JP2019148716A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

To provide a substrate with a liquid crystal alignment film for lateral electric field-driven liquid crystal display elements, which offers highly efficient and stable alignment control capability and a superior burn-in property, and to provide a lateral electric field-driven liquid crystal display element having the same.SOLUTION: A polymeric composition is provided, containing a specific polymer (P) having a photoalignable group and a polar group, and a specific solvent (X) represented by a formula (OS-1) below. In the formula, Rthrough Rindependently represent a hydrogen atom or alkyl group with a carbon number in a range of 1 to 3.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent image sticking characteristics.

  The liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years. 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 element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

  The liquid crystal alignment film is formed on a surface in contact with the liquid crystal of the substrate sandwiching the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. The ability to control the alignment of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as alignment control ability) is given by performing an alignment treatment on the 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 such as cotton, nylon or polyester in the 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 crystals, it has been industrially used in the manufacturing process of conventional liquid crystal display elements. As an organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.

  However, in the rubbing method in which the surface of the liquid crystal alignment film is rubbed, generation of dust and static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized.

  Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed.

  There are various photo alignment 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.

  A decomposition type photo-alignment method is known as a main photo-alignment method. For example, the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see Patent Document 1).

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

  As in the above example, the liquid crystal alignment film alignment treatment method by the photo alignment method eliminates the need for rubbing, and there is no fear of generation of dust or static electricity. An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning 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 as a technique replacing the rubbing method. And compared with the rubbing method in which the orientation control ability becomes almost constant by rubbing, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, when an alignment control ability comparable to that in the rubbing method is required, a large amount of polarized light irradiation is required, or stable liquid crystal alignment may not be realized.

  For example, in the decomposition type photo-alignment method described in Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes. Become. Even in the case of a dimerization type or photoisomerization type photo-alignment method, a large amount of ultraviolet irradiation of about several J (joule) to several tens of J may be required. Furthermore, in the case of the photo-crosslinking type or photoisomerization type photo-alignment method, since the thermal stability and light stability of the liquid crystal alignment are inferior, there is a problem that alignment failure or display burn-in occurs when a liquid crystal display element is used. was there. In particular, in a horizontal electric field drive type liquid crystal display element, since liquid crystal molecules are switched in a plane, alignment misalignment of liquid crystal after liquid crystal driving is likely to occur, and display burn-in caused by AC driving is a major issue.

  Therefore, in the photo-alignment method, there is a demand for higher efficiency of alignment treatment and realization of stable liquid crystal alignment, and liquid crystal alignment films and liquid crystals that can impart high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for aligning agents.

  The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. With the goal.

As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
(1) A polymer composition containing a specific polymer (P) having a photo-alignment group and a polar group, and a specific solvent (X) represented by the following formula (OS-1).

In the formula, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

According to the liquid crystal aligning agent using the composition of the present invention, the substrate having the liquid crystal alignment film for a lateral electric field driving type liquid crystal display element, which has high efficiency and high alignment control ability and excellent image sticking characteristics, and the substrate are provided. A horizontal electric field drive type liquid crystal display element can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
<Specific polymer (P)>
The specific polymer (P) contained in the liquid crystal aligning agent of the present invention has a photoalignable group and a polar group (however, the group containing the photoalignable group is excluded). By adopting such a form, it becomes possible to interact with the hydroxy group contained in the specific solvent, and it becomes possible to obtain a liquid crystal aligning agent having excellent storage stability and an appropriate viscosity. Examples of the polar group include a carboxy group, an amino group, and a hydroxyl group. In the specific polymer (P), the photoalignable group and the polar group may be the same structural unit or different structural units, but are included in different structural units in that they are easily synthesized. It is preferable. The specific polymer (P) includes a structural unit containing a side chain group (f) having a photoalignable group and a structural unit containing a side chain group (g) having a polar group, from the viewpoint of high sensitivity to light. It is preferable.
[Photo-alignment group]
The photo-alignment group is a functional group that gives anisotropy to the film by causing a crosslinking reaction, an isomerization reaction, or a photo-Fries rearrangement in response to light. The photo-alignment group is not particularly limited, but a functional group that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a functional group that undergoes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.

Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing a cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, a chalcone or a derivative thereof. Chalcone-containing group including as a basic skeleton, benzophenone-containing group including benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group including coumarin or a derivative thereof as a basic skeleton, a tolan-containing group including tran or a derivative thereof as a basic skeleton, stilbene or a derivative thereof Examples thereof include a stilbene-containing group including a derivative, a phenylbenzoate-containing group including phenylbenzoate or a derivative thereof.
When the specific polymer (P) of the present invention is used for the production of a horizontal alignment type liquid crystal element, it preferably has a partial structure that exhibits liquid crystallinity, and the liquid crystal alignment film obtained in this case is stable. Liquid crystal alignment can be realized.
[Partial structure that exhibits liquid crystallinity]
Examples of the partial structure (m) that exhibits liquid crystallinity include a structure having a mesogen moiety. In the specific polymer (P), the mesogen moiety may be the same structural unit as the photoalignable group or a different structural unit. When the mesogenic moiety is the same structural unit as the photoalignable group, the side chain group (f) preferably has a partial structure (m) from the viewpoint of stable liquid crystal alignment, and the mesogenic moiety used in this case Examples of the structure having a biphenyl ring, a terphenyl ring, a phenylcyclohexyl ring, an azobenzene, a phenylbenzoate, a naphthalene ring, and a benzylideneaniline. When the mesogen moiety is a structural unit different from the photoalignable group, the side chain group (g) has a partial structure (m) or other than the side chain group (g) from the viewpoint of easy polymerization. The liquid crystalline side chain group (j) preferably has a partial structure (m). Examples of the structure having a mesogen moiety used in this case include a phenylbicyclohexyl ring, a bicyclohexyl ring, The structure shown in (l1) to (l2), such as benzoic acid, can be used as a structure that becomes a mesogenic site by hydrogen bonding between side chains.

  When the specific polymer (P) has a partial structure that exhibits liquid crystallinity, the temperature range showing liquid crystallinity (hereinafter also referred to as “liquid crystal temperature range”) is not particularly limited, but the alignment regulating power of the obtained liquid crystal alignment film is not limited. From the viewpoint of sufficiently increasing the alignment stability, the liquid crystal temperature range is preferably in the range of 90 to 380 ° C, and more preferably in the range of 100 to 350 ° C.

  When the specific polymer (P) is used for the production of a horizontal alignment type liquid crystal element, the side chain groups (f) include the following formulas (1) to (6) and the following formulas (T-1) to (T-2). It is preferable that at least one side chain selected from the group consisting of

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded 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 with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded through a bonding group B, and the hydrogen atom bonded to them is substituted with —CH═C (CN) ₂ , —CH═CH—CN. Is also good;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group or a methoxy group;
V represents —CO— or —CO—O— (C ₆ H ₄ ) _n —CO— (n is an integer of 1 to 3);
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, methyl group, ethyl group, methoxy group, ethoxy group;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
k is 0 or 1;
l1 is 0 or 1 and satisfies l1 + k ≧ 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

In the formula, A, B and D each independently represent a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH— or —NH—CO—;
S is an alkylene group having 1 to 12 carbon atoms, and each hydrogen atom bonded thereto may be independently replaced with 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 with a halogen group;
When T is a single bond, B also represents a single bond;
Y ₁ is a divalent benzene ring;
P ₁ , Q ₁ and Q ₂ are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
R1 is —CN, a halogen group, a methyl group, a methylcarbonyl group, a cycloalkyl group having 3 to 7 carbon atoms, or a methoxy group.
In Y ₁ , P ₁ , Q ₁ and Q ₂ , the hydrogen atom bonded to the benzene ring is independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an (alkyl group having 1 to 5 carbon atoms) carbonyl group. Or may be substituted with an alkyloxy group having 1 to 5 carbon atoms;
X1 and X2 each independently represents a single bond, —O—, —COO— or —OCO—;
t1a, t1b, t2a and t2b are each independently 0, 1 or 2;
When the number of X ₁ is 2, X ₁ may be the same or different, and when the number of X ₂ is 2, X ₂ may be the same or different;
When the number of Q ₁ is 2, Q ₁ may be the same or different, and when the number of Q ₂ is 2, Q ₂ may be the same or different;
When the specific polymer (P) is used for the production of a horizontal alignment type liquid crystal device such as an IPS mode or an FFS mode, the side chain group (f) is selected from the above formula ( It is preferable that it is at least 1 type of side chain group chosen from 1)-(6), More preferably, following formula (1-1)-(1-3), (2-1)-(2-6) , (4-1) to (4-2), (5-1) to (5-2), and (6-1), preferably at least one side chain group selected from the group consisting of.

In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and 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).

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

In the formula, A, B, Y ₁ , q ₁ , q ₂ , m ₁ , and m ₂ have the same definition as above.

R ₁ represents a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group.

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

  When the specific polymer (P) is used for the production of a horizontal alignment type liquid crystal element such as a TN mode or an STN mode, the side chain group (f) has the above formula (from the viewpoint of achieving both liquid crystal alignment and storage stability. It is preferable to use at least one side chain group selected from the group consisting of 1), (2) and the above formulas (T-1) to (T-2), more preferably the above formulas (1-1) to (1-3), (2-1) to (2-6), the following formulas (A-1-1) to (A-1-7) and (A-2-1) to (A-2-14) And at least one side chain group selected from the group consisting of:

  In the formula, each of s1 and s2 independently represents the number of methylene groups, and is a natural number of 2 to 9.

(In the formula, s1 and s2 are each independently a natural number of 2 to 9.)
[Other liquid crystalline side groups (j)]
The other liquid crystalline side chain group (j) is preferably at least one selected from the group consisting of the following formulas (R-1) to (R-4) from the viewpoint of enhancing the orientation.

In the formula, A has the same definition as the above formulas (1-1) to (1-6);
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 2 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms;
l represents an integer of 1 to 12, and m1a to m1e, m2a to m2e, m3a, m3b, m4a, and m4b each independently represents an integer of 0 to 2, provided that the formulas (R-1) to (R— 2), m1a + m1b + m1c + m1d + m1e ≧ 2 or m2a + m2b + m2c + m2d + m2e ≧ 2 is satisfied, and in formulas (R-3) to (R-4), all m3a + m3b ≧ 1 or m4a + m4b ≧ 1 are satisfied;
R ₃ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ represents a single bond, —CO—, —CH ₂ O—, or —CF ₂ —.
[Partial structure expressing pretilt]
When the specific polymer (P) of the present invention is used for the production of a vertical alignment type liquid crystal element, the specific polymer (P) preferably has a partial structure that exhibits a pretilt.

  The partial structure that exhibits pretilt is a structure that imparts a pretilt angle to a polymer thin film formed using a liquid crystal aligning agent. Specific examples include a partial structure represented by the following formula (H).

A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furylene, 1,4- or 2,6-naphthylene or phenylene, and any hydrogen atom Is a group selected from fluorine, chlorine, cyano, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (an arbitrary hydrogen atom contained in an alkyl residue is one Substituted with a cyano group or one or more halogen atoms), R ₁ is a single bond, an oxygen atom, —COO— or —OCO—, and R ₂ is a divalent aromatic group. A divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ₃ is a single bond, an oxygen atom, —COO— or —OCO—, and R ₄ is carbon. Carbon containing a linear or branched alkyl group of 3 to 20 It is a monovalent organic group of several 3 to 40, a is an integer of 0 to 3, and * represents a bonding position.

Examples of the divalent aromatic group for R ₂ include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetra Examples thereof include a fluoro-1,4-phenylene group and a naphthylene group.

Examples of the divalent alicyclic group represented by R ₂ include trans 1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, and the like.

Examples of the divalent heterocyclic group for R ₂ include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group, 1,4-piperazine group, 1,4-piperidine group, and the like. be able to.

R ₂ may be a 1,4-phenylene group, trans 1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

Examples of the monovalent organic group having 3 to 40 carbon atoms including the linear or branched alkyl group having 3 to 20 carbon atoms of R ₄ include, for example, a linear or branched alkyl group having 13 to 20 carbon atoms, or A structure in which these alkyl groups are bonded to a cyclic group such as a cholestenyl group, a cholestanyl group, an adamantyl group, a cyclohexyl group, or a bicyclohexyl group can be mentioned, and a part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms. May be. Examples of the linear or branched alkyl group having 3 to 20 carbon atoms include, for example, n-propyl, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -Octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6 , 6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoro Propyl group, 2- (perfluorobut ) Ethyl group, 2- (perfluorooctyl) ethyl group and a 2- (perfluorodecyl) ethyl group or the like.

  The partial structure exhibiting pretilt may be the same structural unit as the photo-alignment group or may be a structural unit different from the photo-alignment. From the viewpoint of easy adjustment of the pretilt, the partial structure that develops the pretilt is preferably the same structural unit as the photoalignable group, and from the viewpoint of easy synthesis, the side chain group (f) is a moiety that exhibits the pretilt. It preferably has a structure, and specific examples of such a side chain group (f) include a side chain group of the following formula (V).

  Z is an oxygen atom or a sulfur atom.

  Xa and Xb are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms.

R ₁ , R ₂ , R ₃ , R ₄ and a have the same meanings as in formula (H).

R ₅ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom.

  b is an integer of 0-4.

The linear or branched alkylene group having 1 to 10 carbon atoms of Sb is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, an n-propylene group, An n-butylene group, a t-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group are preferable.
Sb is a linking group represented by the following formula (Sp).

In the formula, W ₁ , W ₂ and W ₃ each independently represent a single bond, a divalent heterocyclic ring, — (CH ₂ ) _n — (wherein _n represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C. In these substituents, one or more of non-adjacent CH ₂ groups independently represent —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR— , —CH═CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms) Can be substituted, right coupling of W ₃ being represents a bond to Z,
A ₁ and A ₂ are each independently a group selected from a single bond, a divalent alkyl group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group. Each group may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

  Examples of the divalent aromatic group of Sb include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro. A -1,4-phenylene group can be exemplified.

  In the formula (pa-1-a) or (pa-1-ma), as the divalent alicyclic group of Sb, for example, trans-1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene Etc.

  Examples of the divalent heterocyclic group of Sb include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group, 1,4-piperazine group, 1,4-piperidine group and the like. Can do.

  Sb is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

  The side chain group (f) having a partial structure that exhibits pretilt is at least one side chain selected from the group consisting of the following formulas (V-1) to (V-11) from the viewpoint of excellent pretilt expression. It is preferably a group.

  The type of the main skeleton of the specific polymer (P) is preferably a polymer of a monomer having a polymerizable unsaturated bond from the viewpoint of high storage stability. The monomer used for the polymerization of the specific polymer (P) is not particularly limited as long as it has a polymerizable unsaturated bond. For example, a (meth) acrylic compound, a conjugated diene compound, an aromatic vinyl compound, a maleimide compound, α -Methylene-γ-butyrolactone compound, norbornene compound and the like. From the viewpoint of easy polymerization, the specific polymer (P) is preferably a polymer obtained using a monomer containing a (meth) acrylic compound as a raw material.

  In the synthesis of the specific polymer (P), the proportion of the (meth) acrylic compound used is preferably 50 mol% or more, and preferably 60 mol% or more, based on the total amount of monomers used for the synthesis. Is more preferably 70 mol or more. In this specification, “(meth) acryl” includes acryl and methacryl.

The specific polymer (P) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. The monomer to be used preferably contains a compound having a polymerizable unsaturated bond and the side chain group (f) (hereinafter also referred to as “photo-aligning monomer”). Specific examples of the photoalignable monomer include, for example, side chain groups represented by the above formula (1) to formula (6), the above formula (T-1) to the formula (T-2), or the above formula (V). A monomer having a polymerizable unsaturated bond is exemplified. When the specific polymer (P) of the present invention contains other liquid crystalline side chain groups (j), a compound having a polymerizable unsaturated bond and other liquid crystalline side chain groups (j) ( In the following, it is preferable to include a monomer having a polymerizable unsaturated bond bonded to the other liquid crystalline side chain group (j) as a part of the raw material. It is preferable.
[Side chain group (g)]
As described above, the side chain group (g) may have a partial structure (m), and such a side chain group (g) has the following formula (R) from the viewpoint of enhancing liquid crystal alignment. It is preferably at least one side chain group selected from the group consisting of -5) to (R-9).

In the formula, A and B have the same definition as the above formulas (1-1) to (1-6);
l represents an integer of 1 to 12, _{m 5} represents an integer of _{1~3, m 7, m 8,} m 9 represents an integer of 1-2.

  The side chain group (g) may be selected from other polar group-containing side chains other than the above formulas (R-5) to (R-9). Examples of other polar group-containing side chains include side chain groups represented by the following formula (U). When the specific polymer (P) is used in a vertical alignment type liquid crystal display element, the specific polymer (P) includes a side chain group (f) and a side chain group (u) from the viewpoint of improving the vertical alignment property. It is preferable to include.

S _a represents a single bond or a divalent linking group, and I _a1 represents a monovalent organic group selected from a carboxy group, a hydroxyl group, a group having at least one partial structure of the following formula (a2), or a primary amino group. Indicates a group. However, the following formula (a2) represents a group other than the primary amino group.

In the formula, * indicates a bond.

Examples of the group having the partial structure represented by the formula (a2) include a 5-membered or 6-membered nitrogen-containing heterocycle, and examples thereof include piperidine and morpholine. Each of these groups may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups. Preferable examples of I _a1 include a monovalent organic group selected from a carboxy group and a hydroxyl group.

The divalent linking group of S _a, for example, an alkanediyl group having 1 to 10 carbon atoms (preferably 1-6), an arylene group having 6 to 20 carbon atoms (preferably having 6 to 14), (* A) -CONH-R ₆ -(* B) group, (* A) -COO-R ₇ -(* B) group and the like can be mentioned. Here, R ₆ and R ₇ are each independently a single bond, an alkanediyl group having 1 to 12 (preferably 1 to 6) carbon atoms, or an arylene having 6 to 20 (preferably 6 to 14) carbon atoms. Group, an alkyleneoxyarylene group, and any carbon-carbon bond of the alkanediyl group may have an —O— bond, and (* A) is a bond bonded to a carbon atom having an unsaturated bond. It indicates that indicates that (* B) is a bond that binds to the I _a1. Examples of the alkanediyl group include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, Propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, etc. can be mentioned. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. Examples of the alkyleneoxyarylene group include an ethyleneoxyphenylene group, a hexyleneoxyphenylene group, a hexyleneoxybiphenyl group, and the like. Among them, the divalent linking group for _{S a,} alkanediyl group having 1 to 10 carbon atoms (preferably 1-6), an arylene group having 6 to 20 carbon atoms (preferably having 6 to 14), (* A) A —COO—R ₇ — (* B) group is preferable, and R ₇ is preferably an alkanediyl group having 2 to 6 carbon atoms.

The monomer used for the synthesis of the specific polymer (P) of the present invention preferably contains a compound having a polymerizable unsaturated bond and the side chain group (g) (hereinafter also referred to as “polar monomer”). As such a compound, a compound having a side chain group selected from the formulas (R-5) to (R-9) and a polymerizable unsaturated bond, a group represented by the formula (u) and a polymerizable property Examples thereof include a compound having an unsaturated bond (hereinafter also referred to as monomer (u-1)). Among them, the polar monomer is selected from the group consisting of a compound having a polymerizable unsaturated bond bonded to a side chain group selected from (R-5) to (R-9) and a compound represented by monomer (u-1). It is preferable to use at least one selected from the above.
[Monomer (u-1)]
Examples of the monomer (u-1) include the structure of the following formula (u-1).

In the formula, I _a1 and S _a are as defined in the above formula (u), and r ¹ is 1 or 2.

Specific examples of the above formula (u-1) having a carboxy group include, for example, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, isocrotonic acid, α-ethylacrylic acid, Examples include β-ethylacrylic acid, β-propylacrylic acid, β-isopropylacrylic acid, itaconic acid, fumaric acid, and vinyl benzoic acid. Specific examples of the above formula (u-1) having an amino group include t-butylaminoethyl (meth) acrylate. Specific examples of the above formula (u-1) having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and the like; hydroxyethyl ( Other examples include (meth) acrylamide, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, and N-hydroxy (meth) acrylamide.
Specific examples of the formula (u-1) having a group having a partial structure of the formula (a2) include 2,2,6,6-tetramethyl-4-piperidyl methacrylate and the like.

  The photo-alignment monomer, polar monomer, or other liquid crystalline side chain monomer used for the synthesis of the specific polymer (P) of the present invention may be used alone or in combination of two or more. Good.

  The proportion of the photo-alignment monomer used for the synthesis of the specific polymer (P) is 5 mol% or more from the viewpoint of enhancing the photo-alignment with respect to the total amount of monomers used for the synthesis of the specific polymer (P). It is preferable that it is 10 mol% or more. The total amount of the use ratio of the photo-alignment monomer and the use ratio of the polar group monomer is preferably 100 mol% or less and more preferably 95 mol% or less from the viewpoint of enhancing storage stability.

  In synthesizing the specific polymer (P), other monomers other than those described above may be used in combination as the monomer having a polymerizable unsaturated bond. The use ratio of other monomers is preferably 50 mol% or less, more preferably 40 mol% or less, with respect to the total amount of monomers used for the synthesis of the specific polymer (P). .

  As another monomer, the monomer which can be superposed | polymerized and can be obtained industrially, for example is mentioned.

  Specific examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

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

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

  About the manufacturing method of specific polymer (P), it does not specifically limit and the general purpose method currently treated industrially can be utilized. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Sanic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

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, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl]
2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4, 4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) 4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di ( Ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloro Methyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3 '-Carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimi Sol, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′bis (2,4-dibromophenyl) -4,4 ′, 5,5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3 -(2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2, 4-cyclopentadi N-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2, -(3-Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1,3-benzothi Tetrazole -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

  The organic solvent used for the polymerization reaction of the liquid crystal aligning agent of the present invention is not particularly limited as long as the produced polymer can be dissolved. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-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 can be mentioned.

  These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.

  In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

  The polymerization temperature during radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out 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, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
[Recovery of polymer]
When the produced polymer is recovered from the reaction solution of the specific polymer (P) obtained by the above reaction, the reaction solution is poured into a poor solvent to precipitate the polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

The molecular weight of the specific polymer (P) of the present invention is a weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film. The average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
<Polymer composition>
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing the specific polymer (P) already described. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

  In the polymer composition of the present embodiment, all of the above-described resin components may be the specific polymer (P) described above, but from the viewpoint of increasing electrical characteristics and voltage holding ratio, other heavy components other than those may be used. The coalescence may be mixed. In that case, content of the other polymer in a resin component is 0.5 mass%-80 mass%, Preferably it is 1 mass%-50 mass%.

Such other polymers are made of, for example, poly (meth) acrylate, polyamic acid, polyimide, or the like, and examples include polymers other than those described above.
<Specific solvent>
The specific solvent contained in the polymer composition of the present invention is represented by the following formula (X).

Examples of the alkyl group having 1 to ³ carbon atoms of R ^{1 to} R ³ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among them, a methyl group is preferable. Specific examples of the compound represented by the above formula (OS-1) include, for example, lactamide, N, N-dimethyl lactamide, N, N-diethyl lactamide, N-methyl-N-propyl lactamide, N-ethyl. Examples include lactamide and N-isopropyl lactamide, and among them, N, N-dimethyl lactamide is particularly preferable.

1-100 mass% of the whole solvent contained in a liquid crystal aligning agent is preferable, and, as for content of the said specific solvent, 1-90 mass% is more preferable.
<Other solvents>
The other organic solvent used in the polymer composition of the present invention is not particularly limited as long as it is an organic solvent that 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, Dimethylsulfone, hexamethylsulfoxide, 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 in combination.

  The polymer composition used in the present invention may contain components other than the specific polymer (P). Examples include solvents and compounds that improve film thickness uniformity and surface smoothness when a polymer composition is applied, compounds that improve adhesion to the substrate, and the like. Not.

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

  For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol 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, 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- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.

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

  Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  More specifically, for example, Ftop (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 Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

  Specific examples of the compound that improves the adhesion to 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-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

  Furthermore, the following phenoplast type or epoxy group-containing compound additives are included in the polymer composition for the purpose of preventing deterioration of electrical characteristics due to the backlight when the substrate and the liquid crystal display element are constituted. May be. Specific phenoplast 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, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (for example, manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “TE RAD-C ", etc.), N, N, N ', N', - such as tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

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

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

As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino substituted Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.

  Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

In addition to the polymer composition described above, a dielectric material or a conductive material may be added to the polymer composition for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the obtained liquid crystal alignment film.
<Manufacturing method of liquid crystal element>
The liquid crystal element of the present invention comprises an alignment film formed using the polymer composition of the present invention as described above. The driving mode of the liquid crystal element of the present invention is not particularly limited, and can be applied to various driving modes. A liquid crystal element can be manufactured by the method including the following processes 1 to 3, for example. In step 1, the substrate to be used varies depending on the desired operation mode. Step 2 and step 3 are common to each operation mode.
(1) The process of forming a coating film on a board | substrate using the polymer composition of this invention,
(2) a step of applying a treatment for imparting orientation to the coating film surface, and (3) a pair of substrates on which the coating film is formed are arranged opposite to each other so that the coating film faces each other through a layer of liquid crystal molecules. A step of configuring a cell.

  Hereafter, each said manufacturing method is demonstrated in order.

[First manufacturing method]
In the step (1) in the first manufacturing method, the substrate to be used differs depending on the desired operation mode. Step (3) is common to each operation mode.
[Step (1); Formation of coating film]
First, the polymer composition of the present invention is applied on a substrate, and then the coated surface is heated to form a coating film on the substrate.
(1-1) For example, when manufacturing a TN mode, STN mode, or VA mode liquid crystal display element, first, a pair of two substrates provided with patterned transparent conductive films is formed, and each transparent conductive film is formed. On the surface, the polymer composition of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. As the substrate, for example, glass such as float glass and soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. From the viewpoint of expanding the application range of the liquid crystal element, it is preferable to use a transparent substrate made of the above plastic. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), or the like can be used.

After applying the polymer composition, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied polymer composition. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. The pre-baking may be performed in one stage or in multiple stages including two or more stages.
(1-2) When manufacturing a liquid crystal display element of IPS mode or FFS mode, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. A coating film is formed by applying the polymer composition of the present invention to one surface of the counter substrate that is not formed, and then heating each coated surface. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, and the preferred film thickness of the coating film to be formed, A film made of a metal such as chromium can be used.

In both cases (1-1) and (1-2), after the polymer composition is applied on the substrate, the organic solvent is removed to form a coating film that becomes an alignment film.
[Step (2-A): Orientation treatment]
By irradiating the coating film formed on the substrate as described above with light, liquid crystal alignment ability is imparted to the coating film to form a liquid crystal alignment film. Examples of light to be irradiated here include ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. Irradiation light may be polarized or non-polarized. As the polarized light, it is preferable to use light including linearly polarized light.

  When the light to be used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized light, it is necessary to carry out from a direction oblique to the substrate surface.

  Examples of the light source used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). Polarized light can be obtained by means of using these light sources in combination with, for example, a filter or a diffraction grating.

The amount of light irradiation is preferably 0.1 mJ / cm 2 or more and less than 1,000 mJ / cm 2, more preferably 1 to 500 mJ / cm 2, and even more preferably 2 to 200 mJ / cm 2. When the liquid crystal aligning agent of the present invention is used, the light irradiation amount is 500 mJ.
Even if it is / cm 2 or less, and even 200 mJ / cm 2 or less, good liquid crystal alignment ability can be imparted by the photo-alignment method, which contributes to the reduction of the manufacturing cost of the liquid crystal alignment film.

Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.
[Step (2-B): Heat treatment]
When manufacturing a TN mode, STN mode, IPS mode, or FFS mode liquid crystal element, in addition to the above step (2-A), heat treatment is performed from the viewpoint of reducing the amount of light irradiation and obtaining stable liquid crystal alignment. It is preferable to do. For the heat treatment, heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven can be used.

  When the specific polymer (P) has a partial structure that exhibits liquid crystallinity, the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is manifested.

  From the viewpoint of high anisotropy amplification effect due to heat in the coating film, the temperature range of the heat treatment is lower than the lower limit of the temperature range of the liquid crystal expression temperature of the specific polymer (P) used, The temperature is preferably in a range where the upper limit is a temperature 10 ° C. lower than the upper limit of the liquid crystal temperature range.

The film thickness of the film formed by the alignment treatment step is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.
[Step (3): Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film obtained by the alignment treatment is prepared are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other.

  In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. can do. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

  In step 3, a liquid crystal cell containing a polymerizable monomer in the liquid crystal layer is constructed, and the polymerizable liquid crystal cell is polymerized by irradiating light to the constructed liquid crystal cell to give an initial alignment of the liquid crystal. May be. By performing this treatment, it is preferable in that a liquid crystal element excellent in response speed can be obtained.

  As the polymerizable monomer, a compound having two or more (meth) acryloyl groups can be preferably used from the viewpoint of high polymerizability by light. Specific examples thereof include, for example, di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, di (meth) acrylate having a 2,2-diphenylpropane structure, and di (meth) acrylate having a diphenylmethane structure ( (Meth) acrylate, di-thio (meth) acrylate having a diphenylthioether structure, di (meth) acrylate having a naphthalene structure, di (meth) acrylate having an anthracene structure, di (meth) acrylate having a phenanthrene structure, by light irradiation Examples thereof include di (meth) acrylate having a structure that generates radicals. The mixing ratio of the polymerizable monomer is preferably 0.1 to 1.0% by mass with respect to the total amount of the liquid crystal composition used for forming the liquid crystal layer. In addition, a polymerizable monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The light irradiation to the liquid crystal cell may be performed in a state in which no voltage is applied between the pair of electrodes, may be performed in a state in which a predetermined voltage (for example, 0 V) that does not drive the liquid crystal molecules in the liquid crystal layer is applied, or You may carry out in the state which applied the predetermined voltage which a liquid crystal molecule drives. When applying the liquid crystal aligning agent of this indication to a liquid crystal element provided with a transverse electric field type liquid crystal cell, it is preferred to irradiate light to a liquid crystal cell in the state where voltage is not applied between a pair of electrodes. As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. When the radiation to be used is linearly polarized light or partially polarized light, the light irradiation direction may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the irradiation direction is an oblique direction.

  As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the above-mentioned preferable wavelength region can be obtained by means using a light source in combination with, for example, a filter diffraction grating. The irradiation amount of light is preferably 1,000 to 200,000 J / m2, and more preferably 1,000 to 100,000 J / m2.

  Instead of mixing the polymerizable monomer in the liquid crystal layer, the liquid crystal alignment film may be mixed, and the liquid crystal cell may be irradiated with light to impart initial alignment to the liquid crystal. In this case, in Step 1, a coating film is formed on the substrate using a polymer composition containing a polymerizable monomer. As the polymerizable monomer contained in the polymer composition, the explanation of the polymerizable monomer contained in the liquid crystal layer is applied. The content ratio of the polymerizable monomer is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the polymer components contained in the polymer composition. .

  Subsequently, a liquid crystal element is obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as necessary. Examples of the polarizing plate include a polarizing plate comprising a polarizing film called an “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself.

The liquid crystal element of the present disclosure can be effectively applied to various applications, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors. It can be used for various display devices such as liquid crystal televisions and information displays, and light control films. Moreover, the liquid crystal element formed using the polymer composition of this indication can also be applied to retardation film.
<Example>
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

Abbreviations used in the examples are as follows.
(Methacrylic monomer)

In formulas (MA1) and (MA3) to (MA5), the double bond represents the E form. )
(Polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile (crosslinking agent component)
TETRAD-C: 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane

  MA1 was synthesized by a synthesis method described in a patent document (WO2011 / 084546).

MA2 was synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
MA3 was synthesized by the synthesis method described in Synthesis Example 1 below.
MA4 was synthesized by the synthesis method described in British Patent GB2306470B.
MA5 was synthesized by a synthesis method described in non-patent literature (Macromolecules 2007, 40, 6355-6360).
For MAA (methacrylic acid) and TETRAD-C, commercially available reagents were used.
Abbreviations of organic solvents used in this example are shown below.
<Organic solvent>
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone DML: N, N-dimethyllactoamide BCS: Butyl cellosolve PGME: Propylene glycol monomethyl ether CHN: Cyclohexanone HG: Hexylene glycol <Molecular weight measurement>
The molecular weight of the polymer in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200, Shodex column (KD-803, KD-805), manufactured by Senshu Scientific.
Column temperature: 50 ° C
Eluent: DMF (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, THF 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).
<Measurement of ¹ HNMR>
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) “INOVA-400” (manufactured by Varian) 400 MHz.
Solvent: deuterated chloroform (CDCl ₃ ) or deuterated N, N-dimethyl sulfoxide ([D ₆ ] -DMSO).
Standard substance: Tetramethylsilane (TMS).
<< Synthesis of monomer and polymer >>
<Monomer Synthesis Example 1>
Synthesis of [MA3]:

  In a 2 L four-necked flask, 1-bromo-4- (trans- ■ 4-pentylcyclohexyl) -benzene (150.0 g, 485 mmol), tert-butyl acrylate (93.24 g, 728 mmol), palladium acetate (2.18 g, 9.7 mmol), tri (o-tolyl) phosphine (5.90 g, 20 mmol), tripropylamine (208.5 g, 1455 mmol) and DMAc (750 g) are added and heated to 100 ° C. Stir. After completion of the reaction, the reaction solution was filtered to remove insoluble matters, and the filtrate was poured into pure water (3.8 L) and neutralized with 12N-HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured and extracted. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator, and the crude product was repulped with cold methanol (190 g) to obtain 137.0 g of [MA-3-1] (white solid) (yield) 79%).

[MA-3-1] (137.0 g, 384 mmol) and formic acid (1000 g) were added to a 2 L four-necked flask and stirred while heating to 50 ° C. After completion of the reaction, the reaction solution was poured into pure water (3.0 L), and the precipitate was filtered. The obtained crude product was repulped with ethyl acetate (200 g) to obtain 111.8 g of [MA-3-2] (white solid) (yield 96%). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [MA-3-2].
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 12.34 (s, 1H), 7.53-7.60 (m, 3H), 7.25-7.27 (d, 2H), 6.44-6.48 (d, 1H), 2.45-2.51 (t, 1H), 1.77-1.83 (t, 4H), 1.38-1.48 (m, 2H) ), 1.17-1.34 (m, 9H), 0.97-1.07 (m, 2H), 0.87-0.89 (t, 3H).
In a 2 L four-necked flask, [MA-2-2] (30.0 g, 100 mmol), 2-hydroxyethyl methacrylate (15.6 g, 119 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide Hydrochloride (EDC) (28.7 g, 150 mmol), 4-dimethylaminopyridine (1.22 g, 10 mmol) and THF (150 g) were added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was poured into ethyl acetate (1.0 L) and extracted with pure water (800 ml). To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated by a rotary evaporator. The obtained residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 5 volume ratio) to obtain 36.6 g of [MA3] (white solid) (yield 88%). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [MA3].
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 7.62-7.66 (m, 3H), 7.25-7.27 (d, 2H), 6.58-6.62 (d , 1H), 6.04 (s, 1H), 5.70 (s, 1H), 4.36-4.42 (m, 4H), 2.48-2.52 (t, 1H), 1. 88 (s, 3H), 1.76-1.83 (t, 4H), 1.36-1.44 (m, 2H), 1.18-1.31 (m, 9H), 1.00- 1.03 (m, 2H), 0.85-0.88 (t, 3H).
<Polymer synthesis example 1>
MA1 (3.99 g, 12.0 mmol), MA2 (5.52 g, 18.0 mmol) were dissolved in THF (88.5 g), and after deaeration with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder (A). This polymer had a number average molecular weight of 15,000 and a weight average molecular weight of 30,000.
<Polymer synthesis example 2>
After MA3 (2.5 g, 6.0 mmol) and MAA (2.0 g, 24.0 mmol) were dissolved in CHN (12.8 g) and PGME (12.8 g) and deaerated with a diaphragm pump AIBN (0.2 g, 1.0 mmol) was added as a polymerization initiator, and deaeration was performed again. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer powder (B) was obtained. The number average molecular weight of this polymer was 41,000, and the weight average molecular weight was 139000.
<Polymer synthesis example 3>
MA5 (34.5 g: 60 mmol) and MA4 (17.3 g: 40 mmol) are dissolved in THF (282 g), deaerated with a diaphragm pump, then AIBN (0.5 g: 3 mmol) is added to deaerate again. Went. Thereafter, the mixture was reacted at 60 ° C. for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder (C). This polymer had a number average molecular weight of 25,000 and a weight average molecular weight of 95,000.
<< Preparation of liquid crystal aligning agent >>
<Example 1>
DML (56.0 g) was added to the obtained methacrylate polymer powder (A) (4.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. By adding BCS (40.0 g) to this solution and stirring, a liquid crystal aligning agent (A1) was obtained.
<Example 2>
CHN (10.0 g), PGME (30.0 g), DML (56.0 g) and TETRAD-C (1.2 g) are added to 4.0 g of the obtained methacrylate polymer powder (B) and stirred at room temperature. As a result, a liquid crystal aligning agent (B1) was obtained.
<Comparative Example 1>
NMP (56.0 g) was added to the resulting methacrylate polymer powder (A) (4.0 g) and dissolved by stirring at room temperature for 5 hours. BCS (40.0 g) was added to this solution and stirred to obtain a liquid crystal aligning agent (A2).
<Comparative example 2>
NMP (66.0 g) was added to the resulting methacrylate polymer powder (A) (4.0 g) and dissolved by stirring at room temperature for 5 hours. HG (30.0 g) was added to this solution and stirred to obtain a liquid crystal aligning agent (A3).
<Comparative Example 3>
CHN (10.0 g), PGME (30.0 g), NMP (56.0 g) and TETRAD-C (1.2 g) are added to 4.0 g of the obtained methacrylate polymer powder (B), and the mixture is stirred at room temperature. As a result, a liquid crystal aligning agent (B2) was obtained.
<Comparative Example 4>
NMP (46.0 g) was added to the resulting methacrylate polymer powder (C) (4.0 g) and dissolved by stirring at room temperature for 1 hour. CHN (50.0 g) was added to this solution to obtain a liquid crystal aligning agent (C1) having a solid content concentration of 4.0 wt%.
<Comparative Example 5>
DML (46.0 g) was added to the obtained methacrylate polymer powder (C) (4.0 g), and the mixture was dissolved by stirring at room temperature for 1 hour. CHN (50.0 g) was added to this solution to obtain a liquid crystal aligning agent (C2) having a solid content concentration of 4.0 wt%.

  Table 1 shows the monomer compositions of the liquid crystal aligning agents obtained in the examples and comparative examples.

<Viscosity measurement>
The viscosity of the liquid crystal aligning agent was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample amount of 1.1 mL, a cone rotor TE-1 (1 ° 34 ′, R24), and a temperature of 25 ° C. .
It was 13.0 mPa * s when the liquid crystal aligning agent (A1) obtained in Example 1 was measured. For Example 2 and Comparative Examples 1 to 5, the viscosity was measured using the same method as in Example 1. The results are shown in Table 2.
<Storage stability>
The storage stability was evaluated based on whether the liquid crystal aligning agent was stored at −20 ° C. for 24 hours and then no cloudiness or precipitation was observed in the solution. Table 2 shows the results obtained using the liquid crystal aligning agents obtained in Examples 1 to 2 and Comparative Examples 1 to 5.

* 1 Figures in parentheses indicate the weight ratio of the additive to 100 parts by weight of the polymer.
* 2 Figures in parentheses indicate the weight ratio of the polymer to 100 parts by weight of the polymer solids and the solvent.
* 3 Figures in parentheses indicate the weight ratio of each solvent to the total 100 parts by weight of polymer solids and solvent.
As shown in Table 2, when the polymer powder (A): Example 1 and Comparative Example 1 and the polymer powder (B): Example 2 and Comparative Example 2 were compared, the viscosity of the liquid crystal aligning agent containing DML was greatly increased. I can read that.
On the other hand, since the viscosity of the polymer powder (C): Comparative Example 3 and Comparative Example 4 is not much different, the carboxyl groups contained in the side chain sites of the polymer powders (A) and (B) are specifically salted with DML. , I think that it is thickened by the interaction.
<< Preparation of liquid crystal alignment film >>
The liquid crystal aligning agents obtained in Examples and Comparative Examples were pressure filtered through a membrane filter having a pore diameter of 1 μm, and a liquid crystal aligning film was prepared according to the following procedure.
<Liquid crystal aligning agents A1 to A3>
The obtained solution was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, and dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film having a thickness of 100 nm. Next, the surface of the coating film is irradiated with 313 nm linearly polarized ultraviolet light having an irradiation intensity of 4.3 mW / cm ^{2 in} the normal direction of the substrate through 10 mJ / cm ² through a polarizing plate, and then baked on a 120 ° C. hot plate for 10 minutes. Thus, a substrate with a liquid crystal alignment film was obtained.
The linearly polarized ultraviolet light was prepared by passing a 313 nm band-pass filter through the ultraviolet light of a high-pressure mercury lamp and then passing it through a 313 nm polarizing plate.
<Liquid crystal aligning agent B1-B2>
The obtained solution was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, dried on a hot plate at 50 ° C. for 120 seconds, and then baked on a hot plate at 120 ° C. for 2 minutes. A liquid crystal alignment film was formed. The coating surface is irradiated with 313 nm linearly polarized ultraviolet rays having an irradiation intensity of 4.3 mW / cm ² through an angle inclined by 40 ° from the normal direction of the substrate through 50 mJ / cm ² to obtain a substrate with a liquid crystal alignment film. It was. The linearly polarized ultraviolet light was prepared by passing a 313 nm band-pass filter through the ultraviolet light of a high-pressure mercury lamp and then passing it through a 313 nm polarizing plate.
<Liquid crystal aligning agent C1-C2>
The obtained solution was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, and dried on a hot plate at 40 ° C. for 300 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Next, the coating surface was irradiated with 313 nm linearly polarized ultraviolet light having an irradiation intensity of 4.3 mW / cm ² through an angle of 40 ° from the normal direction of the substrate through 40 mJ / cm ² and then hot at 120 ° C. By baking for 10 minutes with the plate, the board | substrate with a liquid crystal aligning film was obtained.
The linearly polarized ultraviolet light was prepared by passing a 313 nm band-pass filter through the ultraviolet light of a high-pressure mercury lamp and then passing it through a 313 nm polarizing plate.

Claims (18)

The polymer composition containing the specific polymer (P) which has a photo-alignment group and a polar group, and the specific solvent (X) represented by a following formula (OS-1).

In the formula, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The specific polymer (P) according to claim 1, comprising a structural unit containing a side chain group (f) having a photoalignable group and a structural unit containing a side chain group (g) having a polar group. Polymer composition. The polymer composition according to claim 1, wherein the specific polymer (P) is a polymer of a monomer having a polymerizable unsaturated bond. The polymer composition according to any one of claims 1 to 3, wherein the polymer composition is used for forming a liquid crystal alignment film. The said photo-alignment group is a functional group which gives anisotropy to a film | membrane by causing a crosslinking reaction, an isomerization reaction, or a light Fleece rearrangement in response to light. The polymer composition described in 1. The polymer composition according to any one of claims 1 to 5, wherein the specific polymer (P) has a partial structure (m) that exhibits liquid crystallinity. The polymer composition according to any one of claims 2 to 6, wherein the side chain group (f) has the partial structure (m). The side chain group (f) is at least one side chain group selected from the group consisting of the following formulas (1) to (6) and the following formulas (T-1) to (T-2). The polymer composition according to claim 7.

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded 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 with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded through a bonding group B, and the hydrogen atom bonded to them is substituted with —CH═C (CN) ₂ , —CH═CH—CN. Is also good;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group or a methoxy group;
V represents —CO— or —CO—O— (C ₆ H ₄ ) _n —CO— (n is an integer of 1 to 3);
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, methyl group, ethyl group, methoxy group, ethoxy group;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
k is 0 or 1;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

In the formula, A, B and D each independently represent a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH— or —NH—CO—;
S is an alkylene group having 1 to 12 carbon atoms, and each hydrogen atom bonded thereto may be independently replaced with 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 with a halogen group;
When T is a single bond, B also represents a single bond;
Y1 is a divalent benzene ring;
P1, Q1 and Q2 are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
R1 is —CN, a halogen group, a methyl group, a methylcarbonyl group, a cycloalkyl group having 3 to 7 carbon atoms, or a methoxy group.
In Y1, P1, Q1, and Q2, hydrogen atoms bonded to the benzene ring are each independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, (an alkyl having 1 to 5 carbon atoms) carbonyl group, or a carbon number. Optionally substituted with 1 to 5 alkyloxy groups;
X1 and X2 each independently represents a single bond, —O—, —COO— or —OCO—;
t1a, t1b, t2a and t2b are each independently 0, 1 or 2;
When the number of X1 is 2, X1 may be the same or different; when the number of X2 is 2, X2 may be the same or different;
When the number of Q1 is 2, Q1 may be the same or different, and when the number of Q2 is 2, Q2 may be the same or different; The polymer according to any one of claims 2 to 8, wherein the side chain group (g) is at least one selected from the group consisting of the following formulas (R-5) to (R-9). Composition.

In the formula, A and B have the same definition as the above formulas (1-1) to (1-6); l represents an integer of 1 to 12. The said specific polymer (P) has the partial structure which expresses a pretilt, The polymer composition as described in any one of Claims 1-9 characterized by the above-mentioned. The polymer composition according to claim 10, wherein the side chain group (f) has a partial structure that exhibits pretilt, and the structure is represented by the following formula (V).

Z is an oxygen atom or a sulfur atom.
Xa and Xb are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms.
R ₁ is a single bond, an oxygen atom, —COO— or —OCO—, and R ₂ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring. R ₃ is a single bond, an oxygen atom, —COO— or —OCO—, and R ₄ is a 1 to 3 carbon atom containing a linear or branched alkyl group having 3 to 20 carbon atoms. Valent organic group,
R ₅ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom.
a is an integer of 0 to 3, and b is an integer of 0 to 4. Sb is a linking group represented by the following formula (Sp).

In the formula, W ₁ , W ₂ and W ₃ each independently represent a single bond, a divalent heterocyclic ring, — (CH ₂ ) _n — (wherein _n represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C. In these substituents, one or more of non-adjacent CH ₂ groups independently represent —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR— , —CH═CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms) Can be substituted, right coupling of W ₃ being represents a bond to Z,
A ₁ and A ₂ are each independently a group selected from a single bond, a divalent alkyl group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group. Each group may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group. The specific polymer (P) is a polymer obtained by polymerizing a monomer having a polymerizable unsaturated bond, and the photo-alignment in which the monomer has a polymerizable unsaturated bond and a side chain group (f) The polymer composition as described in any one of Claims 1-11 containing a sex monomer. The use ratio of the photo-alignment monomer used for the synthesis of the specific polymer (P) is 5 mol% or more based on the total amount of the monomers used for the synthesis of the specific polymer (P). Polymer composition. The polymer according to any one of claims 1 to 13, wherein the monomer used for the synthesis of the specific polymer (P) includes a polar monomer having a polymerizable unsaturated bond and a side chain group (g). Composition. The polymer composition according to claim 14, wherein the total of the usage ratio of the photo-alignment monomer and the usage ratio of the polar monomer is 100 mol% or less. The liquid crystal aligning film formed using the polymer composition as described in any one of Claims 1-15. A liquid crystal device comprising the liquid crystal alignment film according to claim 16. The process of apply | coating the polymer composition as described in any one of Claims 1-14 on a board | substrate, forming a coating film, and light-irradiating the board | substrate surface which apply | coated the said polymer composition, and said And a step of imparting liquid crystal alignment ability to the coating film.