of polarized light is used. Is heated to a liquid crystal state. Then, as shown in FIG. 1C, in the coating film 1, the amount of the generated cross-linking reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet light and the direction perpendicular thereto. In this case, since the amount of the cross-linking reaction generated in the direction parallel to the polarization direction of the irradiation ultraviolet light is extremely small, the cross-linking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiation ultraviolet rays becomes higher than the liquid crystallinity in the parallel direction, and self-organizes in the direction parallel to the polarization direction of the irradiation ultraviolet rays, and the side chain 2 containing the mesogen component is reoriented. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.

  Similarly, in the first embodiment of the present invention, when the amount of ultraviolet irradiation in the step [II] is within the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, the coating film after polarized light irradiation 3 is heated to a liquid crystal state. Then, as shown in FIG. 2C, in the side-chain type polymer film 3, the amount of the generated cross-linking reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet light and the direction perpendicular to the direction. Therefore, the side chains 4 containing the mesogen component are self-organized in a direction parallel to the polarization direction of the irradiation ultraviolet light, and are re-oriented. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, so that the coating film 3 is given more anisotropy.

  Similarly, in the second embodiment, a coating film using a photoisomerizable group or a side chain type polymer having a structure having a photo-fleece rearrangement group represented by the above formula (18) is used. Then, when the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, the coating film 5 after irradiation with polarized light 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 Fries rearrangement reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet light and the direction perpendicular to the polarization direction. In this case, since the liquid crystal alignment force of the optical fleece dislocation generated in the direction perpendicular to the polarization direction of the irradiation 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 irradiation ultraviolet light. The side chain 6 containing the mesogen component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photo-fleece rearrangement reaction is amplified by heat, so that a larger anisotropy is imparted to the coating film 5.

  Similarly, in the second embodiment, a coating film using a side chain type polymer having a structure having a photo-fleece rearrangement group and represented by the above-mentioned formula (19) is used, and the step [II] is performed. When the amount of ultraviolet irradiation is in the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes ΔA, the coating film 7 after polarized light irradiation is heated to be in a liquid crystal state. Then, as shown in FIG. 4 (c), in the side-chain type polymer film 7, the amount of the generated photo-fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiation ultraviolet light and the direction perpendicular to the direction. . Since the anchoring force of the optical fleece dislocation 8 (a) is stronger than that of the side chain 8 before dislocation, when a certain amount or more of the optical fleece dislocation is generated, the dislocation self-organizes in a direction parallel to the polarization direction of the irradiation ultraviolet light. The side chain 8 containing the mesogen component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photo-Fries rearrangement reaction is amplified by heat, so that the coating film 7 is given more anisotropy.

  Therefore, the coating film used in the method of the present invention is a liquid crystal alignment film having high anisotropy introduced with high efficiency by sequentially performing irradiation of polarized ultraviolet light and heating treatment to the coating film, and having excellent alignment control ability. can do.

  In the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet light to the coating film and the heating temperature in the heat treatment are optimized. Thereby, highly efficient introduction of anisotropy into the coating film can be realized.

  The irradiation amount of polarized ultraviolet light that is optimal for introducing highly efficient anisotropy into the coating film used in the present invention is such that a photosensitive group in the coating film undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photo-Fries rearrangement reaction. Corresponds to the dose of polarized UV radiation to optimize the dose. As a result of irradiating the coating film used in the present invention with polarized ultraviolet light, if the number of photosensitive groups in the side chain that undergoes photocrosslinking reaction or photoisomerization reaction, or photofleece rearrangement reaction is small, the amount of photoreaction will not be sufficient. . In that case, even after heating, sufficient self-organization does not proceed. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to the structure having a photocrosslinkable group, a crosslinking reaction between the side chains occurs when the photosensitive group of the side chain to be crosslinked becomes excessive. It will go too far. In that case, the obtained film becomes rigid, which may hinder the progress of self-assembly by subsequent heating. Further, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to the structure having a photo-Fries rearrangement group, if the photosensitive group of the side chain that undergoes a photo-Fries rearrangement reaction becomes excessive, the liquid crystallinity of the coating film is increased. Will be too low. In that case, the liquid crystallinity of the obtained film is also reduced, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the irradiation amount of the ultraviolet light is too large, the side chain type polymer is photolyzed, and the progress of self-assembly by subsequent heating is hindered. It may be.

  Therefore, in the coating film used in the present invention, the optimal amount of the photo-crosslinking reaction, photo-isomerization reaction, or photo-Fries rearrangement reaction of the photosensitive group in the side chain by irradiation with polarized ultraviolet light is determined by the amount of the side-chain type polymer film. Preferably, it is 0.1 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%, of the photosensitive group contained in. By setting the amount of the photoreactive side chain photosensitive group in such a range, the self-assembly in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy can be formed in the film. Become.

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

  That is, for the coating film used in the present invention, after the irradiation of the polarized ultraviolet light, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption in the perpendicular direction are measured. Based on 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 direction perpendicular to the polarization direction, 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 rays realizing the maximum value are obtained. In the production method of the present invention, a preferable amount of polarized ultraviolet light to be irradiated in the production of the liquid crystal alignment film can be determined based on the amount of polarized ultraviolet light that achieves the ΔAmax.

  In the production method of the present invention, the irradiation amount of 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 that achieves ΔAmax, and more preferably 1% to More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet light within the range of 1% to 50% of the amount of the polarized ultraviolet light that achieves ΔAmax is 0.1% of the entire photosensitive group of the side chain type polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light for photocrosslinking reaction.

  From the above, in the production method of the present invention, in order to realize highly efficient anisotropy introduction into the coating film, the above-described suitable heating temperature is set based on the liquid crystal temperature range of the side chain type polymer. It is better 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 that the heating temperature after irradiation with polarized ultraviolet rays is 90 ° C to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

  By doing so, 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 driving type liquid crystal display element manufactured by the method of the present invention or the lateral electric field driving type liquid crystal display element having the substrate has excellent reliability, and has a large screen and high definition. It can be suitably used for liquid crystal televisions.
Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

The abbreviations used in the examples are as follows.
<Methacrylic monomer>

MA1 was synthesized by the synthesis method described in Patent Document (WO2011-084646).
MA2 was synthesized by the synthesis method described in Patent Document (JP-A-9-118717).
A1 was synthesized by a synthesis method described in Patent Document (WO2014-054785).

<Diisocyanate component>
ISO: isophorone diisocyanate

<Diamine component>
DDM: 4,4'-diaminodiphenylmethane Me-4APhA: N-methyl-2- (4-aminophenyl) ethylamine Me-DADPA: 4,4'-diaminodiphenyl (N-methyl) amine

<Tetracarboxylic dianhydride>
TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride BODA: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride

<Organic solvent>
THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyl lactone

<Polymerization initiator>
AIBN: 2,2'-azobisisobutyronitrile

<Synthesis example 1 of methacrylate polymer>
MA1 (5.3 g), MA2 (19.6 g), HBAGE (0.34 g) and A1 (0.18 g) were dissolved in THF (102.6 g), deaerated by a diaphragm pump, and then AIBN. (0.39 g) was added, and the mixture was degassed again. Thereafter, the mixture was reacted at 60 ° C. for 8 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried in an oven at 40 ° C. under reduced pressure to obtain a methacrylate polymer powder MP1.

<Synthesis example 1 of polyurea-amic acid>
As a diamine component, DDM (5.35 g), Me-DADPA (0.32 g), and Me-4APhA (0.22 g) were dissolved in 76.8 g of NMP, and ISO (6.53 g) as a diisocyanate was added thereto at room temperature. The mixture was stirred for 1 hour, and then TDA (4.32 g) as an acid dianhydride was added at room temperature and reacted at 60 ° C. for 18 hours to obtain a solution of polyurea-amic acid (PUPAA-1) having a concentration of 15% by weight.

<Synthesis example 2 of polyurea-amic acid>
As a diamine component, DDM (5.35 g), Me-DADPA (0.32 g), and Me-4APhA (0.22 g) were dissolved in 76.8 g of NMP, and ISO (6.53 g) as a diisocyanate was added thereto at room temperature. The mixture was added and stirred for 1 hour, and then BODA (1.93 g) as an acid dianhydride was added at room temperature and reacted at 60 ° C. for 1 hour. Thereafter, acid dianhydride TDA (2.14 g) was further added and reacted for 18 hours to obtain a solution of polyurea-amic acid (PUPAA-2) having a concentration of 15% by weight.

<Synthesis example 1 of polyurea-imide>
NMP (50 g) was added to the solution having a concentration of 15 wt% (PUPAA-1, 30 g) obtained in Synthesis Example 1 of polyurea-amic acid to dilute the solution to a concentration of 6 wt%. .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure to obtain a polyurea-imide powder. The imidation ratio of this polyurea-imide was 96%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI1) having a concentration of 15 wt%.

<Polyurea-imide synthesis example 2>
NMP (50 g) was added to the 15 wt% solution (PUPAA-2, 30 g) obtained in Synthesis Example 2 of polyurea-amic acid to dilute the solution to a concentration of 6 wt%, and then acetic anhydride (6 g) was used as an imidization catalyst. .42 g) and pyridine (2.49 g) were added, and the mixture was stirred at room temperature for 30 minutes and reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried at 40 ° C. under reduced pressure to obtain a polyurea-imide powder. The imidation ratio of this polyurea-imide was 73%. Thereafter, NMP was added and redissolved to obtain a polyurea-imide solution (PUPI2) having a concentration of 15% by weight.

(Example 1)
NMP (2.35 g) is added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the methacrylate polymer synthesis example 1 and stirred for 30 minutes to obtain a methacrylate polymer solution. 2.8 g of a polyurea-imide solution (PUPI-1) and GBL (5.25 g) were added thereto, and the mixture was stirred at room temperature for 1 hour. Further, BCS (5.5 g) was added to the solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid content of 3.5 wt%. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.

(Example 2, Controls 1, 2)
With the composition shown in Table 5, the same method as in Example 1 was used to obtain a polymer solution of Example 2. Controls 1 and 2 were adjusted in the same manner.

[Production of liquid crystal cell]
Using the liquid crystal aligning agent (A1) obtained in Example 1, a liquid crystal cell was manufactured in the following procedure. The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which a comb-shaped pixel electrode formed by patterning an ITO film was arranged. The pixel electrode has a comb-like shape formed by arranging a plurality of square-shaped electrode elements whose central portion is bent. The width in the lateral direction of each electrode element was 10 μm, and the interval between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent-shaped electrode elements at the center portion, the shape of each pixel is not rectangular but is similar to the electrode element at the center portion. It had a shape that resembled a bold, U-shaped bend. Each pixel was vertically divided with the center bent portion as a boundary, and had a first region above the bent portion and a second region below the bent 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 orientation direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed so as to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode element of the pixel electrode was formed so as to form an angle of -15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the application of the voltage between the pixel electrode and the counter electrode in the substrate plane 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 substrate with electrodes. Next, drying was performed for 90 seconds on a hot plate at 70 ° C. to form a liquid crystal alignment film having a thickness of 100 nm. Next, the coating film surface was irradiated with 313 nm ultraviolet rays at 15 mJ / cm ² through a polarizing plate, and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as an opposing substrate, and was subjected to an alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical) was printed on the liquid crystal alignment film on one substrate. Next, the other substrate was bonded so that the surfaces of the liquid crystal alignment films faced each other so that the alignment direction was 0 °, and then the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-3019 (manufactured by Merck Ltd.) is injected into the empty cell by a reduced pressure 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.

  Regarding the liquid crystal aligning agent (A2) obtained in Example 2 and the liquid crystal aligning agents (C1 and C2) obtained in Controls 1 and 2, liquid crystal cells were prepared in the same manner as in A1.

(Evaluation of voltage holding ratio (VHR))
The evaluation of VHR was performed by applying a voltage of 1 V to the obtained liquid crystal cell at a temperature of 70 ° C., measuring the voltage after 1000 ms, and calculating how much the voltage could be held as a voltage holding ratio. The initial voltage holding ratio measured after manufacturing the liquid crystal cell was VHR1, and the voltage holding ratio measured after one week after performing the backlight aging test was VHR2.
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Corporation.

The results were as shown in Table 2 below.

  As shown in Table 2, in Examples 1 and 2 according to the present invention, the initial voltage holding ratio (VHR1) and the voltage holding ratio after backlight aging (VHR2) were higher than those of the control. found.

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

Claims (14)

(A) a side chain type polymer having a photosensitive side chain which exhibits liquid crystallinity in a predetermined temperature range and causes photocrosslinking, photoisomerization, or photofries transition;
(B) a polyurea polyimide produced by a polymerization reaction of a diisocyanate compound, a tetracarboxylic acid derivative, and an aromatic diamine compound, followed by imidization, and (C) an organic solvent. Coalescing composition. Diisocyanate compound, an aromatic diisocyanate and / or aliphatic diisocyanate composition of claim 1. The component (A) is represented by the following formulas (1) to (6)
(Wherein, A, B, D are each independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO Represents -O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto 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 thereto may be replaced by a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a same selected from the substituents thereof; A group in which two to six different rings are bonded via a bonding group B, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 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 a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are each independently —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—. May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are 1 on the one hand and 0 on the other hand;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. Provided that when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; 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;
11 is 0 or 1;
12 is an integer from 0 to 2;
When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
The composition according to claim 1, which has any one type of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formulas (7) to (10)
(Wherein, A, B, 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-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a same selected from the substituents thereof; A group in which two to six different rings are bonded via a bonding group B, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms). represents a 5 alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
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 (however, when n = 0, B is a single bond);
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; _-NO 2 each a hydrogen atom is bound _{independently, -CN, -CH = C (CN} ) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or 1 to 5 carbon atoms May be substituted with an alkyloxy group;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁₎
The composition according to claim 1, which has any one type of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formulas (11) to (13)
(In the formula, A is independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O- Or -O-CO-CH = CH-;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is the same or different from those rings. _Two to six rings are a single bond, -O-, -CH2-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O -CO-CH = CH- is formed by bonding group via a, -COOR ₀ (wherein each independently hydrogen atom which binds them, the _{R 0} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms _{represented),} - NO 2, substituted _{-CN, -CH = C (CN)} 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Or a hydroxy group or an alkoxy having 1 to 6 carbon atoms Represents a group)
The composition according to claim 1, which has any one type of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formula (14) or (15)
(In the formula, A independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, Or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those rings. _Two to six different rings are a single bond, -O-, -CH2-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or- O—CO—CH ＝ CH— is a group bonded via a CH—, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) the _{represented), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted;
l represents an integer of 1 to 12, m1 and m2 represent integers of 1 to 3)
The composition according to claim 1, having a photosensitive side chain represented by the formula:

The component (A) is represented by the following formula (16) or (17)
(In the formula, A is a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, or -O- Represents CO-CH = CH-;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition according to claim 1, having a photosensitive side chain represented by the formula:

The component (A) is represented by the following formula (18) or (19)
(Wherein, A, B are each independently a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-COO —, Or —O—CO—CH ＝ CH—;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those rings. _Two to six different rings are a single bond, -O-, -CH2-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or- O—CO—CH ＝ CH— is a group bonded via a CH—, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) the _{represented), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted;
q1 and q2 are 1 on the one hand and 0 on the other hand;
l represents an integer of 1 to 12, m1 and m2 represent an integer of 1 to 3;
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group)
The composition according to claim 1, which has any one type of photosensitive side chain selected from the group consisting of:

The component (A) is represented by the following formula (20)
(In the formula, A represents a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-CO-O-, or -O Represents -CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those rings. _Two to six different rings are a single bond, -O-, -CH2-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or- O—CO—CH ＝ CH— is a group bonded via a CH—, and the hydrogen atoms bonded thereto are each independently —COOR ₀ (where R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) the _{represented), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted;
X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH represents 2 and the number of X is 2, Xs may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2)
The composition according to claim 1, having a photosensitive side chain represented by the formula:

The component (A) is represented by the following formulas (21) to (31)
(Wherein, A and B each independently represents a single _{bond, -O -, - CH 2 -} , - COO -, - OCO -, - CONH -, - NH-CO -, - CH = CH-COO —, Or —O—CO—CH ＝ CH—;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. There, -NO 2 each a hydrogen atom independently connecting them, _-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms or may be substituted with an alkyl group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, —NO ₂ , —CN, —CH ＝ C (CN) ₂ , —CH ＝ CH—CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, and a nitrogen-containing group. Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
q1 and q2 are 1 on the one hand and 0 on the other hand;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that, in the formulas (23) to (24), the sum of all m is 2 or more, and the formulas (25) to (26) )), 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 heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms; And represents 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 composition according to any one of claims 1 to 9, having any one type of liquid crystalline side chain selected from the group consisting of:

[I] a step of applying the composition according to any one of claims 1 to 10 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 [III] a step of heating the coating film obtained in [II];
A method for producing a substrate having a liquid crystal alignment film, wherein a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element having an alignment control ability is provided by having the above.   A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device obtained from the composition according to claim 1.   A horizontal electric field drive type liquid crystal display device having the substrate according to claim 12. Preparing a substrate (first substrate) according to claim 12;
[I ′] a step of applying the polymer composition according to any one of claims 1 to 10 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 [III '] a step of heating the coating film obtained in [II'];
Obtaining a liquid crystal alignment film provided with alignment control ability by having: a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal. A step of disposing the first and second substrates to face each other so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, wherein a liquid crystal display element is obtained.

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